# Patent

## Title
Rubber composition and pneumatic tire

## Abstract

The present invention provides a rubber composition that can enhance the fuel economy, wet-grip performance, and abrasion resistance in a balanced manner, and a pneumatic tire using this rubber composition. The present invention relates to a rubber composition that contains a rubber component, silica, and a silane coupling agent, wherein the rubber component contains, based on 100% by mass of the rubber component, not less than 5% by mass of a conjugated diene polymer containing a constituent unit based on a conjugated diene and a constituent unit represented by formula (I) below, at least one terminal of the polymer being modified with a specific compound; an amount of the silica is 5 to 150 parts by mass per 100 parts by mass of the rubber component; and the silane coupling agent contains a mercapto group.

## Background
TECHNICAL FIELD
The present invention relates to a rubber composition and a pneumatic tire produced using the rubber composition.
BACKGROUND ART
The demands on automobiles for better fuel economy have been increasing in recent years as concern with environmental issues has been rising. Good fuel economy is also being required of the rubber compositions used for automotive tires. For example, rubber compositions containing a conjugated diene polymer (e.g., polybutadiene, butadiene-styrene copolymer) and a filler (e.g., carbon black, silica) are used for the rubber compositions for automotive tires.
Patent Literature 1, for example, proposes a method for enhancing the fuel economy. This method uses a diene rubber that has been modified with an organosilicon compound containing an amino group and an alkoxy group. These days, however, further enhancement of the fuel economy has been demanded. Meanwhile, wet-grip performance and abrasion resistance are also properties required of the rubber compositions for automotive tires; however, these properties generally assume an inverse relationship with the fuel economy. Thus, it has been difficult to achieve the respective properties at high levels in a balanced manner.
Moreover, in order to meet the demand for fuel economy, silica-containing rubber compositions have been used in not only treads but also other various components. However, silica has a lower affinity for rubber (in particular, natural rubber, butadiene rubber, styrene butadiene rubber, and others that are often used for tires) than carbon black due to hydrophilic silanol groups on its surface. Thus, silica is often inferior in terms of abrasion resistance and mechanical strength (tensile strength, elongation at break).
Use of a silane coupling agent and use of highly reinforcing silica such as finely divided silica are known as the methods for improving the above properties.
However, such highly reinforcing silica generally exhibits low dispersion in rubber compositions. Therefore, the abrasion resistance and mechanical strength may not be much improved, or even may be deteriorated.
Conventional silane coupling agents generally used in rubber compositions for tires (e.g. bis(3-triethoxysilylpropyl)disulfide, bis(3-triethoxysilylpropyl)tetrasulfide) greatly improve the dispersibility of silica to impart good mechanical properties. However, since a large amount of silane coupling agent is necessary to favorably disperse highly reinforcing silica, the cost increases greatly. Moreover, the addition of even a sufficient amount of silane coupling agent may fail to provide good dispersion.
Use of a mercapto group-containing silane coupling agent has been proposed which has higher reactivity than the aforementioned conventional coupling agents (for example, see Patent Literature 2). Although such highly reactive silane coupling agents have high performance, they cause the scorch time to be considerably shortened, making their practical use difficult in the tire industry. Therefore, currently such silane coupling agents are hardly ever used.
Patent Literature 3 discloses a silica-containing rubber composition for a tire that can enhance the wet-grip performance without deteriorating the performance in terms of rolling resistance and abrasion resistance. However, this rubber composition still needs to be improved in terms of enhancing these properties in a balanced manner.
CITATION LIST
Patent Literature


    Patent Literature 1: JP 2000-344955 A
    Patent Literature 2: JP 2009-126907 A
    Patent Literature 3: JP 2008-31244 A


SUMMARY OF INVENTION
Technical Problem
An object of the present invention is to solve the problems identified above by providing a rubber composition that provides a well-balanced enhancement of fuel economy, wet-grip performance, and abrasion resistance, and by providing a pneumatic tire produced using the rubber composition.
Solution to Problem
The present invention relates to a rubber composition, including a rubber component, silica, and a silane coupling agent,
wherein the rubber component contains, based on 100% by mass of the rubber component, not less than 5% by mass of a conjugated diene polymer containing a constituent unit based on a conjugated diene and a constituent unit represented by formula (I) below, at least one terminal of the polymer being modified with at least one compound selected from the group consisting of a compound represented by formula (II) below, a compound containing a group represented by formula (III) below, a compound represented by formula (IV) below, a silicon compound containing at least one of a group represented by formula (V) below and a group represented by formula (VI) below, and a compound containing a group represented by formula (VII) below,
an amount of the silica is 5 to 150 parts by mass per 100 parts by mass of the rubber component, and
the silane coupling agent contains a mercapto group,




wherein X1, X2, and X3 each independently represent a group represented by formula (Ia) below, a hydroxy group, a hydrocarbyl group, or a substituted hydrocarbyl group, and at least one of X1, X2, and X3 is a hydroxy group or a group represented by the following formula (Ia):





wherein R1 and R2 each independently represent a C1-6 hydrocarbyl group, a C1-6 substituted hydrocarbyl group, a silyl group, or a substituted silyl group, and R1 and R2 may be bonded to each other to form a cyclic structure together with the nitrogen atom;





wherein n represents an integer of 1 to 10; R11, R12, and R13 each independently represent a C1-4 hydrocarbyl group or a C1-4 hydrocarbyloxy group, and at least one of R11, R12, and R13 is a hydrocarbyloxy group; and A1 represents a nitrogen atom-bearing functional group;





wherein p represents an integer of 0 or 1; T represents a C1-20 hydrocarbylene group or a substituted hydrocarbylene group; and A2 represents a nitrogen atom-bearing functional group;





wherein g represents an integer of 1 to 10; R21 represents a hydrogen atom, a C1-6 hydrocarbyl group, or a C1-6 substituted hydrocarbyl group; A3 represents an oxygen atom or the following group: —NR22— where R22 represents a hydrogen atom or a C1-10 hydrocarbyl group; and A4 represents a functional group bearing at least one of a nitrogen atom and an oxygen atom;





wherein w represents an integer of 1 to 11, and A5 represents a nitrogen atom-bearing functional group.

R1 and R2 in formula (Ia) are preferably C1-6 hydrocarbyl groups.
Two of X1, X2, and X3 in formula (I) are preferably selected from a group represented by formula (Ia) and a hydroxy group.
A1 in formula (II) is preferably a group represented by the following formula (IIa):




wherein R14 and R15 each independently represent a C1-6 group optionally containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a silicon atom, R14 and R15 may be bonded to each other to form a cyclic structure together with the nitrogen atom, and R14 and R15 may form a single group bonded to the nitrogen via a double bond.

The group represented by formula (III) is preferably a group represented by the following formula (IIIa):




The compound containing a group represented by formula (III) is preferably at least one compound selected from the group consisting of a compound represented by formula (IIIa-1) below, a compound represented by formula (IIIa-2) below, and a compound represented by formula (IIIa-3) below,




wherein R31 represents a hydrogen atom, a C1-10 hydrocarbyl group, a C1-10 substituted hydrocarbyl group, or a heterocyclic group containing at least one of a nitrogen atom and an oxygen atom as a heteroatom; and R32 and R33 each independently represent a C1-10 group optionally containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a silicon atom, R32 and R33 may be bonded to each other to form a cyclic structure together with the nitrogen atom, and R32 and R33 may form a single group bonded to the nitrogen via a double bond;





wherein e represents an integer of 0 to 10, and R34 and R35 each independently represent a C1-20 hydrocarbyl group or a C1-20 substituted hydrocarbyl group;





wherein f represents an integer of 0 to 10, and R36 represents a C1-20 hydrocarbyl group or a C1-20 substituted hydrocarbyl group.

The compound containing a group represented by formula (III) is preferably a compound represented by the following formula (IIIb-1):




wherein R37 represents a hydrogen atom, a C1-10 hydrocarbyl group, a C1-10 substituted hydrocarbyl group, or a heterocyclic group containing at least one of a nitrogen atom and an oxygen atom as a heteroatom; R38 and R39 each independently represent a C1-10 group optionally containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a silicon atom, R38 and R39 may be bonded to each other to form a cyclic structure together with the nitrogen atom, and R38 and R39 may form a single group bonded to the nitrogen via a double bond; and T represents a C1-20 hydrocarbylene group or a C1-20 substituted hydrocarbylene group.

The compound represented by formula (IIIb-1) is preferably at least one compound selected from the group consisting of a compound represented by formula (IIIb-1-1) below, and a compound represented by formula (IIIb-1-2) below,




wherein r represents an integer of 1 or 2; and Y1 represents a nitrogen atom-bearing functional group that is a substituent on the benzene ring, and when a plurality of Y1's are present, the plurality of Y1's may be the same as or different from one another;





wherein s represents an integer of 1 or 2; t represents an integer of 0 to 2; Y2 and Y3 each represent a nitrogen atom-bearing functional group that is a substituent on the benzene ring, and when a plurality of Y2's are present, the plurality of Y2's may be the same as or different from one another, and when a plurality of Y3's are present, the plurality of Y3's may be the same as or different from one another.

A4 in formula (IV) is preferably a hydroxy group or a group represented by the following formula (IVa):




wherein R23 and R24 each independently represent a C1-6 group optionally containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a silicon atom, R23 and R24 may be bonded to each other to form a cyclic structure together with the nitrogen atom, and R23 and R24 may form a single group bonded to the nitrogen via a double bond.

The silicon compound preferably contains a group represented by the following formula (VIII):




wherein R41, R42, and R43 each independently represent a C1-4 hydrocarbyl group or a C1-4 hydrocarbyloxy group, and at least one of R41, R42, and R43 is a hydrocarbyloxy group.

The silicon compound preferably contains a group represented by the following formula (Va):




wherein h represents an integer of 1 to 10, and R44, R45, and R46 each independently represent a C1-4 hydrocarbyl group or a C1-4 hydrocarbyloxy group, and at least one of R44, R45, and R46 is a hydrocarbyloxy group.

The compound containing a group represented by formula (VII) is preferably a compound represented by the following formula (VII-1):




wherein z represents an integer of 0 to 10; R71 represents a C1-5 hydrocarbyl group; R72, R73, R74 and R75 each independently represent a hydrogen atom, a C1-5 hydrocarbyl group, a C1-5 substituted hydrocarbyl group, or a C1-5 hydrocarbyloxy group, and when a plurality of R72's and a plurality of R73's are present, the plurality of R72's and the plurality of R73's may be the same as or different from one another; and R76 and R77 each independently represent a C1-6 group optionally containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a silicon atom, R76 and R77 may be bonded to each other to form a cyclic structure together with the nitrogen atom, and R76 and R77 may form a single group bonded to the nitrogen via a double bond.

One of R74 and R75 in formula (VII-1) is preferably a hydrogen atom.
The conjugated diene polymer preferably has a vinyl bond content of at least 10 mol % but not more than 80 mol % per 100 mol % of the constituent unit based on a conjugated diene.
Preferably, the rubber composition contains at least one of natural rubber and butadiene rubber.
The silica preferably has a nitrogen adsorption specific surface area of 40 to 400 m2/g.
The silane coupling agent is preferably at least one of a compound represented by formula (1) below and a compound containing a linking unit A represented by formula (2) below and a linking unit B represented by formula (3) below,




wherein R101 to R103 may be the same as or different from one another, and R101 to R103 each represent a branched or unbranched C1-12 alkyl group, a branched or unbranched C1-12 alkoxy group, or a group represented by —O—(R111—O)b—R112 where b R111s may be the same as or different from one another, and b R111s each represent a branched or unbranched C1-30 divalent hydrocarbon group; R112 represents a branched or unbranched C1-30 alkyl group, a branched or unbranched C2-30 alkenyl group, a C6-30 aryl group, or a C7-30 aralkyl group; and b represents an integer of 1 to 30; and R104 represents a branched or unbranched C1-6 alkylene group;





wherein R201 represents a hydrogen atom, a halogen atom, a branched or unbranched C1-30 alkyl group, a branched or unbranched C2-30 alkenyl group, a branched or unbranched C2-30 alkynyl group, or the alkyl group in which a terminal hydrogen atom is substituted by a hydroxy group or a carboxyl group; R202 represents a branched or unbranched C1-30 alkylene group, a branched or unbranched C2-30 alkenylene group, or a branched or unbranched C2-30 alkynylene group; and R201 and R202 together may form a cyclic structure.

The rubber composition is preferably for use as a rubber composition for a tread.
The present invention also relates to a pneumatic tire, produced using the foregoing rubber composition.
Advantageous Effects of Invention
The present invention relates to a rubber composition including a specific conjugated diene polymer, silica, and a silane coupling agent containing a mercapto group (mercapto-based silane coupling agent). Thus, the present invention can provide a pneumatic tire that is improved in fuel economy, wet-grip performance, and abrasion resistance in a balanced manner.


DESCRIPTION OF EMBODIMENTS
The rubber composition of the present invention contains silica, a mercapto-based silane coupling agent, and a conjugated diene polymer containing a constituent unit based on a conjugated diene and a constituent unit represented by formula (I) below, at least one terminal of the polymer being modified with at least one compound selected from the group consisting of a compound represented by formula (II) below, a compound containing a group represented by formula (III) below, a compound represented by formula (IV) below, a silicon compound containing a group represented by formula (V) below and/or a group represented by formula (VI) below, and a compound containing a group represented by formula (VII) below.




In the formula, X1, X2, and X3 each independently represent a group represented by formula (Ia) below, a hydroxy group, a hydrocarbyl group, or a substituted hydrocarbyl group, and at least one of X1, X2, and X3 is a hydroxy group or a group represented by the following formula (Ia):




wherein R1 and R2 each independently represent a C1-6 hydrocarbyl group, a C1-6 substituted hydrocarbyl group, a silyl group, or a substituted silyl group, and R1 and R2 may be bonded to each other to form a cyclic structure together with the nitrogen atom.





In the formula, n represents an integer of 1 to 10; R11, R12, and R13 each independently represent a C1-4 hydrocarbyl group or a C1-4 hydrocarbyloxy group, and at least one of R11, R12, and R13 is a hydrocarbyloxy group; and A1 represents a nitrogen atom-bearing functional group.




In the formula, p represents an integer of 0 or 1; T represents a C1-20 hydrocarbylene group or a C1-20 substituted hydrocarbylene group; and A2 represents a nitrogen atom-bearing functional group.




In the formula, g represents an integer of 1 to 10; R21 represents a hydrogen atom, a C1-6 hydrocarbyl group, or a C1-6 substituted hydrocarbyl group; A3 represents an oxygen atom or the following group: —NR22— where R22 represents a hydrogen atom or a C1-10 hydrocarbyl group; and A4 represents a functional group bearing a nitrogen atom and/or an oxygen atom.




In the formula, w represents an integer of 1 to 11, and A5 represents a nitrogen atom-bearing functional group.
The conjugated dienes for the conjugated diene-based constituent unit can be exemplified by 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and 1,3-hexadiene, and one, or two or more of these may be used. Preferred are 1,3-butadiene and isoprene, in view of ease of availability.
X1, X2, and X3 in formula (I) of the constituent unit represented by formula (I) each independently represent a group represented by formula (Ia), a hydroxy group, a hydrocarbyl group, or a substituted hydrocarbyl group, and at least one of X1, X2, and X3 is a group represented by formula (Ia) or a hydroxy group.
R1 and R2 in formula (Ia) each independently represent a C1-6 hydrocarbyl group, a C1-6 substituted hydrocarbyl group, a silyl group, or a substituted silyl group, and R1 and R2 may be bonded to each other to form a cyclic structure together with the nitrogen atom.
As used herein, the term “hydrocarbyl group” denotes a monovalent hydrocarbon residue. This hydrocarbon residue refers to a group obtained by removing hydrogen from a hydrocarbon. The term “substituted hydrocarbyl group” denotes a group obtained by substituting one or more hydrogen atoms of a monovalent hydrocarbon residue by substituent groups. The term “hydrocarbyloxy group” denotes a group obtained by substituting the hydrogen atom of a hydroxyl group by a hydrocarbyl group. The term “substituted hydrocarbyloxy group” denotes a group obtained by substituting one or more hydrogen atoms of a hydrocarbyloxy group by substituent groups. The term “hydrocarbylene group” denotes a divalent hydrocarbon residue. The term “substituted hydrocarbylene group” denotes a group obtained by substituting one or more hydrogen atoms of a divalent hydrocarbon residue by substituent groups. The term “substituted silyl group” denotes a group obtained by substituting one or more hydrogen atoms of a silyl group by substituent groups.
The C1-6 hydrocarbyl groups encompassed by R1 and R2 can be exemplified by alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, isopentyl, and n-hexyl groups; cycloalkyl groups such as a cyclohexyl group; and a phenyl group.
The C1-6 substituted hydrocarbyl groups encompassed by R1 and R2 can be exemplified by substituted hydrocarbyl groups containing as a substituent at least one group selected from the group consisting of nitrogen atom-bearing groups, oxygen atom-bearing groups, and silicon atom-bearing groups. The groups containing a nitrogen atom-bearing group as a substituent can be exemplified by dialkylaminoalkyl groups such as dimethylaminoethyl and diethylaminoethyl groups. The groups containing an oxygen atom-bearing group as a substituent can be exemplified by alkoxyalkyl groups such as methoxymethyl, methoxyethyl, ethoxymethyl, and ethoxyethyl groups. The groups containing a silicon atom-bearing group as a substituent can be exemplified by trialkylsilylalkyl groups such as a trimethylsilylmethyl group.
The substituted silyl groups encompassed by R1 and R2 can be exemplified by trialkylsilyl groups such as trimethylsilyl, triethylsilyl, and t-butyldimethylsilyl groups.
The groups in which R1 and R2 are bonded to each other can be exemplified by C1-12 divalent groups optionally containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a silicon atom. Specific examples thereof include alkylene groups such as trimethylene, tetramethylene, pentamethylene, and hexamethylene groups; oxydialkylene groups such as oxydiethylene and oxydipropylene groups; and nitrogenous groups such as a group represented by —CH2CH2—NH—CH2— and a group represented by —CH2CH2—N═CH—.
The group in which R1 and R2 are bonded to each other is preferably a nitrogenous group, and more preferably a group represented by —CH2CH2—NH—CH2— or a group represented by —CH2CH2—N═CH—.
The hydrocarbyl group encompassed by R1 and R2 is preferably an alkyl group, more preferably a C1-4 alkyl group, further preferably a methyl group, an ethyl group, an n-propyl group, or an n-butyl group, and particularly preferably an ethyl group or an n-butyl group. The substituted hydrocarbyl group encompassed by R1 and R2 is preferably an alkoxyalkyl group, and more preferably a C1-4 alkoxyalkyl group. The substituted silyl group encompassed by R1 and R2 is preferably a trialkylsilyl group, and more preferably a trimethylsilyl group.
Preferably, R1 and R2 are a nitrogenous group in which R1 and R2 are bonded to each other, or are each independently an alkyl group, an alkoxyalkyl group, or a substituted silyl group, more preferably an alkyl group, still more preferably a C1-4 alkyl group, and further preferably a methyl group, an ethyl group, an n-propyl group, or an n-butyl group.
The group represented by formula (Ia) may be an acyclic amino group or a cyclic amino group.
The acyclic amino groups can be exemplified by dialkylamino groups such as dimethylamino, diethylamino, di(n-propyl)amino, di(isopropyl)amino, di(n-butyl)amino, di(sec-butyl)amino, di(tert-butyl)amino, di(neopentyl)amino, and ethylmethylamino groups; di(alkoxyalkyl)amino groups such as di(methoxymethyl)amino, di(methoxyethyl)amino, di(ethoxymethyl)amino, and di(ethoxyethyl)amino groups; and di(trialkylsilyl)amino groups such as di(trimethylsilyl)amino and di(t-butyldimethylsilyl)amino groups.
The cyclic amino groups can be exemplified by 1-polymethyleneimino groups such as 1-pyrrolidinyl, 1-piperidino, 1-hexamethyleneimino, 1-heptamethyleneimino, 1-octamethyleneimino, 1-decamethyleneimino, and 1-dodecamethyleneimino groups. The cyclic amino groups can also be exemplified by 1-imidazolyl, 4,5-dihydro-1-imidazolyl, 1-imidazolidinyl, 1-piperazinyl, and morpholino groups.
In view of economic efficiency and ease of availability, the group represented by formula (Ia) is preferably an acyclic amino group, more preferably a dialkylamino group, still more preferably a dialkylamino group which contains a C1-4 alkyl group as a substituent, and further preferably a dimethylamino group, a diethylamino group, a di(n-propyl)amino group, or a di(n-butyl)amino group.
The hydrocarbyl groups encompassed by X1, X2, and X3 in formula (I) can be exemplified by alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl groups. The substituted hydrocarbyl groups can be exemplified by alkoxyalkyl groups such as methoxymethyl, ethoxymethyl, methoxyethyl, and ethoxyethyl groups.
The hydrocarbyl group encompassed by X1, X2, and X3 is preferably an alkyl group, more preferably a C1-4 alkyl group, and still more preferably a methyl group or an ethyl group. The substituted hydrocarbyl group encompassed by X1, X2, and X3 is preferably an alkoxyalkyl group, and more preferably a C1-4 alkoxyalkyl group.
The hydrocarbyl group or substituted hydrocarbyl group encompassed by X1, X2, and X3 is preferably an alkyl group or an alkoxyalkyl group, more preferably a C1-4 alkyl group or a C1-4 alkoxyalkyl group, still more preferably a C1-4 alkyl group, and further preferably a methyl group or an ethyl group.
At least one of X1, X2, and X3 in formula (I) is a hydroxy group or a group represented by formula (Ia). Preferably at least two of X1, X2, and X3 are each a hydroxy group or a group represented by formula (Ia), and more preferably two of X1, X2, and X3 are each a hydroxy group or a group represented by formula (Ia). In view of achieving the fuel economy, wet-grip performance, and abrasion resistance at high levels in a balanced manner, preferably at least one of X1, X2, and X3 is a hydroxy group, more preferably at least two of X1, X2, and X3 are hydroxy groups, and still more preferably two of X1, X2, and X3 are hydroxy groups.
In view of enhancing the fuel economy, wet-grip performance, and abrasion resistance in a balanced manner, the constituent unit represented by formula (I) is preferably a constituent unit in which two of X1, X2, and X3 are, independently, an acyclic amino group or a hydroxy group. The constituent unit in which two of X1, X2, and X3 are acyclic amino groups is preferably a bis(dialkylamino)alkylvinylsilane unit and is more preferably a bis(dimethylamino)methylvinylsilane unit, bis(diethylamino)methylvinylsilane unit, bis(di(n-propyl)amino)methylvinylsilane unit, or bis(di(n-butyl)amino)methylvinylsilane unit. The constituent unit in which two of X1, X2, and X3 are hydroxy groups is preferably a dihydroxyalkylvinylsilane unit, and more preferably a dihydroxymethylvinylsilane unit.
In view of enhancing the fuel economy, wet-grip performance, and abrasion resistance in a balanced manner, the content of the constituent unit represented by formula (I) in the conjugated diene polymer, expressed per unit mass of the polymer, is preferably at least 0.001 mmol/g-polymer but not more than 0.1 mmol/g-polymer, more preferably at least 0.002 mmol/g-polymer but not more than 0.07 mmol/g-polymer, and even more preferably at least 0.003 mmol/g-polymer but not more than 0.05 mmol/g-polymer.
At least one terminal of the conjugated diene polymer is modified with a specific compound (modifying agent 1 to 5). This causes interaction with silica, thereby enhancing the fuel economy, wet-grip performance, and abrasion resistance in a balanced manner.
The following explains the compound (modifying agent 1) represented by formula (II) below.




In the formula, n represents an integer of 1 to 10; R11, R12, and R13 each independently represent a C1-4 hydrocarbyl group or a C1-4 hydrocarbyloxy group, and at least one of R11, R12, and R13 is a hydrocarbyloxy group; and A1 represents a nitrogen atom-bearing functional group.
R11, R12, and R13 in formula (II) each independently represent a C1-4 hydrocarbyl group or a C1-4 hydrocarbyloxy group, and at least one of R11, R12, and R13 is a hydrocarbyloxy group.
The hydrocarbyl groups encompassed by R11, R12, and R13 can be exemplified by alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl groups. The hydrocarbyloxy groups encompassed by R11, R12, and R13 can be exemplified by alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, and t-butoxy groups.
The hydrocarbyl group encompassed by R11, R12, and R13 is preferably an alkyl group, more preferably a C1-3 alkyl group, and still more preferably a methyl group or an ethyl group. The hydrocarbyloxy group encompassed by R11, R12, and R13 is preferably an alkoxy group, more preferably a C1-3 alkoxy group, and still more preferably a methoxy group or an ethoxy group.
In view of enhancing the fuel economy, wet-grip performance, and abrasion resistance in a balanced manner, preferably at least two of R11, R12, and R13 are hydrocarbyloxy groups, and more preferably the three of R11, R12, and R13 are hydrocarbyloxy groups.
In formula (II), n represents an integer of 1 to 10. In view of enhancing the fuel economy, wet-grip performance, and abrasion resistance in a balanced manner, n is preferably not less than 3. In view of enhancing the economic efficiency, n is preferably not more than 4. Particularly preferably, n is 3.
A1 in formula (II) is a nitrogen atom-bearing functional group and examples thereof include amino, isocyano, cyano, pyridyl, piperidyl, pyrazinyl, and morpholino groups.
A1 is preferably a group represented by the following formula (IIa).




In the formula, R14 and R15 each independently represent a C1-6 group optionally containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a silicon atom, R14 and R15 may be bonded to each other to form a cyclic structure together with the nitrogen atom, and R14 and R15 may form a single group bonded to the nitrogen via a double bond.
Examples of R14 and R15 in formula (IIa) include C1-6 hydrocarbyl groups, C1-6 substituted hydrocarbyl groups, and substituted silyl groups.
The hydrocarbyl groups encompassed by R14 and R15 can be exemplified by alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, isopentyl, and n-hexyl groups; cycloalkyl groups such as a cyclohexyl group; and a phenyl group.
The substituted hydrocarbyl groups encompassed by R14 and R15 can be exemplified by substituted hydrocarbyl groups containing as a substituent at least one group selected from the group consisting of nitrogen atom-bearing groups, oxygen atom-bearing groups, and silicon atom-bearing groups. The groups containing a nitrogen atom-bearing group as a substituent can be exemplified by dialkylaminoalkyl groups such as dimethylaminoethyl and diethylaminoethyl groups. The groups containing an oxygen atom-bearing group as a substituent can be exemplified by alkoxyalkyl groups such as methoxymethyl, methoxyethyl, ethoxymethyl, and ethoxyethyl groups; alkylene oxide groups such as epoxy and tetrahydrofuranyl groups; and alkylene oxide alkyl groups such as glycidyl and tetrahydrofurfuryl groups. The groups containing a silicon atom-bearing group as a substituent can be exemplified by trialkylsilylalkyl groups such as a trimethylsilylmethyl group.
As used herein, the term “alkylene oxide group” denotes a monovalent group obtained by removing a hydrogen atom from the ring of a cyclic ether compound. The term “alkylene oxide alkyl group” denotes a group obtained by substituting at least one hydrogen atom of an alkyl group by an alkylene oxide group.
The substituted silyl groups encompassed by R14 and R15 can be exemplified by trialkylsilyl groups such as trimethylsilyl, triethylsilyl, and t-butyldimethylsilyl groups, and trialkoxysilyl groups such as a trimethoxysilyl group.
The groups in which R14 and R15 are bonded to each other can be exemplified by C2-12 divalent groups optionally containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a silicon atom. Specific examples thereof include alkylene groups such as trimethylene, tetramethylene, pentamethylene, and hexamethylene groups; oxydialkylene groups such as oxydiethylene and oxydipropylene groups; and nitrogenous groups such as a group represented by —CH2CH2—NH—CH2— and a group represented by —CH2CH2—N═CH—.
The group in which R14 and R15 are bonded to each other is preferably a nitrogenous group, and more preferably a group represented by —CH2CH2—NH—CH2— or a group represented by —CH2CH2—N═CH—.
Examples of the single group bonded to the nitrogen via a double bond, formed by R14 and R15, include C2-12 divalent groups optionally containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a silicon atom. Specific examples thereof include an ethylidene group, a 1-methylpropylidene group, a 1,3-dimethylbutylidene group, a 1-methylethylidene group, and a 4-N,N-dimethylaminobenzylidene group.
The hydrocarbyl group encompassed by R14 and R15 is preferably an alkyl group, more preferably a C1-4 alkyl group, still more preferably a methyl group, an ethyl group, an n-propyl group, or an n-butyl group, and further preferably a methyl group or an ethyl group. The substituted hydrocarbyl group encompassed by R14 and R15 is preferably an alkoxyalkyl group, an alkylene oxide group, or an alkylene oxide alkyl group. The substituted silyl group encompassed by R14 and R15 is preferably a trialkylsilyl group or a trialkoxysilyl group, more preferably a trialkylsilyl group, and still more preferably a trimethylsilyl group or a triethylsilyl group.
Preferably, R14 and R15 are a nitrogenous group in which R14 and R15 are bonded to each other, or are each independently an alkyl group, an alkoxyalkyl group, an alkylene oxide group, an alkylene oxide alkyl group, or a substituted silyl group, more preferably an alkyl group, an alkylene oxide group, an alkylene oxide alkyl group, or a trialkylsilyl group.
The groups represented by formula (IIa) can be exemplified by acyclic amino groups and cyclic amino groups.
Examples of the acyclic amino groups include dialkylamino groups such as dimethylamino, diethylamino, di(n-propyl)amino, di(isopropyl)amino, di(n-butyl)amino, di(sec-butyl)amino, di(tert-butyl)amino, di(neopentyl)amino, and ethylmethylamino groups; di(alkoxyalkyl)amino groups such as di(methoxymethyl)amino, di(methoxyethyl)amino, di(ethoxymethyl)amino, and di(ethoxyethyl)amino groups; and di(trialkylsilyl)amino groups such as di(trimethylsilyl)amino and di(t-butyldimethylsilyl)amino groups. Other examples include di(alkylene oxide)amino groups such as di(epoxy)amino and di(tetrahydrofuranyl)amino groups; and di(alkylene oxide alkylamino groups such as di(glycidyl)amino and di(tetrahydrofurfuryl)amino groups. Additional examples include ethylideneamino, 1-methylpropylideneamino, 1,3-dimethylbutylideneamino, 1-methylethylideneamino, and 4-N,N-dimethylaminobenzylideneamino groups.
As used herein, the term “di(alkylene oxide)amino group” denotes an amino group in which two hydrogen atoms bonded to the nitrogen atom are substituted by two alkylene oxide groups. The term “di(alkylene oxide alkyl)amino group” denotes an amino group in which two hydrogen atoms bonded to the nitrogen atom are substituted by two alkylene oxide alkyl groups.
The cyclic amino groups can be exemplified by 1-polymethyleneimino groups such as 1-pyrrolidinyl, 1-piperidino, 1-hexamethyleneimino, 1-heptamethyleneimino, 1-octamethyleneimino, 1-decamethyleneimino, and 1-dodecamethyleneimino groups. The cyclic amino groups can also be exemplified by 1-imidazolyl, 4,5-dihydro-1-imidazolyl, 1-imidazolidinyl, 1-piperazinyl, and morpholino groups.
In view of fuel economy, wet-grip performance, abrasion resistance, and long-term stability and easy availability of the compound, the group represented by formula (IIa) is preferably an acyclic amino group, and more preferably a dialkylamino group, a di(alkylene oxide)amino group, a di(alkylene oxide alkyl)amino group, or a di(trialkylsilyl)amino group.
The compounds represented by formula (II) can be exemplified by compounds in which formula (IIa) is an acyclic amino group such as a dialkylamino group, a di(alkoxyalkyl)amino group, a di(alkylene oxide)amino group, a di(alkylene oxide alkyl)amino group, or a trialkylsilyl group.
The compounds in which formula (IIa) is a dialkylamino group can be exemplified by the following:
[3-(dialkylamino)propyl]trialkoxysilanes such as


    [3-(dimethylamino)propyl]trimethoxysilane,
    [3-(diethylamino)propyl]trimethoxysilane,
    [3-(ethylmethylamino)propyl]trimethoxysilane,
    [3-(dimethylamino)propyl]triethoxysilane,
    [3-(diethylamino)propyl]triethoxysilane, and
    [3-(ethylmethylamino)propyl]triethoxysilane;

[3-(dialkylamino)propyl]alkyldialkoxysilanes such as

    [3-(dimethylamino)propyl]methyldimethoxysilane,
    [3-(diethylamino)propyl]methyldimethoxysilane,
    [3-(ethylmethylamino)propyl]methyldimethoxysilane,
    [3-(dimethylamino)propyl]ethyldimethoxysilane,
    [3-(diethylamino)propyl]ethyldimethoxysilane,
    [3-(ethylmethylamino)propyl]ethyldimethoxysilane,
    [3-(dimethylamino)propyl]methyldiethoxysilane,
    [3-(diethylamino)propyl]methyldiethoxysilane,
    [3-(ethylmethylamino)propyl]methyldiethoxysilane,
    [3-(dimethylamino)propyl]ethyldiethoxysilane,
    [3-(diethylamino)propyl]ethyldiethoxysilane, and
    [3-(ethylmethylamino)propyl]ethyldiethoxysilane; and

[3-(dialkylamino)propyl]dialkylalkoxysilanes such as

    [3-(dimethylamino)propyl]dimethylmethoxysilane,
    [3-(diethylamino)propyl]dimethylmethoxysilane,
    [3-(dimethylamino)propyl]diethylmethoxysilane,
    [3-(diethylamino)propyl]diethylmethoxysilane,
    [3-(dimethylamino)propyl]dimethylethoxysilane,
    [3-(diethylamino)propyl]dimethylethoxysilane,
    [3-(dimethylamino)propyl]diethylethoxysilane, and
    [3-(diethylamino)propyl]diethylethoxysilane.


