# Patent

## Title
Method for manufacturing rubber composition

## Abstract

The present invention provides a method for producing a rubber composition containing a rubber component (A) of at least one selected from natural rubbers and synthetic dienic rubbers, an inorganic filler (B), a silane coupling agent (C) and an acidic compound (D), wherein the rubber composition is kneaded in multiple stages, and in the final stage of kneading, the acidic compound (D) is added, and the highest temperature of the rubber composition in the final stage of kneading is from 60 to 120° C. The production method enables production of a rubber composition having a low-heat-generation property while successfully preventing the coupling function activity of the silane coupling agent from lowering.

## Background
TECHNICAL FIELD
The present invention relates to a method for producing a rubber composition containing an inorganic filler and having an improved low-heat-generation property.
BACKGROUND ART
Recently, in association with the movement of global regulation of carbon dioxide emission associated with the increase in attraction to environmental concerns, the demand for low fuel consumption by automobiles is increasing. To satisfy the requirement, it is desired to reduce rolling resistance relating to tire performance. Heretofore, as a means for reducing the rolling resistance of tires, a method of optimizing tire structures has been investigated; however, at present, a technique of using a low-heat-generating rubber composition for tires has become employed as the most common method.
For obtaining such a low-heat-generating rubber composition, there is known a method of using an inorganic filler such as silica or the like.
However, in incorporating an inorganic filler such as silica or the like in a rubber composition to prepare an inorganic filler-containing rubber composition, the inorganic filler, especially silica aggregates in the rubber composition (owing to the hydroxyl group in the surface of silica), and therefore, for preventing the aggregation, a silane coupling agent is used.
Accordingly, for successfully solving the above-mentioned problem by incorporation of a silane coupling agent, various trials have been made for increasing the activity of the coupling function of the silane coupling agent.
For example, Patent Reference 1 proposes a rubber composition containing, as basic components, at least (i) one diene elastomer, (ii) a white filler as a reinforcing filler and (iii) an alkoxysilane polysulfide as a coupling agent (white filler/diene elastomer) along with (iv) an enamine and (v) a guanidine derivative.
Patent Reference 2 discloses a rubber composition containing, as basic components, at least (i) one diene elastomer, (ii) a white filler as a reinforcing filler and (iii) an alkoxysilane polysulfide as a coupling agent (white filler/diene elastomer) along with (iv) zinc thiophosphate and (v) a guanidine derivative.
Patent Reference 3 describes a rubber composition containing, as basic components, at least (i) a diene elastomer, (ii) an inorganic filler as a reinforcing filler and (iii) an alkoxysilane polysulfide (PSAS) as an (inorganic filler/diene elastomer) coupling agent, as combined with (iv) an aldimine (R—CH═N—R) and (v) a guanidine derivative.
Further, Patent Reference 4 proposes a rubber composition basically containing at least (i) a diene elastomer, (ii) an inorganic filer as a reinforcing filer and (iii) an alkoxysilane polysulfide as a coupling agent, as combined with (iv) 1,2-dihydropyridine and (v) a guanidine derivative.
However, in these inventions, nothing is taken into consideration relating to kneading conditions.
As a case of increasing the activity of the coupling function of a silane coupling agent in consideration of kneading conditions, there is mentioned Patent Reference 5; however, it is desired to further improve the effect of enhancing the activity of the coupling function of a silane coupling agent.
CITATION LIST
Patent References
Patent Reference 1: JP-T 2002-521515
Patent Reference 2: JP-T 2002-521516
Patent Reference 3: JP-T 2003-530443
Patent Reference 4: JP-T 2003-523472
Patent Reference 5: WO2008/123306
SUMMARY OF THE INVENTION
Problems that the Invention is to Solve
Given the situation as above, an object of the present invention is to provide a method for producing a rubber composition capable of further increasing the activity of the coupling function of a silane coupling agent to thereby successfully produce a low-heat-generating rubber composition.
Means for Solving the Problems
The present inventors have experimentally found that, in order to solve the above-mentioned problems, it is good to add an acidic compound in the final stage of the kneading step, and have completed the present invention.
Specifically, the present invention is a method for producing a rubber composition containing a rubber component (A) of at least one selected from natural rubbers and synthetic dienic rubbers, an inorganic filler (B), a silane coupling agent (C) and an acidic compound (D), wherein the rubber composition is kneaded in multiple stages, and in the final stage of kneading, the acidic compound (D) is added, and the highest temperature of the rubber composition in the final stage of kneading is from 60 to 120° C.
Advantage of the Invention
According to the present invention, there is provided a method for producing a rubber composition capable of further increasing the activity of the coupling function of a silane coupling agent to produce a rubber composition excellent in low-heat-generation property.


MODE FOR CARRYING OUT THE INVENTION
The present invention is described in detail hereinunder.
The method for producing a rubber composition of the present invention is a method for producing a rubber composition containing a rubber component (A) of at least one selected from natural rubbers and synthetic dienic rubbers, an inorganic filler (B), a silane coupling agent (C) and an acidic compound (D) (hereinafter this may be referred to as “acid compound”), wherein the rubber composition is kneaded in multiple stages, and in the final stage of kneading, the acidic compound (D) is added, and the highest temperature of the rubber composition in the final stage of kneading is from 60 to 120° C.
The acidic compound (D) is added in the final stage of kneading to thereby effectively prevent the activity of the coupling function of the silane coupling agent (C) with the rubber component (A) and the inorganic filler (B) from lowering, and, as a result, the activity of the coupling function of the silane coupling agent can be thereby effectively increased.
When the highest temperature of the rubber composition in the final stage of kneading is lower than 60° C., then much time would be taken for dispersion of the chemicals added in the final stage; but when higher than 120° C., then there is a problem in that the rubber composition would partially vulcanize during kneading.
When the highest temperature of the rubber composition in the final stage of kneading is from 80 to 120° C., then it is favorable since the dispersion of the chemicals is secured and the vulcanization does not start during kneading. More preferably, the temperature is from 100 to 120° C. from the viewpoint of enhancing the dispersibility of the chemicals.
In the rubber composition production method of the present invention, it is desirable that the highest temperature of the rubber composition in the first stage of kneading is from 120 to 190° C.
When the temperature is not lower than 120° C., then the coupling reaction could go on sufficiently; and when not higher than 190° C., then the unvulcanizate viscosity could be successfully prevented from increasing greatly and the workability of the rubber composition could better.
In the present invention, the first stage of kneading is the first stage of kneading the rubber component (A), all or a part of the inorganic filler (B) and all or a part of the silane coupling agent (C), but does not include a case of kneading the rubber component (A) and the other filler than the inorganic filler (B) in the initial stage and a case of pre-kneading the rubber component (A) alone.
Preferably, the kneading time for the first stage of kneading is from 10 seconds to 20 minutes, more preferably from 10 seconds to 10 minutes, even more preferably from 30 seconds to 5 minutes.
Also preferably, the kneading time for the final stage of kneading is from 10 seconds to 20 minutes, more preferably from 10 seconds to 10 minutes, even more preferably from 20 seconds to 5 minutes.
When the method goes on from a stage to the next stage, it is desirable that the temperature of the rubber composition is lowered by at least 10° C. than the temperature thereof at the end of kneading in the previous stage, and thereafter the rubber composition is processed in the next stage.
If desired, the method includes an intermediate stage between the first stage and the final stage of kneading.
[Acidic Compound (D)]
The acidic compound (D) for use in the rubber composition production method of the present invention is described in detail.
Not specifically defined, the acidic compound (D) for use in the present invention may be any acidic compound, but is preferably a mono- or poly-organic acid, or a partial ester of a poly-organic acid, or a metal salt of a mono- or poly-organic acid.
The mono-organic acid includes saturated fatty acids and unsaturated fatty acids such as stearic acid, palmitic acid, myristic acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, capric acid, pelargonic acid, caprylic acid, enanthic acid, caproic acid, oleic acid, vaccenic acid, linolic acid, linolenic acid, nervonic acid, etc.; as well as resin acids such as rosin acids (abietic acid, neoabietic acid, dehydroabietic acid, paralustrinic acid, pimaric acid, isopimaric acid, etc.), modified rosin acids, etc.
The poly-organic acid includes unsaturated dicarboxylic acids or saturated dicarboxylic acids, as well as their partial esters (for example, monoesters) or acid anhydrides, etc.
The unsaturated dicarboxylic acid includes maleic acid, fumaric acid, citraconic acid, mesaconic acid, 2-pentene diacid, methylenesuccinic acid (itaconic acid), allylmalonic acid, isopropylidenesuccinic acid, 2,4-hexadiene diacid, acetylene-dicarboxylic acid, etc.; and the saturated dicarboxylic acid includes oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, tridecene diacid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, tetramethylsuccinic acid, etc.
As the partial ester, preferably mentioned are (poly)esters of an unsaturated carboxylic acid and an oxycarboxylic acid; esters having a carboxyl group at both ends thereof, of a diol such as ethylene glycol, hexanediol, cyclohexanedimethanol or the like and an unsaturated dicarboxylic acid such as maleic acid, fumaric acid, itaconic acid or the like; etc.
The oxycarboxylic acid includes malic acid, tartaric acid, citric acid, etc.
The (poly)ester of an unsaturated carboxylic acid and an oxycarboxylic acid is preferably maleic acid monoesters, and more preferably monomalate of maleic acid.
The ester having a carboxyl group at both ends thereof, of a diol and an unsaturated dicarboxylic acid includes polyalkylene glycol/maleic acid polyester terminated with a carboxylic acid at both ends, such as polybutylene maleate having a carboxyl group at both ends thereof, poly(PEG200) maleate having a carboxyl group at both ends thereof, etc.; polybutylene adipate maleate having a carboxyl group at both ends thereof, etc.
In the present invention, the acidic compound (D) is preferably a fatty acid, more preferably a fatty acid having from 4 to 30 carbon atoms, even more preferably a fatty acid having from 6 to 26 carbon atoms. The fatty acid may be any of a saturated fatty acid or an unsaturated fatty acid, but is preferably a saturated fatty acid, more preferably stearic acid.
In the present invention, the acidic compound (D) must fully exhibit the function thereof as a vulcanization activator, and therefore the acidic compound (D) to be added in the final stage of kneading is preferably stearic acid.
[Silane Coupling Agent (C)]
The silane coupling agent (C) for use in the rubber composition production method of the present invention is preferably at least one compound selected from a group consisting of compounds of the following general formulae (I) to (IV).
Using the silane coupling agent (C) of the type, the rubber composition in the invention is excellent in workability thereof and can give pneumatic tires having good abrasion resistance.
The general formulae (I) to (IV) are sequentially described below.