The compounds in which formula (IIa) is a di(alkoxyalkyl)amino group can be exemplified by the following:
{3-[di(alkoxyalkyl)amino]propyl}trialkoxysilanes such as


    {3-[di(methoxymethyl)amino]propyl}trimethoxysilane,
    {3-[di(ethoxymethyl)amino]propyl}trimethoxysilane,
    {3-[di(methoxyethyl)amino]propyl}trimethoxysilane,
    {3-[di(ethoxyethyl)amino]propyl}trimethoxysilane,
    {3-[di(methoxymethyl)amino]propyl}triethoxysilane,
    {3-[di(ethoxymethyl)amino]propyl}triethoxysilane,
    {3-[di(methoxyethyl)amino]propyl}triethoxysilane, and
    {3-[di(ethoxyethyl)amino]propyl}triethoxysilane;

{3-[di(alkoxyalkyl)amino]propyl}alkyldialkoxysilanes such as

    {3-[di(methoxymethyl)amino]propyl}methyldimethoxysilane,
    {3-[di(ethoxymethyl)amino]propyl}methyldimethoxysilane,
    {3-[di(methoxyethyl)amino]propyl}methyldimethoxysilane,
    {3-[di(ethoxyethyl)amino]propyl}methyldimethoxysilane,
    {3-[di(methoxymethyl)amino]propyl}ethyldimethoxysilane,
    {3-[di(ethoxymethyl)amino]propyl}ethyldimethoxysilane,
    {3-[di(methoxyethyl)amino]propyl}ethyldimethoxysilane,
    {3-[di(ethoxyethyl)amino]propyl}ethyldimethoxysilane,
    {3-[di(methoxymethyl)amino]propyl}methyldiethoxysilane,
    {3-[di(ethoxymethyl)amino]propyl}methyldiethoxysilane,
    {3-[di(methoxyethyl)amino]propyl}methyldiethoxysilane,
    {3-[di(ethoxyethyl)amino]propyl}methyldiethoxysilane,
    {3-[di(methoxymethyl)amino]propyl}ethyldiethoxysilane,
    {3-[di(ethoxymethyl)amino]propyl}ethyldiethoxysilane,
    {3-[di(methoxyethyl)amino]propyl}ethyldiethoxysilane, and
    {3-[di(ethoxyethyl)amino]propyl}ethyldiethoxysilane; and

{3-[di(alkoxyalkyl)amino]propyl}dialkylalkoxysilanes such as

    {3-[di(methoxymethyl)amino]propyl}dimethylmethoxysilane,
    {3-[di(ethoxymethyl)amino]propyl}dimethylmethoxysilane,
    {3-[di(methoxyethyl)amino]propyl}dimethylmethoxysilane,
    {3-[di(ethoxyethyl)amino]propyl}dimethylmethoxysilane,
    {3-[di(methoxymethyl)amino]propyl}diethylmethoxysilane,
    {3-[di(ethoxymethyl)amino]propyl}diethylmethoxysilane,
    {3-[di(methoxyethyl)amino]propyl}diethylmethoxysilane,
    {3-[di(ethoxyethyl)amino]propyl}diethylmethoxysilane,
    {3-[di(methoxymethyl)amino]propyl}dimethylethoxysilane,
    {3-[di(ethoxymethyl)amino]propyl}dimethylethoxysilane,
    {3-[di(methoxyethyl)amino]propyl}dimethylethoxysilane,
    {3-[di(ethoxyethyl)amino]propyl}dimethylethoxysilane,
    {3-[di(methoxymethyl)amino]propyl}diethylethoxysilane,
    {3-[di(ethoxymethyl)amino]propyl}diethylethoxysilane,
    {3-[di(methoxyethyl)amino]propyl}diethylethoxysilane, and
    {3-[di(ethoxyethyl)amino]propyl}diethylethoxysilane.


The compounds in which formula (IIa) is a di(alkylene oxide)amino group can be exemplified by compounds in which formula (IIa) is a di(epoxy)amino group, such as

    {3-[di(epoxy)amino]propyl}trimethoxysilane,
    {3-[di(epoxy)amino]propyl}triethoxysilane,
    {3-[di(epoxy)amino]propyl}methyldimethoxysilane,
    {3-[di(epoxy)amino]propyl}ethyldimethoxysilane,
    {3-[di(epoxy)amino]propyl}methyldiethoxysilane,
    {3-[di(epoxy)amino]propyl}ethyldiethoxysilane,
    {3-[di(epoxy)amino]propyl}dimethylmethoxysilane,
    {3-[di(epoxy)amino]propyl}diethylmethoxysilane,
    {3-[di(epoxy)amino]propyl}dimethylethoxysilane, and
    {3-[di(epoxy)amino]propyl}diethylethoxysilane; and


compounds in which formula (IIa) is a di(tetrahydrofuranyl)amino group, such as

    {3-[di(tetrahydrofuranyl)amino]propyl}trimethoxysilane,
    {3-[di(tetrahydrofuranyl)amino]propyl}triethoxysilane,
    {3-[di(tetrahydrofuranyl)amino]propyl}-methyldimethoxysilane,
    {3-[di(tetrahydrofuranyl)amino]propyl}-ethyldimethoxysilane,
    {3-[di(tetrahydrofuranyl)amino]propyl}-methyldiethoxysilane,
    {3-[di(tetrahydrofuranyl)amino]propyl}-ethyldiethoxysilane,
    {3-[di(tetrahydrofuranyl)amino]propyl}-dimethylmethoxysilane,
    {3-[di(tetrahydrofuranyl)amino]propyl}-diethylmethoxysilane,
    {3-[di(tetrahydrofuranyl)amino]propyl}-dimethylethoxysilane, and
    {3-[di(tetrahydrofuranyl)amino]propyl}-diethylethoxysilane.


The compounds in which formula (IIa) is a di(alkylene oxide alkyl)amino group can be exemplified by compounds in which formula (IIa) is a di(glycidyl)amino group, such as

    {3-[di(glycidyl)amino]propyl}trimethoxysilane,
    {3-[di(glycidyl)amino]propyl}triethoxysilane,
    {3-[di(glycidyl)amino]propyl}methyldimethoxysilane,
    {3-[di(glycidyl)amino]propyl}ethyldimethoxysilane,
    {3-[di(glycidyl)amino]propyl}methyldiethoxysilane,
    {3-[di(glycidyl)amino]propyl}ethyldiethoxysilane,
    {3-[di(glycidyl)amino]propyl}dimethylmethoxysilane,
    {3-[di(glycidyl)amino]propyl}diethylmethoxysilane,
    {3-[di(glycidyl)amino]propyl}dimethylethoxysilane, and
    {3-[di(glycidyl)amino]propyl}diethylethoxysilane; and compounds in which formula (IIa) is a di(tetrahydrofurfuryl)amino group, such as
    {3-[di(tetrahydrofurfuryl)amino]propyl}trimethoxysilane,
    {3-[di(tetrahydrofurfuryl)amino]propyl}triethoxysilane,
    {3-[di(tetrahydrofurfuryl)amino]propyl}-methyldimethoxysilane,
    {3-[di(tetrahydrofurfuryl)amino]propyl}-ethyldimethoxysilane,
    {3-[di(tetrahydrofurfuryl)amino]propyl}-methyldiethoxysilane,
    {3-[di(tetrahydrofurfuryl)amino]propyl}-ethyldiethoxysilane,
    {3-[di(tetrahydrofurfuryl)amino]propyl}-dimethylmethoxysilane,
    {3-[di(tetrahydrofurfuryl)amino]propyl}-diethylmethoxysilane,
    {3-[di(tetrahydrofurfuryl)amino]propyl}-dimethylethoxysilane, and
    {3-[di(tetrahydrofurfuryl)amino]propyl}-diethylethoxysilane.


The compounds in which formula (IIa) is a trialkylsilyl group can be exemplified by the following:
{3-[di(trialkylsilyl)amino]propyl}trialkoxysilanes such as


    {3-[di(trimethylsilyl)amino]propyl}trimethoxysilane,
    {3-[di(t-butyldimethylsilyl)amino]propyl}-trimethoxysilane,
    {3-[di(trimethylsilyl)amino]propyl}triethoxysilane, and
    {3-[di(t-butyldimethylsilyl)amino]propyl}-triethoxysilane;

{3-[di(trialkylsilyl)amino]propyl}alkyldialkoxysilanes such as

    {3-[di(trimethylsilyl)amino]propyl}methyldimethoxysilane,
    {3-[di(t-butyldimethylsilyl)amino]propyl}-methyldimethoxysilane,
    {3-[di(trimethylsilyl)amino]propyl}methyldiethoxysilane, and
    {3-[di(t-butyldimethylsilyl)amino]propyl}-methyldiethoxysilane; and

{3-[di(trialkylsilyl)amino]propyl}dialkylalkoxysilanes such as

    {3-[di(trimethylsilyl)amino]propyl}dimethylmethoxysilane,
    {3-[di(t-butyldimethylsilyl)amino]propyl}-dimethylmethoxysilane,
    {3-[di(trimethylsilyl)amino]propyl}dimethylethoxysilane, and
    {3-[di(t-butyldimethylsilyl)amino]propyl}-dimethylethoxysilane.


Preferred among the preceding are [3-(dialkylamino)propyl]trialkoxysilanes, and more preferred are [3-(dimethylamino)propyl]trimethoxysilane,

    [3-(diethylamino)propyl]trimethoxysilane,
    [3-(dimethylamino)propyl]triethoxysilane, and
    [3-(diethylamino)propyl]triethoxysilane.


The compounds represented by formula (II) can also be exemplified by compounds in which formula (IIa) is a cyclic amino group such as a 1-piperidino group, a 1-hexamethyleneimino group, a 1-imidazolyl group, a 4,5-dihydro-1-imidazolyl group, a 1-piperazinyl group, or a morpholino group.
The compounds in which formula (IIa) is a 1-piperidino group can be exemplified by

    3-(1-piperidino)propyltrimethoxysilane,
    3-(1-piperidino)propyltriethoxysilane,
    3-(1-piperidino)propylmethyldimethoxysilane,
    3-(1-piperidino)propylethyldimethoxysilane,
    3-(1-piperidino)propylmethyldiethoxysilane, and
    3-(1-piperidino)propylethyldiethoxysilane.


The compounds in which formula (IIa) is a 1-hexamethyleneimino group can be exemplified by

    3-(1-hexamethyleneimino)propyltrimethoxysilane,
    3-(1-hexamethyleneimino)propyltriethoxysilane,
    3-(1-hexamethyleneimino)propylmethyldimethoxysilane,
    3-(1-hexamethyleneimino)propylethyldimethoxysilane,
    3-(1-hexamethyleneimino)propylmethyldiethoxysilane, and
    3-(1-hexamethyleneimino)propylethyldiethoxysilane.


The compounds in which formula (IIa) is a 1-imidazolyl group can be exemplified by

    N-(3-trimethoxysilylpropyl)imidazole and
    N-(3-triethoxysilylpropyl)imidazole.


The compounds in which formula (IIa) is a 4,5-dihydro-1-imidazolyl group can be exemplified by

    N-(3-trimethoxysilylpropyl)-4,5-dihydroimidazole and
    N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole.


The compounds in which formula (IIa) is a 1-piperazinyl group can be exemplified by

    3-(1-piperazinyl)propyltrimethoxysilane,
    3-(1-piperazinyl)propyltriethoxysilane,
    3-(1-piperazinyl)propylmethyldimethoxysilane,
    3-(1-piperazinyl)propylethyldimethoxysilane,
    3-(1-piperazinyl)propylmethyldiethoxysilane, and
    3-(1-piperazinyl)propylethyldiethoxysilane.


The compounds in which formula (IIa) is a morpholino group can be exemplified by

    3-morpholinopropyltrimethoxysilane,
    3-morpholinopropyltriethoxysilane,
    3-morpholinopropylmethyldimethoxysilane,
    3-morpholinopropylethyldimethoxysilane,
    3-morpholinopropylmethyldiethoxysilane, and
    3-morpholinopropylethyldiethoxysilane.


Among the preceding, compounds in which formula (IIa) is a 1-imidazolyl group and compounds in which formula (IIa) is a 4,5-dihydro-1-imidazolyl group are preferred, and N-(3-trimethoxysilylpropyl)imidazole,

    N-(3-triethoxysilylpropyl)imidazole,
    N-(3-trimethoxysilylpropyl)-4,5-dihydroimidazole, and
    N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole are more preferred.


The following explains the compound (modifying agent 2) containing a group represented by formula (III) below.




In the formula, p represents an integer of 0 or 1; T represents a C1-20 hydrocarbylene group or a C1-20 substituted hydrocarbylene group; and A2 represents a nitrogen atom-bearing functional group.
Here, p represents an integer of 0 or 1. T represents a C1-20 hydrocarbylene group or a C1-20 substituted hydrocarbylene group. A2 represents a nitrogen atom-bearing functional group and examples thereof include amino, isocyano, cyano, pyridyl, piperidyl, pyrazinyl, and morpholino groups.
The compounds containing a group represented by formula (III) can be exemplified by compounds containing a group represented by formula (III) in which p is 0 and A2 is an amino group, namely, the following formula (IIIa).




Examples of the compounds containing a group represented by formula (IIIa) include carboxylic acid amide compounds such as formamide, acetamide, and propionamide. Other examples include cyclic compounds such as imidazolidinone and derivatives thereof and lactams.
The compounds containing a group represented by formula (IIIa) can be exemplified by carboxylic acid amide compounds represented by the following formula (IIIa-1):




wherein R31 represents a hydrogen atom, a C1-10 hydrocarbyl group, a C1-10 substituted hydrocarbyl group, or a heterocyclic group containing a nitrogen atom and/or an oxygen atom as a heteroatom; and R32 and R33 each independently represent a C1-10 group optionally containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a silicon atom, R32 and R33 may be bonded to each other to form a cyclic structure together with the nitrogen atom, and R32 and R33 may form a single group bonded to the nitrogen via a double bond.

The hydrocarbyl groups encompassed by R31 can be exemplified by alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and t-butyl groups; aryl groups such as phenyl, methylphenyl, ethylphenyl, and naphthyl groups; and aralkyl groups such as a benzyl group.
The substituted hydrocarbyl groups encompassed by R31 can be exemplified by substituted hydrocarbyl groups containing as a substituent at least one group selected from the group consisting of nitrogen atom-bearing groups and oxygen atom-bearing groups. The groups containing a nitrogen atom-bearing group as a substituent can be exemplified by dialkylaminoalkyl groups such as dimethylaminoethyl and diethylaminoethyl groups. The groups containing an oxygen atom-bearing group as a substituent can be exemplified by alkoxyalkyl groups such as methoxymethyl, methoxyethyl, ethoxymethyl, and ethoxyethyl groups.
The heterocyclic group containing a nitrogen atom and/or an oxygen atom as a heteroatom, encompassed by R31, refers to a residue of a heterocyclic compound that contains a nitrogen atom and/or an oxygen atom in the ring. Such groups can be exemplified by a 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group, and a 2-furyl group.
R31 is preferably a C1-10 hydrocarbyl group or a C1-10 substituted hydrocarbyl group, more preferably a C1-4 alkyl group, and particularly preferably a methyl group, an ethyl group, an n-propyl group, or an n-butyl group.
Examples of R32 and R33 in formula (IIIa-1) include C1-10 hydrocarbyl groups and C1-10 substituted hydrocarbyl groups. The hydrocarbyl groups encompassed by R32 and R33 can be exemplified by alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and t-butyl groups; aryl groups such as phenyl, methylphenyl, ethylphenyl, and naphthyl groups; and aralkyl groups such as a benzyl group.
The substituted hydrocarbyl groups encompassed by R32 and R33 can be exemplified by substituted hydrocarbyl groups containing as a substituent at least one group selected from the group consisting of nitrogen atom-bearing groups and oxygen atom-bearing groups. The groups containing a nitrogen atom-bearing group as a substituent can be exemplified by dialkylaminoalkyl groups such as dimethylaminoethyl and diethylaminoethyl groups. The groups containing an oxygen atom-bearing group as a substituent can be exemplified by alkoxyalkyl groups such as methoxymethyl, methoxyethyl, ethoxymethyl, and ethoxyethyl groups.
The groups in which R32 and R33 are bonded to each other can be exemplified by C2-20 divalent groups optionally containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a silicon atom. Specific examples thereof include alkylene groups such as trimethylene, tetramethylene, pentamethylene, and hexamethylene groups; oxydialkylene groups such as oxydiethylene and oxydipropylene groups; and nitrogenous groups such as a group represented by —CH2CH2—NH—CH2— and a group represented by —CH2CH2—N═CH—.
Examples of the single group bonded to the nitrogen via a double bond, formed by R32 and R33, include C2-12 divalent groups optionally containing at least one atom selected from the group consisting of a nitrogen atom and an oxygen atom. Specific examples thereof include an ethylidene group, a 1-methylpropylidene group, a 1,3-dimethylbutylidene group, a 1-methylethylidene group, and a 4-N,N-dimethylaminobenzylidene group.
R32 and R33 are each independently preferably a hydrocarbyl group, more preferably an alkyl group, still more preferably a C1-4 alkyl group, and particularly preferably a methyl group, an ethyl group, an n-propyl group, or an n-butyl group.
The carboxylic acid amide compounds represented by formula (IIIa-1) can be exemplified by formamide compounds such as formamide, N,N-dimethylformamide, and N,N-diethylformamide;
acetamide compounds such as acetamide, N,N-dimethylacetamide, N,N-diethylacetamide, aminoacetamide, N,N-dimethyl-N′,N′-dimethylaminoacetamide, N,N-dimethylaminoacetamide, N-ethylaminoacetamide, N,N-dimethyl-N′-ethylaminoacetamide, N,N-dimethylaminoacetamide, and N-phenyldiacetamide;
propionamide compounds such as propionamide and N,N-dimethylpropionamide;
pyridylamide compounds such as 4-pyridylamide and N,N-dimethyl-4-pyridylamide;
benzamide compounds such as benzamide, N,N-dimethylbenzamide, N′,N′-(p-dimethylamino)benzamide, N′,N′-(p-diethylamino)benzamide, N,N-dimethyl-N′,N′-(p-dimethylamino)benzamide, and N,N-dimethyl-N′,N′-(p-diethylamino)benzamide;
acrylamide compounds such as N,N-dimethylacrylamide and N,N-diethylacrylamide;
methacrylamide compounds such as N,N-dimethylmethacrylamide and N,N-diethylmethacrylamide;
nicotinamide compounds such as N,N-dimethylnicotinamide and N,N-diethylnicotinamide;
phthalamide compounds such as N,N,N′,N′-tetramethylphthalamide and N,N,N′,N′-tetraethylphthalamide; and
phthalimide compounds such as N-methylphthalimide and N-ethylphthalimide.
The cyclic compounds containing a group represented by formula (IIIa) can be exemplified by compounds represented by the following formula (IIIa-2) and compounds represented by the following formula (IIIa-3).




In the formula, e represents an integer of 0 to 10, and R34 and R35 each independently represent a C1-20 hydrocarbyl group or a C1-20 substituted hydrocarbyl group.




In the formula, f represents an integer of 0 to 10, and R36 represents a C1-20 hydrocarbyl group or a C1-20 substituted hydrocarbyl group.
R34, R35, and R36 in formulas (IIIc-2) and (IIIa-3) each independently represent a C1-20 hydrocarbyl group or a C1-20 substituted hydrocarbyl group. The hydrocarbyl groups encompassed by R34, R35, and R36 can be exemplified by alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and t-butyl groups; aryl groups such as phenyl, methylphenyl, ethylphenyl, and naphthyl groups; and aralkyl groups such as a benzyl group.
The substituted hydrocarbyl groups encompassed by R34, R35, and R36 can be exemplified by substituted hydrocarbyl groups containing as a substituent at least one group selected from the group consisting of nitrogen atom-bearing groups, oxygen atom-bearing groups, and silicon atom-bearing groups. The groups containing a nitrogen atom-bearing group as a substituent can be exemplified by dialkylaminoalkyl groups such as dimethylaminoethyl and diethylaminoethyl groups. The groups containing an oxygen atom-bearing group as a substituent can be exemplified by alkoxyalkyl groups such as methoxymethyl, methoxyethyl, ethoxymethyl, and ethoxyethyl groups; and alkoxyaryl groups such as methoxyphenyl and ethoxyphenyl groups. The groups containing a silicon atom-bearing group as a substituent can be exemplified by trimethylsilylmethyl, t-butyldimethylsilyloxymethyl, and trimethoxysilylpropyl groups.
R34 and R35 in formula (IIIa-2) are each independently preferably a hydrocarbyl group, more preferably an alkyl group, and still more preferably a methyl group.
R36 in formula (IIIa-3) is preferably a hydrocarbyl group, more preferably an alkyl group or an aryl group, and still more preferably a methyl group or a phenyl group.
In formulas (IIIa-2) and (IIIa-3), e and f each represent an integer of 0 to 10. Here, e and f are each independently preferably not less than 2 in view of enhancing the fuel economy, wet-grip performance, and abrasion resistance in a balanced manner, whereas e and f are each independently preferably not more than 7 in view of enhancing the economic efficiency of the production.
The compounds represented by formula (IIIa-2) can be exemplified by 1,3-hydrocarbyl-substituted 2-imidazolidinones such as 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-di(n-propyl)-2-imidazolidinone, 1,3-di(t-butyl)-2-imidazolidinone, and 1,3-diphenyl-2-imidazolidinone. The compound represented by formula (IIIa-2) is preferably a 1,3-substituted 2-imidazolidinone, more preferably a 1,3-hydrocarbyl-substituted 2-imidazolidinone, and still more preferably a 1,3-dialkyl-2-imidazolidinone. The 1,3-dialkyl-2-imidazolidinone is preferably 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, or 1,3-di(n-propyl)-2-imidazolidinone, and more preferably 1,3-dimethyl-2-imidazolidinone.
The compounds represented by formula (IIIa-3) can be exemplified by β-propiolactam compounds such as N-methyl-β-propiolactam, N-(t-butyl)-β-propiolactam, and N-phenyl-β-propiolactam;
2-pyrrolidone compounds such as 1-methyl-2-pyrrolidone, 1-(t-butyl)-2-pyrrolidone, 1-phenyl-2-pyrrolidone, 1-(p-methylphenyl)-2-pyrrolidone, 1-(p-methoxyphenyl)-2-pyrrolidone, 1-benzyl-2-pyrrolidone, 1-naphthyl-2-pyrrolidone, 1-phenyl-5-methyl-2-pyrrolidone, 1-(t-butyl)-5-methyl-2-pyrrolidone, and 1-(t-butyl)-1,3-dimethyl-2-pyrrolidone;
2-piperidone compounds such as 1-(t-butyl)-2-piperidone, 1-phenyl-2-piperidone, 1-(p-methylphenyl)-2-piperidone, 1-(p-methoxyphenyl)-2-piperidone, and 1-naphthyl-2-piperidone;
ε-caprolactam compounds such as N-methyl-ε-caprolactam, N-ethyl-ε-caprolactam, N-(n-propyl)-ε-caprolactam, N-phenyl-ε-caprolactam, N-(p-methoxyphenyl)-ε-caprolactam, and N-benzyl-ε-caprolactam; and
ω-laurylolactam compounds such as N-phenyl-ω-laurylolactam.
The compound represented by formula (IIIa-3) is preferably a 2-pyrrolidone compound or an ε-caprolactam compound, more preferably a 1-hydrocarbyl-substituted 2-pyrrolidone or an N-hydrocarbyl-substituted ε-caprolactam, still more preferably a 1-alkyl-substituted 2-pyrrolidone, a 1-aryl-substituted 2-pyrrolidone, an N-alkyl-substituted ε-caprolactam, or an N-aryl-substituted ε-caprolactam, and particularly preferably 1-phenyl-2-pyrrolidone or N-methyl-ε-caprolactam.
The compounds containing a group represented by formula (III) can also be exemplified by compounds containing a group represented by formula (III) in which p is 1 and A2 is an amino group, namely, the following formula (IIIb).




In the formula, T represents a C1-20 hydrocarbylene group or a C1-20 substituted hydrocarbylene group.
The compounds containing a group represented by formula (IIIb) can be exemplified by benzaldehyde compounds, acetophenone compounds, and benzophenone compounds.
The compounds containing a group represented by formula (IIIb) can also be exemplified by compounds represented by the following formula (IIIb-1):




wherein R37 represents a hydrogen atom, a C1-10 hydrocarbyl group, a C1-10 substituted hydrocarbyl group, or a heterocyclic group containing a nitrogen atom and/or an oxygen atom as a heteroatom; R38 and R39 each independently represent a C1-10 group optionally containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a silicon atom, R38 and R39 may be bonded to each other to form a cyclic structure together with the nitrogen atom, and R38 and R39 may form a single group bonded to the nitrogen via a double bond; and T represents a C1-20 hydrocarbylene group or a C1-20 substituted hydrocarbylene group.

The hydrocarbyl groups encompassed by R37 can be exemplified by alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and t-butyl groups; aryl groups such as phenyl, methylphenyl, ethylphenyl, and naphthyl groups; and aralkyl groups such as a benzyl group.
The substituted hydrocarbyl groups encompassed by R37 can be exemplified by substituted hydrocarbyl groups containing as a substituent at least one group selected from the group consisting of nitrogen atom-bearing groups and oxygen atom-bearing groups. The groups containing a nitrogen atom-bearing group as a substituent can be exemplified by dialkylaminoalkyl groups such as dimethylaminoethyl and diethylaminoethyl groups. The groups containing an oxygen atom-bearing group as a substituent can be exemplified by alkoxyalkyl groups such as methoxymethyl, methoxyethyl, ethoxymethyl, and ethoxyethyl groups.
The heterocyclic group containing a nitrogen atom and/or an oxygen atom as a heteroatom, encompassed by R37, refers to a residue of a heterocyclic compound that contains a nitrogen atom and/or an oxygen atom in the ring, and such groups can be exemplified by a 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group, and a 2-furyl group.
R37 is preferably a hydrogen atom, a C1-10 hydrocarbyl group, or a C1-10 substituted hydrocarbyl group. The C1-10 hydrocarbyl group is preferably a C1-4 alkyl group or a phenyl group, and particularly preferably a methyl group, an ethyl group, an n-propyl group, an n-butyl group, or a phenyl group. The C1-10 substituted hydrocarbyl group is preferably an aryl group containing a nitrogen atom-bearing group as a substituent, and more preferably a dialkylaminophenyl group or a 4-morpholinophenyl group.
Examples of R38 and R39 in formula (IIIb-1) include C1-10 hydrocarbyl groups and C1-10 substituted hydrocarbyl groups.
The hydrocarbyl groups encompassed by R38 and R39 can be exemplified by alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and t-butyl groups; aryl groups such as phenyl, methylphenyl, ethylphenyl, and naphthyl groups; and aralkyl groups such as a benzyl group.
The substituted hydrocarbyl groups encompassed by R38 and R39 can be exemplified by substituted hydrocarbyl groups containing as a substituent at least one group selected from the group consisting of nitrogen atom-bearing groups and oxygen atom-bearing groups. The groups containing a nitrogen atom-bearing group as a substituent can be exemplified by dialkylaminoalkyl groups such as dimethylaminoethyl and diethylaminoethyl groups. The groups containing an oxygen atom-bearing group as a substituent can be exemplified by alkoxyalkyl groups such as methoxymethyl, methoxyethyl, ethoxymethyl, and ethoxyethyl groups.
The groups in which R38 and R39 are bonded to each other can be exemplified by C2-20 divalent groups optionally containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a silicon atom. Specific examples thereof include alkylene groups such as trimethylene, tetramethylene, pentamethylene, and hexamethylene groups; oxydialkylene groups such as oxydiethylene and oxydipropylene groups; and nitrogenous groups such as a group represented by —CH2CH2—NH—CH2— and a group represented by —CH2CH2—N═CH—.
Examples of the single group bonded to the nitrogen via a double bond, formed by R38 and R39, include C2-12 divalent groups optionally containing at least one atom selected from the group consisting of a nitrogen atom and an oxygen atom. Specific examples thereof include an ethylidene group, a 1-methylpropylidene group, a 1,3-dimethylbutylidene group, a 1-methylethylidene group, and a 4-N,N-dimethylaminobenzylidene group.
R38 and R39 are each independently preferably a hydrocarbyl group, more preferably an alkyl group, still more preferably a C1-4 alkyl group, and particularly preferably a methyl group, an ethyl group, an n-propyl group, or an n-butyl group.
The hydrocarbylene groups encompassed by T can be exemplified by alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, and hexamethylene groups; and arylene groups such as phenylene, methylphenylene, ethylphenylene, and naphthylene groups.
The substituted hydrocarbylene groups encompassed by T can be exemplified by substituted hydrocarbylene groups containing as a substituent at least one group selected from the group consisting of nitrogen atom-bearing groups and oxygen atom-bearing groups. The groups containing a nitrogen atom-bearing group as a substituent can be exemplified by dialkylaminoalkylene groups such as dimethylaminoethylene and diethylaminoethylene groups; and dialkylaminoarylene groups such as dimethylaminophenylene and diethylaminophenylene groups. The groups containing an oxygen atom-bearing group as a substituent can be exemplified by alkoxyalkylene groups such as methoxymethylene, methoxyethylene, ethoxymethylene, and ethoxyethylene groups.
T is preferably a hydrocarbylene group, more preferably an arylene group, and still more preferably a phenylene group.
The compounds represented by formula (IIIb-1) can be exemplified by dialkylamino-substituted benzaldehyde compounds such as 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, and 3,5-bis(dihexylamino)benzaldehyde; dialkylamino-substituted acetophenone compounds such as 4-dimethylaminoacetophenone and 4-diethylaminoacetophenone; heterocyclic group-substituted acetophenone compounds such as 4-morpholinoacetophenone, 4′-imidazol-1-yl-acetophenone, and 4-pyrazolylacetophenone; dialkylamino-substituted benzophenone compounds such as 4,4′-bis(dimethylamino)benzophenone, 4,4′-bis(diethylamino)benzophenone, 4-dimethylaminobenzophenone, 4-diethylaminobenzophenone, 3-dimethylaminobenzophenone, and 3-diethylaminobenzophenone; and heterocyclic group-substituted benzophenone compounds such as 4-morpholinobenzophenone, 4′-(imidazol-1-yl)benzophenone, and 4-pyrazolylbenzophenone.
The compound represented by formula (IIIb-1) is preferably a substituted acetophenone compound or a substituted benzophenone compound, and examples thereof include compounds represented by the following formula (IIIb-1-1) and compounds represented by the following formula (IIIb-1-2):




wherein r represents an integer of 1 or 2; and Y1 represents a nitrogen atom-bearing functional group that is a substituent on the benzene ring, and when a plurality of Y1's are present, the plurality of Y1's may be the same as or different from one another;





wherein s represents an integer of 1 or 2; t represents an integer of 0 to 2; and Y2 and Y3 each represent a nitrogen atom-bearing functional group that is a substituent on the benzene ring, and when a plurality of Y2's are present, the plurality of Y2's may be the same as or different from one another, and when a plurality of Y3's are present, the plurality of Y3's may be the same as or different from one another.

Y1, Y2 and Y3 in formulas (IIIb-1-1) and (IIIb-1-2) represent nitrogen atom-bearing functional groups and examples thereof include amino, isocyano, cyano, pyridyl, piperidyl, pyrazinyl, pyrimidinyl, pyrrolyl, imidazolyl, pyrazolyl, and morpholino groups. Dialkylamino, imidazolyl, and morpholino groups are preferred. The alkyl of the dialkylamino group is preferably a C1-10 alkyl group.
The compound represented by formula (IIIb-1) is more preferably a heterocyclic group-substituted acetophenone compound, a dialkylamino-substituted benzophenone compound, or a heterocyclic group-substituted benzophenone compound and is particularly preferably 4′-imidazol-1-yl-acetophenone, 4-morpholinoacetophenone, 4-dimethylaminobenzophenone, 4-diethylaminobenzophenone, 4,4′-bis(dimethylamino)benzophenone, 4,4′-bis(diethylamino)benzophenone, or 4-morpholinobenzophenone.
The following explains the compound (modifying agent 3) represented by formula (IV) below.




In the formula, g represents an integer of 1 to 10; R21 represents a hydrogen atom, a C1-6 hydrocarbyl group, or a C1-6 substituted hydrocarbyl group; A3 represents an oxygen atom or the following group: —NR22— where R22 represents a hydrogen atom or a C1-10 hydrocarbyl group; and A4 represents a functional group bearing a nitrogen atom and/or an oxygen atom.
Here, g represents an integer of 1 to 10. In view of enhancing the fuel economy, wet-grip performance, and abrasion resistance in a balanced manner, g is preferably not less than 2. In view of enhancing the economic efficiency of the production, g is preferably not more than 4. Particularly preferably, g is 3.
R21 in formula (IV) represents a hydrogen atom, a C1-6 hydrocarbyl group, or a C1-6 substituted hydrocarbyl group.
The hydrocarbyl groups encompassed by R21 can be exemplified by alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and t-butyl groups.
The substituted hydrocarbyl groups encompassed by R21 can be exemplified by substituted hydrocarbyl groups containing as a substituent at least one group selected from the group consisting of nitrogen atom-bearing groups, oxygen atom-bearing groups, and silicon atom-bearing groups. The groups containing a nitrogen atom-bearing group as a substituent can be exemplified by dialkylaminoalkyl groups such as dimethylaminoethyl and diethylaminoethyl groups. The groups containing an oxygen atom-bearing group as a substituent can be exemplified by alkoxyalkyl groups such as methoxymethyl, methoxyethyl, ethoxymethyl, and ethoxyethyl groups. The groups containing a silicon atom-bearing group as a substituent can be exemplified by trialkylsilylalkyl groups such as a trimethylsilylmethyl group; trialkylsilyloxyalkyl groups such as a t-butyldimethylsilyloxymethyl group; and trialkoxysilylalkyl groups such as a trimethoxysilylpropyl group.
The hydrocarbyl group encompassed by R21 is preferably an alkyl group, more preferably a C1-4 alkyl group, still more preferably a methyl group or an ethyl group, and further preferably a methyl group. The substituted hydrocarbyl group encompassed by R21 is preferably an alkoxyalkyl group, more preferably a C1-4 alkoxyalkyl group, still more preferably a methoxymethyl or an ethoxyethyl group, and further preferably a methoxymethyl group.
In view of economic efficiency and in view of enhancing the fuel economy, wet-grip performance, and abrasion resistance in a balanced manner, R21 is preferably a hydrogen atom, an alkyl group, or an alkoxyalkyl group, more preferably a hydrogen atom, a C1-4 alkyl group, or a C1-4 alkoxyalkyl group, still more preferably a hydrogen atom, a methyl group, or a methoxymethyl group, and further preferably a hydrogen atom or a methyl group.
A3 in formula (IV) represents an oxygen atom or the following group: —NR22— where R22 represents a hydrogen atom or a C1-10 hydrocarbyl group.
The hydrocarbyl groups encompassed by R22 can be exemplified by alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and t-butyl groups; aryl groups such as phenyl, methylphenyl, ethylphenyl, and naphthyl groups; and aralkyl groups such as a benzyl group.
The hydrocarbyl group encompassed by R22 is preferably an alkyl group, more preferably a C1-4 alkyl group, and still more preferably a methyl group or an ethyl group.
R22 is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a C1-4 alkyl group, still more preferably a hydrogen atom, a methyl group or an ethyl group, and further preferably a hydrogen atom or a methyl group.
A4 in formula (IV) represents a functional group bearing a nitrogen atom and/or an oxygen atom. Examples of the nitrogen atom-bearing functional group include amino, isocyano, cyano, pyridyl, piperidyl, piperazinyl, and morpholino groups.
Examples of the oxygen atom-bearing functional group include alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, and t-butoxy groups; alkoxyalkyl groups such as methoxymethyl, methoxyethyl, ethoxymethyl, and ethoxyethyl groups; alkoxyaryl groups such as methoxyphenyl and ethoxyphenyl groups; and alkylene oxide groups such as epoxy and tetrahydrofuranyl groups. Other examples include trialkylsilyloxy groups such as trimethylsilyloxy, triethylsilyloxy, and t-butyldimethylsilyloxy groups. Additional examples include a hydroxy group.
A4 is preferably a hydroxy group or a group represented by formula (IVa) below, and more preferably a group represented by the following formula (IVa):




wherein R23 and R24 each independently represent a C1-6 group optionally containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a silicon atom, R23 and R24 may be bonded to each other to form a cyclic structure together with the nitrogen atom, and R23 and R24 may form a single group bonded to the nitrogen via a double bond.

Examples of R23 and R24 in formula (IVa) include C1-6 hydrocarbyl groups, C1-6 substituted hydrocarbyl groups, and substituted silyl groups.
The hydrocarbyl groups encompassed by R23 and R24 can be exemplified by alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, isopentyl, and n-hexyl groups; cycloalkyl groups such as a cyclohexyl group; and a phenyl group.
The substituted hydrocarbyl groups encompassed by R23 and R24 can be exemplified by substituted hydrocarbyl groups containing as a substituent at least one group selected from the group consisting of nitrogen atom-bearing groups, oxygen atom-bearing groups, and silicon atom-bearing groups. The groups containing a nitrogen atom-bearing group as a substituent can be exemplified by dialkylaminoalkyl groups such as dimethylaminoethyl and diethylaminoethyl groups. The groups containing an oxygen atom-bearing group as a substituent can be exemplified by alkoxyalkyl groups such as methoxymethyl, methoxyethyl, ethoxymethyl, and ethoxyethyl groups; alkylene oxide groups such as epoxy and tetrahydrofuranyl groups; and alkylene oxide alkyl groups such as glycidyl and tetrahydrofurfuryl groups. The groups containing a silicon atom-bearing group as a substituent can be exemplified by trialkylsilylalkyl groups such as a trimethylsilylmethyl group.
As used herein, the term “alkylene oxide group” denotes a monovalent group obtained by removing a hydrogen atom from the ring of a cyclic ether compound. The term “alkylene oxide alkyl group” denotes a group obtained by substituting at least one hydrogen atom of an alkyl group by an alkylene oxide group.
The substituted silyl groups encompassed by R23 and R24 can be exemplified by trialkylsilyl groups such as trimethylsilyl, triethylsilyl, and t-butyldimethylsilyl groups; and trialkoxysilyl groups such as a trimethoxysilyl group.
The groups in which R23 and R24 are bonded to each other can be exemplified by C2-12 divalent groups optionally containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a silicon atom. Specific examples thereof include alkylene groups such as trimethylene, tetramethylene, pentamethylene, and hexamethylene groups; oxydialkylene groups such as oxydiethylene and oxydipropylene groups; and nitrogenous groups such as a group represented by —CH2CH2—NH—CH2— and a group represented by —CH2CH2—N═CH—.
The group in which R23 and R24 are bonded to each other is preferably a nitrogenous group, and more preferably a group represented by —CH2CH2—NH—CH2— or a group represented by —CH2CH2—N═CH—.
Examples of the single group bonded to the nitrogen via a double bond, formed by R23 and R24, include C2-12 divalent groups optionally containing at least one atom selected from the group consisting of a nitrogen atom; an oxygen atom, and a silicon atom. Specific examples thereof include an ethylidene group, a 1-methylpropylidene group, a 1,3-dimethylbutylidene group, a 1-methylethylidene group, and a 4-N,N-dimethylaminobenzylidene group.
The hydrocarbyl group encompassed by R23 and R24 is preferably an alkyl group, more preferably a C1-4 alkyl group, still more preferably a methyl group, an ethyl group, an n-propyl group, or an n-butyl group, and further preferably a methyl group or an ethyl group. The substituted hydrocarbyl group encompassed by R23 and R24 is preferably an alkoxyalkyl group, an alkylene oxide group, or an alkylene oxide alkyl group. The substituted silyl group encompassed by R23 and R24 is preferably a trialkylsilyl group or a trialkoxysilyl group, more preferably a trialkylsilyl group, and still more preferably a trimethylsilyl group or a triethylsilyl group.
Preferably, R23 and R24 are a nitrogenous group in which R23 and R24 are bonded to each other, or are each independently an alkyl group, an alkoxyalkyl group, an alkylene oxide group, an alkylene oxide alkyl group, or a substituted silyl group, more preferably an alkyl group, an alkylene oxide group, an alkylene oxide alkyl group, or a trialkylsilyl group.
The groups represented by formula (IVa) can be exemplified by acyclic amino groups and cyclic amino groups.
Examples of the acyclic amino groups include dialkylamino groups such as dimethylamino, diethylamino, di(n-propyl)amino, di(isopropyl)amino, di(n-butyl)amino, di(sec-butyl)amino, di(tert-butyl)amino, di(neopentyl)amino, and ethylmethylamino groups; di(alkoxyalkyl)amino groups such as di(methoxymethyl)amino, di(methoxyethyl)amino, di(ethoxymethyl)amino, and di(ethoxyethyl)amino groups; and di(trialkylsilyl)amino groups such as di(trimethylsilyl)amino and di(t-butyldimethylsilyl)amino groups. Other examples include di(alkylene oxide)amino groups such as di(epoxy)amino and di(tetrahydrofuranyl)amino groups; and di(alkylene oxide alkyl)amino groups such as di(glycidyl)amino and di(tetrahydrofurfuryl)amino groups. Additional examples include ethylideneamino, 1-methylpropylideneamino, 1,3-dimethylbutylideneamino, 1-methylethylideneamino, and 4-N,N-dimethylaminobenzylideneamino groups.
As used herein, the term “di(alkylene oxide)amino group” denotes an amino group in which two hydrogen atoms bonded to the nitrogen atom are substituted by two alkylene oxide groups. The term “di(alkylene oxide alkyl)amino group” denotes an amino group in which two hydrogen atoms bonded to the nitrogen atom are substituted by two alkylene oxide alkyl groups.
The cyclic amino groups can be exemplified by 1-polymethyleneimino groups such as 1-pyrrolidinyl, 1-piperidino, 1-hexamethyleneimino, 1-heptamethyleneimino, 1-octamethyleneimino, 1-decamethyleneimino, and 1-dodecamethyleneimino groups. The cyclic amino groups can also be exemplified by 1-imidazolyl, 4,5-dihydro-1-imidazolyl, 1-imidazolidinyl, 1-piperazinyl, and morpholino groups.
In view of fuel economy, wet-grip performance, abrasion resistance, and long-term stability and easy availability of the compound, the group represented by formula (IVa) is preferably an acyclic amino group, and is more preferably a dialkylamino group, a di(alkylene oxide)amino group, a di(alkylene oxide alkyl)amino group, or a di(trialkylsilyl)amino group.
The compounds represented by formula (IV) can be exemplified by compounds in which A3 is a secondary amino group, such as acrylamide compounds and methacrylamide compounds.
The acrylamide compounds in which A4 is a nitrogen atom-bearing group can be exemplified by

    N-(2-dimethylaminoethyl)acrylamide,
    N-(2-diethylaminoethyl)acrylamide,
    N-(3-dimethylaminopropyl)acrylamide,
    N-(3-diethylaminopropyl)acrylamide,
    N-(4-dimethylaminobutyl)acrylamide,
    N-(4-diethylaminobutyl)acrylamide,
    N-(3-morpholinopropyl)acrylamide, and
    N-(3-cyanopropyl)acrylamide.


The methacrylamide compounds in which A4 is a nitrogen atom-bearing group can be exemplified by

    N-(2-dimethylaminoethyl)methacrylamide,
    N-(2-diethylaminoethyl)methacrylamide,
    N-(3-dimethylaminopropyl)methacrylamide,
    N-(3-diethylaminopropyl)methacrylamide,
    N-(4-dimethylaminobutyl)methacrylamide,
    N-(4-diethylaminobutyl)methacrylamide,
    N-(3-morpholinopropyl)methacrylamide, and
    N-(3-cyanopropyl)methacrylamide.


The acrylamide compounds in which A4 is an oxygen atom-bearing group can be exemplified by

    N-(3-methoxypropyl)acrylamide,
    N-(3-ethoxypropyl)acrylamide,
    N-(propoxymethyl)acrylamide,
    N-(butoxymethyl)acrylamide,
    N-glycidylacrylamide, and
    N-tetrahydrofurfurylacrylamide.


The methacrylamide compounds in which A4 is an oxygen atom-bearing group can be exemplified by

    N-(3-methoxypropyl)methacrylamide,
    N-(3-ethoxypropyl)methacrylamide,
    N-(propoxymethyl)methacrylamide,
    N-(butoxymethyl)methacrylamide,
    N-glycidylmethacrylamide, and
    N-tetrahydrofurfurylmethacrylamide.


The acrylamide compounds in which A4 is a group bearing both nitrogen and oxygen atoms can be exemplified by N-(3-di(glycidyl)aminopropyl)acrylamide, and

    N-(3-di(tetrahydrofurfuryl)aminopropyl)acrylamide.


The methacrylamide compounds in which A4 is a group bearing both nitrogen and oxygen atoms can be exemplified by N-(3-di(glycidyl)aminopropyl)methacrylamide, and

    N-(3-di(tetrahydrofurfuryl)aminopropyl)methacrylamide.


The compounds represented by formula (IV) can also be exemplified by compounds in which A3 is an oxygen atom, such as acrylate compounds and methacrylate compounds.
The acrylate compounds in which A4 is a nitrogen atom-bearing group can be exemplified by

    2-dimethylaminoethyl acrylate,
    2-diethylaminoethyl acrylate,
    3-dimethylaminopropyl acrylate,
    3-diethylaminopropyl acrylate,
    4-dimethylaminobutyl acrylate, and
    4-diethylaminobutyl acrylate.


The methacrylate compounds in which A4 is a nitrogen atom-bearing group can be exemplified by

    2-dimethylaminoethyl methacrylate,
    2-diethylaminoethyl methacrylate,
    3-dimethylaminopropyl methacrylate,
    3-diethylaminopropyl methacrylate,
    4-dimethylaminobutyl methacrylate, and
    4-diethylaminobutyl methacrylate.


The acrylate compounds in which A4 is an oxygen atom-bearing group can be exemplified by

    2-ethoxyethyl acrylate,
    2-propoxyethyl acrylate,
    2-butoxyethyl acrylate,
    3-methoxypropyl acrylate,
    3-ethoxypropyl acrylate,
    glycidyl acrylate, and
    tetrahydrofurfuryl acrylate.


The methacrylate compounds in which A4 is an oxygen atom-bearing group can be exemplified by

    2-ethoxyethyl methacrylate,
    2-propoxyethyl methacrylate,
    2-butoxyethyl methacrylate,
    3-methoxypropyl methacrylate,
    3-ethoxypropyl methacrylate,
    glycidyl methacrylate, and
    tetrahydrofurfuryl methacrylate.


The acrylate compounds in which A4 is a group bearing both nitrogen and oxygen atoms can be exemplified by

    3-di(glycidyl)aminopropyl acrylate, and
    3-di(tetrahydrofurfuryl)aminopropyl acrylate.


The methacrylate compounds in which A4 is a group bearing both nitrogen and oxygen atoms can be exemplified by 3-di(glycidyl)aminopropyl methacrylate, and 3-di(tetrahydrofurfuryl)aminopropyl methacrylate.
In view of enhancing the fuel economy, wet-grip performance, and abrasion resistance in a balanced manner, the compound represented by formula (IV) is preferably a compound in which A4 is a group represented by formula (IVa), more preferably a compound in which A3 is an amino group and A4 is a group represented by formula (IVa), and still more preferably a compound in which A3 is a secondary amino group (—NH—) and A4 is a group represented by formula (IVa).
The compound in which A3 is a secondary amino group and A4 is a group represented by formula (IVa) is preferably an N-(3-dialkylaminopropyl)acrylamide or an N-(3-dialkylaminopropyl) methacrylamide, and more preferably

    N-(3-dimethylaminopropyl)acrylamide,
    N-(3-diethylaminopropyl)acrylamide,
    N-(3-dimethylaminopropyl)methacrylamide, or
    N-(3-diethylaminopropyl)methacrylamide.


The following explains the silicon compound (modifying agent 4) containing a group represented by formula (V) below and/or a group represented by formula (VI) below.




Examples of groups containing the group represented by formula (V) include an amide group, a carboxylic acid ester group, a methacryloyl group, and an acryloyl group. Examples of groups containing the group represented by formula (VI) include oxydialkylene groups such as oxydimethylene and oxydiethylene groups; and alkylene oxide groups such as epoxy and tetrahydrofuranyl groups.
As used herein, the term “alkylene oxide group” denotes a monovalent group obtained by removing a hydrogen atom from the ring of a cyclic ether compound.
The silicon compound preferably contains a group represented by the following formula (VIII):




wherein R41, R42, and R43 each independently represent a C1-4 hydrocarbyl group or a C1-4 hydrocarbyloxy group, and at least one of R41, R42, and R43 is a hydrocarbyloxy group.

The hydrocarbyl groups encompassed by R41, R42, and R43 in formula (VIII) can be exemplified by alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl groups. The hydrocarbyloxy groups encompassed by R41, R42, and R43 can be exemplified by alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, and t-butoxy groups.
The hydrocarbyl group encompassed by R41, R42, and R43 is preferably an alkyl group, more preferably a C1-3 alkyl group, and still more preferably a methyl group or an ethyl group. The hydrocarbyloxy group encompassed by R41, R42, and R43 is preferably an alkoxy group, more preferably a C1-3 alkoxy group, and still more preferably a methoxy group or an ethoxy group.
In view of enhancing the fuel economy, wet-grip performance, and abrasion resistance in a balanced manner, preferably at least two of R41, R42, and R43 are hydrocarbyloxy groups, and more preferably the three of R41, R42, and R43 are hydrocarbyloxy groups.
The silicon compounds containing a group represented by formula (V) and a group represented by formula (VIII) can be exemplified by silicon compounds containing a group represented by the following formula (Va):




wherein h represents an integer of 1 to 10; and R44, R45, and R46 each independently represent a C1-4 hydrocarbyl group or a C1-4 hydrocarbyloxy group, and at least one of R44, R45, and R46 is a hydrocarbyloxy group.

Here, h represents an integer of 1 to 10, and is preferably not less than 2 in view of enhancing the fuel economy, wet-grip performance, and abrasion resistance in a balanced manner, whereas h is preferably not more than 4 in view of enhancing the economic efficiency of the production. Particularly preferably, h is 3.
Exemplary groups and preferred groups for R44, R45, and R46 are the same as the exemplary groups and preferred groups mentioned above for R42, and R43 in formula (VIII).
The silicon compounds containing a group represented by formula (Va) can be exemplified by compounds represented by the following formula (Va-1) and compounds represented by the following formula (Va-2):




wherein i represents an integer of 1 to 10; R47, R46, and R49 each independently represent a C1-4 hydrocarbyl group or a C1-4 hydrocarbyloxy group, and at least one of R47, R48, and R49 is a hydrocarbyloxy group; and R50 and R51 each independently represent a C1-10 hydrocarbyl group, a C1-10 substituted hydrocarbyl group, a hydrocarbyloxy group, or a substituted hydrocarbyloxy group, and R50 and R51 may be bonded to each other;





wherein j, k, and l each independently represent an integer of 1 to 10; and R52 to R60 each independently represent a C1-4 hydrocarbyl group or a C1-4 hydrocarbyloxy group, at least one of R52, R53, and R54 is a hydrocarbyloxy group, at least one of R55, R56, and R57 is a hydrocarbyloxy group, and at least one of R58, R59, and R60 is a hydrocarbyloxy group.

In formula (Va-1), i represents an integer of 1 to 10. Here, i is preferably not less than 2 in view of enhancing the fuel economy, wet-grip performance, and abrasion resistance in a balanced manner, whereas i is preferably not more than 4 in view of enhancing the economic efficiency of the production. Particularly preferably, i is 3.
The hydrocarbyl groups encompassed by R47, R48, and R49 in formula (Va-1) can be exemplified by alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl groups. The hydrocarbyloxy groups encompassed by R47, R48, and R49 can be exemplified by alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, and t-butoxy groups.
The hydrocarbyl group encompassed by R47, R48, and R49 is preferably an alkyl group, more preferably a C1-3 alkyl group, and still more preferably a methyl group or an ethyl group. The hydrocarbyloxy group encompassed by R47, R48, and R49 is preferably an alkoxy group, more preferably a C1-3 alkoxy group, and still more preferably a methoxy group or an ethoxy group.
With regard to R47, R48, and R49, in view of enhancing the fuel economy, wet-grip performance, and abrasion resistance in a balanced manner, preferably at least two of R47, R48, and R49 are hydrocarbyloxy groups, and more preferably the three of R47, R48, and R49 are hydrocarbyloxy groups.
The hydrocarbyl groups encompassed by R50 and R51 can be exemplified by alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl groups.
The substituted hydrocarbyl groups encompassed by R50 and R51 can be exemplified by substituted hydrocarbyl groups containing as a substituent at least one group selected from the group consisting of nitrogen atom-bearing groups, oxygen atom-bearing groups, and silicon atom-bearing groups. The groups containing a nitrogen atom-bearing group as a substituent can be exemplified by dialkylaminoalkyl groups such as dimethylaminoethyl and diethylaminoethyl groups. The groups containing an oxygen atom-bearing group as a substituent can be exemplified by alkoxyalkyl groups such as methoxymethyl, methoxyethyl, ethoxymethyl, and ethoxyethyl groups. The groups containing a silicon atom-bearing group as a substituent can be exemplified by trialkylsilylalkyl groups such as trimethylsilylmethyl and triethylsilylmethyl groups.
The hydrocarbyloxy groups encompassed by R50 and R51 can be exemplified by alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, and t-butoxy groups. The substituted hydrocarbyloxy groups encompassed by R50 and R51 can be exemplified by alkoxyalkoxy groups such as methoxymethoxy, methoxyethoxy, ethoxymethoxy, and ethoxyethoxy groups.
The groups in which R50 and R51 are bonded to each other can be exemplified by C2-12 divalent groups optionally containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a silicon atom. Specific examples thereof include alkylene groups such as trimethylene, tetramethylene, pentamethylene, and hexamethylene groups; oxydialkylene groups such as oxydiethylene and oxydipropylene groups; and nitrogenous groups such as a group represented by —CH2CH2—NH—CH2— and a group represented by —CH2CH2—N═CH—.
R50 is preferably an alkyl group, more preferably a C1-4 alkyl group, and still more preferably a methyl group or an ethyl group.
R51 is preferably an alkyl group, more preferably a C1-4 alkyl group, and still more preferably a methyl group or an ethyl group.
In formula (Va-2), j, k, and l each independently represent an integer of 1 to 10, and are each independently preferably not less than 2 in view of enhancing the fuel economy, wet-grip performance, and abrasion resistance in a balanced manner, whereas j, k, and 1 are each independently preferably not more than 4 in view of enhancing the economic efficiency of the production. Particularly preferably, j, k, and l are each independently 3.
The hydrocarbyl groups encompassed by R52 to R60 in formula (Va-2) can be exemplified by alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl groups. The hydrocarbyloxy groups encompassed by R52 to R60 can be exemplified by alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, and t-butoxy groups.
The hydrocarbyl group encompassed by R52 to R60 is preferably an alkyl group, more preferably a C1-3 alkyl group, and still more preferably a methyl group or an ethyl group. The hydrocarbyloxy group encompassed by R52 to R50 is preferably an alkoxy group, more preferably a C1-3 alkoxy group, and still more preferably a methoxy group or an ethoxy group.
With regard to R52, R53, and R54, in view of enhancing the fuel economy, wet-grip performance, and abrasion resistance in a balanced manner, preferably at least two of R52, R53, and R54 are hydrocarbyloxy groups, and more preferably the three of R52, R53, and R54 are hydrocarbyloxy groups. With regard to R55, R56, and R57, in view of enhancing the fuel economy, wet-grip performance, and abrasion resistance in a balanced manner, preferably at least two of R55, R56, and R57 are hydrocarbyloxy groups, and more preferably the three of R55, R56, and R57 are hydrocarbyloxy groups. With regard to R58, R59, and R60, in view of enhancing the fuel economy, wet-grip performance, and abrasion resistance in a balanced manner, preferably at least two of R56, R59, and R60 are hydrocarbyloxy groups, and more preferably the three of R58, R59, and R60 are hydrocarbyloxy groups.
The compounds represented by formula (Va-1) can be exemplified by N-alkyl-N-trialkoxysilylalkyl-substituted carboxylic acid amides such as N-alkyl-N-trialkoxysilylalkyl-acetamides, e.g.,

    N-methyl-N-(trimethoxysilylmethyl)acetamide,
    N-methyl-N-(triethoxysilylmethyl)acetamide,
    N-methyl-N-(2-trimethoxysilylethyl)acetamide,
    N-methyl-N-(2-triethoxysilylethyl)acetamide,
    N-methyl-N-(3-trimethoxysilylpropyl)acetamide, and
    N-methyl-N-(3-triethoxysilylpropyl)acetamide; and
    N-alkyl-N-trialkoxysilylalkyl-propionamides, e.g.,
    N-methyl-N-(trimethoxysilylmethyl)propionamide,
    N-methyl-N-(triethoxysilylmethyl)propionamide,
    N-methyl-N-(2-trimethoxysilylethyl)propionamide,
    N-methyl-N-(2-triethoxysilylethyl)propionamide,
    N-methyl-N-(3-trimethoxysilylpropyl)propionamide, and
    N-methyl-N-(3-triethoxysilylpropyl)propionamide.


The compound represented by formula (Va-1) is preferably an N-alkyl-N-trialkoxysilylalkyl-substituted carboxylic acid amide, more preferably an N-alkyl-N-trialkoxysilylalkyl-propionamide, and still more preferably N-methyl-N-(3-trimethoxysilylpropyl)-propionamide or N-methyl-N-(3-triethoxysilylpropyl)-propionamide.
The compounds represented by formula (Va-2) can be exemplified by 1,3,5-tris(trialkoxysilylalkyl)-isocyanurates such as

    1,3,5-tris(trimethoxysilylmethyl)isocyanurate,
    1,3,5-tris(triethoxysilylmethyl)isocyanurate,
    1,3,5-tris(trimethoxysilylethyl)isocyanurate,
    1,3,5-tris(triethoxysilylethyl)isocyanurate,
    1,3,5-tris(3-trimethoxysilylpropyl)isocyanurate, and
    1,3,5-tris(3-triethoxysilylpropyl)isocyanurate.


The compound represented by formula (Va-2) is preferably 1,3,5-tris(3-trimethoxysilylpropyl)isocyanurate, or 1,3,5-tris(3-triethoxysilylpropyl)isocyanurate.
The silicon compounds containing a group represented by formula (VI) and a group represented by formula (VIII) can be exemplified by silicon compounds represented by the following formula (VIa):




wherein v represents an integer of 1 to 10; R61, R62, and R63 each independently represent a C1-4 hydrocarbyl group or a C1-4 hydrocarbyloxy group, and at least one of R61, R62, and R63 is a hydrocarbyloxy group; and R64 represents a C1-10 hydrocarbyl group or a C1-10 substituted hydrocarbyl group.

In formula (VIa), v represents an integer of 1 to 10. Preferably, v is not less than 2 in view of enhancing the fuel economy, wet-grip performance, and abrasion resistance in a balanced manner. Preferably, v is not more than 4 in view of enhancing the economic efficiency of the production. Particularly preferably, v is 3.
The hydrocarbyl groups encompassed by R61, R62, and R63 in formula (VIa) can be exemplified by alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl groups. The hydrocarbyloxy groups encompassed by R61, R62, and R63 can be exemplified by alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, and t-butoxy groups.
The hydrocarbyl group encompassed by R61, R62, and R63 is preferably an alkyl group, more preferably a C1-3 alkyl group, and still more preferably a methyl group or an ethyl group. The hydrocarbyloxy group encompassed by R61, R62, and R63 is preferably an alkoxy group, more preferably a C1-3 alkoxy group, and still more preferably a methoxy group or an ethoxy group.
With regard to R61, R62, and R63, in view of enhancing the fuel economy, wet-grip performance, and abrasion resistance in a balanced manner, preferably at least two of R61, R62, and R63 are hydrocarbyloxy groups, and more preferably the three of R61, R62, and R63 are hydrocarbyloxy groups.
The hydrocarbyl groups encompassed by R64 can be exemplified by alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl groups.
The substituted hydrocarbyl groups encompassed by R64 can be exemplified by substituted hydrocarbyl groups containing as a substituent at least one group selected from the group consisting of nitrogen atom-bearing groups, oxygen atom-bearing groups, and silicon atom-bearing groups. The groups containing a nitrogen atom-bearing group as a substituent can be exemplified by dialkylaminoalkyl groups such as dimethylaminoethyl and diethylaminoethyl groups. The groups containing an oxygen atom-bearing group as a substituent can be exemplified by alkoxyalkyl groups such as methoxymethyl, methoxyethyl, ethoxymethyl, and ethoxyethyl groups; and alkylene oxide alkyl groups such as glycidyl and tetrahydrofurfuryl groups. The groups containing a silicon atom-bearing group as a substituent can be exemplified by trialkylsilylalkyl groups such as a trimethylsilylmethyl group.
As used herein, the term “alkylene oxide alkyl group” denotes a group obtained by substituting at least one hydrogen atom of an alkyl group by an alkylene oxide group.
R64 is preferably an alkylene oxide alkyl group, and more preferably a glycidyl group or a tetrahydrofurfuryl group.
The compounds represented by formula (VIa) in which R64 is an alkyl group can be exemplified by 3-(alkoxy)propyltrialkoxysilanes such as

    3-(methoxy)propyltrimethoxysilane,
    3-(ethoxy)propyltrimethoxysilane,
    3-(n-propoxy)propyltrimethoxysilane,
    3-(isopropoxy)propyltrimethoxysilane,
    3-(n-butoxy)propyltrimethoxysilane,
    3-(sec-butoxy)propyltrimethoxysilane, and
    3-(t-butoxy)propyltrimethoxysilane.


The compounds represented by formula (VIa) in which R64 is an alkylene oxide alkyl group can be exemplified by glycidoxyalkyltrialkoxysilanes such as

    2-glycidoxyethyltrimethoxysilane,
    3-glycidoxypropyltrimethoxysilane,
    2-glycidoxyethyltriethoxysilane, and
    3-glycidoxypropyltriethoxysilane; and

tetrahydrofurfuryloxyalkyltrialkoxysilanes such as

    2-tetrahydrofurfuryloxyethyltrimethoxysilane,
    3-tetrahydrofurfuryloxypropyltrimethoxysilane,
    2-tetrahydrofurfuryloxyethyltriethoxysilane, and
    3-tetrahydrofurfuryloxypropyltriethoxysilane.


The compounds represented by formula (VIa) in which R64 is an alkoxyalkyl group can be exemplified by 3-(alkoxyalkoxy)propyltrialkoxysilanes such as

    3-(methoxymethoxy)propyltrimethoxysilane,
    3-(methoxyethoxy)propyltrimethoxysilane,
    3-(ethoxymethoxy)propyltrimethoxysilane,
    3-(ethoxyethoxy)propyltrimethoxysilane,
    3-(methoxymethoxy)propyltriethoxysilane,
    3-(methoxyethoxy)propyltriethoxysilane,
    3-(ethoxymethoxy)propyltriethoxysilane, and
    3-(ethoxyethoxy)propyltriethoxysilane.


The compound represented by formula (VIa) is preferably a compound in which R64 is an alkylene oxide alkyl group, and more preferably

    3-glycidoxypropyltrimethoxysilane,
    3-glycidoxypropyltriethoxysilane,
    3-tetrahydrofurfuryloxypropyltrimethoxysilane, or
    3-tetrahydrofurfuryloxypropyltriethoxysilane.


The silicon compounds containing a group represented by formula (V), a group represented by formula (VI), and a group represented by formula (VIII) can be exemplified by acryloxyalkyltrialkoxysilanes, and methacryloxyalkyltrialkoxysilanes.
The acryloxyalkyltrialkoxysilanes can be exemplified by 3-acryloxypropyltrialkoxysilanes such as

    3-acryloxypropyltrimethoxysilane and
    3-acryloxypropyltriethoxysilane.