[Chemical Formula 1]

(R1O)3-p(R2)pSi—R3—Sa—R3—Si(OR1)3-r(R2)r  (I)

wherein multiple R1's may be the same or different, each representing a linear, cyclic or branched alkyl group having from 1 to 8 carbon atoms, a linear or branched alkoxylalkyl group having from 2 to 8 carbon atoms, or a hydrogen atom; multiple R2's may be the same or different, each representing a linear, cyclic or branched alkyl group having from 1 to 8 carbon atoms; multiple R3's may be the same or different, each representing a linear or branched alkylene group having from 1 to 8 carbon atoms; a indicates from 2 to 6 as a mean value; p and r may be the same or different, each indicating from 0 to 3 as a mean value, provided that both p and r are not 3 at the same time.

Specific examples of the silane coupling agent (C) represented by the above-mentioned general formula (I) include bis(3-triethoxysilylpropyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(3-methyldimethoxysilylpropyl)tetrasulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(3-triethoxysilylpropyl)disulfide, bis(3-trimethoxysilylpropyl)disulfide, bis(3-methyldimethoxysilylpropyl)disulfide, bis(2-triethoxysilylethyl)disulfide, bis(3-triethoxysilylpropyl)trisulfide, bis(3-trimethoxysilylpropyl)trisulfide, bis(3-methyldimethoxysilylpropyl)trisulfide, bis(2-triethoxysilylethyl)trisulfide, bis(3-monoethoxydimethylsilylpropyl)tetrasulfide, bis(3-monoethoxydimethylsilylpropyl)trisulfide, bis(3-monoethoxydimethylsilylpropyl)disulfide, bis(3-monomethoxydimethylsilylpropyl)tetrasulfide, bis(3-monomethoxydimethylsilylpropyl)trisulfide, bis(3-monomethoxydimethylsilylpropyl)disulfide, bis(2-monoethoxydimethylsilylethyl)tetrasulfide, bis(2-monoethoxydimethylsilylethyl)trisulfide, bis(2-monoethoxydimethylsilylethyl)disulfide.




wherein R4 represents a monovalent group selected from —Cl, —Br, R9O—, R9C(═O)O—, R9R10C═NO—, R9R10CNO—, R9R10N—, and —(OSiR9R10)h(OSiR9R10R11) (where R9, R10 and R11 each represents a hydrogen atom or a monovalent hydrocarbon group having from 1 to 18 carbon atoms; and h indicates from 1 to 4 as a mean value); R5 represents R4, a hydrogen atom, or a hydrocarbon group having from 1 to 18 carbon atoms; R6 represents R4, R5, a hydrogen atom, or a group —[O(R12O)j]0.5 (where R12 represents an alkylene group having from 1 to 18 carbon atoms; and j indicates an integer of from 1 to 4); R7 represents a divalent hydrocarbon group having from 1 to 18 carbon atoms; R8 represents a monovalent hydrocarbon group having from 1 to 18 carbon atoms; x, y and z each indicates a number satisfying the relationship of x+y+2z=3, 0≦x≦3, 0≦y≦2, 0≦z≦1.

In the general formula (II), R8, R9, R10 and R11 may be the same or different, each preferably representing a linear, cyclic or branched alkyl, alkenyl, aryl or aralkyl group having from 1 to 18 carbon atoms. In case where R5 is a monovalent hydrocarbon group having from 1 to 18 carbon atoms, the group is preferably a linear, cyclic or branched alkyl, alkenyl, aryl or aralkyl group. Preferably, R12 is a linear, cyclic or branched alkylene group, and is more preferably a linear one. R7 is, for example, an alkylene group having from 1 to 18 carbon atoms, an alkenylene group having from 2 to 18 carbon atoms, a cycloalkylene group having from 5 to 18 carbon atoms, a cycloalkylalkylene group having from 6 to 18 carbon atoms, an arylene group having from 6 to 18 carbon atoms, or an aralkylene group having from 7 to 18 carbon atoms. The alkylene group and the alkenylene group may be linear or branched; and the cycloalkylene group, the cycloalkylalkylene group, the arylene group and the aralkylene group may have a substituent such as a lower alkyl group or the like on the ring thereof. Preferably, R7 is an alkylene group having from 1 to 6 carbon atoms, more preferably a linear alkylene group, for example, a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group or a hexamethylene group.
Specific examples of the monovalent hydrocarbon group having from 1 to 18 carbon atoms of R5, R8, R9, R10 and R11 in the general formula (II) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, a cyclopentyl group, a cyclohexyl group, a vinyl group, a propenyl group, an allyl group, a hexenyl group, an octenyl group, a cyclopentenyl group, a cyclohexenyl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a benzyl group, a phenethyl group, a naphthylmethyl group, etc.
Examples of R12 in the general formula (II) include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, a decamethylene group, a dodecamethylene group, etc.
Specific examples of the silane coupling agent (C) represented by the general formula (II) include 3-hexanoylthiopropyltriethoxysilane, 3-octanoylthiopropyltriethoxysilane, 3-decanoylthiopropyltriethoxysilane, 3-lauroylthiopropyltriethoxysilane, 2-hexanoylthioethyltriethoxysilane, 2-octanoylthioethyltriethoxysilane, 2-decanoylthioethyltriethoxysilane, 2-lauroylthioethyltriethoxysilane, 3-hexanoylthiopropyltrimethoxysilane, 3-octanoylthiopropyltrimethoxysilane, 3-decanoylthiopropyltrimethoxysilane, 3-lauroylthiopropyltrimethoxysilane, 2-hexanoylthioethyltrimethoxysilane, 2-octanoylthioethyltrimethoxysilane, 2-decanoylthioethyltrimethoxysilane, 2-lauroylthioethyltrimethoxysilane, etc. Of those, especially preferred is 3-octanoylthiopropyltriethoxysilane (General Electric Silicones' trade name NXT Silane).

[Chemical Formula 3]

(R13O)3-s(R14)sSi—R15—Sk—R16—Sk—R15—Si(OR13)3-t(R14)t  (III)

wherein multiple R13's may be the same or different, each representing a linear, cyclic or branched alkyl group having from 1 to 8 carbon atoms, a linear or branched alkoxylalkyl group having from 2 to 8 carbon atoms, or a hydrogen atom; multiple R14's may be the same or different, each representing a linear, cyclic or branched alkyl group having from 1 to 8 carbon atoms; multiple R15's may be the same or different, each representing a linear or branched alkylene group having from 1 to 8 carbon atoms; R16 represents a divalent group of a general formula (—S—R17—S—), (—R18—Sm1—R19—) or (—R20—Sm2—R21—Sm3—R22—) (where R17 to R22 each represents a divalent hydrocarbon group, a divalent aromatic group or a divalent organic group containing a hetero element except sulfur and oxygen, having from 1 to 20 carbon atoms; m1, m2 and m3 may be the same or different, each indicating from 1 to less than 4 as a mean value); multiple k's may be the same or different, each indicating from 1 to 6 as a mean value; s and t each indicates from 0 to 3 as a mean value, provided that both s and t are not 3 at the same time.

Preferred examples of the silane coupling agent (C) represented by the above-mentioned general formula (III) are compounds represented by an average compositional formula (CH3CH2O)3Si—(CH2)3—S2—(CH2)6—S2—(CH2)3—Si(OCH2CH3)3, an average compositional formula (CH3CH2O)3Si—(CH2)3—S2—(CH2)10—S2—(CH2)3—Si(OCH2CH3)3, an average compositional formula (CH3CH2O)3Si—(CH2)3—S3—(CH2)6—S6—(CH2)3—Si(OCH2CH3)3, an average compositional formula (CH3CH2O)3Si—(CH2)3—S4—(CH2)6—S4—(CH2)3—Si(OCH2CH3)3—Si(OCH2CH3)3, an average compositional formula (CH3CH2O)3Si—(CH2)3—S—(CH2)6—S2—(CH2)6—S—(CH2)3—Si(OCH2CH3)3, an average compositional formula (CH3CH2O)3Si—(CH2)3—S—(CH2)6—S2.5—(CH2)6—S—(CH2)3—Si(OCH2CH3)3, an average compositional formula (CH3CH2O)3Si—(CH2)3—S—(CH2)6—S3—(CH2)6—S—(CH2)3—Si(OCH2CH3)3, an average compositional formula (CH3CH2O)3Si—(CH2)3—S—(CH2)6—S4—(CH2)6—S—(CH2)3—Si(OCH2CH3)3, an average compositional formula (CH3CH2O)3S—(CH2)3—S—(CH2)10—S2—(CH2)10—S—(CH2)3—Si(OCH2CH3)3, an average compositional formula (CH3CH2O)3Si—(CH2)3—S4—(CH2)6—S4—(CH2)6—S4—(CH2)3—Si(OCH2CH3)3, an average compositional formula (CH3CH2O)3Si—(CH2)3—S2—(CH2)6—S2—(CH2)6—S2—(CH2)3—Si(OCH2CH3)3, an average compositional formula (CH3CH2O)3Si—(CH2)3—S—(CH2)6—S2—(CH2)6—S2—(CH2)6—S—(CH2)3—Si(OCH2CH3)3, etc.




wherein R23 represents a linear, branched or cyclic alkyl group having from 1 to 20 carbon atoms; multiple G's may be the same or different, each representing an alkanediyl group or an alkenediyl group having from 1 to 9 carbon atoms; multiple Za's may be the same or different, each representing a functional group capable of bonding to the two silicon atoms and selected from [—O—]0.5, [—O-G-]0.5 and [—O-G-O—]0.5; multiple Zb's may be the same or different, each representing a functional group capable of bonding to the two silicon atoms and represented by [—O-G-O—]0.5; multiple Zc's may be the same or different, each representing a functional group selected from —Cl, —Br, —ORa, RaC(═O)O—, RaRbC═NO—, RaRbN—, Ra— and HO-G-O— (where G is the same as above); Ra and Rb each represents a linear, branched or cyclic alkyl group having from 1 to 20 carbon atoms; m, n, u, v and w each are 1≦m≦20, 0≦n≦20, 0≦u≦3, 0≦v≦2, 0≦w≦1, and (u/2)+v+2w is 2 or 3; in case where the formula has multiple A's, then Zau, Zbv and Zcw may be the same or different in those multiple A's; in case where the formula has multiple B's, then Zau, Zbv and Zcw may be the same or different in those multiple B's.

Specific examples of the silane coupling agent (C) represented by the general formula (IV) include the following chemical formula (V), chemical formula (VI) and chemical formula (VII):