The methacryloxyalkyltrialkoxysilanes can be exemplified by 3-methacryloxypropyltrialkoxysilanes such as 3-methacryloxypropyltrimethoxysilane, and

    3-methacryloxypropyltriethoxysilane.


The silicon compounds containing a group represented by formula (V), a group represented by formula (VI), and a group represented by formula (VIII) can be further exemplified by trialkoxysilylalkylsuccinic anhydrides and trialkoxysilylalkylmaleic anhydrides.
The trialkoxysilylalkylsuccinic anhydrides can be exemplified by 3-trialkoxysilylpropylsuccinic anhydrides such as 3-trimethoxysilylpropylsuccinic anhydride and 3-triethoxysilylpropylsuccinic anhydride.
The trialkoxysilylalkylmaleic anhydrides can be exemplified by 3-trialkoxysilylpropylmaleic anhydrides such as 3-trimethoxysilylpropylmaleic anhydride and 3-triethoxysilylpropylmaleic anhydride.
The following explains the compound (modifying agent 5) containing a group represented by formula (VII) below.




In the formula, w represents an integer of 1 to 11, and A5 represents a nitrogen atom-bearing functional group.
Here, w represents an integer of 1 to 11, and is preferably not less than 1 in view of enhancing the fuel economy, wet-grip performance, and abrasion resistance in a balanced manner, whereas w is preferably not more than 4 in view of enhancing the economic efficiency of the production. A5 represents a nitrogen atom-bearing functional group and examples thereof include amino, isocyano, cyano, pyridyl, piperidyl, pyrazinyl, and morpholino groups.
The compounds containing a group represented by formula (VII) can be exemplified by compounds represented by the following formula (VII-1):




wherein z represents an integer of 0 to 10; R71 represents a C1-5 hydrocarbyl group; R72, R73, R74 and R75 each independently represent a hydrogen atom, a C1-5 hydrocarbyl group, a C1-5 substituted hydrocarbyl group, or a C1-5 hydrocarbyloxy group, and when a plurality of R72's and a plurality of R73's are present, the plurality of R72's and the plurality of R73's may be the same as or different from one another; and R76 and R77 each independently represent a C1-6 group optionally containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a silicon atom, R76 and R77 may be bonded to each other to form a cyclic structure together with the nitrogen atom, and R76 and R77 may form a single group bonded to the nitrogen via a double bond.

In formula (VII-1), z represents an integer of 0 to 10. In view of enhancing the economic efficiency, z is preferably not more than 3, and more preferably 0.
R71 in formula (VII-1) represents a C1-5 hydrocarbyl group. The hydrocarbyl groups encompassed by R71 can be exemplified by alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and t-butyl groups.
The hydrocarbyl group encompassed by R71 is preferably an alkyl group, more preferably a C1-4 alkyl group, and still more preferably a methyl group or an ethyl group.
R72 to R75 in formula (VII-1) each independently represent a hydrogen atom, a C1-5 hydrocarbyl group, a C1-5 substituted hydrocarbyl group, or a C1-5 hydrocarbyloxy group, and when a plurality of R72's and a plurality of R73's are present, the plurality of R72's and the plurality of R73's may be the same as or different from one another.
The hydrocarbyl groups encompassed by R72 to R75 can be exemplified by alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and t-butyl groups.
The substituted hydrocarbyl groups encompassed by R72 to R75 can be exemplified by substituted hydrocarbyl groups containing as a substituent at least one group selected from the group consisting of nitrogen atom-bearing groups and oxygen atom-bearing groups. The groups containing a nitrogen atom-bearing group as a substituent can be exemplified by dialkylaminoalkyl groups such as dimethylaminoethyl and diethylaminoethyl groups. The groups containing an oxygen atom-bearing group as a substituent can be exemplified by alkoxyalkyl groups such as methoxymethyl, methoxyethyl, ethoxymethyl, and ethoxyethyl groups.
The hydrocarbyloxy groups encompassed by R72 to R75 can be exemplified by alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, and t-butoxy groups.
The hydrocarbyl group encompassed by R72 to R75 is preferably an alkyl group, more preferably a C1-4 alkyl group, and still more preferably a methyl group or an ethyl group.
The substituted hydrocarbyl group encompassed by R72 to R75 is preferably an alkoxyalkyl group, more preferably a C1-4 alkoxyalkyl group, and still more preferably a methoxymethyl group or an ethoxyethyl group.
The hydrocarbyloxy group encompassed by R72 to R75 is preferably an alkoxy group, more preferably a C1-3 alkoxy group, and still more preferably a methoxy group or an ethoxy group.
In view of economic efficiency and in view of enhancing the fuel economy, wet-grip performance, and abrasion resistance in a balanced manner, preferably one of R74 and R75 is a hydrogen atom. More preferably, one of R74 and R75 is a hydrogen atom and the other is an alkyl group or an alkoxy group. Still more preferably, one of R74 and R75 is a hydrogen atom and the other is an alkoxy group, particularly preferably a methoxy group or an ethoxy group.
R76 and R77 in formula (VII-1) each independently represent a C1-6 group optionally containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a silicon atom; R76 and R77 may be bonded to each other to form a cyclic structure together with the nitrogen atom; and R76 and R77 may form a single group bonded to the nitrogen via a double bond.
Examples of R76 and R77 in formula (VII-1) include C1-6 hydrocarbyl groups, C1-6 substituted hydrocarbyl groups, and substituted silyl groups.
The hydrocarbyl groups encompassed by R76 and R77 can be exemplified by alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, isopentyl, and n-hexyl groups; cycloalkyl groups such as a cyclohexyl group; and a phenyl group.
The substituted hydrocarbyl groups encompassed by R76 and R77 can be exemplified by substituted hydrocarbyl groups containing as a substituent at least one group selected from the group consisting of nitrogen atom-bearing groups, oxygen atom-bearing groups, and silicon atom-bearing groups. The groups containing a nitrogen atom-bearing group as a substituent can be exemplified by dialkylaminoalkyl groups such as dimethylaminoethyl and diethylaminoethyl groups. The groups containing an oxygen atom-bearing group as a substituent can be exemplified by alkoxyalkyl groups such as methoxymethyl, methoxyethyl, ethoxymethyl, and ethoxyethyl groups; alkylene oxide groups such as epoxy and tetrahydrofuranyl groups; and alkylene oxide alkyl groups such as glycidyl and tetrahydrofurfuryl groups. The groups containing a silicon atom-bearing group as a substituent can be exemplified by trialkylsilylalkyl groups such as a trimethylsilylmethyl group.
As used herein, the term “alkylene oxide group” denotes a monovalent group obtained by removing a hydrogen atom from the ring of a cyclic ether compound. The term “alkylene oxide alkyl group” denotes a group obtained by substituting at least one hydrogen atom of an alkyl group by an alkylene oxide group.
The substituted silyl groups encompassed by R76 and R77 can be exemplified by trialkylsilyl groups such as trimethylsilyl, triethylsilyl, and t-butyldimethylsilyl groups; and trialkoxysilyl groups such as a trimethoxysilyl group.
The groups in which R76 and R77 are bonded to each other can be exemplified by C2-12 divalent groups optionally containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a silicon atom. Specific examples thereof include alkylene groups such as trimethylene, tetramethylene, pentamethylene, and hexamethylene groups; oxydialkylene groups such as oxydiethylene and oxydipropylene groups; and nitrogenous groups such as a group represented by —CH2CH2—NH—CH2— and a group represented by —CH2CH2—N═CH—.
The group in which R76 and R77 are bonded to each other is preferably a nitrogenous group, and more preferably a group represented by —CH2CH2—NH—CH2— or a group represented by —CH2CH2—N═CH—.
Examples of the single group bonded to the nitrogen via a double bond, formed by R76 and R77, include C2-12 divalent groups optionally containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a silicon atom. Specific examples include an ethylidene group, a 1-methylpropylidene group, a 1,3-dimethylbutylidene group, a 1-methylethylidene group, and a 4-N,N-dimethylaminobenzylidene group.
The hydrocarbyl group encompassed by R76 and R77 is preferably an alkyl group, more preferably a C1-4 alkyl group, still more preferably a methyl group, an ethyl group, an n-propyl group, or an n-butyl group, and further preferably a methyl group or an ethyl group. The substituted hydrocarbyl group encompassed by R76 and R77 is preferably an alkoxyalkyl group, an alkylene oxide group, or an alkylene oxide alkyl group. The substituted silyl group encompassed by R76 and R77 is preferably a trialkylsilyl group or a trialkoxysilyl group, more preferably a trialkylsilyl group, and still more preferably a trimethylsilyl group or a triethylsilyl group.
Preferably, R76 and R77 are a nitrogenous group in which R76 and R77 are bonded to each other, or are each independently an alkyl group, an alkoxyalkyl group, or a substituted silyl group. R76 and R77 are each independently more preferably a C1-4 alkyl group, still more preferably a methyl group, an ethyl group, an n-propyl group, or an n-butyl group, and further preferably a methyl group or an ethyl group.
Examples of the amino group in which R76 and R77 are bonded to the nitrogen atom include acyclic amino groups and cyclic amino groups.
Examples of the acyclic amino groups include dialkylamino groups such as dimethylamino, diethylamino, di(n-propyl)amino, di(isopropyl)amino, di(n-butyl)amino, di(sec-butyl)amino, di(tert-butyl)amino, di(neopentyl)amino, and ethylmethylamino groups; di(alkoxyalkyl)amino groups such as di(methoxymethyl)amino, di(methoxyethyl)amino, di(ethoxymethyl)amino, and di(ethoxyethyl)amino groups; and di(trialkylsilyl)amino groups such as di(trimethylsilyl)amino and di(t-butyldimethylsilyl)amino groups. Other examples include di(alkylene oxide)amino groups such as di(epoxy)amino and di(tetrahydrofuranyl)amino groups; and di(alkylene oxide alkyl)amino groups such as di(glycidyl)amino and di(tetrahydrofurfuryl)amino groups. Additional examples include ethylideneamino, 1-methylpropylideneamino, 1,3-dimethylbutylideneamino, 1-methylethylideneamino, and 4-N,N-dimethylaminobenzylideneamino groups.
The cyclic amino groups can be exemplified by 1-polymethyleneimino groups such as 1-pyrrolidinyl, 1-piperidino, 1-hexamethyleneimino, 1-heptamethyleneimino, 1-octamethyleneimino, 1-decamethyleneimino, and 1-dodecamethyleneimino groups. The cyclic amino groups can also be exemplified by 1-imidazolyl, 4,5-dihydro-1-imidazolyl, 1-imidazolidinyl, 1-piperazinyl, and morpholino groups.
In view of fuel economy, wet-grip performance, abrasion resistance, and long-term stability and easy availability of the compound, the amino group in which R76 and R77 are bonded to the nitrogen atom is preferably an acyclic amino group, more preferably a dialkylamino group, and still more preferably a dimethylamino group or a diethylamino group.
The compounds represented by formula (VII-1) can be exemplified by N,N-dialkyl-substituted carboxylic acid amide dialkyl acetal compounds.
The N,N-dialkyl-substituted carboxylic acid amide dialkyl acetal compounds can be exemplified by N,N-dialkylformamide dialkyl acetals such as

    N,N-dimethylformamide dimethyl acetal,
    N,N-diethylformamide dimethyl acetal,
    N,N-di(n-propyl)formamide dimethyl acetal,
    N,N-dimethylformamide diethyl acetal,
    N,N-diethylformamidediethyl acetal,
    N,N-di(n-propyl)formamide diethyl acetal,
    N,N-dimethylformamide ethyl methyl acetal,
    N,N-diethylformamide ethyl methyl acetal, and
    N,N-di(n-propyl)formamide ethyl methyl acetal;

N,N-dialkylacetamide dialkyl acetals such as

    N,N-dimethylacetamide dimethyl acetal,
    N,N-diethylacetamide dimethyl acetal,
    N,N-di(n-propyl)acetamide dimethyl acetal,
    N,N-dimethylacetamide diethyl acetal,
    N,N-diethylacetamide diethyl acetal,
    N,N-di(n-propyl)acetamide diethyl acetal,
    N,N-dimethylacetamide ethyl methyl acetal,
    N,N-diethylacetamide ethyl methyl acetal, and
    N,N-di(n-propyl)acetamide ethyl methyl acetal; and

N,N-dialkylpropionamide dialkyl acetals such as

    N,N-dimethylpropionamide dimethyl acetal,
    N,N-diethylpropionamide dimethyl acetal,
    N,N-di(n-propyl)propionamide dimethyl acetal,
    N,N-dimethylpropionamide diethyl acetal,
    N,N-diethylpropionamide diethyl acetal,
    N,N-di(n-propyl)propionamide diethyl acetal,
    N,N-dimethylpropionamide ethyl methyl acetal,
    N,N-diethylpropionamide ethyl methyl acetal, and
    N,N-di(n-propyl)propionamide ethyl methyl acetal.


In view of enhancing the fuel economy, wet-grip performance, and abrasion resistance in a balanced manner, N,N-dialkylformamide dialkyl acetals are preferred among the preceding, and N,N-dimethylformamide dimethyl acetal,

    N,N-diethylformamide dimethyl acetal,
    N,N-dimethylformamide diethyl acetal, and
    N,N-diethylformamide diethyl acetal are more preferred.


In addition to the conjugated diene-based constituent unit (conjugated diene unit), the conjugated diene polymer may also contain a constituent unit based on another monomer. Such other monomers include aromatic vinyls, vinyl nitriles, unsaturated carboxylic acid esters, and the like. The aromatic vinyls can be exemplified by styrene, α-methylstyrene, vinyltoluene, vinylnaphthalene, divinylbenzene, trivinylbenzene, and divinylnaphthalene. The vinyl nitriles can be exemplified by acrylonitrile. The unsaturated carboxylic acid esters can be exemplified by methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate. Aromatic vinyls are preferred among the preceding, and styrene is more preferred.
The conjugated diene polymer preferably contains an aromatic vinyl-based constituent unit (aromatic vinyl unit) in consideration of abrasion resistance. In this case, the aromatic vinyl unit content, based on a total of 100% by mass of the conjugated diene unit and the aromatic vinyl unit, is preferably at least 10% by mass (the conjugated diene unit content is not more than 90% by mass), and more preferably at least 15% by mass (the conjugated diene unit content is not more than 85% by mass). In view of fuel economy, the aromatic vinyl unit content is preferably not more than 50% by mass (the conjugated diene unit content is at least 50% by mass), and more preferably not more than 45% by mass (the conjugated diene unit content is at least 55% by mass).
In view of fuel economy, the conjugated diene polymer preferably has a vinyl bond content of not more than 80 mol %, more preferably not more than 70 mol %, per 100 mol % of the conjugated diene unit. In view of wet-grip performance, the vinyl bond content is preferably at least 10 mol %, more preferably at least 15 mol %, still more preferably at least 20 mol %, and particularly preferably at least 40 mol %. The vinyl bond content can be determined by infrared spectroscopic analysis from the intensity of the absorption in the vicinity of 910 cm−1, which is an absorption peak for a vinyl group.
The molecular weight distribution of the conjugated diene polymer, in view of fuel economy, is preferably 1 to 5, and more preferably 1 to 2. The molecular weight distribution can be determined by measuring the number-average molecular weight (Mn) and the weight-average molecular weight (Mw) by gel permeation chromatography (GPC) and dividing Mw by Mn.
The conjugated diene polymer may suitably be produced by a method including the following Step A and Step B.
(Step A): A step of polymerizing monomers including a conjugated diene and a vinyl compound represented by formula (IX) below in the presence of an alkali metal catalyst in a hydrocarbon solvent to obtain a polymer that contains a constituent unit based on the conjugated diene and a constituent unit based on the vinyl compound represented by the formula (IX) and has an alkali metal derived from the catalyst at at least one polymer chain terminal:




wherein X4, X5, and X6 each independently represent a group represented by formula (IXa) below, a hydrocarbyl group, or a substituted hydrocarbyl group, and at least one of X4, X5, and X6 is a group represented by the following formula (IXa):





wherein R81 and R82 each independently represent a C1-6 hydrocarbyl group, a C1-6 substituted hydrocarbyl group, a silyl group, or a substituted silyl group, and R81 and R82 may be bonded to each other to form a cyclic structure together with the nitrogen atom.

(Step B): A step of reacting the polymer obtained in Step A with at least one of the modifying agents 1 to 5.
The alkali metal catalysts that can be used in (Step A) can be exemplified by alkali metals, organoalkali metal compounds, alkali metal/polar compound complexes, and alkali metal-containing oligomers. Examples of the alkali metals include lithium, sodium, potassium, rubidium, and cesium. Examples of the organoalkali metal compounds include ethyllithium, n-propyllithium, iso-propyllithium, n-butyllithium, sec-butyllithium, t-octyllithium, n-decyllithium, phenyllithium, 2-naphthyllithium, 2-butylphenyllithium, 4-phenylbutyllithium, cyclohexyllithium, 4-cyclopentyllithium, dimethylaminopropyllithium, diethylaminopropyllithium, t-butyldimethylsilyloxypropyllithium, N-morpholinopropyllithium, lithium hexamethyleneimide, lithium pyrrolidide, lithium piperidide, lithium heptamethyleneimide, lithium dodecamethyleneimide, 1,4-dilithio-2-butene, sodium naphthalenide, sodium biphenylide, and potassium naphthalenide. Examples of the alkali metal/polar compound complex include potassium-tetrahydrofuran complexes and potassium-diethoxyethane complexes. Examples of the alkali metal-containing oligomers include sodium salts of α-methylstyrene tetramer. Organolithium compounds and organosodium compounds are preferred among the preceding, and C2-20 organolithium or organosodium compounds are more preferred.
The hydrocarbon solvent used in (Step A) is a solvent that does not deactivate the organoalkali metal compound catalyst, and examples thereof include aliphatic hydrocarbons, aromatic hydrocarbons, and alicyclic hydrocarbons. The aliphatic hydrocarbons can be exemplified by propane, n-butane, iso-butane, n-pentane, iso-pentane, n-hexane, propene, 1-butene, iso-butene, trans-2-butene, cis-2-butene, 1-pentene, 2-pentene, 1-hexene, and 2-hexene. The aromatic hydrocarbons can be exemplified by benzene, toluene, xylene, and ethylbenzene. The alicyclic hydrocarbons can be exemplified by cyclopentane and cyclohexane. These may be used alone or two or more may be used in combination. C2-12 hydrocarbons are preferred among the preceding.
In (Step A), monomers including a conjugated diene and a vinyl compound represented by formula (IX) are polymerized to produce a conjugated diene polymer having an alkali metal derived from the above-described alkali metal catalyst at a polymer chain terminal. The conjugated dienes can be exemplified by 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and 1,3-hexadiene. These may be used alone or two or more may be used in combination. In view of ease of availability, 1,3-butadiene and isoprene are preferred among the preceding.
X4, X5, and X6 in formula (IX) each independently represent a group represented by formula (IXa), a hydrocarbyl group, or a substituted hydrocarbyl group, and at least one of X4, X5, and X6 is a group represented by formula (IXa).
R81 and R82 in formula (IXa) each independently represent a C1-6 hydrocarbyl group, a C1-6 substituted hydrocarbyl group, a silyl group, or a substituted silyl group, and R81 and R82 may be bonded to each other to form a cyclic structure together with the nitrogen atom.
The C1-6 hydrocarbyl groups encompassed by R81 and R82 can be exemplified by alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, isopentyl, and n-hexyl groups; cycloalkyl groups such as a cyclohexyl group; and a phenyl group.
The C1-6 substituted hydrocarbyl groups encompassed by R81 and R82 can be exemplified by substituted hydrocarbyl groups containing as a substituent at least one group selected from the group consisting of nitrogen atom-bearing groups, oxygen atom-bearing groups, and silicon atom-bearing groups. The groups containing a nitrogen atom-bearing group as a substituent can be exemplified by dialkylaminoalkyl groups such as dimethylaminoethyl and diethylaminoethyl groups. The groups containing an oxygen atom-bearing group as a substituent can be exemplified by alkoxyalkyl groups such as methoxymethyl, methoxyethyl, ethoxymethyl, and ethoxyethyl groups. The groups containing a silicon atom-bearing group as a substituent can be exemplified by trialkylsilylalkyl groups such as a trimethylsilylmethyl group.
The substituted silyl groups encompassed by R81 and R82 can be exemplified by trialkylsilyl groups such as trimethylsilyl, triethylsilyl, and t-butyldimethylsilyl groups.
The groups in which R81 and R82 are bonded to each other can be exemplified by C1-12 divalent groups optionally containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a silicon atom. Specific examples thereof include alkylene groups such as trimethylene, tetramethylene, pentamethylene, and hexamethylene groups; oxydialkylene groups such as oxydiethylene and oxydipropylene groups; and nitrogenous groups such as a group represented by —CH2CH2—NH—CH2— and a group represented by —CH2CH2—N═CH—.
The group in which R81 and R82 are bonded to each other is preferably a nitrogenous group, and more preferably a group represented by —CH2CH2—NH—CH2— or a group represented by —CH2CH2—N═CH—.
The hydrocarbyl group encompassed by R81 and R82 is preferably an alkyl group, more preferably a C1-4 alkyl group, still more preferably a methyl group, an ethyl group, an n-propyl group, or an n-butyl group, and particularly preferably an ethyl group or an n-butyl group. The substituted hydrocarbyl group encompassed by R81 and R82 is preferably an alkoxyalkyl group, and more preferably a C1-4 alkoxyalkyl group. The substituted silyl group encompassed by R81 and R82 is preferably a trialkylsilyl group, and more preferably a trimethylsilyl group.
Preferably, R81 and R82 are each independently an alkyl group, an alkoxyalkyl group, or a substituted silyl group, or are a nitrogenous group in which R81 and R82 are bonded to each other. R81 and R82 are each independently more preferably an alkyl group, still more preferably a C1-4 alkyl group, and further preferably a methyl group, an ethyl group, an n-propyl group, or an n-butyl group.
Examples of the group represented by formula (IXa) include acyclic amino groups and cyclic amino groups.
The acyclic amino groups can be exemplified by dialkylamino groups such as dimethylamino, diethylamino, di(n-propyl)amino, di(isopropyl)amino, di(n-butyl)amino, di(sec-butyl)amino, di(tert-butyl)amino, di(neopentyl)amino, and ethylmethylamino groups; di(alkoxyalkyl)amino groups such as di(methoxymethyl)amino, di(methoxyethyl)amino, di(ethoxymethyl)amino, and di(ethoxyethyl)amino groups; and di(trialkylsilyl)amino groups such as di(trimethylsilyl)amino and di(t-butyldimethylsilyl)amino groups.
The cyclic amino groups can be exemplified by 1-polymethyleneimino groups such as 1-pyrrolidinyl, 1-piperidino, 1-hexamethyleneimino, 1-heptamethyleneimino, 1-octamethyleneimino, 1-decamethyleneimino, and 1-dodecamethyleneimino groups. The cyclic amino group can also be exemplified by 1-imidazolyl, 4,5-dihydro-1-imidazolyl, 1-imidazolidinyl, 1-piperazinyl, and morpholino groups.
In view of economic efficiency and ease of availability, the group represented by formula (IXa) is preferably an acyclic amino group, more preferably a dialkylamino group, still more preferably a dialkylamino group which contains a C1-4 alkyl group as a substituent, and further preferably a dimethylamino group, a diethylamino group, a di(n-propyl)amino group, or a di(n-butyl)amino group.
The hydrocarbyl groups encompassed by X4, X5, and X6 in formula (IX) can be exemplified by alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and tert-butyl groups. The substituted hydrocarbyl groups can also be exemplified by alkoxyalkyl groups such as methoxymethyl, ethoxymethyl, methoxyethyl, and ethoxyethyl groups.
The hydrocarbyl group encompassed by X4, X5, and X6 is preferably an alkyl group, more preferably a C1-4 alkyl group, and still more preferably a methyl group or an ethyl group. The substituted hydrocarbyl group encompassed by X4, X5, and X6 is preferably an alkoxyalkyl group, and more preferably a C1-4 alkoxyalkyl group.
The hydrocarbyl group or substituted hydrocarbyl group encompassed by X4, X5, and X6 is preferably an alkyl group or an alkoxyalkyl group, more preferably a C1-4 alkyl group or a C1-4 alkoxyalkyl group, still more preferably a C1-4 alkyl group, and further preferably a methyl group or an ethyl group.
At least one of X4, X5, and X6 in formula (IX) is a group represented by formula (IXa). Preferably at least two of X4, X5, and X6 are groups represented by formula (IXa). More preferably two of X4, X5, and X6 are groups represented by formula (IXa).
Examples of the vinyl compound represented by formula (IX) used in (Step A) include compounds in which one of X4, X5, and X6 is an acyclic amino group represented by formula (IXa) and the other two are, independently, a hydrocarbyl group or a substituted hydrocarbyl group, e.g., (dialkylamino)dialkylvinylsilanes, {di(trialkylsilyl)amino}dialkylvinylsilanes, and (dialkylamino)dialkoxyalkylvinylsilanes.
The (dialkylamino)dialkylvinylsilanes can be exemplified by

    (dimethylamino)dimethylvinylsilane,
    (ethylmethylamino)dimethylvinylsilane,
    (diethylamino)dimethylvinylsilane,
    (ethyl-n-propylamino)dimethylvinylsilane,
    (ethylisopropylamino)dimethylvinylsilane,
    (di(n-propyl)amino)dimethylvinylsilane,
    (diisopropylamino)dimethylvinylsilane,
    (n-butyl-n-propylamino)dimethylvinylsilane,
    (di(n-butyl)amino)dimethylvinylsilane,
    (dimethylamino)diethylvinylsilane,
    (ethylmethylamino)diethylvinylsilane,
    (diethylamino)diethylvinylsilane,
    (ethyl-n-propylamino) diethylvinylsilane,
    (ethylisopropylamino)diethylvinylsilane,
    (di(n-propyl)amino)diethylvinylsilane,
    (diisopropylamino)diethylvinylsilane,
    (n-butyl-n-propylamino) diethylvinylsilane,
    (di(n-butyl)amino)diethylvinylsilane,
    (dimethylamino)dipropylvinylsilane,
    (ethylmethylamino)dipropylvinylsilane,
    (diethylamino)dipropylvinylsilane,
    (ethyl-n-propylamino)dipropylvinylsilane,
    (ethylisopropylamino)dipropylvinylsilane,
    (di(n-propyl)amino)dipropylvinylsilane,
    (diisopropylamino)dipropylvinylsilane,
    (n-butyl-n-propylamino)dipropylvinylsilane,
    (di(n-butyl)amino)dipropylvinylsilane,
    (dimethylamino)dibutylvinylsilane,
    (ethylmethylamino)dibutylvinylsilane,
    (diethylamino)dibutylvinylsilane,
    (ethyl-n-propylamino)dibutylvinylsilane,
    (ethylisopropylamino)dibutylvinylsilane,
    (di(n-propyl)amino)dibutylvinylsilane,
    (diisopropylamino)dibutylvinylsilane,
    (n-butyl-n-propylamino)dibutylvinylsilane, and
    (di(n-butyl)amino)dibutylvinylsilane.


The {di(trialkylsilyl)amino}dialkylvinylsilanes can be exemplified by

    {di(trimethylsilyl)amino}dimethylvinylsilane,
    {di(t-butyldimethylsilyl)amino}dimethylvinylsilane,
    {di(trimethylsilyl)amino}diethylvinylsilane, and
    {di(t-butyldimethylsilyl)amino}diethylvinylsilane.


The (dialkylamino)dialkoxyalkylvinylsilanes can be exemplified by

    (dimethylamino)dimethoxymethylvinylsilane,
    (dimethylamino)dimethoxyethylvinylsilane,
    (dimethylamino)diethoxymethylvinylsilane,
    (dimethylamino)diethoxyethylvinylsilane,
    (diethylamino)dimethoxymethylvinylsilane,
    (diethylamino)dimethoxyethylvinylsilane,
    (diethylamino)diethoxymethylvinylsilane, and
    (diethylamino)diethoxyethylvinylsilane.


Examples of compounds in which two of X4, X5, and X6 are acyclic amino groups represented by formula (IXa) and the other one is a hydrocarbyl group or a substituted hydrocarbyl group include bis(dialkylamino)-alkylvinylsilanes, bis{di(trialkylsilyl)amino}-alkylvinylsilanes, and bis(dialkylamino)-alkoxyalkylvinylsilanes.
The bis(dialkylamino)alkylvinylsilanes can be exemplified by

    bis(dimethylamino)methylvinylsilane,
    bis(ethylmethylamino)methylvinylsilane,
    bis(diethylamino)methylvinylsilane,
    bis(ethyl-n-propylamino)methylvinylsilane,
    bis(ethylisopropylamino)methylvinylsilane,
    bis(di(n-propyl)amino)methylvinylsilane,
    bis(diisopropylamino)methylvinylsilane,
    bis(n-butyl-n-propylamino)methylvinylsilane,
    bis(di(n-butyl)amino)methylvinylsilane,
    bis(dimethylamino)ethylvinylsilane,
    bis(ethylmethylamino)ethylvinylsilane,
    bis(diethylamino)ethylvinylsilane,
    bis(ethyl-n-propylamino)ethylvinylsilane,
    bis(ethylisopropylamino)ethylvinylsilane,
    bis(di(n-propyl)amino)ethylvinylsilane,
    bis(diisopropylamino)ethylvinylsilane,
    bis(n-butyl-n-propylamino)ethylvinylsilane,
    bis(di(n-butyl)amino)ethylvinylsilane,
    bis(dimethylamino)propylvinylsilane,
    bis(ethylmethylamino)propylvinylsilane,
    bis(diethylamino)propylvinylsilane,
    bis(ethyl-n-propylamino)propylvinylsilane,
    bis(ethylisopropylamino)propylvinylsilane,
    bis(di(n-propyl)amino)propylvinylsilane,
    bis(diisopropylamino)propylvinylsilane,
    bis(n-butyl-n-propylamino)propylvinylsilane,
    bis(di(n-butyl)amino)propylvinylsilane,
    bis(dimethylamino)butylvinylsilane,
    bis(ethylmethylamino)butylvinylsilane,
    bis(diethylamino)butylvinylsilane,
    bis(ethyl-n-propylamino)butylvinylsilane,
    bis(ethylisopropylamino)butylvinylsilane,
    bis(di(n-propyl)amino)butylvinylsilane,
    bis(diisopropylamino)butylvinylsilane,
    bis(n-butyl-n-propylamino)butylvinylsilane, and
    bis(di(n-butyl)amino)butylvinylsilane.


The bis{di(trialkylsilyl)amino}alkylvinylsilanes can be exemplified by

    bis{di(trimethylsilyl)amino}methylvinylsilane,
    bis{di(t-butyldimethylsilyl)amino}methylvinylsilane,
    bis{di(trimethylsilyl)amino}ethylvinylsilane, and
    bis{di(t-butyldimethylsilyl)amino}ethylvinylsilane.


The bis(dialkylamino)alkoxyalkylvinylsilanes can be exemplified by

    bis(dimethylamino)methoxymethylvinylsilane,
    bis(dimethylamino)methoxyethylvinylsilane,
    bis(dimethylamino)ethoxymethylvinylsilane,
    bis(dimethylamino)ethoxyethylvinylsilane,
    bis(diethylamino)methoxymethylvinylsilane,
    bis(diethylamino)methoxyethylvinylsilane,
    bis(diethylamino)ethoxymethylvinylsilane, and
    bis(diethylamino)ethoxyethylvinylsilane.


Examples of compounds in which the three of X4, X5, and X6 are acyclic amino groups represented by formula (IXa) include tri(dialkylamino)vinylsilanes. Specific examples thereof include:

    tri(dimethylamino)vinylsilane,
    tri(ethylmethylamino)vinylsilane,
    tri(diethylamino)vinylsilane,
    tri(ethylpropylamino)vinylsilane,
    tri(dipropylamino)vinylsilane, and
    tri(butylpropylamino)vinylsilane.


Examples of compounds in which two of X4, X5, and X6 are cyclic amino groups represented by formula (IXa) and the other one is a hydrocarbyl group or a substituted hydrocarbyl group include:

    bis(morpholino)methylvinylsilane,
    bis(piperidino)methylvinylsilane,
    bis(4,5-dihydroimidazolyl)methylvinylsilane, and
    bis(hexamethyleneimino)methylvinylsilane.