In the formula, L each independently represents an alkanediyl group or an alkenediyl group having from 1 to 9 carbon atoms; and x=m and y=n.
As the silane coupling agent represented by the chemical formula (V), a commercial product is available as “NXT Low-V Silane”, a trade name by Momentive Performance Materials.
As the silane coupling agent represented by the chemical formula (VI), a commercial product is available as “NXT Ultra Low-V Silane”, a trade name by Momentive Performance Materials.
Further, as the silane coupling agent represented by the chemical formula (VII), there is mentioned a commercial product of “NXT-Z”, a trade name by Momentive Performance Materials.
The silane coupling agent represented by the general formula (II), the chemical formula (V) or the chemical formula (VI) has a protected mercapto group, and is therefore effective for preventing initial scorching in the processing process before the vulcanization step, and accordingly, the processability thereof is good.
In the silane coupling agent represented by the general formula (V), (VI) or (VII), the carbon number of the alkoxysilane is large, and therefore the amount of the volatile compound VOC (especially alcohol) to be generated from the agent is small, and accordingly, the agent is favorable in point of working environment. Further, the silane coupling agent of the chemical formula (VII) provides a low-heat-generation property as tire performance, and is therefore more preferred.
With respect to the silane coupling agent (C) of the present invention, the compounds represented by the above-mentioned general formula (I), among the compounds represented by the general formulae (I) to (IV), are especially preferred as having high reactivity.
In the present invention, one alone or two or more different types of the silane coupling agents (C) may be used either singly or as combined.
Regarding the amount of the silane coupling agent (C) to be in the rubber composition in the present invention, preferably, the ratio by mass of {silane coupling agent (C)/inorganic filler (B)} is from (1/100) to (20/100). When the ratio is at least (1/100), then the effect of enhancing the low-heat-generation property of the rubber composition can be more successfully exhibited; and when at most (20/100), the cost of the rubber composition is low and the economic potential thereof increases. Further, the ratio by mass is more preferably from (3/100) to (20/100), even more preferably from (4/100) to (10/100).
[Vulcanization Promoter (E)]
In the production method of the present invention, it is desirable to add at least one vulcanization promoter (E) selected from guanidines, sulfenamides, thiazoles, thiurams, dithiocarbamate salts, thioureas and xanthate salts in the stage before the final stage of kneading for enhancing the reactivity of the coupling agent.
The vulcanization promoter (E) is described in detail.
The guanidines for use in the rubber composition production method of the present invention include 1,3-diphenylguanidine, 1,3-di-o-tolylguanidine, 1-o-tolylbiguanide, dicatechol borate di-o-tolylguanidine salt, 1,3-di-o-cumenylguanidine, 1,3-di-o-biphenylguanidine, 1,3-di-o-cumenyl-2-propionylguanidine, etc. Preferred are 1,3-diphenylguanidine, 1,3-di-o-tolylguanidine and 1-o-tolylbiguanide as having high reactivity.
The sulfenamides for use in the rubber composition production method of the present invention include N-cyclohexyl-2-benzothiazolylsulfenamide, N,N-dicyclohexyl-2-benzothiazolylsulfenamide, N-tert-butyl-2-benzothiazolylsulfenamide, N-oxydiethylene-2-benzothiazolylsulfenamide, N-methyl-2-benzothiazolylsulfenamide, N-ethyl-2-benzothiazolylsulfenamide, N-propyl-2-benzothiazolylsulfenamide, N-butyl-2-benzothiazolylsulfenamide, N-pentyl-2-benzothiazolylsulfenamide, N-hexyl-2-benzothiazolylsulfenamide, N-pentyl-2-benzothiazolylsulfenamide, N-octyl-2-benzothiazolylsulfenamide, N-2-ethylhexyl-2-benzothiazolylsulfenamide, N-decyl-2-benzothiazolylsulfenamide, N-dodecyl-2-benzothiazolylsulfenamide, N-stearyl-2-benzothiazolylsulenamide, N,N-dimethyl-2-benzothiazolylsulenamide, N,N-diethyl-2-benzothiazolylsulenamide, N,N-dipropyl-2-benzothiazolylsulenamide, N,N-dibutyl-2-benzothiazolylsulenamide, N,N-dipentyl-2-benzothiazolylsulenamide, N,N-dihexyl-2-benzothiazolylsulenamide, N,N-dipentyl-2-benzothiazolylsulenamide, N,N-dioctyl-2-benzothiazolylsulenamide, N,N-di-2-ethylhexylbenzothiazolylsulfenamide, N-decyl-2-benzothiazolylsulenamide, N,N-didodecyl-2-benzothiazolylsulenamide, N,N-distearyl-2-benzothiazolylsulenamide, etc. Of those, preferred are N-cyclohexyl-2-benzothiazolylsulenamide and N-tert-butyl-2-benzothiazolylsulenamide, as having high reactivity.
The thiazoles for use in the rubber composition production method of the present invention include 2-mercaptobenzothiazole, di-2-benzothiazolyl disulfide, 2-mercaptobenzothiazole zinc salt, 2-mercaptobenzothiazole cyclohexylamine salt, 2-(N,N-diethylthiocarbamoylthio)benzothiazole, 2-(4′-morpholinodithio)benzothiazole, 4-methyl-2-mercaptobenzothiazole, di-(4-methyl-2-benzothiazolyl)disulfide, 5-chloro-2-mercaptobenzothiazole, 2-mercaptobenzothiazole sodium, 2-mercapto-6-nitrobenzothiazole, 2-mercapto-naphtho[1,2-d]thiazole, 2-mercapto-5-methoxybenzothiazole, 6-amino-2-mercaptobenzothiazole, etc. Of those, preferred are 2-mercaptobenzothiazole and di-2-benzothiazolyl disulfide, as having high reactivity.
The thiurams for use in the rubber composition production method of the present invention include tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrapropylthiuram disulfide, tetraisopropylthiuram disulfide, tetrabutylthiuram disulfide, tetrapentylthiuram disulfide, tetrahexylthiuram disulfide, tetraheptylthiuram disulfide, tetraoctylthiuram disulfide, tetranonylthiuram disulfide, tetradecylthiuram disulfide, tetradodecylthiuram disulfide, tetrastearylthiuram disulfide, tetrabenzylthiuram disulfide, tetrakis(2-ethylhexyl)thiuram disulfide, tetramethylthiuram monosulfide, tetraethylthiuram monosulfide, tetrapropylthiuram monosulfide, tetraisopropylthiuram monosulfide, tetrabutylthiuram monosulfide, tetrapentylthiuram monosulfide, tetrahexylthiuram monosulfide, tetraheptylthiuram monosulfide, tetraoctylthiurammonosulfide, tetranonylthiurammonosulfide, tetradecylthiuram monosulfide, tetradodecylthiuram monosulfide, tetrastearylthiuram monosulfide, tetrabenzylthiuram monosulfide, dipentamethylthiuram tetrasulfide, etc. Of those, preferred are tetrakis(2-ethylhexyl)thiuram disulfide and tetrabenzylthiuram disulfide, as having high reactivity.
The thioureas for use in the rubber composition production method of the present invention include N,N′-diphenylthiourea, trimethylthiourea, N,N′-diethylthiourea, N,N′-dimethylthiourea, N,N′-dibutylthiourea, ethylenethiourea, N,N′-diisopropylthiourea, N,N′-dicyclohexylthiourea, 1,3-di(o-tolyl)thiourea, 1,3-di(p-tolyl)thiourea, 1,1-diphenyl-2-thiourea, 2,5-dithiobiurea, guanylthiourea, 1-(1-naphthyl)-2-thiourea, 1-phenyl-2-thiourea, p-tolylthiourea, o-tolylthiourea, etc. Of those, preferred are N,N′-diethylthiourea, trimethylthiourea, N,N′-diphenylthiourea and N,N′-dimethylthiourea, as having high reactivity.
The dithiocarbamate salts for use in the rubber composition production method of the present invention include zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dipropyldithiocarbamate, zinc diisopropyldithiocarbamate, zinc dibutyldithiocarbamate, zinc dipentyldithiocarbamate, zinc dihexyldithiocarbamate, zinc diheptyldithiocarbamate, zinc dioctyldithiocarbamate, zinc di(2-ethylhexyl)dithiocarbamate, zinc didecyldithiocarbamate, zinc didodecyldithiocarbamate, zinc N-pent amethylenedithiocarbamate, zinc N-ethyl-N-phenyldithiocarbamate, zinc dibenzyldithiocarbamate, copper dimethyldithiocarbamate, copper diethyldithiocarbamate, copper dipropyldithiocarbamate, copper diisopropyldithiocarbamate, copper dibutyldithiocarbamate, copper dipentyldithiocarbamate, copper dihexyldithiocarbamate, copper diheptyldithiocarbamate, copper dioctyldithiocarbamate, copper di(2-ethylhexyl)dithiocarbamate, copper didecyldithiocarbamate, copper didodecyldithiocarbamate, copper N-pent amethylenedithiocarbamate, copper dibenzyldithiocarbamate, sodium dimethyldithiocarbamate, sodium diethyldithiocarbamate, sodium dipropyldithiocarbamate, sodium diisopropyldithiocarbamate, sodium dibutyldithiocarbamate, sodium dipentyldithiocarbamate, sodium dihexyldithiocarbamate, sodium diheptyldithiocarbamate, sodium dioctyldithiocarbamate, sodium di(2-ethylhexyl)dithiocarbamate, sodium didecyldithiocarbamate, sodium didodecyldithiocarbamate, sodium N-pentamethylenedithiocarbamate, sodium dibenzyldithiocarbamate, ferric dimethyldithiocarbamate, ferric diethyldithiocarbamate, ferric dipropyldithiocarbamate, ferric diisopropyldithiocarbamate, ferric dibutyldithiocarbamate, ferric dipentyldithiocarbamate, ferric dihexyldithiocarbamate, ferric diheptyldithiocarbamate, ferric dioctyldithiocarbamate, ferric di(2-ethylhexyl)dithiocarbamate, ferric didecyldithiocarbamate, ferric didodecyldithiocarbamate, ferric N-pentamethylenedithiocarbamate, ferric dibenzyldithiocarbamate, etc. Of those, preferred are zinc dibenzyldithiocarbamate, zinc N-ethyl-N-phenyldithiocarbamate, zinc dimethyldithiocarbamate and copper dimethyldithiocarbamate, as having high reactivity.
The xanthate salts for use in the rubber composition production method of the present invention include zinc methylxanthate, zinc ethylxanthate, zinc propylxanthate, zinc isopropylxanthate, zinc butylxanthate, zinc pentylxanthate, zinc hexylxanthate, zinc heptylxanthate, zinc octylxanthate, zinc 2-ethylhexylxanthate, zinc decylxanthate, zinc dodecylxanthate, potassium methylxanthate, potassium ethylxanthate, potassium propylxanthate, potassium isopropylxanthate, potassium butylxanthate, potassium pentylxanthate, potassium hexylxanthate, potassium heptylxanthate, potassium octylxanthate, potassium 2-ethylhexylxanthate, potassium decylxanthate, potassium dodecylxanthate, sodium methylxanthate, sodium ethylxanthate, sodium propylxanthate, sodium isopropylxanthate, sodium butylxanthate, sodium pentylxanthate, sodium hexylxanthate, sodium heptylxanthate, sodium octylxanthate, sodium 2-ethylhexylxanthate, sodium decylxanthate, sodium dodecylxanthate, etc. Of those, preferred is zinc isopropylxanthate, as having high reactivity.
In the rubber composition production method of the present invention, it is desirable that the rubber component (A), all or a part of the inorganic filler (B) and all or a part of the silane coupling agent (C) are kneaded in the first stage of kneading, and on the way of the first stage, the vulcanization promoter (E) is added and further kneaded, as the reactivity of the silane coupling agent can be enhanced in the embodiment.
It is also desirable that the rubber component (A), all or a part of the inorganic filler (B) and all or a part of the silane coupling agent (C) are kneaded in the first stage of kneading, and the vulcanization promoter (E) is added and kneaded in the second stage of kneading, for the same reason as above.
In case where the vulcanization promoter (E) is added in the first stage of kneading in the present invention, preferably, the number of molecules (molar number) of the vulcanization promoter (E) in the rubber composition is from 0.1 to 1.0 times the number of molecules (molar number) of the silane coupling agent (C). When the molar number is at least 0.1 times, then the silane coupling agent (C) can be fully activated; and when at most 1.0 time, then the agent would not have any significant influence on the vulcanization speed. More preferably, the number of molecules (molar number) of the vulcanization promoter (E) is from 0.2 to 0.6 times the number of molecules (molar number) of the silane coupling agent (C).
The vulcanization promoter (E) may act also as a promoter for sulfur vulcanization, and if desired, a suitable amount thereof may be incorporated also in the final stage of kneading. In case where a vulcanization promoter is incorporated in the final stage of kneading, the agent is not limited to the vulcanization promoter (E) of the present invention but may be any known vulcanization promoter.
[Rubber Component (A)]
As the synthetic dienic rubber of the rubber component (A) for use in the rubber composition production method of the present invention, usable here are styrene-butadiene copolymer rubber (SBR), polybutadiene rubber (BR), polyisoprene rubber (IR), butyl rubber (IIR), ethylene-propylene-diene tercopolymer rubber (EPDM), etc. One or more different types of natural rubbers and synthetic dienic rubbers may be used here either singly or as combined.
In the rubber composition production method of the present invention, it is desirable that a synthetic rubber produced according to a solution polymerization method (for example, solution-polymerized SBR, solution-polymerized BR, etc.) accounts for at least 70% by mass of the rubber component (A), more preferably at least 80% by mass, even more preferably at least 90% by mass. Especially preferably, the rubber component (A) is entirely a synthetic rubber produced according to a solution polymerization method. This is in order to reduce the influence of the acidic compound (D) derived from the emulsifier contained in the synthetic rubber produced according to an emulsion polymerization method.
[Inorganic Filler (B)]
As the inorganic filler (B) for use in the rubber composition production method of the present invention, usable are silica and an inorganic compound represented by the following general formula (VIII):

dM1.xSiOy.zH2O  (VIII)

In the general formula (VIII), M1 represents at least one selected from a metal selected from aluminium, magnesium, titanium, calcium and zirconium, and oxides or hydroxides of those metals, their hydrates, or carbonates of the metals; d, x, y and z each indicates an integer of from 1 to 5, an integer of from 0 to 10, an integer of from 2 to 5, and an integer of from 0 to 10, respectively.
In the general formula (VIII), when x and z are both 0, then the inorganic compound is at least one metal selected from aluminium, magnesium, titanium, calcium and zirconium, or a metal oxide or metal hydroxide thereof.
In the present invention, silica is preferred as the inorganic filler (B) from the viewpoint of satisfying both low rolling property and abrasion resistance. As silica, any commercially-available one is usable here; and above all, preferred is wet silica, dry silica or colloidal silica, and more preferred is wet silica. Preferably, the BET specific surface area (as measured according to ISO 5794/1) of silica for use herein is from 40 to 350 m2/g. Silica of which the BET specific surface area falls within the range is advantageous in that it satisfies both rubber-reinforcing capability and dispersibility in rubber component. From this viewpoint, silica of which the BET specific surface area falls within a range of from 80 to 350 m2/g is more preferred; silica of which the BET specific surface area falls within a range of more than 130 m2/g to 350 m2/g is even more preferred; and silica of which the BET specific surface area falls within a range of from 135 to 350 m2/g is even more preferred. As silicas of those types, usable here are commercial products of Tosoh Silica's trade names “Nipseal AQ” (BET specific surface area=205 m2/g) and “Nipseal KQ” (BET specific surface area=240 m2/g); Degussa's trade name “Ultrasil VN3” (BET specific surface area=175 m2/g), etc.
As the inorganic compound represented by the general formula (VIII), usable here are alumina (Al2O3) such as γ-alumina, α-alumina, etc.; alumina monohydrate (Al2O3.H2O) such as boehmite, diaspore, etc.; aluminium hydroxide [Al(OH)3] such as gypsite, bayerite, etc.; aluminium carbonate [Al2(CO3)2], magnesium hydroxide [Mg(OH)2], magnesium oxide (MgO), magnesium carbonate (MgCO3), talc (3MgO.4SiO2.H2O), attapulgite (5MgO.8SiO2.9H2O), titanium white (TiO2), titanium black (TiO2n-1) calcium oxide (CaO), calcium hydroxide [Ca(OH)2], aluminium magnesium oxide (MgO.Al2O3) clay (Al2O3.2SiO2), kaolin (Al2O3.2SiO2.2H2O), pyrophyllite (Al2O3.4SiO2.H2O), bentonite (Al2O3.4SiO2.2H2O), aluminium silicate (Al2SiO5, Al4.3SiO4.5H2O, etc.), magnesium silicate (Mg2SiO4, MgSiO3, etc.), calcium silicate (Ca2.SiO4, etc.), aluminium calcium silicate (Al2O3.CaO.2SiO2, etc.), magnesium calcium silicate (CaMgSiO4), calcium carbonate (CaCO3), zirconium oxide (ZrO2), zirconium hydroxide [ZrO(OH)2.nH2O], zirconium carbonate [Zr(CO3)2]; as well as crystalline aluminosilicate salts containing a charge-correcting hydrogen, alkali metal or alkaline earth metal such as various types of zeolite. Preferably, M3 in the general formula (5) is at least one selected from aluminium metal, aluminium oxide or hydroxide, and their hydrates, or aluminium carbonate.
One or more different types of the inorganic compounds of the general formula (VIII) may be used here either singly or as combined. The mean particle size of the inorganic compound is preferably within a range of from 0.01 to 10 μm from the viewpoint of the balance of kneading workability, abrasion resistance and wet grip performance, and more preferably within a range of from 0.05 to 5 μm.
As the inorganic filler (B) in the present invention, silica alone may be used, or silica as combined with at least one inorganic compound of the general formula (VIII) may be used.
If desired, the filler in the rubber composition in the present invention may contain carbon black in addition to the above-mentioned inorganic filler (B). Containing carbon black, the filler enjoys the effect of lowering the electric resistance of the rubber composition to thereby prevent static electrification thereof. Carbon black for use herein is not specifically defined. For example, preferred is use of high, middle or low-structure SAF, ISAF, IISAF, N339, HAF, FEF, GPF, SRF-grade carbon black; and more preferred is use of SAF, ISAF, IISAF, N339, HAF, FEF-grade carbon black. Preferably, the nitrogen adsorption specific surface area (N2SA, as measured according to JIS K 6217-2:2001) of such carbon black is from 30 to 250 m2/g. One alone or two or more different types of such carbon black may be used here either singly or as combined. In the present invention, the inorganic filler (B) does not contain carbon black.
The inorganic filler (B) in the rubber composition in the present invention is preferably in an amount of from 20 to 120 parts by mass relative to 100 parts by mass of the rubber component (A). When the amount is at least 20 parts by mass, then it is favorable from the viewpoint of securing wet performance; and when at most 120 parts by mass, then it is favorable from the viewpoint of reducing rolling resistance. Further, the amount is more preferably from 30 to 100 parts by mass.
Also preferably, the inorganic filler (B) or a filler comprising the inorganic filler (B) and carbon black or the like in the rubber composition in the present invention is in an amount of from 20 to 150 parts by mass relative to 100 parts by mass of the rubber component (A). When the amount is at least 20 parts by mass, then it is favorable from the viewpoint of enhancing rubber composition reinforcing capability; and when at most 150 parts by mass, then it is favorable from the viewpoint of reducing rolling resistance.
In the filler, preferably, the amount of the inorganic filler (B) is at least 30% by mass from the viewpoint of satisfying both wet performance and reduced rolling resistance, more preferably at least 40% by mass, and even more preferably at least 70% by mass.
In case where silica is used as the inorganic filler (B), it is desirable that silica accounts for at least 30% by mass of the filler, more preferably at least 35% by mass.
In the rubber composition production method of the present invention, various additives that are generally incorporated in a rubber composition, for example, a vulcanization activator such as zinc flower or the like, an antiaging agent and others may be optionally added and kneaded in the first stage or the final stage of kneading, or in the intermediate stage between the first stage and the final stage.
As the kneading apparatus for the production method of the present invention, usable is any of a Banbury mixer, a roll, an intensive mixer, a kneader, a double-screw extruder, etc.
EXAMPLES
The present invention is described in more detail with reference to the following Examples; however, the present invention is not limited at all by the following Examples.
Low-heat-generating property (tan δ index) was evaluated according to the following method.
Low-Heat-Generation Property (Tan δ Index)
Using a viscoelasticity measuring device (by Rheometric), tan δ of the rubber composition sample was measured at a temperature of 60° C., at a dynamic strain of 5% and at a frequency of 15 Hz. Based on the reciprocal of tan δ in Comparative Example 1, 23, 30, 38, 46 or 54, as referred to 100, the data were expressed as index indication according to the following formula. The samples having a larger index value have a better low-heat-generation property and have a smaller hysteresis loss.