The vinyl compound represented by formula (IX) in which two of X4, X5, and X6 are groups represented by formula (IXa) is preferably a vinyl compound in which two of X4, X5, and X6 are acyclic amino groups. In view of fuel economy, wet-grip performance, and abrasion resistance, the vinyl compound is more preferably a bis(dialkylamino)alkylvinylsilane, and still more preferably bis(dimethylamino)methylvinylsilane, bis(diethylamino)methylvinylsilane, bis(di(n-propyl)amino)methylvinylsilane, or bis(di(n-butyl)amino)methylvinylsilane. Among the preceding, bis(diethylamino)methylvinylsilane and bis(di(n-butyl)amino)methylvinylsilane are preferred in terms of easy availability of the compound.
In (Step A), polymerization may be carried out by using the conjugated diene and the vinyl compound represented by formula (IX) in combination with another monomer. Such other monomers include aromatic vinyls, vinyl nitriles, unsaturated carboxylic acid esters, and the like. The aromatic vinyls can be exemplified by styrene, α-methylstyrene, vinyltoluene, vinylnaphthalene, divinylbenzene, trivinylbenzene, and divinylnaphthalene. The vinyl nitriles can be exemplified by acrylonitrile. The unsaturated carboxylic acid esters can be exemplified by methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate. Aromatic vinyls are preferred among the preceding, and styrene is more preferred.
In (Step A), polymerization may be carried out in the presence of an agent that adjusts the vinyl bond content of the conjugated diene unit, an agent that adjusts the distribution of the conjugated diene unit and constituent unit(s) based on monomer(s) other than the conjugated diene in the conjugated diene polymer chain, or the like (these agents are collectively referred to below as “regulators”). These agents can be exemplified by ether compounds, tertiary amines, and phosphine compounds. The ether compounds can be exemplified by cyclic ethers such as tetrahydrofuran, tetrahydropyran, and 1,4-dioxane; aliphatic monoethers such as diethyl ether and dibutyl ether; aliphatic diethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether; and aromatic ethers such as diphenyl ether and anisole. The tertiary amines can be exemplified by triethylamine, tripropylamine, tributylamine, N,N,N′,N′-tetramethylethylenediamine, N,N-diethylaniline, pyridine, and quinoline. The phosphine compounds can be exemplified by trimethylphosphine, triethylphosphine, and triphenylphosphine. These may be used alone or two or more may be used in combination.
The polymerization temperature in (Step A) is typically 25 to 100° C., preferably 35 to 90° C., and more preferably 50 to 80° C. The polymerization time is typically 10 minutes to 5 hours.
In (Step B), the amount of the modifying agent(s) 1 to 5 to be contacted with the polymer prepared in Step A is typically 0.1 to 3 moles, preferably 0.5 to 2 moles, more preferably 0.7 to 1.5 moles, and further preferably 1 to 1.5 moles, per mole of an alkali metal derived from the organoalkali metal catalyst.
In (Step B), the temperature for the contact between the polymer prepared in Step A and at least one of the modifying agents 1 to 5 is typically 25 to 100° C., preferably 35 to 90° C., and more preferably 50 to 80° C. The contact time is typically 60 seconds to 5 hours, preferably 5 minutes to 1 hour, and more preferably 15 minutes to 1 hour.
In the method for producing the conjugated diene polymer, a coupling agent may be added to the hydrocarbon solution of the conjugated diene polymer as necessary, from the initiation of polymerization of monomers in the presence of the alkali metal catalyst to the termination of polymerization. The coupling agent may be a compound represented by the following formula (X):

R91aML4-a  (X)

wherein R91 represents an alkyl group, an alkenyl group, a cycloalkenyl group, or an aromatic residue; M represents a silicon atom or a tin atom; L represents a halogen atom or a hydrocarbyloxy group; and a represents an integer of 0 to 2.

The term “aromatic residue” denotes a monovalent group obtained by removing hydrogen bonded to the aromatic ring of an aromatic hydrocarbon.
The coupling agents represented by formula (X) can be exemplified by silicon tetrachloride, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, tin tetrachloride, methyltrichlorotin, dimethyldichlorotin, trimethylchlorotin, tetramethoxysilane, methyltrimethoxysilane, dimethoxydimethylsilane, methyltriethoxysilane, ethyltrimethoxysilane, dimethoxydiethylsilane, diethoxydimethylsilane, tetraethoxysilane, ethyltriethoxysilane, and diethoxydiethylsilane.
The amount of the coupling agent, in view of the processability of the conjugated diene polymer, is preferably not less than 0.03 moles, and more preferably not less than 0.05 moles, per mole of an alkali metal derived from the alkali metal catalyst. In view of fuel economy, the amount is preferably not more than 0.4 moles, and more preferably not more than 0.3 moles.
The conjugated diene polymer can be recovered from the hydrocarbon solution of the conjugated diene polymer by a known recovery method, for example, by (1) addition of a coagulant to the hydrocarbon solution of the conjugated diene polymer or (2) addition of steam to the hydrocarbon solution of the conjugated diene polymer. The recovered conjugated diene polymer may be dried using a known drier, for example, a band drier or an extrusion drier.
In the method for producing the conjugated diene polymer, a treatment in which the group represented by formula (Ia) in the polymer is replaced by a hydroxy group is preferably carried out by, for example, hydrolysis. This treatment may be carried out on the polymer alone or on a below-mentioned composition including the polymer. Examples of the hydrolysis method include known hydrolysis methods, e.g., methods using steam stripping. The treatment can convert at least one of X1, X2, and X3 in formula (I) into hydroxy group(s) and can thereby enhance the fuel economy, wet-grip performance, and abrasion resistance in a more balanced manner.
The conjugated diene polymer can be used in the rubber component of the rubber composition of the present invention, and is preferably used in combination with other rubber materials, additives and the like.
Examples of other rubber materials include commonly used diene rubbers such as styrene-butadiene copolymer rubber (SBR), polybutadiene rubber (BR), butadiene-isoprene copolymer rubber, and butyl rubber. Moreover, natural rubber (NR), ethylene-propylene copolymers, ethylene-octene copolymers and the like may also be mentioned. Two or more kinds of these rubber materials may be used in combination. In particular, in view of enhancing the fuel economy, wet-grip performance, and abrasion resistance in a balanced manner, NR and/or BR are preferably used, and both of NR and BR are more preferably used.
The conjugated diene polymer content, based on 100% by mass of the rubber component, is not less than 5% by mass, preferably not less than 10% by mass, more preferably not less than 30% by mass, and still more preferably not less than 50% by mass. A conjugated diene polymer content of less than 5% by mass tends to result in less improvement in fuel economy. The conjugated diene polymer content is preferably not more than 90% by mass, more preferably not more than 80% by mass, and still more preferably not more than 70% by mass. A conjugated diene polymer content in excess of 90% by mass tends to result in a decline in abrasion resistance and also drive up the cost.
There are no particular limitations on the NR. For example, natural rubbers commonly used in the tire industry can be used, such as SIR20, RSS #3, TSR20, deproteinized natural rubber (DPNR), and highly purified natural rubber (HPNR).
The NR content, based on 100% by mass of the rubber component, is preferably not less than 5% by mass, more preferably not less than 10% by mass, and still more preferably not less than 15% by mass. The abrasion resistance exhibits a declining trend when the NR content is less than 5% by mass. The NR content is preferably not more than 70% by mass, more preferably not more than 60% by mass, and still more preferably not more than 30% by mass. The wet-grip performance exhibits a declining trend when the NR content is more than 70% by mass.
There are no particular limitations on the BR, and commonly used BRs in the tire industry can be used, for example, high-cis BR such as BR1220 produced by Zeon Corporation and BR130B and BR150B produced by Ube Industries, Ltd., and BR containing syndiotactic polybutadiene crystals, such as VCR412 and VCR617 produced by Ube Industries, Ltd.
The BR content, based on 100% by mass of the rubber component, is preferably not less than 5% by mass, more preferably not less than 10% by mass, and still more preferably not less than 15% by mass. The abrasion resistance exhibits a declining trend when the BR content is less than 5% by mass. The BR content is preferably not more than 60% by mass, more preferably not more than 50% by mass, still more preferably not more than 35% by mass, further preferably not more than 30% by mass, and particularly preferably not more than 25% by mass. The wet-grip performance exhibits a declining trend when the BR content is more than 60% by mass.
The total content of NR and BR, based on 100% by mass of the rubber component, is preferably not less than 10% by mass, more preferably not less than 20% by mass, and still more preferably not less than 30% by mass. The abrasion resistance exhibits a declining trend when the total content is less than 10% by mass. The total content is also preferably not more than 70% by mass, and more preferably not more than 50% by mass. The wet-grip performance exhibits a declining trend when the total content is more than 70% by mass.
The rubber composition of the present invention characteristically incorporates silica as a reinforcing agent. The amount (content) of silica, expressed per 100 parts by mass of the rubber component, is 5 to 150 parts by mass. The abrasion resistance tends to be unsatisfactory when the amount of silica is less than 5 parts by mass, whereas the processability tends to deteriorate when the amount of silica exceeds 150 parts by mass. The amount of silica is preferably not less than 10 parts by mass, more preferably not less than 15 parts by mass, and still more preferably not less than 45 parts by mass, and is also preferably not more than 120 parts by mass, and more preferably not more than 100 parts by mass.
The silica may be used alone, or two or more kinds of silica may be used in combination.
The silica content, based on a total of 100% by mass of silica and carbon black, is preferably not less than 60% by mass, and more preferably not less than 85% by mass, and is also preferably not more than 98% by mass, and more preferably not more than 95% by mass. The fuel economy, wet-grip performance, and abrasion resistance can be enhanced to high levels in a balanced manner when the silica content is in the foregoing range.
The silica preferably has a nitrogen adsorption specific surface area (N2SA) of not less than 40 m2/g, more preferably not less than 50 m2/g, still more preferably not less than 60 m2/g, and particularly preferably not less than 150 m2/g. The silica preferably has a N2SA of not more than 400 m2/g, more preferably not more than 360 m2/g, still more preferably not more than 300 m2/g, and particularly preferably not more than 200 m2/g. If the silica has a nitrogen adsorption specific surface area of less than 40 m2/g, a little reinforcing effect is likely to be obtained and the abrasion resistance tends to be reduced. The silica having a N2SA of more than 400 m2/g is likely to have poor dispersibility which tends to cause increased hysteresis loss and therefore reduced fuel economy.
The nitrogen adsorption specific surface area of silica is a value measured by the BET method in accordance with ASTM D3037-81.
A silane coupling agent containing a mercapto group (mercapto-based silane coupling agent) is used in the present invention. In view of achieving the effects of the present invention better, the mercapto-based silane coupling agent is suitably a compound represented by formula (1) below, and/or a compound containing a linking unit A represented by formula (2) below and a linking unit B represented by formula (3) below.




In formula (1), R101 to R103 may be the same as or different from one another, and R101 to R103 each represent a branched or unbranched C1-12 alkyl group, a branched or unbranched C1-12 alkoxy group, or a group represented by —O—(R111—O)b—R112 where b R111s may be the same as or different from one another and b R111s each represent a branched or unbranched C1-30 divalent hydrocarbon group; R112 represents a branched or unbranched C1-30 alkyl group, a branched or unbranched C2-30 alkenyl group, a C6-30 aryl group, or a C7-30 aralkyl group; and b represents an integer of 1 to 30, and R104 represents a branched or unbranched C1-6 alkylene group.




In formulas (2) and (3), R201 represents a hydrogen atom, a halogen atom, a branched or unbranched C1-30 alkyl group, a branched or unbranched C2-30 alkenyl group, a branched or unbranched C2-30 alkynyl group, or the alkyl group in which a terminal hydrogen atom is substituted by a hydroxy group or a carboxyl group; R202 represents a branched or unbranched C1-30 alkylene group, a branched or unbranched C2-30 alkenylene group, or a branched or unbranched C2-30 alkynylene group; and R201 and R202 together may form a cyclic structure.
The following explains the compound represented by formula (1).
The addition of a silane coupling agent represented by formula (1) enables to further enhance the wet-grip performance and the performance in terms of rolling resistance (fuel economy).
R101 to R103 each independently represent a branched or unbranched C1-12 alkyl group, a branched or unbranched C1-12 alkoxy group, or a group represented by —O—(R111—O)b—R112. In view of achieving the effects of the present invention better, preferably at least one of R101 to R103 is a group represented by —O—(R111—O)b—R112, and more preferably two of R101 to R103 are groups represented by —O—(R111—O)b—R112 and the other one is a branched of unbranched C1-12 alkoxy group.
Examples of the branched or unbranched C1-12 (preferably C1-5) alkyl group encompassed by R101 to R103 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, an octyl group, and a nonyl group.
Examples of the branched or unbranched C1-12 (preferably C1-5) alkoxy group encompassed by R101 to R103 include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an iso-butoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, a 2-ethylhexyloxy group, an octyloxy group, and a nonyloxy group.
R111 in the group: —O—(R11—O)b—R112 encompassed by R101 to R103 represents a branched or unbranched C1-30 (preferably C1-15, more preferably C1-3) divalent hydrocarbon group.
Examples of the hydrocarbon group include branched or unbranched C1-30 alkylene groups, branched or unbranched C2-30 alkenylene groups, branched or unbranched C2-30 alkynylene groups, and branched or unbranched C6-30 arylene groups. Branched or unbranched C1-30 alkylene groups are preferred among the examples.
Examples of the branched or unbranched C1-30 (preferably C1-15, more preferably C1-3) alkylene group encompassed by R111 include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a tetradecylene group, a pentadecylene group, a hexadecylene group, a heptadecylene group, and an octadecylene group.
Examples of the branched or unbranched C2-30 (preferably C2-15, more preferably C2-3) alkenylene group encompassed by R111 include a vinylene group, a 1-propenylene group, a 2-propenylene group, a 1-butenylene group, a 2-butenylene group, a 1-pentenylene group, a 2-pentenylene group, a 1-hexenylene group, a 2-hexenylene group, and a 1-octenylene group.
Examples of the branched or unbranched C2-30 (preferably C2-15/more preferably C2-3) alkynylene group encompassed by R111 include an ethynylene group, a propynylene group, a butynylene group, a pentynylene group, a hexynylene group, a heptynylene group, an octynylene group, a nonynylene group, a decynylene group, an undecynylene group, and a dodecynylene group.
Examples of the C6-30 (preferably C6-15) arylene group encompassed by R111 include a phenylene group, a tolylene group, a xylylene group, and a naphthylene group.
Here, b represents an integer of 1 to 30 (preferably 2 to 20, more preferably 3 to 7, and still more preferably 5 or 6).
R112 represents a branched or unbranched C1-30 alkyl group, a branched or unbranched C2-30 alkenyl group, a C6-30 aryl group, or a C7-30 aralkyl group. R112 is especially preferably a branched or unbranched C1-30 alkyl group.
Examples of the branched or unbranched C1-30 (preferably C3-25, more preferably C10-15) alkyl group encompassed by R112 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, and an octadecyl group.
Examples of the branched or unbranched C2-30 (preferably C3-25, more preferably C10-15) alkenyl group encompassed by R112 include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group, a 1-pentenyl group, a 2-pentenyl group, a 1-hexenyl group, a 2-hexenyl group, a 1-octenyl group, a decenyl group, an undecenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, and an octadecenyl group.
Examples of the C6-30 (preferably C10-20) aryl group encompassed by R112 include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a biphenyl group.
Examples of the C7-30 (preferably C10-20) aralkyl group encompassed by R112 include a benzyl group and a phenethyl group.
Specific examples of the group represented by —O—(R111—O)b—R112 include —O—(C2H4—O)5—C11H23, —O—(C2H4—O)5—C12H25, —O—(C2H4—O)5—C13H27, —O—(C2H4—O)5—C14H29, —O—(C2H4—O)5—C15H31, —O—(C2H4—O)3—C13H27, —O— (C2H4—O)4—C13H27, —O—(C2H4—O)6—C13H27 and —O—(C2H4—O)7—C13H27. Among the examples, —O—(C2H4—O)5—C11H23, —O—(C2H4—O)5—C13H27, —O—(C2H4—O)5—C15H31, and —O—(C2H4—O)6—C13H27 are preferred.
Examples of the branched or unbranched C1-6 (preferably C1-5) alkylene group encompassed by R104 include groups as mentioned for the branched or unbranched C1-30 alkylene groups encompassed by R111.
Examples of the compound represented by formula (1) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyl-trimethoxysilane, 2-mercaptoethyltriethoxysilane, and a compound represented by the following formula (Si363 produced by Evonik Degussa). Use of the compound represented by the following formula is preferred. These may be used alone or two or more may be used in combination.




The following explains the compound containing a linking unit A represented by formula (2) and a linking unit B represented by formula (3).
When the compound containing a linking unit A represented by formula (2) and a linking unit B represented by formula (3) is used, the increase in viscosity during the processing can be suppressed compared to the case where polysulfide silane such as bis-(3-triethoxysilylpropyl)tetrasulfide is used. This is presumably because, since the sulfide moiety of the linking unit A is a C—S—C bond, the compound is thermally more stable than tetrasulfide or disulfide, and thus the Mooney viscosity is less likely to increase.
Moreover, the decrease in the scorch time can be suppressed compared to the case where mercapto silane such as 3-mercaptopropyltrimethoxysilane is used. This is presumably because, though the linking unit B has a mercapto silane structure, the —C7H15 moiety of the linking unit A covers a —SH group of the linking unit B, as a result of which the SH group is less likely to react with polymers. Thus, favorable processability can be achieved even when a larger amount of a vulcanization accelerator is used, or when SBR, which is easily scorched, is mixed.
From the viewpoint of enhancing the effects of suppressing the viscosity increase during the processing and of suppressing the decrease in the scorch time as mentioned above, the linking unit A content in the silane coupling agent having the foregoing structure is preferably not less than 30 mol %, and more preferably not less than 50 mol %, and is also preferably not more than 99 mol %, and more preferably not more than 90 mol %. The linking unit B content is preferably not less than 1 mol %, more preferably not less than 5 mol %, and still more preferably not less than 10 mol %, and is also preferably not more than 70 mol %, more preferably not more than 65 mol %, and still more preferably not more than 55 mol %. The total content of the linking unit A and the linking unit B is preferably not less than 95 mol %, more preferably not less than 98 mol %, and particularly preferably 100 mol %.
The content of the linking unit A or B is the amount including the linking unit A or B that is present at the terminal of the silane coupling agent, if any. In the case where the linking unit A or B is present at the terminal of the silane coupling agent, its form is not particularly limited as long as it forms a unit corresponding to the formula (2) representing the linking unit A or the formula (3) representing the linking unit B.
Examples of the halogen atom encompassed by R201 include chlorine, bromine, and fluorine.
Examples of the branched or unbranched C1-30 alkyl group encompassed by R201 and R202 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, an octyl group, a nonyl group, and a decyl group. The alkyl group preferably has 1 to 12 carbon atoms.
Examples of the branched or unbranched C1-30 alkylene group encompassed by R201 and R202 include an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a tetradecylene group, a pentadecylene group, a hexadecylene group, a heptadecylene group, and an octadecylene group. The alkylene group preferably has 1 to 12 carbon atoms.
Examples of the branched or unbranched C2-30 alkenyl group encompassed by R201 and R202 include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group, a 1-pentenyl group, a 2-pentenyl group, a 1-hexenyl group, a 2-hexenyl group, and a 1-octenyl group. The alkenyl group preferably has 2 to 12 carbon atoms.
Examples of the branched or unbranched C2-30 alkenylene group encompassed by R201 and R202 include a vinylene group, a 1-propenylene group, a 2-propenylene group, a 1-butenylene group, a 2-butenylene group, a 1-pentenylene group, a 2-pentenylene group, a 1-hexenylene group, a 2-hexenylene group, and a 1-octenylene group. The alkenylene group preferably has 2 to 12 carbon atoms.
Examples of the branched or unbranched C2-30 alkynyl group encompassed by R201 and R202 include an ethynyl group, a propynyl group, a butynyl group, a pentynyl group, a hexynyl group, a heptynyl group, an octynyl group, a nonynyl group, a decynyl group, an undecynyl group, and a dodecynyl group. The alkynyl group preferably has 2 to 12 carbon atoms.
Examples of the branched or unbranched C2-30 alkynylene group encompassed by R201 and R202 include an ethynylene group, a propynylene group, a butynylene group, a pentynylene group, a hexynylene group, a heptynylene group, an octynylene group, a nonynylene group, a decynylene group, an undecynylene group, and a dodecynylene group. The alkynylene group preferably has 2 to 12 carbon atoms.
In the compound containing the linking unit A represented by formula (2) and the linking unit B represented by formula (3), the total number of repetitions (x+y) of the number of repetitions (x) of the linking unit A and the number of repetitions (y) of the linking unit B is preferably in the range of 3 to 300. If the total number of repetitions is in the above range, the —C7H15 moiety of the linking unit A covers the mercaptosilane of the linking unit B, which enables to suppress the decrease in the scorch time and to secure favorable reactivity to silica and the rubber component.
Examples of the compound containing the linking unit A represented by formula (2) and the linking unit B represented by formula (3) include NXT-Z30, NXT-Z45, and NXT-Z60 (produced by Momentive Performance Materials). These may be used alone, or two or more of these may be used in combination.
The mercapto-based silane coupling agent content, expressed per 100 parts by mass of silica, is preferably not less than 0.5 parts by mass, more preferably not less than 1 part by mass, still more preferably not less than 1.5 parts by mass, further preferably not less than 2 parts by mass, and particularly preferably not less than 2.5 parts by mass. A mercapto-based silane coupling agent content of less than 0.5 parts by mass may make it difficult to favorably disperse silica. The lower limit of the content may be not less than 4 parts by mass, not less than 5 parts by mass, or not less than 8 parts by mass. The mercapto-based silane coupling agent content is preferably not more than 20 parts by mass, more preferably not more than 15 parts by mass, and still more preferably not more than 10 parts by mass. A mercapto-based silane coupling agent content in excess of 20 parts by mass may fail to produce an improvement effect commensurate with the added amount, which may result in unnecessary cost increase. In addition, the scorch time is likely to be reduced so that the processability tends to deteriorate in the kneading or extrusion process.
Known additives may be used as the additives. Examples of the additives include vulcanizing agents such as sulfur; vulcanization accelerators such as thiazole vulcanization accelerators, thiuram vulcanization accelerators, sulfenamide vulcanization accelerators, and guanidine vulcanization accelerators; vulcanization activators such as stearic acid and zinc oxide; organoperoxides; fillers such as carbon black, calcium carbonate, talc, alumina, clay, aluminum hydroxide, and mica; processing aids such as extender oils and lubricants; and antioxidants.
The carbon blacks can be exemplified by furnace blacks (furnace carbon blacks) such as SAF, ISAF, HAF, MAF, FEF, SRF, GPF, APF, FF, CF, SCF, and ECF; acetylene blacks (acetylene carbon blacks); thermal blacks (thermal carbon blacks) such as FT and MT; channel blacks (channel carbon blacks) such as EPC, MPC, and CC; and graphite. These may be used alone or two or more may be used in combination. In view of enhancing the fuel economy, wet-grip performance, and abrasion resistance to high levels in a balanced manner, the carbon black content, per 100 parts by mass of the rubber component, is preferably not less than 1 part by mass, and more preferably not less than 3 parts by mass. The carbon black content is also preferably not more than 60 parts by mass, more preferably not more than 50 parts by mass, still more preferably not more than 30 parts by mass, and particularly preferably not more than 10 parts by mass.
The carbon black preferably has a nitrogen adsorption specific surface area (N2SA) of not less than 5 m2/g, more preferably not less than 30 m2/g, still more preferably not less than 50 m2/g, and particularly preferably not less than 70 m2/g. The nitrogen adsorption specific surface area is also preferably not more than 250 m2/g, more preferably not more than 200 m2/g, and still more preferably not more than 150 m2/g. The carbon black preferably has a dibutyl phthalate (DBP) absorption of not less than 5 mL/100 g, more preferably not less than 80 mL/100 g. The dibutyl phthalate (DBP) absorption is also preferably not more than 300 mL/100 g, and more preferably not more than 180 mL/100 g. If the carbon black has a N2SA or DBP absorption of less than the corresponding lower limit of the range, a little reinforcing effect is likely to be obtained and the abrasion resistance tends to be reduced. If the N2SA or DBP absorption exceeds the corresponding upper limit of the range, the dispersibility is likely to be poor and the hysteresis loss is likely to increase so that the fuel economy tends to be reduced. The nitrogen adsorption specific surface area is measured in accordance with ASTM D4820-93, and the DBP absorption is measured in accordance with ASTM D2414-93. Applicable commercial products are available under the trade names SEAST 6, SEAST 7HM, and SEAST KH produced by Tokai Carbon Co., Ltd., CK3 and Special Black 4A produced by Evonik Degussa, and so forth.
The extender oils can be exemplified by aromatic mineral oils (viscosity-gravity constant (VGC value)=0.900 to 1.049), naphthenic mineral oils (VGC value=0.850 to 0.899), and paraffinic mineral oils (VGC value=0.790 to 0.849). The polycyclic aromatic content of the extender oil is preferably less than 3% by mass, and more preferably less than 1% by mass. The polycyclic aromatic content is measured based on the British Institute of Petroleum method 346/92. Moreover, the aromatic compound content (CA) of the extender oil is preferably not less than 20% by mass. Two or more of these extender oils may be used in combination.
The vulcanization accelerators can be exemplified by thiazole vulcanization accelerators such as 2-mercaptobenzothiazole, dibenzothiazyl disulfide, and N-cyclohexyl-2-benzothiazylsulfenamide; thiuram vulcanization accelerators such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; sulfenamide vulcanization accelerators such as N-cyclohexyl-2-benzothiazolesulfenamide, N-t-butyl-2-benzothiazolesulfenamide, N-oxyethylene-2-benzothiazolesulfenamide, N-oxyethylene-2-benzothiazolesulfenamide, and N,N′-diisopropyl-2-benzothiazolesulfenamide; and guanidine vulcanization accelerators such as diphenylguanidine, di-ortho-tolylguanidine, and ortho-tolylbiguanidine. The amount thereof used, expressed per 100 parts by mass of the rubber component, is preferably 0.1 to 5 parts by mass, and more preferably 0.2 to 3 parts by mass.
A known method can be used to mix the conjugated diene polymer with another rubber material, additives and so forth to prepare the rubber composition. For example, a method can be used in which the ingredients are kneaded using a known mixer, e.g., a roll mixer or a Banbury mixer.
With regard to the kneading conditions during the incorporation of additives other than vulcanizing agents and vulcanization accelerators, the kneading temperature is typically 50 to 200° C., preferably 80 to 190° C., and the kneading time is typically 30 seconds to 30 minutes, preferably 1 to 30 minutes.
During the incorporation of a vulcanizing agent and vulcanization accelerator, the kneading temperature is typically not more than 100° C. and is preferably in the range of room temperature to 80° C. The composition in which the vulcanizing agent and vulcanization accelerator have been incorporated is typically subjected to a vulcanizing treatment such as press vulcanization before use. The vulcanization temperature is typically 120 to 200° C., preferably 140 to 180° C.
The rubber composition of the present invention has an excellent balance among fuel economy, wet-grip performance, and abrasion resistance, and thus can provide a significant improvement in these properties.
The rubber composition of the present invention can be suitably used for various tire components and is particularly well suited for treads.
The pneumatic tire of the present invention can be produced by a usual method using the aforementioned rubber composition. Specifically, the rubber composition that incorporates various additives as necessary, before vulcanization, is extrusion processed into the shape of a tire tread, for example, and is then arranged by a usual method and assembled with other tire components in a tire building machine to form an unvulcanized tire. This unvulcanized tire is heat-pressed in a vulcanizer to produce a pneumatic tire of the present invention.
The pneumatic tire of the present invention can be suitably used as a tire for passenger vehicles and for trucks/buses (heavy-load tire).
EXAMPLES
The present invention is described by the following examples.
The physical properties were evaluated by the following methods. In the physical property evaluations below, Comparative Example 1 was considered as a standard comparative example in Table 6; Comparative Example 4 was considered as a standard comparative example in Table 7; Comparative Example 11 was considered as a standard comparative example in Table 8; Comparative Example 14 was considered as a standard comparative example in Tables 9 and 10; Comparative Example 32 was considered as a standard comparative example in Table 11; Comparative Example 38 was considered as a standard comparative example in Table 12; Comparative Example 46 was considered as a standard comparative example in Tables 13 and 14; Comparative Example 52 was considered as a standard comparative example in Tables 15 and 16; Comparative Example 59 was considered as a standard comparative example in Table 17; and Comparative Example 67 was considered as a standard comparative example in Table 18.
1. Vinyl Bond Content (Unit: Mol %)
The vinyl bond content of a polymer was determined by infrared spectroscopic analysis from the strength of the absorption in the vicinity of 910 cm−1, which is an absorption peak for a vinyl group.
2. Styrene Unit Content (Unit: % by Mass)
The styrene unit content of a polymer was determined from the refractive index according to JIS K6383 (1995).
3. Molecular Weight Distribution (Mw/Mn)
The weight-average molecular weight (Mw) and the number-average molecular weight (Mn) were measured by gel permeation chromatography (GPC) under the conditions (1) to (8) described below. The molecular weight distribution (Mw/Mn) of the polymer was then determined from the measured Mw and Mn.

    (1) instrument: HLC-8020 produced by Tosoh Corporation
    (2) separation columns: 2×GMH-XL in series, produced by Tosoh Corporation
    (3) measurement temperature: 40° C.
    (4) carrier: tetrahydrofuran
    (5) flow rate: 0.6 mL/minute
    (6) quantity of injection: 5 μL
    (7) detector: differential refractometer
    (8) molecular weight standards: polystyrene standards

4. Tan δ



A strip test sample (width: 1 mm or 2 mm, length: 40 mm) was punched out of a vulcanized rubber composition sheet for testing. The tan δ of the test sample was determined with a spectrometer (produced by Ueshima Seisakusho Co., Ltd.) at a dynamic strain amplitude of 1%, a frequency of 10 Hz, and a temperature of 50° C. The reciprocal of the value of tan δ was expressed as an index relative to that in the standard comparative example regarded as 100. A larger index indicates a lower rolling resistance, which in turn indicates better fuel economy.
5. Rolling Resistance
The rolling resistance was measured using a rolling resistance tester by running a test tire with a 15×6JJ rim at an internal pressure of 230 kPa, a load of 3.43 kN, and a speed of 80 km/h. The obtained rolling resistance was expressed as an index relative to that in the standard comparative example regarded as 100. A larger index indicates a lower rolling resistance, which in turn indicates better fuel economy.
6. Wet-Grip Performance
The produced test tires were mounted on all the wheels of a vehicle (Japanese FF car, 2000 cc), and the braking distance with an initial speed of 100 km/h was measured on a wet asphalt road surface. Based on the equation below, the wet-skid performance (wet-grip performance) of the tires of each composition was expressed as an index relative to the wet-grip performance in the standard comparative example regarded as 100. A larger index indicates better wet-grip performance.

(Wet-grip performance index)=(Braking distance in standard comparative example)/(Braking distance of each composition)×100

7. Abrasion Resistance 1

The volume loss of each vulcanized rubber composition was measured with a LAT tester (Laboratory Abrasion and Skid Tester) at a load of 50 N, a speed of 20 km/h, and a slip angle of 5 degrees. The values (abrasion resistance index 1) in Tables are relative values to the volume loss in the standard comparative example regarded as 100. A larger value indicates better abrasion resistance.
8. Abrasion Resistance 2
The produced test tires were mounted on all the wheels of a vehicle (Japanese FF car, 2000 cc), and the vehicle was driven. The change in the groove depth of the tread pattern before and after 3000 km running was determined. Based on the equation below, the change in the groove depth of the tires of each composition was expressed as an index relative to the abrasion resistance index 2 of the standard comparative example regarded as 100. A larger index indicates better abrasion resistance.