Low-Heat-Generation Index={(tan δ of vulcanized rubber composition of Comparative Example 1, 23, 30, 38, 46 or 54)/(tan δ of vulcanized rubber composition tested)}×100

Production Example 1
Production of Silane Coupling Agent Represented by Average Compositional Formula (CH3CH2O)3Si—(CH2)3—S—(CH2)6—S2.5—(CH2)6—S—(CH2)3—Si(OCH2CH3)3 
119 g (0.5 mol) of 3-mercaptopropyltriethoxysilane was put into a 2-liter separable flask equipped with a nitrogen-introducing duct, a thermometer, a Dimroth condenser and a dropping funnel, and with stirring, 151.2 g (0.45 mol) of an ethanol solution of sodium ethoxide having an effective ingredient concentration of 20% by mass was added thereto. Subsequently, this was heated up to 80° C. and stirred for 3 hours. Afterwards, this was cooled and transferred into a dropping funnel.
Next, 69.75 g (0.45 mol) of 1,6-dichlorohexane was put into the same separable flask as above, heated up to 80° C., and the reaction product of 3-mercaptopropyltriethoxysilane and sodium ethoxide was slowly and dropwise added thereto. After the addition, this was stirred for 5 hours at 80° C. Subsequently, this was cooled, and salt was separated from the obtained solution through filtration, and ethanol and excessive 1,6-dichlorohexane were removed therefrom through reduced-pressure distillation. The obtained solution was distilled under reduced pressure to give 137.7 g of a colorless transparent liquid having a boiling point of 148 to 150° C./0.005 Torr (0.67 Pa). As a result of IR analysis, 1H-NMR analysis and mass spectrometry analysis (MS analysis), the product was a compound represented by (CH3CH2O)3Si—(CH2)3S—(CH2)6—Cl. Through gas chromatography analysis (GC analysis), the purity of the compound was 97.5%.
Next, 80 g of ethanol, 5.46 g (0.07 mol) of anhydrous sodium sulfide and 3.36 g (0.105 mol) of sulfur were put into a 0.5-liter separable flask similar to the above, and heated up to 80° C. With stirring the solution, 49.91 g (0.14 mol) of the above (CH3CH2O)3Si—(CH2)3—S—(CH2)6—Cl was gradually and dropwise added thereto. After the addition, this was stirred for 10 hours at 80° C. After the stirring, this was cooled, the formed salt was taken out through filtration, and then the solvent ethanol was evaporated away under reduced pressure.
The obtained, red-brown transparent solution was analyzed through IR analysis, 1H-NMR analysis and ultra-critical chromatography analysis, which confirmed that the product is a compound represented by an average compositional formula, (CH3CH2O)3Si—(CH2)3—S—(CH2)6—S2.5—(CH2)6—S—(CH2)3—Si(OCH2CH3)3. In GPC analysis, the purity of the product was 85.2%.
Examples 1 to 109 and Comparative Examples 1 to 61
According to the compositional formulation and the kneading method shown in Table 1 to Table 13, the ingredients were kneaded with a Banbury mixer to prepare 170 types of rubber compositions. In Examples 1 to 66, 71 to 109 and Comparative Examples 1 to 61, the ingredients were kneaded in two stages of the first stage and the final stage of kneading; and in Examples 67 to 70, the ingredients were kneaded in three stages of the first stage, the second stage and the final stage of kneading. In Examples 62 to 66, the rubber component, silica, and the silane coupling agent were mixed and kneaded in the first stage of kneading, and on the way of the first stage, the vulcanization promoter (E) was added and further kneaded. Table 6 shows the elapsed time after addition of the silane coupling agent and before addition of the vulcanization promoter (E) on the way of the first stage. The obtained 170 rubber compositions were evaluated in point of the low-heat-generation property (tan δ index) thereof according to the above-mentioned method. The results are shown in Table 1 to Table 13.
*1 to *38 in Table 1 to Table 13 are described in [Notes] given below. In Table 1 to Table 13, the acidic compound (D) is expressed as “acid compound”








TABLE 1








Example















part by mass
1
2
3
4
5
6
7
8




















For-
First 
Solution-Polymerized SBR-1 *1
100
100
100
100
100
100
100
100


mulation
Stage 
Carbon Black-1 N220 *2
10
10
10
10
10
10
10
10



of 
Silica *3
50
50
50
50
50
50
50
50



Kneading
Silane Coupling Agent Si75 *4
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0




Aromatic Oil
30
30
30
30
30
30
30
30




Stearic Acid *5
—
—
—
—
—
—
—
—




Maleic Acid Monoester *6
—
—
—
—
—
—
—
—




Antiaging Agent 6PPD *7
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0



Final 
Stearic Acid *5
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0



Stage 
Maleic Acid Monoester *6
—
2.0
—
2.0
—
2.0
—
2.0



of
Antiaging Agent TMDQ *8
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0



Kneading
Zinc Flower
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5




1,3-Diphenylguanidine *9
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0




Vulcanization Promoter MBTS *10
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0




Vulcanization Promoter TBBS *11
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6




Sulfur
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5















Highest Temperature of Rubber 
105
105
75
75
85
85
115
115


Composition in Final Stage of Kneading (° C.)










Type of Acid Compound Added
—
—
—
—
—
—
—
—


in First Stage of Kneading










*5: Stearic Acid










*6: Maleic Acid Monoester










Kneading Stage of 
Final
Final
Final
Final
Final
Final
Final
Final


Acid Compound Addition
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage


Vulcanizate Physical Property:
115
114
107
105
111
110
116
114


Low-Heat-Generation Property (tanδ index) 




















Comparative Example















part by mass
1
2
3
4
5
6
7
8




















For-
First 
Solution-Polymerized SBR-1 *1
100
100
100
100
100
100
100
100


mulation
Stage 
Carbon Black-1 N220 *2
10
10
10
10
10
10
10
10



of 
Silica *3
50
50
50
50
50
50
50
50



Kneading
Silane Coupling Agent Si75 *4
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0




Aromatic Oil
30
30
30
30
30
30
30
30




Stearic Acid *5
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0




Maleic Acid Monoester *6
—
2.0
—
2.0
—
2.0
—
2.0




Antiaging Agent 6PPD *7
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0



Final 
Stearic Acid *5
—
—
—
—
—
—
—
—



Stage 
Maleic Acid Monoester *6
—
—
—
—
—
—
—
—



of
Antiaging Agent TMDQ *8
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0



Kneading
Zinc Flower
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5




1,3-Diphenylguanidine *9
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0




Vulcanization Promoter MBTS *10
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0




Vulcanization Promoter TBBS *11
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6




Sulfur
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5















Highest Temperature of Rubber 
105
105
75
75
85
85
115
115


Composition in Final Stage of Kneading (° C.)










Type of Acid Compound Added
*5
*5
*5
*5
*5
*5
*5
*5


in First Stage of Kneading

*6

*6

*6

*6


*5: Stearic Acid










*6: Maleic Acid Monoester










Kneading Stage of 
First
First
First
First
First
First
First
First


Acid Compound Addition
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage


Vulcanizate Physical Property:
100
99
99
98
100
100
98
98


Low-Heat-Generation Property (tanδ index)


























TABLE 2








Example
Comparative Example




















part by mass
1
2
9
10
11
12
13
14
15
16
1
2
9

























Formulation
First 
Solution-Polymerized SBR-1 *1
100
100
100
100
100
100
100
100
100
100
100
100
100



Stage of
Carbon Black-1 N220 *2
10
10
10
10
10
10
10
10
10
10
10
10
10



Kneading
Silica *3
50
50
50
50
50
50
50
50
50
50
50
50
50




Silane Coupling Agent Si75 *4
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0




Aromatic Oil
30
30
30
30
30
30
30
30
30
30
30
30
30




Stearic Acid *5
—
—
—
—
—
—
—
—
—
—
2.0
2.0
—




Maleic Acid Monoester *6
—
—
—
—
—
—
—
—
—
—
—
2.0
2.0




Valeric Acid *12
—
—
—
—
—
—
—
—
—
—
—
—
—




Ascorbic Acid *13
—
—
—
—
—
—
—
—
—
—
—
—
—




Catechol *14
—
—
—
—
—
—
—
—
—
—
—
—
—




Phenol *15
—
—
—
—
—
—
—
—
—
—
—
—
—




Phthalic Acid *16
—
—
—
—
—
—
—
—
—
—
—
—
—




O-nitrophenol *17
—
—
—
—
—
—
—
—
—
—
—
—
—




M-nitrophenol *18
—
—
—
—
—
—
—
—
—
—
—
—
—




P-nitrophenol *19
—
—
—
—
—
—
—
—
—
—
—
—
—




Antiaging Agent 6PPD *7
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0



Final
Stearic Acid *5
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
—
—
2.0



Stage
Maleic Acid Monoester *6
—
2.0
—
—
—
—
—
—
—
—
—
—
—



of
Valeric Acid *12
—
—
2.0
—
—
—
—
—
—
—
—
—
—



Kneading
Ascorbic Acid *13
—
—
—
2.0
—
—
—
—
—
—
—
—
—




Catechol *14
—
—
—
—
2.0
—
—
—
—
—
—
—
—




Phenol *15
—
—
—
—
—
1.0
—
—
—
—
—
—
—




Phthalic Acid *16
—
—
—
—
—
—
1.0
—
—
—
—
—
—




O-nitrophenol *17
—
—
—
—
—
—
—
1.0
—
—
—
—
—




M-nitrophenol * 18
—
—
—
—
—
—
—
—
1.0
—
—
—
—




P-nitrophenol *19
—
—
—
—
—
—
—
—
—
1.0
—
—
—




Antiaging Agent TMDQ *8
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0




Zinc Flower
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




1,3-Diphenylguanidine *9
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0




Vulcanization Promoter MBTS *10
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0




Vulcanization Promoter TBBS *11
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6




Sulfur
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




















Highest Temperature of Rubber Composition in Final Stage of Kneading (° C.)
105
105
105
105
105
105
105
105
105
105
105
105
105


Type of Acid Compound Added in First Stage of Kneading
—
—
—
—
—
—
—
—
—
—
*5
*5
*6


*5 to *19: Same as above











*6



Kneading Stage of Acid Compound Addition
Final
Final
Final
Final
Final
Final
Final
Final
Final
Final
First
First
First 



Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage and 















Final















Stage


Vulcanizate Physical Property: Low-Heat-Generation
115
114
115
115
117
114
113
114
114
114
100
99
102


Property (tanδ index)



























Comparative Example



















part by mass
10
11
12
13
14
15
16
17
18
19
























Formulation
First Stage of Kneading
Solution-Polymerized SBR-1 *1
100
100
100
100
100
100
100
100
100
100





Carbon Black-1 N220 *2
10
10
10
10
10
10
10
10
10
10





Silica *3
50
50
50
50
50
50
50
50
50
50





Silane Coupling Agent Si75 *4
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0





Aromatic Oil
30
30
30
30
30
30
30
30
30
30





Stearic Acid *5
2.0
—
2.0
—
—
—
—
—
—
—





Maleic Acid Monoester *6
—
—
—
—
—
—
—
—
—
—





Valeric Acid *12
2.0
2.0
—
—
—
—
—
—
—
—





Ascorbic Acid *13
—
—
2.0
2.0
—
—
—
—
—
—





Catechol *14
—
—
—
—
2.0
—
—
—
—
—





Phenol *15
—
—
—
—
—
1.0
—
—
—
—





Phthalic Acid *16
—
—
—
—
—
—
1.0
—
—
—





O-nitrophenol *17
—
—
—
—
—
—
—
1.0
—
—





M-nitrophenol *18
—
—
—
—
—
—
—
—
1.0
—





P-nitrophenol *19
—
—
—
—
—
—
—
—
—
1.0





Antiaging Agent 6PPD *7
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0




Final Stage of Kneading
Stearic Acid *5
—
2.0
—
2.0
2.0
2.0
2.0
2.0
2.0
2.0





Maleic Acid Monoester *6
—
—
—
—
—
—
—
—
—
—





Valeric Acid *12
—
—
—
—
—
—
—
—
—
—





Ascorbic Acid *13
—
—
—
—
—
—
—
—
—
—





Catechol *14
—
—
—
—
—
—
—
—
—
—





Phenol *15
—
—
—
—
—
—
—
—
—
—





Phthalic Acid *16
—
—
—
—
—
—
—
—
—
—





O-nitrophenol *17
—
—
—
—
—
—
—
—
—
—





M-nitrophenol *18
—
—
—
—
—
—
—
—
—
—





P-nitrophenol *19
—
—
—
—
—
—
—
—
—
—





Antiaging Agent TMDQ *8
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0





Zinc Flower
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5





1,3-Diphenylguanidine *9
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0





Vulcanization Promoter MBTS
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0





*10















Vulcanization Promoter TBBS 
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6





*11















Sulfur
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5



















Highest Temperature of Rubber Composition in Final Stage
105
105
105
105
105
105
105
105
105
105



of Kneading (° C.)













Type of Acid Compound Added in First Stage of Kneading
*5
*12
*5
*13
*14
*15
*16
*17
*18
*19



*5 to *19: Same as above
*12

*13










Kneading Stage of Acid Compound Addition
First
First
First
First
First
First
First
First
First
First




Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage





and

and
and
and
and
and
and
and





Final

Final
Final 
Final
Final
Final
Final
Final





Stage

Stage
Stage
Stage
Stage
Stage
Stage
Stage



Vulcanizate Physical Property: Low-Heat-Generation
98
100
100
103
104
104
102
104
104
103



Property (tanδ index)


















TABLE 3








Example
Comparative






















part by mass
17
18
19
20
21
22
23
24
25
26
27
28
29
30
Example 1

























Formulation

















First Stage of Kneading

















Solution-Polymerized SBR-1 *1
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100


Carbon Black-1 N220 *2
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10


Silica *3
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50


Silane Coupling Agent Si75 *4
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0


Aromatic Oil
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30


Stearic Acid *5
—
—
—
—
—
—
—
—
—
—
—
—
—
—
2.0


1,3-Diphenylguanidine *9
1.0
—
—
—
—
—
—
—
—
—
—
—
—
—
—


N-cyclohexyl-2-benzo-
—
1.0
—
—
—
—
—
—
—
—
—
—
—
—
—


thiazolylsulfenamide *20

















N-tert-butyl-2-benzo-
—
—
1.0
—
—
—
—
—
—
—
—
—
—
—
—


thiazolylsulfenamide *11

















2-Mercaptobenzothiazole *21
—
—
—
0.6
—
—
—
—
—
—
—
—
—
—
—


Di-2-benzothiazolyl Disulfide *10
—
—
—
—
1.0
—
—
—
—
—
—
—
—
—
—


Tetrakis(2-ethylhexyl)
—
—
—
—
—
1.0
—
—
—
—
—
—
—
—
—


thiuram Disulfide *22

















Tetrakis(benzyl)thiuram 
—
—
—
—
—
—
1.0
—
—
—
—
—
—
—
—


Disulfide *23

















Trimethylthiourea *24
—
—
—
—
—
—
—
1.0
—
—
—
—
—
—
—


N,N′-diethylthiourea *25
—
—
—
—
—
—
—
—
1.0
—
—
—
—
—
—


Zinc Dibenzyldithiocarbamate *26
—
—
—
—
—
—
—
—
—
1.0
—
—
—
—
—


Zinc N-ethyl-N-phenyl-
—
—
—
—
—
—
—
—
—
—
1.0
—
—
—
—


dithiocarbamate *27

















Zinc Dimethyldithiocarbamate *28
—
—
—
—
—
—
—
—
—
—
—
1.0
—
—
—


Copper Dimethyl-
—
—
—
—
—
—
—
—
—
—
—
—
1.0
—
—


dithiocarbamate *29

















Zinc Isopropylxanthate *30
—
—
—
—
—
—
—
—
—
—
—
—
—
1.0
—


Antiaging Agent 6PPD *7
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0


Final Stage of Kneading

















Stearic Acid *5
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
—


Antiaging Agent TMDQ *8
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0


Zinc Flower
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
2.5
2.5


1,3-Diphenylguanidine *9
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6


Vulcanization Promoter MBTS *10
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0


Vulcanization Promoter TBBS *11
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6


Sulfur
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
1.5
1.5


Highest Temperature of Rubber 
105
105
105
105
105
105
105
105
105
105
105
105
105
105
105


Composition in Final Stage of 

















Kneading (° C.)

















Type of Acid Compound Added in 
—
—
—
—
—
—
—
—
—
—
—
—
—
—
*5


First Stage of Kneading 

















*5: Stearic Acid

















Kneading Stage of Acid 
Final
Final
Final
Final
Final
Final
Final
Final
Final
Final
Final
Final
Final
Final
First


Compound Addition
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage


Vulcanizate Physical Property: 
128
121
123
127
122
121
123
119
119
131
130
133
125
128
100


Low-Heat-Generation Property 

















(tanδ index)


















TABLE 4








Example
Comparative Example























part by mass
1
31
32
33
17
34
35
36
37
38
39
40
1
20
21
22


























Formulation


















First Stage of Kneading


















Solution-Polymerized 
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100


SBR-1 *1


















Carbon Black-1 
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10


N220 *2


















Silica *3
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50


Silane Coupling 
4.0
—
—
—
4.0
—
—
—
4.0
—
—
—
4.0
—
—
—


Agent Si75 *4


















Silane Coupling 
—
4.0
—
—
—
4.0
—
—
—
4.0
—
—
—
4.0
—
—


Agent NXT *31


















Silane Coupling 
—
—
4.0
—
—
—
4.0
—
—
—
4.0
—
—
—
4.0
—


Agent NXT-Z *32


















Silane Coupling 
—
—
—
4.0
—
—
—
4.0
—
—
—
4.0
—
—
—
4.0


Agent LCS *33


















Aromatic Oil
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30


Stearic Acid *5
—
—
—
—
—
—
—
—
—
—
—
—
2.0
2.0
2.0
2.0


1,3-Diphenyl-
—
—
—
—
1.0
1.0
1.0
1.0
—
—
—
—
—
—
—
—


guanidine *9


















2-Mercapto-
—
—
—
—
—
—
—
—
0.5
0.5
0.5
0.5
—
—
—
—


benzothiazole *21


















Antiaging Agent 
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0


6PPD *7


















Final Stage of Kneading


















Stearic Acid *5
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
—
—
—
—


Antiaging Agent 
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0


TMDQ *8


















Zinc Flower
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
2.5
2.5
2.5


1,3-Diphenyl-
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0


guanidine *9


















Vulcanization 
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0


Promoter MBTS *10


















Vulcanization 
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6


Promoter TBBS *11


















Sulfur
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
1.5
1.5
1.5


Highest Temperature of Rubber 
105
105
105
105
105
105
105
105
105
105
105
105
105
105
105
105


Composition in Final Stage of 


















Kneading (° C.)


