Abrasion resistance index 2=(Groove depth change in standard comparative example)/(Groove depth change of each composition)×100

Production Example 1
Synthesis of Polymer 1
The interior of a 20-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 10.2 kg of hexane (specific gravity=0.68 g/cm3), 547 g of 1,3-butadiene, 173 g of styrene, 6.1 mL of tetrahydrofuran, and 5.0 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 11.1 mmol of bis(diethylamino)methylvinylsilane in cyclohexane and 13.1 mmol of n-butyllithium in n-hexane were further introduced to initiate polymerization.
The 1,3-butadiene and styrene were copolymerized for 3 hours under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor. During the entire polymerization, the amount of 1,3-butadiene fed was 821 g, and the amount of styrene fed was 259 g.
The resulting polymer solution was then stirred at a rate of 130 rpm, and 11.1 mmol of 3-diethylaminopropyl-triethoxysilane was added thereto, followed by stirring for 15 minutes. Then, 20 mL of a hexane solution containing 0.54 mL of methanol was added to the polymer solution, and the polymer solution was stirred for additional 5 minutes.
To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, Polymer 1 was recovered from the polymer solution by steam stripping. Table 1 shows the evaluation results of Polymer 1. The content of the constituent unit represented by formula (I) in the polymer, as calculated from the amounts of raw materials introduced and the amounts of raw materials fed into the polymerization reactor, was 0.006 mmol/g-polymer per unit mass of the polymer.
Production Example 2
Synthesis of Polymer 2
The interior of a 5-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 2.55 kg of hexane (specific gravity=0.68 g/cm3), 137 g of 1,3-butadiene, 43 g of styrene, 1.5 mL of tetrahydrofuran, and 1.2 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 3.6 mmol of n-butyllithium in n-hexane was further introduced and the 1,3-butadiene and styrene were copolymerized for 2.5 hours. The polymerization was carried out under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor. The amount of 1,3-butadiene fed was 205 g, and the amount of styrene fed was 65 g.
After the 2.5-hour polymerization, 2.8 mmol of bis(diethylamino)methylvinylsilane in cyclohexane was introduced into the polymerization reactor under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C., followed by stirring for 30 minutes.
Next, 20 mL of a hexane solution containing 0.14 mL of methanol was introduced into the polymerization reactor, and the polymer solution was stirred for 5 minutes.
To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, Polymer 2 was recovered from the polymer solution by steam stripping. Table 1 shows the evaluation results of Polymer 2. The content of the constituent unit represented by formula (I) in the polymer, as calculated from the amounts of raw materials introduced and the amounts of raw materials fed into the polymerization reactor, was 0.006 mmol/g-polymer per unit mass of the polymer.
Production Example 3
Synthesis of Polymer 3
The interior of a 20-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 10.2 kg of hexane (specific gravity=0.68 g/cm3), 547 g of 1,3-butadiene, 173 g of styrene, 6.1 mL of tetrahydrofuran, and 5.0 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 11.1 mmol of bis(diethylamino)methylvinylsilane in cyclohexane and 13.1 mmol of n-butyllithium in n-hexane were further introduced to initiate polymerization.
The 1,3-butadiene and styrene were copolymerized for 3 hours under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor. During the entire polymerization, the amount of 1,3-butadiene fed was 821 g, and the amount of styrene fed was 259 g.
Then, 20 mL of a hexane solution containing 0.54 mL of methanol was added to the polymer solution, and the polymer solution was stirred for additional 5 minutes.
To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, Polymer 3 was recovered from the polymer solution by steam stripping. Table 1 shows the evaluation results of Polymer 3. The content of the constituent unit represented by formula (I) in the polymer, as calculated from the amounts of raw materials introduced and the amounts of raw materials fed into the polymerization reactor, was 0.006 mmol/g-polymer per unit mass of the polymer.
Production Example 4
Synthesis of Polymer 4
The interior of a 20-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 10.2 kg of hexane (specific gravity=0.68 g/cm3), 547 g of 1,3-butadiene, 173 g of styrene, 6.1 mL of tetrahydrofuran, and 5.0 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 13.1 mmol of n-butyllithium in n-hexane was further introduced to initiate polymerization.
The 1,3-butadiene and styrene were copolymerized for 3 hours under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor. During the entire polymerization, the amount of 1,3-butadiene fed was 821 g, and the amount of styrene fed was 259 g.
The resulting polymer solution was then stirred at a rate of 130 rpm, and 11.1 mmol of 3-diethylaminopropyltriethoxysilane was added thereto, followed by stirring for 15 minutes. Then, 20 mL of a hexane solution containing 0.54 mL of methanol was added to the polymer solution, and the polymer solution was stirred for additional 5 minutes.
To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, Polymer 4 was recovered from the polymer solution by steam stripping. Table 1 shows the evaluation results of Polymer 4. Since the compound represented by formula (IX) was not used in the synthesis of Polymer 4, Polymer 4 did not contain the constituent unit represented by formula (I).
Production Example 5
Synthesis of Polymer 5
The interior of a 20-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 10.2 kg of hexane (specific gravity=0.68 g/cm3), 547 g of 1,3-butadiene, 173 g of styrene, 6.1 mL of tetrahydrofuran, and 5.0 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 13.1 mmol of n-butyllithium in n-hexane was further introduced to initiate polymerization.
The 1,3-butadiene and styrene were copolymerized for 3 hours under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor. During the entire polymerization, the amount of 1,3-butadiene fed was 821 g, and the amount of styrene fed was 259 g.
Then, 20 mL of a hexane solution containing 0.54 mL of methanol was added to the polymer solution, and the polymer solution was stirred for additional 5 minutes.
To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, Polymer 5 was recovered from the polymer solution by steam stripping. Table 1 shows the evaluation results of Polymer 5. Since the compound represented by formula (IX) was not used in the synthesis of Polymer 5, Polymer 5 did not contain the constituent unit represented by formula (I).
Production Example 6
Synthesis of Polymer 6
The interior of a 20-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 10.2 kg of hexane (specific gravity=0.68 g/cm3), 547 g of 1,3-butadiene, 173 g of styrene, 6.1 mL of tetrahydrofuran, and 5.0 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 11.1 mmol of bis(diethylamino)methylvinylsilane in cyclohexane and 13.1 mmol of n-butyllithium in n-hexane were further introduced to initiate polymerization.
The 1,3-butadiene and styrene were copolymerized for 3 hours under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor. During the entire polymerization, the amount of 1,3-butadiene fed was 821 g, and the amount of styrene fed was 259 g.
The resulting polymer solution was then stirred at a rate of 130 rpm, and 11.1 mmol of 3-diethylaminopropyl-triethoxysilane was added thereto, followed by stirring for 15 minutes. Then, 20 mL of a hexane solution containing 0.54 mL of methanol was added to the polymer solution, and the polymer solution was stirred for additional 5 minutes.
To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, the polymer solution was evaporated at ordinary temperature over 24 hours, and further dried under reduced pressure at 55° C. for 12 hours, so that Polymer 6 was obtained. Table 1 shows the evaluation results of Polymer 6. The content of the constituent unit represented by formula (I) in the polymer, as calculated from the amounts of raw materials introduced and the amounts of raw materials fed into the polymerization reactor, was 0.006 mmol/g-polymer per unit mass of the polymer.








TABLE 1








Polymer














1
2
3
4
5
6
















Styrene unit content (% by mass)
25
25
24
25
24
25


Vinyl bond content (mol %)
59
59
60
59
58
60


Molecular weight 
1.2
1.1
1.2
1.1
1.1
1.2


distribution (Mw/Mn)









Production Example 7
Synthesis of Polymer 7
The interior of a 20-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 10.2 kg of hexane (specific gravity=0.68 g/cm3), 547 g of 1,3-butadiene, 173 g of styrene, 6.1 mL of tetrahydrofuran, and 5.0 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 11.0 mmol of bis(diethylamino)methylvinylsilane in cyclohexane and 14.3 mmol of n-butyllithium in n-hexane were further introduced to initiate polymerization.
The 1,3-butadiene and styrene were copolymerized for 3 hours under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor. During the entire polymerization, the amount of 1,3-butadiene fed was 821 g, and the amount of styrene fed was 259 g.
The resulting polymer solution was then stirred at a rate of 130 rpm, and 11.0 mmol of 1,3-dimethyl-2-imidazolidinone was added thereto, followed by stirring for 15 minutes. Then, 20 mL of a hexane solution containing 0.54 mL of methanol was added to the polymer solution, and the polymer solution was stirred for additional 5 minutes.
To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, Polymer 7 was recovered from the polymer solution by steam stripping. Table 2 shows the evaluation results of Polymer 7. The content of the constituent unit represented by formula (I) in the polymer, as calculated from the amounts of raw materials introduced and the amounts of raw materials fed into the polymerization reactor, was 0.006 mmol/g-polymer per unit mass of the polymer.
Production Example 8
Synthesis of Polymer 8
The interior of a 20-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 10.2 kg of hexane (specific gravity=0.68 g/cm3), 547 g of 1,3-butadiene, 173 g of styrene, 6.1 mL of tetrahydrofuran, and 5.0 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 12.9 mmol of n-butyllithium in n-hexane was further introduced. The 1,3-butadiene and styrene were copolymerized for 0.83 hours. The polymerization was carried out under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor.
After the 0.83-hour polymerization, 11.0 mmol of bis(diethylamino)methylvinylsilane in cyclohexane was introduced into the polymerization reactor under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C.
Next, the monomers were continuously fed into the polymerization reactor, and the 1,3-butadiene and styrene were copolymerized for 1.67 hours. During the entire polymerization, the amount of 1,3-butadiene fed was 821 g, and the amount of styrene fed was 259 g.
The resulting polymer solution was stirred at a rate of 130 rpm, and 11.0 mmol of 1,3-dimethyl-2-imidazolidinone was added thereto, followed by stirring for 15 minutes. Then, 20 mL of a hexane solution containing 0.54 mL of methanol was added to the polymer solution, and the polymer solution was stirred for additional 5 minutes.
To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, Polymer 8 was recovered from the polymer solution by steam stripping. Table 2 shows the evaluation results of Polymer 8. The content of the constituent unit represented by formula (I) in the polymer, as calculated from the amounts of raw materials introduced and the amounts of raw materials fed into the polymerization reactor, was 0.006 mmol/g-polymer per unit mass of the polymer.
Production Example 9
Synthesis of Polymer 9
The interior of a 20-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 10.2 kg of hexane (specific gravity=0.68 g/cm3), 547 g of 1,3-butadiene, 173 g of styrene, 6.1 mL of tetrahydrofuran, and 5.0 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 13.7 mmol of n-butyllithium in n-hexane was further introduced, and the 1,3-butadiene and styrene were copolymerized for one hour. The polymerization was carried out under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor.
After the one hour polymerization, 11.0 mmol of bis(diethylamino)methylvinylsilane in cyclohexane was introduced into the polymerization reactor under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C.
Next, the monomers were continuously fed into the polymerization reactor, and the 1,3-butadiene and styrene were copolymerized for 0.5 hours. The polymerization was carried out under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. After the 0.5-hour polymerization, 11.0 mmol of bis(diethylamino)methylvinylsilane in cyclohexane was introduced into the polymerization reactor under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. Next, the monomers were continuously fed into the polymerization reactor, and the 1,3-butadiene and styrene were copolymerized for 0.5 hours. The polymerization was carried out under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C.
After the 0.5-hour polymerization, 11.0 mmol of bis(diethylamino)methylvinylsilane in cyclohexane was introduced into the polymerization reactor under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C.
Next, the monomers were continuously fed into the polymerization reactor, and the 1,3-butadiene and styrene were copolymerized for 0.5 hours. The polymerization was carried out under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. During the entire polymerization, the amount of 1,3-butadiene fed was 821 g, and the amount of styrene fed was 259 g.
The resulting polymer solution was stirred at a rate of 130 rpm, and 11.0 mmol of 1,3-dimethyl-2-imidazolidinone was added thereto, followed by stirring for 15 minutes. Then, 20 mL of a hexane solution containing 0.54 mL of methanol was added to the polymer solution, and the polymer solution was stirred for additional 5 minutes.
To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, Polymer 9 was recovered from the polymer solution by steam stripping. Table 2 shows the evaluation results of Polymer 9. The content of the constituent unit represented by formula (I) in the polymer, as calculated from the amounts of raw materials introduced and the amounts of raw materials fed into the polymerization reactor, was 0.018 mmol/g-polymer per unit mass of the polymer.
Production Example 10
Synthesis of Polymer 10
The interior of a 20-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 10.2 kg of hexane (specific gravity=0.68 g/cm3), 547 g of 1,3-butadiene, 173 g of styrene, 6.1 mL of tetrahydrofuran, and 5.0 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 11.0 mmol of bis(diethylamino)methylvinylsilane in cyclohexane and 14.3 mmol of n-butyllithium in n-hexane were further introduced to initiate polymerization.
The 1,3-butadiene and styrene were copolymerized for 3 hours under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor. During the entire polymerization, the amount of 1,3-butadiene fed was 821 g, and the amount of styrene fed was 259 g.
The resulting polymer solution was stirred at a rate of 130 rpm, and 11.0 mmol of 1-phenyl-2-pyrrolidone was added thereto, followed by stirring for 15 minutes. Then, 20 mL of a hexane solution containing 0.54 mL of methanol was added to the polymer solution, and the polymer solution was stirred for additional 5 minutes.
To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, Polymer 10 was recovered from the polymer solution by steam stripping. Table 2 shows the evaluation results of Polymer 10. The content of the constituent unit represented by formula (I) in the polymer, as calculated from the amounts of raw materials introduced and the amounts of raw materials fed into the polymerization reactor, was 0.006 mmol/g-polymer per unit mass of the polymer.
Production Example 11
Synthesis of Polymer 11
The interior of a 20-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 10.2 kg of hexane (specific gravity=0.68 g/cm3), 547 g of 1,3-butadiene, 173 g of styrene, 6.1 mL of tetrahydrofuran, and 5.0 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 15.1 mmol of n-butyllithium in n-hexane was further introduced, and the 1,3-butadiene and styrene were copolymerized for one hour. The polymerization was carried out under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor.
After the one hour polymerization, 11.0 mmol of bis(diethylamino)methylvinylsilane in cyclohexane was introduced into the polymerization reactor under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C.
Next, the monomers were continuously fed into the polymerization reactor, and the 1,3-butadiene and styrene were copolymerized for 0.5 hours. The polymerization was carried out under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C.
After the 0.5-hour polymerization, 11.0 mmol of bis(diethylamino)methylvinylsilane in cyclohexane was introduced into the polymerization reactor under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C.
Next, the monomers were continuously fed into the polymerization reactor, and the 1,3-butadiene and styrene were copolymerized for 0.5 hours. The polymerization was carried out under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C.
After the 0.5-hour polymerization, 11.0 mmol of bis(diethylamino)methylvinylsilane in cyclohexane was introduced into the polymerization reactor under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C.
Next, the monomers were continuously fed into the polymerization reactor, and the 1,3-butadiene and styrene were copolymerized for 0.5 hours. The polymerization was carried out under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. During the entire polymerization, the amount of 1,3-butadiene fed was 821 g, and the amount of styrene fed was 259 g.
The resulting polymer solution was then stirred at a rate of 130 rpm, and 11.0 mmol of 1-phenyl-2-pyrrolidone was added thereto, followed by stirring for 15 minutes. Then, 20 mL of a hexane solution containing 0.54 mL of methanol was added to the polymer solution, and the polymer solution was stirred for additional 5 minutes.
To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, Polymer 11 was recovered from the polymer solution by steam stripping. Table 2 shows the evaluation results of Polymer 11. The content of the constituent unit represented by formula (I) in the polymer, as calculated from the amounts of raw materials introduced and the amounts of raw materials fed into the polymerization reactor, was 0.018 mmol/g-polymer per unit mass of the polymer.
Production Example 12
Synthesis of Polymer 12
The interior of a 20-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 10.2 kg of hexane (specific gravity=0.68 g/cm3), 547 g of 1,3-butadiene, 173 g of styrene, 6.1 mL of tetrahydrofuran, and 5.0 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 11.0 mmol of bis(diethylamino)methylvinylsilane in cyclohexane and 13.4 mmol of n-butyllithium in n-hexane were further introduced to initiate polymerization.
The 1,3-butadiene and styrene were copolymerized for 3 hours under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor. During the entire polymerization, the amount of 1,3-butadiene fed was 821 g, and the amount of styrene fed was 259 g.
The resulting polymer solution was then stirred at a rate of 130 rpm, and 11.0 mmol of N-methyl-ε-caprolactam was added thereto, followed by stirring for 15 minutes. Then, 20 mL of a hexane solution containing 0.54 mL of methanol was added to the polymer solution, and the polymer solution was stirred for additional 5 minutes.
To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, Polymer 12 was recovered from the polymer solution by steam stripping. Table 2 shows the evaluation results of Polymer 12. The content of the constituent unit represented by formula (I) in the polymer, as calculated from the amounts of raw materials introduced and the amounts of raw materials fed into the polymerization reactor, was 0.006 mmol/g-polymer per unit mass of the polymer.
Production Example 13
Synthesis of Polymer 13
The interior of a 20-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 10.2 kg of hexane (specific gravity=0.68 g/cm3), 547 g of 1,3-butadiene, 173 g of styrene, 6.1 mL of tetrahydrofuran, and 5.0 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 13.7 mmol of n-butyllithium in n-hexane was further introduced, and the 1,3-butadiene and styrene were copolymerized for one hour. The polymerization was carried out under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor.
After the one hour polymerization, 11.0 mmol of bis(diethylamino)methylvinylsilane in cyclohexane was introduced into the polymerization reactor under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C.
Next, the monomers were continuously fed into the polymerization reactor, and the 1,3-butadiene and styrene were copolymerized for 0.5 hours. The polymerization was carried out under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C.
After the 0.5-hour polymerization, 11.0 mmol of bis(diethylamino)methylvinylsilane in cyclohexane was introduced into the polymerization reactor under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C.
Next, the monomers were continuously fed into the polymerization reactor, and the 1,3-butadiene and styrene were copolymerized for 0.5 hours. The polymerization was carried out under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C.
After the 0.5-hour polymerization, 11.0 mmol of bis(diethylamino)methylvinylsilane in cyclohexane was introduced into the polymerization reactor under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C.
Next, the monomers were continuously fed into the polymerization reactor, and the 1,3-butadiene and styrene were copolymerized for 0.5 hours. The polymerization was carried out under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. During the entire polymerization, the amount of 1,3-butadiene fed was 821 g, and the amount of styrene fed was 259 g.
The resulting polymer solution was stirred at a rate of 130 rpm, and 11.0 mmol of N-methyl-ε-caprolactam was added thereto, followed by stirring for 15 minutes. Then, 20 mL of a hexane solution containing 0.54 mL of methanol was added to the polymer solution, and the polymer solution was stirred for additional 5 minutes.
To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, Polymer 13 was recovered from the polymer solution by steam stripping. Table 2 shows the evaluation results of Polymer 13. The content of the constituent unit represented by formula (I) in the polymer, as calculated from the amounts of raw materials introduced and the amounts of raw materials fed into the polymerization reactor, was 0.018 mmol/g-polymer per unit mass of the polymer.
Production Example 14
Synthesis of Polymer 14
The interior of a 20-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 10.2 kg of hexane (specific gravity=0.68 g/cm3), 547 g of 1,3-butadiene, 173 g of styrene, 6.1 mL of tetrahydrofuran, and 5.0 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 8.26 mmol of bis(diethylamino)methylvinylsilane in cyclohexane and 14.3 mmol of n-butyllithium in n-hexane were further introduced to initiate polymerization.
The 1,3-butadiene and styrene were copolymerized for 3 hours under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor. During the entire polymerization, the amount of 1,3-butadiene fed was 821 g, and the amount of styrene fed was 259 g.
The resulting polymer solution was then stirred at a rate of 130 rpm, and 11.8 mmol of 4,4′-bis(diethylamino)benzophenone was added thereto, followed by stirring for 15 minutes. Then, 20 mL of a hexane solution containing 0.54 mL of methanol was added to the polymer solution, and the polymer solution was stirred for additional 5 minutes.
To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, Polymer 14 was recovered from the polymer solution by steam stripping. Table 2 shows the evaluation results of Polymer 14. The content of the constituent unit represented by formula (I) in the polymer, as calculated from the amounts of raw materials introduced and the amounts of raw materials fed into the polymerization reactor, was 0.005 mmol/g-polymer per unit mass of the polymer.
Production Example 15
Synthesis of Polymer 15
The interior of a 20-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 10.2 kg of hexane (specific gravity=0.68 g/cm3), 547 g of 1,3-butadiene, 173 g of styrene, 6.1 mL of tetrahydrofuran, and 5.0 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 12.2 mmol of bis(diethylamino)methylvinylsilane in cyclohexane and 15.1 mmol of n-butyllithium in n-hexane were further introduced to initiate polymerization.
The 1,3-butadiene and styrene were copolymerized for 3 hours under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor. During the entire polymerization, the amount of 1,3-butadiene fed was 821 g, and the amount of styrene fed was 259 g.
The resulting polymer solution was then stirred at a rate of 130 rpm, and 12.2 mmol of 4′-(imidazol-1-yl)-acetophenone was added thereto, followed by stirring for 15 minutes. Then, 20 mL of a hexane solution containing 0.54 mL of methanol was added to the polymer solution, and the polymer solution was stirred for additional 5 minutes.
To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, Polymer 15 was recovered from the polymer solution by steam stripping. Table 2 shows the evaluation results of Polymer 15. The content of the constituent unit represented by formula (I) in the polymer, as calculated from the amounts of raw materials introduced and the amounts of raw materials fed into the polymerization reactor, was 0.007 mmol/g-polymer per unit mass of the polymer.
Production Example 16
Synthesis of Polymer 16
The interior of a 5-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 2.55 kg of hexane (specific gravity=0.68 g/cm3), 137 g of 1,3-butadiene, 43 g of styrene, 1.5 mL of tetrahydrofuran, and 1.2 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 3.6 mmol of n-butyllithium in n-hexane was further introduced, and the 1,3-butadiene and styrene were copolymerized for 2.5 hours. The polymerization was carried out under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor. The amount of 1,3-butadiene fed was 205 g, and the amount of styrene fed was 65 g.
After the 2.5-hour polymerization, 2.8 mmol of bis(diethylamino)methylvinylsilane in cyclohexane was introduced into the polymerization reactor under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C., followed by stirring for 30 minutes.
Next, 20 mL of a hexane solution containing 0.14 mL of methanol was introduced into the polymerization reactor, and the polymer solution was stirred for 5 minutes.
To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, Polymer 16 was recovered from the polymer solution by steam stripping. Table 2 shows the evaluation results of Polymer 16. The content of the constituent unit represented by formula (I) in the polymer, as calculated from the amounts of raw materials introduced and the amounts of raw materials fed into the polymerization reactor, was 0.006 mmol/g-polymer per unit mass of the polymer.
Production Example 17
Synthesis of Polymer 17
The interior of a 20-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 10.2 kg of hexane (specific gravity=0.68 g/cm3), 547 g of 1,3-butadiene, 173 g of styrene, 6.1 mL of tetrahydrofuran, and 5.0 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 11.0 mmol of bis(diethylamino)methylvinylsilane in cyclohexane and 14.3 mmol of n-butyllithium in n-hexane were further introduced to initiate polymerization.
The 1,3-butadiene and styrene were copolymerized for 3 hours under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor. During the entire polymerization, the amount of 1,3-butadiene fed was 821 g, and the amount of styrene fed was 259 g.
Then, 20 mL of a hexane solution containing 0.54 mL of methanol was added to the polymer solution, and the polymer solution was stirred for additional 5 minutes.
To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, Polymer 17 was recovered from the polymer solution by steam stripping. Table 2 shows the evaluation results of Polymer 17. The content of the constituent unit represented by formula (I) in the polymer, as calculated from the amounts of raw materials introduced and the amounts of raw materials fed into the polymerization reactor, was 0.006 mmol/g-polymer per unit mass of the polymer.
Production Example 18
Synthesis of Polymer 18
The interior of a 20-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 10.2 kg of hexane (specific gravity=0.68 g/cm3), 547 g of 1,3-butadiene, 173 g of styrene, 6.1 mL of tetrahydrofuran, and 5.0 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 14.3 mmol of n-butyllithium in n-hexane was further introduced to initiate polymerization.
The 1,3-butadiene and styrene were copolymerized for 3 hours under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor. During the entire polymerization, the amount of 1,3-butadiene fed was 821 g, and the amount of styrene fed was 259 g.
The resulting polymer solution was then stirred at a rate of 130 rpm, and 11.0 mmol of 1,3-dimethyl-2-imidazolidinone was added thereto, followed by stirring for 15 minutes. Then, 20 mL of a hexane solution containing 0.54 mL of methanol was added to the polymer solution, and the polymer solution was stirred for additional 5 minutes.
To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, Polymer 18 was recovered from the polymer solution by steam stripping. Table 2 shows the evaluation results of Polymer 18. Since the compound represented by formula (IX) was not used in the synthesis of Polymer 18, Polymer 18 did not contain the constituent unit represented by formula (I).
Production Example 19
Synthesis of Polymer 19
The interior of a 20-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 10.2 kg of hexane (specific gravity=0.68 g/cm3), 547 g of 1,3-butadiene, 173 g of styrene, 6.1 mL of tetrahydrofuran, and 5.0 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 14.3 mmol of n-butyllithium in n-hexane was further introduced to initiate polymerization.
The 1,3-butadiene and styrene were copolymerized for 3 hours under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor. During the entire polymerization, the amount of 1,3-butadiene fed was 821 g, and the amount of styrene fed was 259 g.
Then, 20 mL of a hexane solution containing 0.54 mL of methanol was added to the polymer solution, and the polymer solution was stirred for additional 5 minutes.
To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, Polymer 19 was recovered from the polymer solution by steam stripping. Table 2 shows the evaluation results of Polymer 19. Since the compound represented by formula (IX) was not used in the synthesis of Polymer 19, Polymer 19 did not contain the constituent unit represented by formula (I).
Production Example 20
Synthesis of Polymer 20
The interior of a 20-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 10.2 kg of hexane (specific gravity=0.68 g/cm3), 547 g of 1,3-butadiene, 173 g of styrene, 6.1 mL of tetrahydrofuran, and 5.0 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 11.0 mmol of bis(diethylamino)methylvinylsilane in cyclohexane and 14.3 mmol of n-butyllithium in n-hexane were further introduced to initiate polymerization.
The 1,3-butadiene and styrene were copolymerized for 3 hours under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor. During the entire polymerization, the amount of 1,3-butadiene fed was 821 g, and the amount of styrene fed was 259 g.
The resulting polymer solution was then stirred at a rate of 130 rpm, and 11.0 mmol of 1,3-dimethyl-2-imidazolidinone was added thereto, followed by stirring for 15 minutes. Then, 20 mL of a hexane solution containing 0.54 mL of methanol was added to the polymer solution, and the polymer solution was stirred for additional 5 minutes.
To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, the polymer solution was evaporated at ordinary temperature over 24 hours, and further dried under reduced pressure at 55° C. for 12 hours, so that Polymer 20 was obtained. Table 2 shows the evaluation results of Polymer 20. The content of the constituent unit represented by formula (I) in the polymer, as calculated from the amounts of raw materials introduced and the amounts of raw materials fed into the polymerization reactor, was 0.006 mmol/g-polymer per unit mass of the polymer.








TABLE 2








Polymer






















7
8
9
10
11
12
13
14
15
16
17
18
19
20
























Styrene unit content (% by mass)
25
25
25
25
25
25
25
25
25
25
25
25
24
25


Vinyl bond content (mol %)
60
60
59
60
59
59
59
59
60
59
60
59
58
62


Molecular weight 
1.2 
1.3
1.4 
1.2
1.4 
1.2
1.3
1.2 
1.3
1.1
1.2
1.1 
1.1
1.2


distribution (Mw/Mn)









Production Example 21
Synthesis of Polymer 21
The interior of a 20-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 10.2 kg of hexane (specific gravity=0.68 g/cm3), 547 g of 1,3-butadiene, 173 g of styrene, 6.1 mL of tetrahydrofuran, and 5.0 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 10.5 mmol of bis(diethylamino)methylvinylsilane in cyclohexane and 14.9 mmol of n-butyllithium in n-hexane were further introduced to initiate polymerization.
The 1,3-butadiene and styrene were copolymerized for 3 hours under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor. During the entire polymerization, the amount of 1,3-butadiene fed was 821 g, and the amount of styrene fed was 259 g.
The resulting polymer solution was stirred at a rate of 130 rpm, and 10.5 mmol of N-(3-dimethylaminopropyl)acrylamide was added thereto, followed by stirring for 15 minutes. Then, 20 mL of a hexane solution containing 0.54 mL of methanol was added to the polymer solution, and the polymer solution was stirred for additional 5 minutes.
To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, Polymer 21 was recovered from the polymer solution by steam stripping. Table 3 shows the evaluation results of Polymer 21. The content of the constituent unit represented by formula (I) in the polymer, as calculated from the amounts of raw materials introduced and the amounts of raw materials fed into the polymerization reactor, was 0.006 mmol/g-polymer per unit mass of the polymer.
Production Example 22
Synthesis of Polymer 22
The interior of a 20-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 10.2 kg of hexane (specific gravity=0.68 g/cm3), 547 g of 1,3-butadiene, 173 g of styrene, 6.1 mL of tetrahydrofuran, and 5.0 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 12.9 mmol of n-butyllithium in n-hexane was further introduced, and the 1,3-butadiene and styrene were copolymerized for 0.83 hours. The polymerization was carried out under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor.
After the 0.83-hour polymerization, 10.5 mmol of bis(diethylamino)methylvinylsilane in cyclohexane was introduced into the polymerization reactor under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C.
Next, the monomers were continuously fed into the polymerization reactor, and the 1,3-butadiene and styrene were copolymerized for 1.67 hours. The polymerization was carried out under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. During the entire polymerization, the amount of 1,3-butadiene fed was 821 g, and the amount of styrene fed was 259 g.
The resulting polymer solution was then stirred at a rate of 130 rpm, and 10.5 mmol of N-(3-dimethylaminopropyl)acrylamide was added thereto, followed by stirring for 15 minutes. Then, 20 mL of a hexane solution containing 0.54 mL of methanol was added to the polymer solution, and the polymer solution was stirred for additional 5 minutes.
To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, Polymer 22 was recovered from the polymer solution by steam stripping. Table 3 shows the evaluation results of Polymer 22. The content of the constituent unit represented by formula (I) in the polymer, as calculated from the amounts of raw materials introduced and the amounts of raw materials fed into the polymerization reactor, was 0.006 mmol/g-polymer per unit mass of the polymer.
Production Example 23
Synthesis of Polymer 23
The interior of a 20-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 10.2 kg of hexane (specific gravity=0.68 g/cm3), 547 g of 1,3-butadiene, 173 g of styrene, 6.1 mL of tetrahydrofuran, and 5.0 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 10.5 mmol of bis(diethylamino)methylvinylsilane in cyclohexane and 13.4 mmol of n-butyllithium in n-hexane were further introduced, and the 1,3-butadiene and styrene were copolymerized for one hour. The polymerization was carried out under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor.
After the one hour polymerization, 10.5 mmol of bis(diethylamino)methylvinylsilane in cyclohexane was introduced into the polymerization reactor under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C.
Next, the monomers were continuously fed into the polymerization reactor, and the 1,3-butadiene and styrene were copolymerized for 0.5 hours. The polymerization was carried out under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C.
After the 0.5-hour polymerization, 10.5 mmol of bis(diethylamino)methylvinylsilane in cyclohexane was introduced into the polymerization reactor under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C.
Next, the monomers were continuously fed into the polymerization reactor, and the 1,3-butadiene and styrene were copolymerized for 1.5 hours. The polymerization was carried out under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. During the entire polymerization, the amount of 1,3-butadiene fed was 821 g, and the amount of styrene fed was 259 g.
The resulting polymer solution was then stirred at a rate of 130 rpm, and 10.5 mmol of N-(3-dimethylaminopropyl)acrylamide was added thereto, followed by stirring for 15 minutes.
Then, 20 mL of a hexane solution containing 0.54 mL of methanol was added to the polymer solution, and the polymer solution was stirred for additional 5 minutes. To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, Polymer 23 was recovered from the polymer solution by steam stripping. Table 3 shows the evaluation results of Polymer 23. The content of the constituent unit represented by formula (I) in the polymer, as calculated from the amounts of raw materials introduced and the amounts of raw materials fed into the polymerization reactor, was 0.017 mmol/g-polymer per unit mass of the polymer.
Production Example 24
Synthesis of Polymer 24
The interior of a 20-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 10.2 kg of hexane (specific gravity=0.68 g/cm3), 547 g of 1,3-butadiene, 173 g of styrene, 6.1 mL of tetrahydrofuran, and 5.0 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 10.5 mmol of bis(di(n-butyl)amino)methylvinylsilane in cyclohexane and 13.4 mmol of n-butyllithium in n-hexane were further introduced to initiate polymerization.
The 1,3-butadiene and styrene were copolymerized for 3 hours under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor. During the entire polymerization, the amount of 1,3-butadiene fed was 821 g, and the amount of styrene fed was 259 g.
The resulting polymer solution was then stirred at a rate of 130 rpm, and 10.5 mmol of N-(3-dimethylaminopropyl)acrylamide was added thereto, followed by stirring for 15 minutes. Then, 20 mL of a hexane solution containing 0.54 mL of methanol was added to the polymer solution, and the polymer solution was stirred for additional 5 minutes.
To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, Polymer 24 was recovered from the polymer solution by steam stripping. Table 3 shows the evaluation results of Polymer 24. The content of the constituent unit represented by formula (I) in the polymer, as calculated from the amounts of raw materials introduced and the amounts of raw materials fed into the polymerization reactor, was 0.006 mmol/g-polymer per unit mass of the polymer.
Production Example 25
Synthesis of Polymer 25
The interior of a 5-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 2.55 kg of hexane (specific gravity=0.68 g/cm3), 137 g of 1,3-butadiene, 43 g of styrene, 1.5 mL of tetrahydrofuran, and 1.2 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 3.6 mmol of n-butyllithium in n-hexane was further introduced, and the 1,3-butadiene and styrene were copolymerized for 2.5 hours. The polymerization was carried out under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor. The amount of 1,3-butadiene fed was 205 g, and the amount of styrene fed was 65 g.
After the 2.5-hour polymerization, 2.8 mmol of bis(diethylamino)methylvinylsilane in cyclohexane was introduced into the polymerization reactor under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C., followed by stirring for 30 minutes.
Next, 20 mL of a hexane solution containing 0.14 mL of methanol was introduced into the polymerization reactor, and the polymer solution was stirred for 5 minutes.
To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, Polymer 25 was recovered from the polymer solution by steam stripping. Table 3 shows the evaluation results of Polymer 25. The content of the constituent unit represented by formula (I) in the polymer, as calculated from the amounts of raw materials introduced and the amounts of raw materials fed into the polymerization reactor, was 0.006 mmol/g-polymer per unit mass of the polymer.
Production Example 26
Synthesis of Polymer 26
The interior of a 20-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 10.2 kg of hexane (specific gravity=0.68 g/cm3), 547 g of 1,3-butadiene, 173 g of styrene, 6.1 mL of tetrahydrofuran, and 5.0 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 10.5 mmol of bis(diethylamino)methylvinylsilane in cyclohexane and 14.9 mmol of n-butyllithium in n-hexane were further introduced to initiate polymerization.
The 1,3-butadiene and styrene were copolymerized for 3 hours under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor. During the entire polymerization, the amount of 1,3-butadiene fed was 821 g, and the amount of styrene fed was 259 g.
Then, 20 mL of a hexane solution containing 0.54 mL of methanol was added to the polymer solution, and the polymer solution was stirred for additional 5 minutes.
To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, Polymer 26 was recovered from the polymer solution by steam stripping. Table 3 shows the evaluation results of Polymer 26. The content of the constituent unit represented by formula (I) in the polymer, as calculated from the amounts of raw materials introduced and the amounts of raw materials fed into the polymerization reactor, was 0.006 mmol/g-polymer per unit mass of the polymer.
Production Example 27
Synthesis of Polymer 27
The interior of a 20-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 10.2 kg of hexane (specific gravity=0.68 g/cm3), 547 g of 1,3-butadiene, 173 g of styrene, 6.1 mL of tetrahydrofuran, and 5.0 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 14.9 mmol of n-butyllithium in n-hexane was further introduced to initiate polymerization.
The 1,3-butadiene and styrene were copolymerized for 3 hours under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor. During the entire polymerization, the amount of 1,3-butadiene fed was 821 g, and the amount of styrene fed was 259 g.
The resulting polymer solution was then stirred at a rate of 130 rpm, and 10.5 mmol of N-(3-dimethylaminopropyl)acrylamide was added thereto, followed by stirring for 15 minutes. Then, 20 mL of a hexane solution containing 0.54 mL of methanol was added to the polymer solution, and the polymer solution was stirred for additional 5 minutes.
To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, Polymer 27 was recovered from the polymer solution by steam stripping. Table 3 shows the evaluation results of Polymer 27. Since the compound represented by formula (IX) was not used in the synthesis of Polymer 27, Polymer 27 did not contain the constituent unit represented by formula (I).
Production Example 28
Synthesis of Polymer 28
The interior of a 20-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 10.2 kg of hexane (specific gravity=0.68 g/cm3), 547 g of 1,3-butadiene, 173 g of styrene, 6.1 mL of tetrahydrofuran, and 5.0 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 14.9 mmol of n-butyllithium in n-hexane was further introduced to initiate polymerization.
The 1,3-butadiene and styrene were copolymerized for 3 hours under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor. During the entire polymerization, the amount of 1,3-butadiene fed was 821 g, and the amount of styrene fed was 259 g.
Then, 20 mL of a hexane solution containing 0.54 mL of methanol was added to the polymer solution, and the polymer solution was stirred for additional 5 minutes.
To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, Polymer 28 was recovered from the polymer solution by steam stripping. Table 3 shows the evaluation results of Polymer 28. Since the compound represented by formula (IX) was not used in the synthesis of Polymer 28, Polymer 28 did not contain the constituent unit represented by formula (I).
Production Example 29
Synthesis of Polymer 29
The interior of a 20-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 10.2 kg of hexane (specific gravity=0.68 g/cm3), 547 g of 1,3-butadiene, 173 g of styrene, 6.1 mL of tetrahydrofuran, and 5.0 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 10.5 mmol of bis(diethylamino)methylvinylsilane in cyclohexane and 14.9 mmol of n-butyllithium in n-hexane were further introduced to initiate polymerization.
The 1,3-butadiene and styrene were copolymerized for 3 hours under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor. During the entire polymerization, the amount of 1,3-butadiene fed was 821 g, and the amount of styrene fed was 259 g.
The resulting polymer solution was then stirred at a rate of 130 rpm, and 10.5 mmol of N-(3-dimethylaminopropyl)acrylamide was added thereto, followed by stirring for 15 minutes. Then, 20 mL of a hexane solution containing 0.54 mL of methanol was added to the polymer solution, and the polymer solution was stirred for additional 5 minutes.
To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, the polymer solution was evaporated at ordinary temperature over 24 hours, and further dried under reduced pressure at 55° C. for 12 hours, so that Polymer 29 was obtained. Table 3 shows the evaluation results of Polymer 29. The content of the constituent unit represented by formula (I) in the polymer, as calculated from the amounts of raw materials introduced and the amounts of raw materials fed into the polymerization reactor, was 0.006 mmol/g-polymer per unit mass of the polymer.








TABLE 3








Polymer

















21
22
23
24
25
26
27
28
29



















Styrene unit content (% by mass)
25
24
24
25
25
25
24
24
25


Vinyl bond content (mol %)
59
60
58
59
59
60
60
58
59


Molecular weight distribution (Mw/Mn)
1.2
1.1
1.1
1.3
1.1
1.2
1.1
1.1
1.2









Production Example 30
Synthesis of Polymer 30
The interior of a 20-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 10.2 kg of hexane (specific gravity=0.68 g/cm3), 547 g of 1,3-butadiene, 173 g of styrene, 6.1 mL of tetrahydrofuran, and 5.0 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 16.0 mmol of bis(diethylamino)methylvinylsilane in cyclohexane and 18.5 mmol of n-butyllithium in n-hexane were further introduced to initiate polymerization.
The 1,3-butadiene and styrene were copolymerized for 3 hours under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor. During the entire polymerization, the amount of 1,3-butadiene fed was 821 g, and the amount of styrene fed was 259 g.
The resulting polymer solution was then stirred at a rate of 130 rpm, and 4.0 mmol of 1,3,5-tris(3-trimethoxysilylpropyl)isocyanurate was added thereto, followed by stirring for 15 minutes. Then, 20 mL of a hexane solution containing 0.80 mL of methanol was added to the polymer solution, and the polymer solution was stirred for additional 5 minutes.
To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, Polymer 30 was recovered from the polymer solution by steam stripping. Table 4 shows the evaluation results of Polymer 30. The content of the constituent unit represented by formula (I) in the polymer, as calculated from the amounts of raw materials introduced and the amounts of raw materials fed into the polymerization reactor, was 0.009 mmol/g-polymer per unit mass of the polymer.
Production Example 31
Synthesis of Polymer 31
The interior of a 20-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 10.2 kg of hexane (specific gravity=0.68 g/cm3), 547 g of 1,3-butadiene, 173 g of styrene, 6.1 mL of tetrahydrofuran, and 5.0 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 17.3 mmol of n-butyllithium in n-hexane was further introduced, and the 1,3-butadiene and styrene were copolymerized for one hour. The polymerization was carried out under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor.
After the one hour polymerization, 14.4 mmol of bis(diethylamino)methylvinylsilane in cyclohexane was introduced into the polymerization reactor under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C.
Next, the monomers were continuously fed into the polymerization reactor, and the 1,3-butadiene and styrene were copolymerized for 0.5 hours. The polymerization was carried out under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C.
After the 0.5-hour polymerization, 14.4 mmol of bis(diethylamino)methylvinylsilane in cyclohexane was introduced into the polymerization reactor under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C.
Next, the monomers were continuously fed into the polymerization reactor, and the 1,3-butadiene and styrene were copolymerized for 0.5 hours. The polymerization was carried out under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C.
After the 0.5-hour polymerization, 14.4 mmol of bis(diethylamino)methylvinylsilane in cyclohexane was introduced into the polymerization reactor under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C.
Next, the monomers were continuously fed into the polymerization reactor, and the 1,3-butadiene and styrene were copolymerized for 0.5 hours. The polymerization was carried out under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. During the entire polymerization, the amount of 1,3-butadiene fed was 821 g, and the amount of styrene fed was 259 g.
The resulting polymer solution was then stirred at a rate of 130 rpm, and 3.6 mmol of 1,3,5-tris(3-trimethoxysilylpropyl)isocyanurate was added thereto, followed by stirring for 15 minutes. Then, 20 mL of a hexane solution containing 0.80 mL of methanol was added to the polymer solution, and the polymer solution was stirred for additional 5 minutes.
To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, Polymer 31 was recovered from the polymer solution by steam stripping. Table 4 shows the evaluation results of Polymer 31. The content of the constituent unit represented by formula (I) in the polymer, as calculated from the amounts of raw materials introduced and the amounts of raw materials fed into the polymerization reactor, was 0.024 mmol/g-polymer per unit mass of the polymer.
Production Example 32
Synthesis of Polymer 32
The interior of a 5-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 2.55 kg of hexane (specific gravity=0.68 g/cm3), 137 g of 1,3-butadiene, 43 g of styrene, 1.5 mL of tetrahydrofuran, and 1.2 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 3.6 mmol of n-butyllithium in n-hexane was further introduced, and the 1,3-butadiene and styrene were copolymerized for 2.5 hours. The polymerization was carried out under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor. The amount of 1,3-butadiene fed was 205 g, and the amount of styrene fed was 65 g.
After the 2.5-hour polymerization, 2.8 mmol of bis(diethylamino)methylvinylsilane in cyclohexane was introduced into the polymerization reactor under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C., followed by stirring for 30 minutes.
Next, 20 mL of a hexane solution containing 0.14 mL of methanol was introduced into the polymerization reactor, and the polymer solution was stirred for 5 minutes.
To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, Polymer 32 was recovered from the polymer solution by steam stripping. Table 4 shows the evaluation results of Polymer 32. The content of the constituent unit represented by formula (I) in the polymer, as calculated from the amounts of raw materials introduced and the amounts of raw materials fed into the polymerization reactor, was 0.006 mmol/g-polymer per unit mass of the polymer.
Production Example 33
Synthesis of Polymer 33
The interior of a 20-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 10.2 kg of hexane (specific gravity=0.68 g/cm3), 547 g of 1,3-butadiene, 173 g of styrene, 6.1 mL of tetrahydrofuran, and 5.0 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 16.0 mmol of bis(diethylamino)methylvinylsilane in cyclohexane and 18.5 mmol of n-butyllithium in n-hexane were further introduced to initiate polymerization.
The 1,3-butadiene and styrene were copolymerized for 3 hours under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor. During the entire polymerization, the amount of 1,3-butadiene fed was 821 g, and the amount of styrene fed was 259 g.
Then, 20 mL of a hexane solution containing 0.80 mL of methanol was added to the polymer solution, and the polymer solution was stirred for additional 5 minutes.
To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, Polymer 33 was recovered from the polymer solution by steam stripping. Table 4 shows the evaluation results of Polymer 33. The content of the constituent unit represented by formula (I) in the polymer, as calculated from the amounts of raw materials introduced and the amounts of raw materials fed into the polymerization reactor, was 0.009 mmol/g-polymer per unit mass of the polymer.
Production Example 34
Synthesis of Polymer 34
The interior of a 20-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 10.2 kg of hexane (specific gravity=0.68 g/cm3), 547 g of 1,3-butadiene, 173 g of styrene, 6.1 mL of tetrahydrofuran, and 5.0 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 18.5 mmol of n-butyllithium in n-hexane was further introduced to initiate polymerization.
The 1,3-butadiene and styrene were copolymerized for 3 hours under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor. During the entire polymerization, the amount of 1,3-butadiene fed was 821 g, and the amount of styrene fed was 259 g.
The resulting polymer solution was then stirred at a rate of 130 rpm, and 4.0 mmol of 1,3,5-tris(3-trimethoxysilylpropyl)isocyanurate was added thereto, followed by stirring for 15 minutes. Then, 20 mL of a hexane solution containing 0.80 mL of methanol was added to the polymer solution, and the polymer solution was stirred for additional 5 minutes.
To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, Polymer 34 was recovered from the polymer solution by steam stripping. Table 4 shows the evaluation results of Polymer 34. Since the compound represented by formula (IX) was not used in the synthesis of Polymer 34, Polymer 34 did not contain the constituent unit represented by formula (I).
Production Example 35
Synthesis of Polymer 35
The interior of a 20-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 10.2 kg of hexane (specific gravity=0.68 g/cm3), 547 g of 1,3-butadiene, 173 g of styrene, 6.1 mL of tetrahydrofuran, and 5.0 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 18.5 mmol of n-butyllithium in n-hexane was further introduced to initiate polymerization.
The 1,3-butadiene and styrene were copolymerized for 3 hours under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor. During the entire polymerization, the amount of 1,3-butadiene fed was 821 g, and the amount of styrene fed was 259 g.
Then, 20 mL of a hexane solution containing 0.80 mL of methanol was added to the polymer solution, and the polymer solution was stirred for additional 5 minutes.
To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, Polymer 35 was recovered from the polymer solution by steam stripping. Table 4 shows the evaluation results of Polymer 35. Since the compound represented by formula (IX) was not used in the synthesis of Polymer 35, Polymer 35 did not contain the constituent unit represented by formula (I).
Production Example 36
Synthesis of Polymer 36
The interior of a 20-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 10.2 kg of hexane (specific gravity=0.68 g/cm3), 547 g of 1,3-butadiene, 173 g of styrene, 6.1 mL of tetrahydrofuran, and 5.0 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 16.0 mmol of bis(diethylamino)methylvinylsilane in cyclohexane and 18.5 mmol of n-butyllithium in n-hexane were further introduced to initiate polymerization.
The 1,3-butadiene and styrene were copolymerized for 3 hours under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor. During the entire polymerization, the amount of 1,3-butadiene fed was 821 g, and the amount of styrene fed was 259 g.
The resulting polymer solution was then stirred at a rate of 130 rpm, and 4.0 mmol of 1,3,5-tris(3-trimethoxysilylpropyl)isocyanurate was added thereto, followed by stirring for 15 minutes. Then, 20 mL of a hexane solution containing 0.80 mL of methanol was added to the polymer solution, and the polymer solution was stirred for additional 5 minutes.
To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, the polymer solution was evaporated at ordinary temperature over 24 hours, and further dried under reduced pressure at 55° C. for 12 hours, so that Polymer 36 was obtained. Table 4 shows the evaluation results of Polymer 36. The content of the constituent unit represented by formula (I) in the polymer, as calculated from the amounts of raw materials introduced and the amounts of raw materials fed into the polymerization reactor, was 0.009 mmol/g-polymer per unit mass of the polymer.
Production Example 37
Synthesis of Polymer 37
The interior of a 20-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 10.2 kg of hexane (specific gravity=0.68 g/cm3), 547 g of 1,3-butadiene, 173 g of styrene, 6.1 mL of tetrahydrofuran, and 5.0 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 16.0 mmol of bis(diethylamino)methylvinylsilane in cyclohexane and 18.5 mmol of n-butyllithium in n-hexane were further introduced to initiate polymerization.
The 1,3-butadiene and styrene were copolymerized for 3 hours under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor. During the entire polymerization, the amount of 1,3-butadiene fed was 821 g, and the amount of styrene fed was 259 g.
The resulting polymer solution was then stirred at a rate of 130 rpm, and 4.0 mmol of 3-(methoxy)propyltrimethoxysilane was added thereto, followed by stirring for 15 minutes. Then, 20 mL of a hexane solution containing 0.80 mL of methanol was added to the polymer solution, and the polymer solution was stirred for additional 5 minutes.
To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, Polymer 37 was recovered from the polymer solution by steam stripping. Table 4 shows the evaluation results of Polymer 37. The content of the constituent unit represented by formula (I) in the polymer, as calculated from the amounts of raw materials introduced and the amounts of raw materials fed into the polymerization reactor, was 0.009 mmol/g-polymer per unit mass of the polymer.








TABLE 4








Polymer
















30
31
32
33
34
35
36
37


















Styrene unit content (% by mass)
25
25
24
24
25
24
25
24


Vinyl bond content (mol %)
59
59
60
60
59
58
60
59


Molecular weight distribution (Mw/Mn)
1.5
1.6
1.1
1.2
1.3
1.1
1.5
1.4









Production Example 38
Synthesis of Polymer 38
The interior of a 20-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 10.2 kg of hexane (specific gravity=0.68 g/cm3), 547 g of 1,3-butadiene, 173 g of styrene, 6.1 mL of tetrahydrofuran, and 5.0 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 11.5 mmol of bis(diethylamino)methylvinylsilane in cyclohexane and 14.1 mmol of n-butyllithium in n-hexane were further introduced to initiate polymerization.
The 1,3-butadiene and styrene were copolymerized for 3 hours under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor. During the entire polymerization, the amount of 1,3-butadiene fed was 821 g, and the amount of styrene fed was 259 g.
The resulting polymer solution was then stirred at a rate of 130 rpm, and 11.5 mmol of N,N-dimethylformamide dimethyl acetal was added thereto, followed by stirring for 15 minutes. Then, 20 mL of a hexane solution containing 0.54 mL of methanol was added to the polymer solution, and the polymer solution was stirred for additional 5 minutes.
To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, Polymer 38 was recovered from the polymer solution by steam stripping. Table 5 shows the evaluation results of Polymer 38. The content of the constituent unit represented by formula (I) in the polymer, as calculated from the amounts of raw materials introduced and the amounts of raw materials fed into the polymerization reactor, was 0.006 mmol/g-polymer per unit mass of the polymer.
Production Example 39
Synthesis of Polymer 39
The interior of a 20-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 10.2 kg of hexane (specific gravity=0.68 g/cm3), 547 g of 1,3-butadiene, 173 g of styrene, 6.1 mL of tetrahydrofuran, and 5.0 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 14.1 mmol of n-butyllithium in n-hexane was further introduced, and the 1,3-butadiene and styrene were copolymerized for one hour. The polymerization was carried out under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor.
After the one hour polymerization, 11.0 mmol of bis(diethylamino)methylvinylsilane in cyclohexane was introduced into the polymerization reactor under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C.
Next, the monomers were continuously fed into the polymerization reactor while the 1,3-butadiene and styrene were copolymerized for 0.5 hours. The polymerization was carried out under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C.
After the 0.5-hour polymerization, 11.0 mmol of bis(diethylamino)methylvinylsilane in cyclohexane was introduced into the polymerization reactor under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C.
Next, the monomers were continuously fed into the polymerization reactor while the 1,3-butadiene and styrene were copolymerized for 0.5 hours. The polymerization was carried out under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C.
After the 0.5-hour polymerization, 11.0 mmol of bis(diethylamino)methylvinylsilane in cyclohexane was introduced into the polymerization reactor under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C.
Next, the monomers were continuously fed into the polymerization reactor while the 1,3-butadiene and styrene were copolymerized for 0.5 hours. The polymerization was carried out under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. During the entire polymerization, the amount of 1,3-butadiene fed was 821 g, and the amount of styrene fed was 259 g.
The resulting polymer solution was then stirred at a rate of 130 rpm, and 11.0 mmol of N,N-dimethylformamide dimethyl acetal was added thereto, followed by stirring for 15 minutes. Then, 20 mL of a hexane solution containing 0.54 mL of methanol was added to the polymer solution, and the polymer solution was stirred for additional 5 minutes.
To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, Polymer 39 was recovered from the polymer solution by steam stripping. Table 5 shows the evaluation results of Polymer 39. The content of the constituent unit represented by formula (I) in the polymer, as calculated from the amounts of raw materials introduced and the amounts of raw materials fed into the polymerization reactor, was 0.018 mmol/g-polymer per unit mass of the polymer.
Production Example 40
Synthesis of Polymer 40
The interior of a 5-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 2.55 kg of hexane (specific gravity=0.68 g/cm3), 137 g of 1,3-butadiene, 43 g of styrene, 1.5 mL of tetrahydrofuran, and 1.2 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 3.6 mmol of n-butyllithium in n-hexane was further introduced, and the 1,3-butadiene and styrene were copolymerized for 2.5 hours. The polymerization was carried out under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor. The amount of 1,3-butadiene fed was 205 g, and the amount of styrene fed was 65 g.
After the 2.5-hour polymerization, 2.8 mmol of bis(diethylamino)methylvinylsilane in cyclohexane was introduced into the polymerization reactor under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C., followed by stirring for 30 minutes. Next, 20 mL of a hexane solution containing 0.14 mL of methanol was introduced into the polymerization reactor, and the polymer solution was stirred for 5 minutes.
To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, Polymer 40 was recovered from the polymer solution by steam stripping. Table 5 shows the evaluation results of Polymer 40. The content of the constituent unit represented by formula (I) in the polymer, as calculated from the amounts of raw materials introduced and the amounts of raw materials fed into the polymerization reactor, was 0.006 mmol/g-polymer per unit mass of the polymer.
Production Example 41
Synthesis of Polymer 41
The interior of a 20-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 10.2 kg of hexane (specific gravity=0.68 g/cm3), 547 g of 1,3-butadiene, 173 g of styrene, 6.1 mL of tetrahydrofuran, and 5.0 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 11.5 mmol of bis(diethylamino)methylvinylsilane in cyclohexane and 14.1 mmol of n-butyllithium in n-hexane were further introduced to initiate polymerization.
The 1,3-butadiene and styrene were copolymerized for 3 hours under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor. During the entire polymerization, the amount of 1,3-butadiene fed was 821 g, and the amount of styrene fed was 259 g.
Then, 20 mL of a hexane solution containing 0.54 mL of methanol was added to the polymer solution, and the polymer solution was stirred for additional 5 minutes.
To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, Polymer 41 was recovered from the polymer solution by steam stripping. Table 5 shows the evaluation results of Polymer 41. The content of the constituent unit represented by formula (I) in the polymer, as calculated from the amounts of raw materials introduced and the amounts of raw materials fed into the polymerization reactor, was 0.006 mmol/g-polymer per unit mass of the polymer.
Production Example 42
Synthesis of Polymer 42
The interior of a 20-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 10.2 kg of hexane (specific gravity=0.68 g/cm3), 547 g of 1,3-butadiene, 173 g of styrene, 6.1 mL of tetrahydrofuran, and 5.0 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 14.1 mmol of n-butyllithium in n-hexane was further introduced to initiate polymerization.
The 1,3-butadiene and styrene were copolymerized for 3 hours under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor. During the entire polymerization, the amount of 1,3-butadiene fed was 821 g, and the amount of styrene fed was 259 g.
The resulting polymer solution was then stirred at a rate of 130 rpm, and 11.5 mmol of N,N-dimethylformamide dimethyl acetal was added thereto, followed by stirring for 15 minutes. Then, 20 mL of a hexane solution containing 0.54 mL of methanol was added to the polymer solution, and the polymer solution was stirred for additional 5 minutes.
To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, Polymer 42 was recovered from the polymer solution by steam stripping. Table 5 shows the evaluation results of Polymer 42. Since the compound represented by formula (IX) was not used in the synthesis of Polymer 42, Polymer 42 did not contain the constituent unit represented by formula (I).
Production Example 43
Synthesis of Polymer 43
The interior of a 20-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 10.2 kg of hexane (specific gravity=0.68 g/cm3), 547 g of 1,3-butadiene, 173 g of styrene, 6.1 mL of tetrahydrofuran, and 5.0 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 14.1 mmol of n-butyllithium in n-hexane was further introduced to initiate polymerization.
The 1,3-butadiene and styrene were copolymerized for 3 hours under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor. During the entire polymerization, the amount of 1,3-butadiene fed was 821 g, and the amount of styrene fed was 259 g.
Then, 20 mL of a hexane solution containing 0.54 mL of methanol was added to the polymer solution, and the polymer solution was stirred for additional 5 minutes.
To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, Polymer 43 was recovered from the polymer solution by steam stripping. Table 5 shows the evaluation results of Polymer 43. Since the compound represented by formula (IX) was not used in the synthesis of Polymer 43, Polymer 43 did not contain the constituent unit represented by formula (I).
Production Example 44
Synthesis of Polymer 44
The interior of a 20-L stainless steel polymerization reactor was washed and dried, and then replaced with dry nitrogen. Next, 10.2 kg of hexane (specific gravity=0.68 g/cm3), 547 g of 1,3-butadiene, 173 g of styrene, 6.1 mL of tetrahydrofuran, and 5.0 mL of ethylene glycol diethyl ether were introduced into the polymerization reactor. Thereafter, 11.5 mmol of bis(diethylamino)methylvinylsilane in cyclohexane and 14.1 mmol of n-butyllithium in n-hexane were further introduced to initiate polymerization.
The 1,3-butadiene and styrene were copolymerized for 3 hours under stirring at a rate of 130 rpm and a temperature within the polymerization reactor of 65° C. while the monomers were continuously fed into the polymerization reactor. During the entire polymerization, the amount of 1,3-butadiene fed was 821 g, and the amount of styrene fed was 259 g.
The resulting polymer solution was then stirred at a rate of 130 rpm, and 11.5 mmol of N,N-dimethylformamide dimethyl acetal was added thereto, followed by stirring for 15 minutes. Then, 20 mL of a hexane solution containing 0.54 mL of methanol was added to the polymer solution, and the polymer solution was stirred for additional 5 minutes.
To the resulting polymer solution were added 1.8 g of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (trade name: Sumilizer GM, produced by Sumitomo Chemical Co., Ltd.) and 0.9 g of pentaerythrityl tetrakis(3-laurylthiopropionate) (trade name: Sumilizer TP-D, produced by Sumitomo Chemical Co., Ltd.). Then, the polymer solution was evaporated at ordinary temperature over 24 hours, and further dried under reduced pressure at 55° C. for 12 hours, so that Polymer 44 was obtained. Table 5 shows the evaluation results of Polymer 44. The content of the constituent unit represented by formula (I) in the polymer, as calculated from the amounts of raw materials introduced and the amounts of raw materials fed into the polymerization reactor, was 0.006 mmol/g-polymer per unit mass of the polymer.








TABLE 5








Polymer















38
39
40
41
42
43
44

















Styrene unit content (% by mass)
25
25
25
25
25
24
24


Vinyl bond content (mol %)
59
59
59
60
59
59
60


Molecular weight distribution (Mw/Mn)
1.6
1.3
1.1
1.3
1.1
1.1
1.2









The chemicals used in examples and comparative examples are described below.

    Natural rubber 1: RSS #3
    Natural rubber 2: SIR20
    Butadiene rubber: Ubepol BR150B produced by Ube Industries, Ltd
    SBR: NS116R (styrene unit content: 20% by mass, vinyl bond content: 60 mol %) produced by Zeon Corporation
    Polymers 1 to 44: see Production Examples 1 to 44 above
    Silica: Ultrasil VN3-G (N2SA: 175 m2/g) produced by Evonik Degussa
    Silane coupling agent 1: Si69 (bis(3-triethoxysilylpropyl)tetrasulfide) produced by Evonik Degussa
    Silane coupling agent 2: Si363 produced by Evonik Degussa, a compound represented by the following formula:






    Silane coupling agent 3: NXT-Z45 (copolymer of linking unit A and linking unit B (linking unit A: 55 mol %, linking unit B: 45 mol %)) produced by Momentive Performance Materials
    Silane coupling agent 4: Si75 (bis(3-triethoxysilylpropyl)disulfide) produced by Evonik Degussa
    Carbon black 1: Diablack N339 (N2SA: 96 m2/g, DBP absorption: 124 mL/100 g) produced by Mitsubishi Chemical Corporation
    Carbon black 2: Diablack N220 (N2SA: 114 m2/g, DBP absorption: 114 mL/100 g) produced by Mitsubishi Chemical Corporation
    Oil 1: X-140 produced by JX Nippon Oil & Energy Corporation
    Oil 2: NH70-S produced by Idemitsu Kosan Co., Ltd.
    Antioxidant 1: Antigene 3C produced by Sumitomo Chemical Co., Ltd.
    Antioxidant 2: Antigene 6C produced by Sumitomo Chemical Co., Ltd.
    Stearic acid: stearic acid beads “Tsubaki” produced by NOF Corporation
    Zinc oxide 1: zinc white #1 produced by Mitsui Mining & Smelting Co., Ltd.
    Zinc oxide 2: zinc oxide #2 produced by Mitsui Mining & Smelting Co., Ltd.
    Wax: Sunnoc N produced by Ouchi Shinko Chemical Industrial Co., Ltd.
    Sulfur 1: sulfur powder produced by Tsurumi Chemical Industry Co., Ltd.
    Sulfur 2: 5% oil-treated sulfur powder produced by Tsurumi Chemical Industry Co., Ltd.
    Vulcanization accelerator 1: Soxinol CZ produced by Sumitomo Chemical Co., Ltd.
    Vulcanization accelerator 2: Soxinol D produced by Sumitomo Chemical Co., Ltd.


Examples and Comparative Examples
According to the each formulation shown in Tables 6 to 18, the materials other than the sulfur and vulcanization accelerators were kneaded for 5 minutes at 150° C. using a 1.7-L Banbury mixer from Kobe Steel, Ltd., to obtain a kneadate. The sulfur and vulcanization accelerators were then added to the obtained kneadate and kneading was performed using an open roll mill for 5 minutes at 80° C. to obtain an unvulcanized rubber composition. The obtained unvulcanized rubber composition was press-vulcanized for 20 minutes at 170° C. using a 0.5 mm-thick mold to obtain a vulcanized rubber composition.
In addition, the unvulcanized rubber composition was formed into a tread shape and assembled with other tire components in a tire building machine to form an unvulcanized tire. The unvulcanized tire was vulcanized for 12 minutes at 170° C. to prepare a test tire (size: 195/65R15).
The obtained vulcanized rubber compositions, and test tires were evaluated by the aforementioned testing methods. Tables 6 to 18 show the results of these tests.









TABLE 6








Example
Comparative Example














1
2
3
1
2
3

















Composition
Natural rubber 1
20
20
20
20
20
20


(parts by mass)
Butadiene rubber
20
20
20
20
20
20



Polymer 1
60
20
—
—
—
60



Polymer 2
—
—
—
—
—
—



Polymer 3
—
—
—
—
—
—



Polymer 4
—
—
—
—
—
—



Polymer 5
—
40
—
60
60
—



Polymer 6
—
—
60
—
—
—



Silica
75
75
75
75
75
75



Silane coupling agent 1
—
—
—
6
—
6



Silane coupling agent 2
6
6
6
—
6
—



Carbon black 1
5
5
5
5
5
5



Oil 1
20
20
20
20
20
20



Antioxidant 1
1.5
1.5
1.5
1.5
1.5
1.5



Stearic acid
2
2
2
2
2
2



Zinc oxide 1
2.5
2.5
2.5
2.5
2.5
2.5



Wax
1
1
1
1
1
1



Sulfur 1
2
2
2
2
2
2



Vulcanization accelerator 1
1.8
1.8
1.8
1.8
1.8
1.8



Vulcanization accelerator 2
1.2
1.2
1.2
1.2
1.2
1.2


Evaluation
tan δ (index)
145
142
137
100
113
120



Rolling resistance (index)
142
136
133
100
111
117



Wet-grip performance (index)
145
143
139
100
105
109



Abrasion resistance 1 (index)
127
123
121
100
107
111


















TABLE 7








Example
Comparative Example



















4
5
6
7
4
5
6
7
8
9
10






















Composition
Natural rubber 1
20
20
20
20
20
20
20
20
20
20
20


(parts by mass)
Butadiene rubber
20
20
20
20
20
20
20
20
20
20
20



Polymer 1
60
20
60
—
—
—
—
—
—
60
—



Polymer 2
—
40
—
—
—
60
—
—
—
—
—



Polymer 3
—
—
—
—
—
—
60
—
—
—
—



Polymer 4
—
—
—
—
—
—
—
60
—
—
—



Polymer 5
—
—
—
—
60
—
—
—
—
—
60



Polymer 6
—
—
—
60
—
—
—
—
60
—
—



Silica
75
75
50
75
75
75
75
75
75
75
75



Silane coupling agent 1
—
—
—
—
4.5
—
—
—
4.5
4.5
—



Silane coupling agent 3
4.5
4.5
3
4.5
—
4.5
4.5
4.5
—
—
4.5



Carbon black 2
5
5
5
5
5
5
5
5
5
5
5



Oil 1
20
20
5
20
20
20
20
20
20
20
20



Antioxidant 1
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5



Stearic acid
2
2
2
2
2
2
2
2
2
2
2



Zinc oxide 1
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5



Wax
1
1
1
1
1
1
1
1
1
1
1



Sulfur 1
2
2
2
2
2
2
2
2
2
2
2



Vulcanization accelerator 1
1.8
1.8
1.8
1.8
1.8
1.8
1.8
1.8
1.8
1.8
1.8



Vulcanization accelerator 2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2


Evaluation
tan δ (index)
153
157
158
146
100
124
128
130
134
122
115



Rolling resistance (index)
148
152
149
141
100
114
117
118
129
113
109



Wet-grip performance (index)
154
157
157
144
100
120
126
130
129
117
114



Abrasion resistance 1 (index)
133
138
128
129
100
115
120
121
118
116
107


















TABLE 8








Comparative




Example
Example















11
12
13
8
9
10
11


















Composition
Natural rubber 1
20
20
20
20
20
20
—


(parts by mass)
Butadiene rubber
20
20
20
20
20
20
20



SBR
60
—
—
—
—
—
—



Polymer 7
—
60
—
60
—
60
80



Polymer 8
—
—
60
—
60
—
—



Silica
75
75
75
75
75
75
75



Silane coupling agent 1
6
6
6
—
—
—
—



Silane coupling agent 3
—
—
—
6
6
3
6



Carbon black 1
5
5
5
5
5
5
5



Oil 1
20
20
20
20
20
20
20



Antioxidant 1
1.5
1.5
1.5
1.5
1.5
1.5
1.5



Stearic acid
2
2
2
2
2
2
2



Zinc oxide 1
2.5
2.5
2.5
2.5
2.5
2.5
2.5



Wax
1
1
1
1
1
1
1



Sulfur 1
2
2
2
2
2
2
2



Vulcanization accelerator 1
1.8
1.8
1.8
1.8
1.8
1.8
1.8



Vulcanization accelerator 2
1.2
1.2
1.2
1.2
1.2
1.2
1.2


Evaluation
tan δ (index)
100
130
132
136
138
134
130



Rolling resistance (index)
100
127
130
131
134
129
127



Wet-grip performance (index)
100
126
128
132
134
130
140



Abrasion resistance 1 (index)
100
119
121
129
131
124
119

















TABLE 9








Example




















12
13
14
15
16
17
18
19
20
21
22
23























Composition
Natural rubber 1
20
20
20
20
20
20
20
20
20
20
20
—


(parts by mass)
Butadiene rubber
20
20
20
20
20
20
20
20
20
20
20
—



Polymer 7
60
—
—
—
—
—
—
—
—
60
—
60



Polymer 8
—
60
—
—
—
—
—
—
—
—
—
—



Polymer 9
—
—
60
—
—
—
—
—
—
—
—
—



Polymer 10
—
—
—
60
—
—
—
—
—
—
—
—



Polymer 11
—
—
—
—
60
—
—
—
—
—
—
—



Polymer 12
—
—
—
—
—
60
—
—
—
—
—
—



Polymer 13
—
—
—
—
—
—
60
—
—
—
—
—



Polymer 14
—
—
—
—
—
—
—
60
—
—
—
—



Polymer 15
—
—
—
—
—
—
—
—
60
—
—
—



Polymer 16
—
—
—
—
—
—
—
—
—
—
—
—



Polymer 17
—
—
—
—
—
—
—
—
—
—
—
—



Polymer 18
—
—
—
—
—
—
—
—
—
—
—
—



Polymer 19
—
—
—
—
—
—
—
—
—
—
—
40



Polymer 20
—
—
—
—
—
—
—
—
—
—
60
—



Silica
75
75
75
75
75
75
75
75
75
50
75
75



Silane coupling agent 1
—
—
—
—
—
—
—
—
—
—
—
—



Silane coupling agent 2
6
6
6
6
6
6
6
6
6
4
6
6



Carbon black 2
5
5
5
5
5
5
5
5
5
5
5
5



Oil 1
20
20
20
20
20
20
20
20
20
20
20
20



Antioxidant 1
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5



Stearic acid
2
2
2
2
2
2
2
2
2
2
2
2



Zinc oxide 1
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5



Wax
1
1
1
1
1
1
1
1
1
1
1
1



Sulfur 1
2
2
2
2
2
2
2
2
2
2
2
2



Vulcanization accelerator 1
1.8
1.8
1.8
1.8
1.8
1.8
1.8
1.8
1.8
1.8
1.8
1.8



Vulcanization accelerator 2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2


Evaluation
tan δ (index)
130
132
135
126
129
127
128
120
122
134
127
130



Rolling resistance (index)
127
130
131
127
124
125
125
120
120
126
122
124



Wet-grip performance (index)
126
128
132
126
127
120
124
116
118
127
119
125



Abrasion resistance 1 (index)
120
121
125
120
122
117
120
117
120
115
114
119

















TABLE 10








Comparative Example




















14
15
16
17
18
19
20
21
22
23





Composition
Natural rubber 1
20
20
20
20
20
20
20
20
20
20


(parts by mass)
Butadiene rubber
20
20
20
20
20
20
20
20
20
20



Polymer 7
—
—
—
—
—
—
—
—
—
60



Polymer 8
—
—
—
—
—
—
—
—
—
—



Polymer 9
—
—
—
—
—
—
—
—
—
—



Polymer 10
—
—
—
—
—
—
—
—
—
—



Polymer 11
—
—
—
—
60
—
—
—
—
—



Polymer 12
—
—
—
—
—
—
—
—
—
—



Polymer 13
—
—
—
—
—
—
—
—
—
—



Polymer 14
—
—
—
—
—
—
—
—
—
—



Polymer 15
—
—
—
—
—
—
—
—
—
—



Polymer 16
—
60
—
—
—
—
60
—
—
—



Polymer 17
—
—
60
—
—
—
—
60
—
—



Polymer 18
—
—
—
60
—
—
—
—
60
—



Polymer 19
60
—
—
—
—
60
—
—
—
—



Polymer 20
—
—
—
—
—
—
—
—
—
—



Silica
75
75
75
75
75
75
75
75
75
75



Silane coupling agent 1
6
6
6
6
6
—
—
—
—
6



Silane coupling agent 2
—
—
—
—
—
6
6
6
6
—



Carbon black 2
5
5
5
5
5
5
5
5
5
5



Oil 1
20
20
20
20
20
20
20
20
20
20



Antioxidant 1
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5



Stearic acid
2
2
2
2
2
2
2
2
2
2



Zinc oxide 1
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5



Wax
1
1
1
1
1
1
1
1
1
1



Sulfur 1
2
2
2
2
2
2
2
2
2
2



Vulcanization accelerator 1
1.8
1.8
1.8
1.8
1.8
1.8
1.8
1.8
1.8
1.8



Vulcanization accelerator 2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2


Evaluation
tan δ (index)
100
116
119
112
123
101
118
120
115
113



Rolling resistance (index)
100
106
109
109
120
102
119
115
112
108



Wet-grip performance (index)
100
112
117
110
119
100
115
125
112
115



Abrasion resistance 1 (index)
100
107
111
112
110
108
109
115
117
112












Comparative Example




















24
25
26
27
28
29
30
31






Composition
Natural rubber 1
20
20
20
20
20
20
20
20



(parts by mass)
Butadiene rubber
20
20
20
20
20
20
20
20




Polymer 7
—
—
—
—
—
—
—
—




Polymer 8
60
—
—
—
—
—
—
—




Polymer 9
—
60
—
—
—
—
—
—




Polymer 10
—
—
60
—
—
—
—
—




Polymer 11
—
—
—
—
—
—
—
—




Polymer 12
—
—
—
60
—
—
—
—




Polymer 13
—
—
—
—
60
—
—
—




Polymer 14
—
—
—
—
—
60
—
—




Polymer 15
—
—
—
—
—
—
60
—




Polymer 16
—
—
—
—
—
—
—
—




Polymer 17
—
—
—
—
—
—
—
—




Polymer 18
—
—
—
—
—
—
—
—




Polymer 19
—
—
—
—
—
—
—
—




Polymer 20
—
—
—
—
—
—
—
60




Silica
75
75
75
75
75
75
75
75




Silane coupling agent 1
6
6
6
6
6
6
6
6




Silane coupling agent 2
—
—
—
—
—
—
—
—




Carbon black 2
5
5
5
5
5
5
5
5




Oil 1
20
20
20
20
20
20
20
20




Antioxidant 1
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5




Stearic acid
2
2
2
2
2
2
2
2




Zinc oxide 1
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5




Wax
1
1
1
1
1
1
1
1




Sulfur 1
2
2
2
2
2
2
2
2




Vulcanization accelerator 1
1.8
1.8
1.8
1.8
1.8
1.8
1.8
1.8




Vulcanization accelerator 2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2



Evaluation
tan δ (index)
115
120
118
105
110
108
105
109




Rolling resistance (index)
111
118
117
103
112
110
107
110




Wet-grip performance (index)
111
123
114
105
110
113
107
109




Abrasion resistance 1 (index)
116
111
108
102
108
112
110
108


















TABLE 11








Example
Comparative Example




















24
25
26
27
28
29
32
33
34
35
36
37























Composition
Natural rubber 1
20
20
20
20
20
20
20
20
20
20
20
20


(parts by mass)
Butadiene rubber
20
20
20
20
20
20
20
20
20
20
20
20



Polymer 21
20
—
—
—
60
—
—
—
—
—
—
60



Polymer 22
—
60
—
—
—
—
—
—
—
—
—
—



Polymer 23
—
—
60
—
—
—
—
—
—
—
—
—



Polymer 24
—
—
—
60
—
—
—
—
—
—
—
—



Polymer 25
40
—
—
—
—
—
—
60
—
—
—
—



Polymer 26
—
—
—
—
—
—
—
—
—
60
—
—



Polymer 27
—
—
—
—
—
—
—
—
—
—
60
—



Polymer 28
—
—
—
—
—
—
60
—
60
—
—
—



Polymer 29
—
—
—
—
—
60
—
—
—
—
—
—



Silica
75
75
75
75
75
75
75
75
75
75
75
75



Silane coupling agent 1
—
—
—
—
—
—
6
6
—
6
6
6



Silane coupling agent 2
6
6
6
6
6
6
—
—
6
—
—
—



Carbon black 2
5
5
5
5
5
5
5
5
5
5
5
5



Oil 1
20
20
20
20
20
20
20
20
20
20
20
20



Antioxidant 1
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5



Stearic acid
2
2
2
2
2
2
2
2
2
2
2
2



Zinc oxide 1
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5



Wax
1
1
1
1
1
1
1
1
1
1
1
1



Sulfur 1
2
2
2
2
2
2
2
2
2
2
2
2



Vulcanization accelerator 1
1.8
1.8
1.8
1.8
1.8
1.8
1.8
1.8
1.8
1.8
1.8
1.8



Vulcanization accelerator 2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2


Evaluation
Rolling resistance (index)
125
130
134
145
152
149
100
118
105
121
113
120



Wet-grip performance (index)
124
128
133
140
149
149
100
109
103
110
122
115



Abrasion resistance 2 (index)
120
124
128
130
135
133
100
101
103
105
108
110




















TABLE 12









Comparative




Example
Example




30
38









Composition (parts by mass)





Natural rubber 1
—
—



Butadiene rubber
—
—



Polymer 21
60
—



Polymer 22
—
—



Polymer 23
—
—



Polymer 24
—
—



Polymer 25
—
—



Polymer 26
—
—



Polymer 27
—
—



Polymer 28
40
100



Polymer 29
—
—



Silica
75
75



Silane coupling agent 1
—
6



Silane coupling agent 2
6
—



Carbon black 2
5
5



Oil 1
20
20



Antioxidant 1
1.5
1.5



Stearic acid
2
2



Zinc oxide 1
2.5
2.5



Wax
1
1



Sulfur 1
2
2



Vulcanization accelerator 1
1.8
1.8



Vulcanization accelerator 2
1.2
1.2



Evaluation





Rolling resistance (index)
122
100



Wet-grip performance (index)
120
100



Abrasion resistance 2 (index)
110
100


















TABLE 13








Comparative Example





















39
40
41
42
43
44
45
46
47
48
49
50
51
























Composition
Natural rubber 1
20
20
20
20
20
20
20
20
20
20
20
20
20


(parts by mass)
Butadiene rubber
20
20
20
20
20
20
20
20
20
20
20
20
20



Polymer 21
60
—
—
—
20
60
—
—
—
—
—
—
—



Polymer 22
—
60
—
—
—
—
—
—
—
—
—
—
—



Polymer 23
—
—
60
—
—
—
—
—
—
—
—
—
—



Polymer 24
—
—
—
60
—
—
—
—
—
—
—
—
—



Polymer 25
—
—
—
—
40
—
—
—
60
—
—
—
—



Polymer 26
—
—
—
—
—
—
—
—
—
60
—
—
—



Polymer 27
—
—
—
—
—
—
—
—
—
—
60
—
60



Polymer 28
—
—
—
—
—
—
—
60
—
—
—
60
—



Polymer 29
—
—
—
—
—
—
60
—
—
—
—
—
—



Silica
75
75
75
75
75
50
75
75
75
75
75
75
75



Silane coupling agent 1
6
6
6
6
6
4
6
6
6
6
6
—
—



Silane coupling agent 3
—
—
—
—
—
—
—
—
—
—
—
6
6



Carbon black 1
5
5
5
5
5
5
5
5
5
5
5
5
5



Oil 1
20
20
20
20
20
5
20
20
20
20
20
20
20



Antioxidant 1
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5



Stearic acid
2
2
2
2
2
2
2
2
2
2
2
2
2



Zinc oxide 1
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5



Wax
1
1
1
1
1
1
1
1
1
1
1
1
1



Sulfur 1
2
2
2
2
2
2
2
2
2
2
2
2
2



Vulcanization accelerator 1
1.8
1.8
1.8
1.8
1.8
1.8
1.8
1.8
1.8
1.8
1.8
1.8
1.8



Vulcanization accelerator 2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2


Evaluation
Rolling resistance (index)
136
138
140
140
115
137
128
100
109
111
113
107
120



Wet-grip performance (index)
139
140
142
144
120
140
131
100
118
121
122
109
131



Abrasion resistance 2 (index)
120
121
125
127
110
119
115
100
109
110
112
108
120

















TABLE 14








Example















31
32
33
34
35
36
37


















Composition
Natural rubber 1
20
20
20
20
20
20
20


(parts by mass)
Butadiene rubber
20
20
20
20
20
20
20



Polymer 21
60
—
—
—
20
60
—



Polymer 22
—
60
—
—
—
—
—



Polymer 23
—
—
60
—
—
—
—



Polymer 24
—
—
—
60
—
—
—



Polymer 25
—
—
—
—
40
—
—



Polymer 26
—
—
—
—
—
—
—



Polymer 27
—
—
—
—
—
—
—



Polymer 28
—
—
—
—
—
—
—



Polymer 29
—
—
—
—
—
—
60



Silica
75
75
75
75
75
50
75



Silane coupling agent 1
—
—
—
—
—
—
—



Silane coupling agent 3
6
6
6
6
6
4
6



Carbon black 2
5
5
5
5
5
5
5



Oil 1
20
20
20
20
20
5
20



Antioxidant 1
1.5
1.5
1.5
1.5
1.5
1.5
1.5



Stearic acid
2
2
2
2
2
2
2



Zinc oxide 1
2.5
2.5
2.5
2.5
2.5
2.5
2.5



Wax
1
1
1
1
1
1
1



Sulfur 1
2
2
2
2
2
2
2



Vulcanization accelerator 1
1.8
1.8
1.8
1.8
1.8
1.8
1.8



Vulcanization accelerator 2
1.2
1.2
1.2
1.2
1.2
1.2
1.2


Evaluation
Rolling resistance (index)
149
151
153
153
128
150
141



Wet-grip performance (index)
155
156
158
160
136
156
147



Abrasion resistance 2 (index)
135
136
140
142
125
134
130


















TABLE 15








Example
Comparative Example




















38
39
40
41
42
43
52
53
54
55
56
57























Composition
Natural rubber 1
20
20
20
20
20
20
20
20
20
20
20
20


(parts by mass)
Butadiene rubber
20
20
20
20
20
20
20
20
20
20
20
20



Polymer 30
60
—
20
—
—
—
—
—
—
—
—
—



Polymer 31
—
60
40
60
—
—
—
—
—
—
—
—



Polymer 32
—
—
—
—
—
—
—
60
—
—
—
—



Polymer 33
—
—
—
—
—
—
—
—
60
—
—
—



Polymer 34
—
—
—
—
—
—
—
—
—
60
—
—



Polymer 35
—
—
—
—
—
—
60
—
—
—
—
60



Polymer 36
—
—
—
—
60
—
—
—
—
—
—
—



Polymer 37
—
—
—
—
—
60
—
—
—
—
60
—



Silica
75
75
75
50
75
75
75
75
75
75
75
75



Silane coupling agent 1
—
—
—
—
—
—
6
6
6
6
6
—



Silane coupling agent 2
6
6
6
4
6
6
—
—
—
—
—
6



Carbon black 1
5
5
5
5
5
5
5
5
5
5
5
5



Oil 1
20
20
20
5
20
20
20
20
20
20
20
20



Antioxidant 1
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5



Stearic acid
2
2
2
2
2
2
2
2
2
2
2
2



Zinc oxide 1
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5



Wax
1
1
1
1
1
1
1
1
1
1
1
1



Sulfur 1
2
2
2
2
2
2
2
2
2
2
2
2



Vulcanization accelerator 1
1.8
1.8
1.8
1.8
1.8
1.8
1.8
1.8
1.8
1.8
1.8
1.8



Vulcanization accelerator 2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2


Evaluation
tan δ (index)
134
137
133
143
127
130
100
118
122
110
125
104



Rolling resistance (index)
135
137
133
141
125
130
100
109
112
106
118
103



Wet-grip performance (index)
135
139
138
133
128
132
100
115
120
110
125
106



Abrasion resistance 1 (index)
124
128
116
122
115
121
100
110
114
112
113
105


















TABLE 16









Comparative



Example
Example















44
45
46
47
48
49
58


















Composition
Natural rubber 1
20
20
20
20
20
20
20


(parts by mass)
Butadiene rubber
20
20
20
20
20
20
20



Polymer 30
60
—
20
—
—
—
—



Polymer 31
—
60
40
60
—
—
—



Polymer 32
—
—
—
—
—
—
—



Polymer 33
—
—
—
—
—
—
—



Polymer 34
—
—
—
—
—
—
—



Polymer 35
—
—
—
—
—
—
60



Polymer 36
—
—
—
—
60
—
—



Polymer 37
—
—
—
—
—
60
—



Silica
75
75
75
50
75
75
75



Silane coupling agent 1
—
—
—
—
—
—
—



Silane coupling agent 3
6
6
6
4
6
6
6



Carbon black 1
5
5
5
5
5
5
5



Oil 1
20
20
20
5
20
20
20



Antioxidant 1
1.5
1.5
1.5
1.5
1.5
1.5
1.5



Stearic acid
2
2
2
2
2
2
2



Zinc oxide 1
2.5
2.5
2.5
2.5
2.5
2.5
2.5



Wax
1
1
1
1
1
1
1



Sulfur 1
2
2
2
2
2
2
2



Vulcanization accelerator 1
1.8
1.8
1.8
1_8
1.8
1.8
1.8



Vulcanization accelerator 2
1.2
1.2
1.2
1.2
1.2
1.2
1.2


Evaluation
tan δ (index)
136
139
135
145
130
132
105



Rolling resistance (index)
130
132
128
136
120
125
106



Wet-grip performance (index)
132
136
135
130
125
129
103



Abrasion resistance 1 (index)
119
123
111
117
110
116
102


















TABLE 17








Example
Comparative Example



















50
51
52
53
54
59
60
61
62
63
64






















Composition
Natural rubber 1
20
20
20
20
20
20
20
20
20
20
20


(parts by mass)
Butadiene rubber
20
20
20
20
20
20
20
20
20
20
20



Polymer 38
60
—
20
60
—
—
—
—
—
—
60



Polymer 39
—
60
—
—
—
—
—
—
—
—
—



Polymer 40
—
—
40
—
—
—
60
—
—
—
—



Polymer 41
—
—
—
—
—
—
—
60
—
—
—



Polymer 42
—
—
—
—
—
—
—
—
60
—
—



Polymer 43
—
—
—
—
—
60
—
—
—
60
—



Polymer 44
—
—
—
—
60
—
—
—
—
—
—



Silica
75
75
75
50
75
75
75
75
75
75
75



Silane coupling agent 1
—
—
—
—
—
6
6
6
6
—
6



Silane coupling agent 2
6
6
6
4
6
—
—
—
—
6
—



Carbon black 2
5
5
5
5
5
5
5
5
5
5
5



Oil 1
20
20
20
5
20
20
20
20
20
20
20



Antioxidant 1
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5



Stearic acid
2
2
2
2
2
2
2
2
2
2
2



Zinc oxide 1
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5



Wax
1
1
1
1
1
1
1
1
1
1
1



Sulfur 1
2
2
2
2
2
2
2
2
2
2
2



Vulcanization accelerator 1
1.8
1.8
1.8
1.8
1.8
1.8
1.8
1.8
1.8
1.8
1.8



Vulcanization accelerator 2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2
1.2


Evaluation
tan δ (index)
131
141
127
137
132
100
117
118
113
105
115



Rolling resistance (index)
136
140
128
138
123
100
110
112
110
105
112



Wet-grip performance (index)
133
138
137
132
127
100
111
114
110
105
112



Abrasion resistance 1 (index)
122
127
121
120
118
100
115
118
113
100
115


















TABLE 18









Comparative



Example
Example













55
56
65
66
67
















Compo-
Natural rubber 2
20
20
20
20
20


sition
Butadiene rubber
20
20
20
20
20


(parts
Polymer 38
60
—
—
60
—


by
Polymer 39
—
60
—
—
—


mass)
Polymer 40
—
—
60
—
60



Silica
75
75
75
75
75



Silane coupling agent 3
6
6
6
—
—



Silane coupling agent 4
—
—
—
6
6



Carbon black 2
5
5
5
5
5



Oil 2
20
20
20
20
20



Antioxidant 2
1.5
1.5
1.5
1.5
1.5



Stearic acid
2
2
2
2
2



Zinc oxide 2
3
3
3
3
3



Sulfur 2
2
2
2
2
2



Vulcanization accelerator 1
1.8
1.8
1.8
1.8
1.8



Vulcanization accelerator 2
1.2
1.2
1.2
1.2
1.2


Evalu-
tan δ (index)
130
125
120
110
100


ation
Rolling resistance (index)
130
130
120
110
100



Wet-grip performance
130
130
120
100
100



(index)








Abrasion resistance 1
121
116
117
108
100



(index)









As shown in Tables 6 to 18, the fuel economy, wet-grip performance, and abrasion resistance were improved synergistically and achieved at high levels in a balanced manner in the rubber compositions of the examples which contained silica, a mercapto-based coupling agent, and a polymer (polymer 1, 6, 7 to 15, 20, 21 to 24, 29 to 31, 36 to 39, or 44) containing a constituent unit based on a conjugated diene and a constituent unit represented by the above formula (I), and having a terminal modified with a specific compound, as compared with the rubber compositions of the comparative examples.

## Claims

1. A rubber composition, comprising a rubber component, silica, and a silane coupling agent, wherein
the rubber component contains, based on 100% by mass of the rubber component, not less than 5% by mass of a conjugated diene polymer containing a constituent unit based on a conjugated diene and a constituent unit represented by formula (I) below, at least one terminal of the polymer being modified with at least one compound selected from the group consisting of a compound represented by formula (II) below, a compound containing a group represented by formula (III) below, a compound represented by formula (IV) below, a silicon compound containing at least one of a group represented by formula (V) below and a group represented by formula (VI) below, and a compound containing a group represented by formula (VII) below





wherein X1, X2, and X3 each independently represent a group represented by formula (Ia) below, a hydroxy group, a hydrocarbyl group, or a substituted hydrocarbyl group, and at least one of X1, X2, and X3 is a hydroxy group or a group represented by the following formula (Ia):




wherein R1 and R2 each independently represent a C1-6 hydrocarbyl group, a C1-6 substituted hydrocarbyl group, a silyl group, or a substituted silyl group, and R1 and R2 may be bonded to each other to form a cyclic structure together with the nitrogen atom;




wherein n represents an integer of 1 to 10; R11, R12, and R13 each independently represent a C1-4 hydrocarbyl group or a C1-4 hydrocarbyloxy group, and at least one of R11, R12, and R13 is a hydrocarbyloxy group; and A1 represents a nitrogen atom-bearing functional group;




wherein p represents an integer of 0 or 1; T represents a C1-20 hydrocarbylene group or a C1-20 substituted hydrocarbylene group; and A2 represents a nitrogen atom-bearing functional group;




wherein g represents an integer of 1 to 10; R21 represents a hydrogen atom, a C1-6 hydrocarbyl group, or a C1-6 substituted hydrocarbyl group; A3 represents an oxygen atom or the following group: —NR22— where R22 represents a hydrogen atom or a C1-10 hydrocarbyl group; and A4 represents a functional group bearing at least one of a nitrogen atom and an oxygen atom;




wherein w represents an integer of 1 to 11, and A5 represents a nitrogen atom-bearing functional group,
an amount of the silica is 5 to 150 parts by mass per 100 parts by mass of the rubber component, and
the silane coupling agent is at least one compound selected from the group consisting of compounds represented by formula (1) below and compounds containing a linking unit A represented by formula (2) below and a linking unit B represented by formula (3) below





wherein R101 to R103 may be the same as or different from one another, R101 represents a group represented by —O—(R111—O)b—R112 where b R111s may be the same as or different from one another and b R111s each represent a branched or unbranched C1-30 divalent hydrocarbon group; R112 represents a branched or unbranched C1-30 alkyl group, a branched or unbranched C2-30 alkenyl group, a C6-30 aryl group, or a C7-30 aralkyl group, R102 to R103 each represent a branched or unbranched C1-12 alkyl group, a branched or unbranched C1-12 alkoxy group, or a group represented by —O—(R111—O)b—R112, and R104 represents a branched or unbranched C1-6 alkylene group;




wherein R201 represents a hydrogen atom, a halogen atom, a branched or unbranched C1-30 alkyl group, a branched or unbranched C2-30 alkenyl group, a branched or unbranched C2-30 alkynyl group, or the alkyl group in which a terminal hydrogen atom is substituted by a hydroxy group or a carboxyl group; R202 represents a branched or unbranched C1-30 alkylene group, a branched or unbranched C2-30 alkenylene group, or a branched or unbranched C2-30 alkynylene group; and R201 and R202 together may form a cyclic structure.

2. The rubber composition according to claim 1, wherein R1 and R2 in formula (Ia) are C1-6 hydrocarbyl groups.

3. The rubber composition according to claim 1, wherein two of X1, X2, and X3 in formula (I) are selected from a group represented by formula (Ia) and a hydroxy group.

4. The rubber composition according to claim 1, wherein A1 in formula (II) is a group represented by the following formula (IIa):




wherein R14 and R15 each independently represent a C1-6 group optionally containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a silicon atom, R14 and R15 may be bonded to each other to form a cyclic structure together with the nitrogen atom, and R14 and R15 may form a single group bonded to the nitrogen via a double bond.

5. The rubber composition according to claim 1, wherein the group represented by formula (III) is a group represented by the following formula (IIIa):

6. The rubber composition according to claim 5, wherein the compound containing a group represented by formula (III) is at least one compound selected from the group consisting of a compound represented by formula (IIIa-1) below, a compound represented by formula (IIIa-2) below, and a compound represented by formula (IIIa-3) below,




wherein R31 represents a hydrogen atom, a C1-10 hydrocarbyl group, a C1-10 substituted hydrocarbyl group, or a heterocyclic group containing at least one of a nitrogen atom and an oxygen atom as a heteroatom; and R32 and R33 each independently represent a C1-10 group optionally containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a silicon atom, R32 and R33 may be bonded to each other to form a cyclic structure together with the nitrogen atom, and R32 and R33 may form a single group bonded to the nitrogen via a double bond;




wherein e represents an integer of 0 to 10, and R34 and R35 each independently represent a C1-20 hydrocarbyl group or a C1-20 substituted hydrocarbyl group;




wherein f represents an integer of 0 to 10, and R36 represents a C1-20 hydrocarbyl group or a C1-20 substituted hydrocarbyl group.

7. The rubber composition according to claim 1, wherein the compound containing a group represented by formula (III) is a compound represented by the following formula (IIIb-1):




wherein R37 represents a hydrogen atom, a C1-10 hydrocarbyl group, a C1-10 substituted hydrocarbyl group, or a heterocyclic group containing at least one of a nitrogen atom and an oxygen atom as a heteroatom; R38 and R39 each independently represent a C1-10 group optionally containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a silicon atom, R38 and R39 may be bonded to each other to form a cyclic structure together with the nitrogen atom, and R38 and R39 may form a single group bonded to the nitrogen via a double bond; and T represents a C1-20 hydrocarbylene group or a C1-20 substituted hydrocarbylene group.

8. The rubber composition according to claim 7, wherein the compound represented by formula (IIIb-1) is at least one compound selected from the group consisting of a compound represented by formula (IIIb-1-1) below, and a compound represented by formula (IIIb-1-2) below,




wherein r represents an integer of 1 or 2; and Y1 represents a nitrogen atom-bearing functional group that is a substituent on the benzene ring, and when a plurality of Y1's are present, the plurality of Y1's may be the same as or different from one another;




wherein s represents an integer of 1 or 2; t represents an integer of 0 to 2; Y2 and Y3 each represent a nitrogen atom-bearing functional group that is a substituent on the benzene ring, and when a plurality of Y2's are present, the plurality of Y2's may be the same as or different from one another, and when a plurality of Y3's are present, the plurality of Y3's may be the same as or different from one another.

9. The rubber composition according to claim 1, wherein A4 in formula (IV) is a hydroxy group or a group represented by the following formula (IVa):




wherein R23 and R24 each independently represent a C1-6 group optionally containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a silicon atom, R23 and R24 may be bonded to each other to form a cyclic structure together with the nitrogen atom, and R23 and R24 may form a single group bonded to the nitrogen via a double bond.

10. The rubber composition according to claim 1, wherein the silicon compound contains a group represented by the following formula (VIII):




wherein R41, R42, and R43 each independently represent a C1-4 hydrocarbyl group or a C1-4 hydrocarbyloxy group, and at least one of R41, R42, and R43 is a hydrocarbyloxy group.

11. The rubber composition according to claim 1, wherein the silicon compound contains a group represented by the following formula (Va):




wherein h represents an integer of 1 to 10, and R44, R45, and R46 each independently represent a C1-4 hydrocarbyl group or a C1-4 hydrocarbyloxy group, and at least one of R44, R45, and R46 is a hydrocarbyloxy group.

12. The rubber composition according to claim 1, wherein the compound containing a group represented by formula (VII) is a compound represented by the following formula (VII-1):




wherein z represents an integer of 0 to 10; R71 represents a C1-5 hydrocarbyl group; R72, R73, R74 and R75 each independently represent a hydrogen atom, a C1-5 hydrocarbyl group, a C1-5 substituted hydrocarbyl group, or a C1-5 hydrocarbyloxy group, and when a plurality of R72's and a plurality of R73's are present, the plurality of R72's and the plurality of R73's may be the same as or different from one another; and R76 and R77 each independently represent a C1-6 group optionally containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a silicon atom, R76 and R77 may be bonded to each other to form a cyclic structure together with the nitrogen atom, and R76 and R77 may form a single group bonded to the nitrogen via a double bond.

13. The rubber composition according to claim 12, wherein one of R74 and R75 in formula (VII-1) is a hydrogen atom.

14. The rubber composition according to claim 1, wherein the conjugated diene polymer has a vinyl bond content of at least 10 mol % but not more than 80 mol % per 100 mol % of the constituent unit based on a conjugated diene.

15. The rubber composition according to claim 1, comprising at least one of natural rubber and butadiene rubber.

16. The rubber composition according to claim 1, wherein the silica has a nitrogen adsorption specific surface area of 40 to 400 m2/g.

17. The rubber composition according to claim 1, which is for use as a rubber composition for a tread.

18. A pneumatic tire, produced using the rubber composition according to claim 1.