Type of Acid Compound Added in 
—
—
—
—
—
—
—
—
—
—
—
—
*5
*5
*5
*5


First Stage of Kneading *5: 


















Stearic Acid


















Kneading Stage of Acid 
Final
Final
Final
Final
Final
Final
Final
Final
Final
Final
Final
Final
First
First
First
First


Compound Addition
stage
stage
stage
stage
stage
stage
stage
stage
stage
stage
stage
stage
Stage
Stage
Stage
Stage


Vulcanizate Physical Property: 
115
118
116
121
128
126
122
132
124
122
123
130
100
113
110
112


Low-Heat-Generation 


















Property (tanδ index)
















TABLE 5







Table 5-1









Example




















part by mass
41
42
43
44
45
46
47
48
49
50
51
52
53























Formulation















First Stage of Kneading















Emulsion-Polymerized SBR-2 *34
100
100
100
100
100
100
100
100
100
100
100
100
100


Carbon Black-1 N220 *2
10
10
10
10
10
10
10
10
10
10
10
10
10


Silica *3
50
50
50
50
50
50
50
50
50
50
50
50
50


Silane Coupling Agent Si75 *4
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0


Aromatic Oil
30
30
30
30
30
30
30
30
30
30
30
30
30


Stearic Acid *5
—
—
—
—
—
—
—
—
—
—
—
—
—


1,3-Diphenylguanidine *9
1.0
1.0
1.0
1.0
1.0
—
—
—
—
—
—
—
—


2-Mercaptobenzothiazole *21
—
—
—
—
—
0.5
0.5
0.5
0.5
—
—
—
—


Tetrakis(2-ethylhexyl)thiuram Disulfide *22
—
—
—
—
—
—
—
—
—
1.0
1.0
1.0
1.0


Tetrakis(benzyl)thiuram Disulfide *23
—
—
—
—
—
—
—
—
—
—
—
—
—


Zinc Dibenzyldithiocarbamate *26
—
—
—
—
—
—
—
—
—
—
—
—
—


Antiaging Agent 6PPD *7
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0


Final Stage of Kneading















Stearic Acid *5
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0


Antiaging Agent TMDQ *8
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0


Zinc Flower
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


1,3-Diphenylguanidine *9
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0


Vulcanization Promoter MBTS *10
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0


Vulcanization Promoter TBBS *11
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6


Sulfur
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


Highest Temperature of Rubber Composition in 
150
170
190
110
120
140
150
170
190
140
150
170
190


First Stage of Kneading (° C.)















Highest Temperature of Rubber Composition in 
105
105
105
105
105
105
105
105
105
105
105
105
105


Final Stage of Kneading















Type of Acid Compound Added in First Stage of 
—
—
—
—
—
—
—
—
—
—
—
—
—


Kneading *5: Stearic Acid















Kneading Stage of Acid Compound Addition
Final
Final
Final
Final
Final
Final
Final
Final
Final
Final
Final
Final
Final



Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage


Vulcanizate Physical Property: 
115
120
122
109
111
115
118
120
120
112
116
117
117


Low-Heat-Generation Property (tanδ index)
















TABLE 6







Table 5-2










Example
Comparative Example


















part by mass
54
55
56
57
58
59
60
61
23
24
25





















Formulation













First Stage of Kneading













Emulsion-Polymerized SBR-2 *34
100
100
100
100
100
100
100
100
100
100
100


Carbon Black-1 N220 *2
10
10
10
10
10
10
10
10
10
10
10


Silica *3
50
50
50
50
50
50
50
50
50
50
50


Silane Coupling Agent Si75 *4
4 .0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0


Aromatic Oil
30
30
30
30
30
30
30
30
30
30
30


Stearic Acid *5
—
—
—
—
—
—
—
—
2.0
2.0
2.0


1,3-Diphenylguanidine *9
—
—
—
—
—
—
—
—
—
—
—


2-Mercaptobenzothiazole *21
—
—
—
—
—
—
—
—
—
—
—


Tetrakis(2-ethylhexyl)thiuram Disulfide *22
—
—
—
—
—
—
—
—
—
—
—


Tetrakis(benzyl)thiuram Disulfide *23
1.0
1.0
1.0
1.0
—
—
—
—
—
—
—


Zinc Dibenzyldithiocarbamate *26
—
—
—
—
1.0
1.0
1.0
1.0
—
—
—


Antiaging Agent 6PPD *7
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0


Final Stage of Kneading













Stearic Acid *5
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
—
—
—


Antiaging Agent TMDQ *8
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0


Zinc Flower
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5


1,3-Diphenylguanidine *9
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0


Vulcanization Promoter MBTS *10
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0


Vulcanization Promoter TBBS *11
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6


Sulfur
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5


Highest Temperature of Rubber Composition in First Stage 
140
150
170
190
140
150
170
190
150
160
170


of Kneading (° C.)













Highest Temperature of Rubber Composition in Final 
105
105
105
105
105
105
105
105
105
105
105


Stage of Kneading













Type of Acid Compound Added in First Stage of Kneading
—
—
—
—
—
—
—
—
*5
*5
*5


*5: Stearic Acid













Kneading Stage of Acid Compound Addition
Final
Final
Final
Final
Final
Final
Final
Final
Final
Final
Final



Stage 
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage


Vulcanizate Physical Property: Low-Heat-Generation 
114
115
117
118
119
124
125
127
100
101
103


Property (tanδ index)
















TABLE 7







Table 6










Example
Comparative













part by mass
62
63
64
65
66
Example 1
















Formulation








First Stage of Kneading








Solution-Polymerized SBR-1 *1
100
100
100
100
100
100


Carbon Black-1 N220 *2
10
10
10
10
10
10


Silica *3
50
50
50
50
50
50


Silane Coupling Agent Si75 *4
4.0
4.0
4.0
4.0
4.0
4.0


Aromatic Oil
30
30
30
30
30
30


Stearic Acid *5
—
—
—
—
—
2


Antiaging Agent 6PPD *7
1.0
1.0
1.0
1.0
1.0
1.0


On the Way of First Stage of Kneading








1,3-Diphenylguanidine *9
1.0
1.0
—
—
—
—


Tetrakis(2-ethylhexyl)thiuram Disulfide *22
—
—
1.0
—
—
—


Tetrakis(benzyl)thiuram Disulfide *23
—
—
—
1.0
—
—


Zinc Dibenzyldithiocarbamate *26
—
—
—
—
1.0
—


Final Stage of Kneading








Stearic Acid *5
2.0
2.0
2.0
2.0
2.0
—


Antiaging Agent TMDQ *8
1.0
1.0
1.0
1.0
1.0
1.0


Zinc Flower
2.5
2.5
2.5
2.5
2.5
2.5


1,3-Diphenylguanidine *9
1.0
1.0
1.0
1.0
1.0
1.0


Vulcanization Promoter MBTS *10
1.0
1.0
1.0
1.0
1.0
1.0


Vulcanization Promoter TBBS *11
0.6
0.6
0.6
0.6
0.6
0.6


Sulfur
1.5
1.5
1.5
1.5
1.5
1.5


Elapsed Time after Addition of Silica and Silane Coupling Agent and before
60
90
90
90
90
—


Addition of Vulcanization Promoter on the Way of First Stage of Kneading








(sec)








Highest Temperature of Rubber Composition in Final Stage of Kneading
105
105
85
85
115
105


(° C.)








Type of Acid Compound Added in First Stage of Kneading
—
—
—
—
—
*5


*5: Stearic Acid








Kneading Stage of Acid Compound Addition
Final Stage
Final Stage
Final Stage
Final Stage
Final Stage
First Stage


Vulcanizate Physical Property: Low-Heat-Generation Property (tanδ index)
125
134
126
127
133
100
















TABLE 8







Table 7










Example
Comparative












part by mass
67
68
69
70
Example 1















Formulation







First Stage of Kneading







Solution-Polymerized SBR-1 *1
100
100
100
100
100


Carbon Black-1 N220 *2
10
10
10
10
10


Silica *3
50
50
50
50
50


Silane Coupling Agent Si75 *4
4.0
4.0
4.0
4.0
4.0


Aromatic Oil
30
30
30
30
30


Stearic Acid *5
—
—
—
—
2.0


Antiaging Agent 6PPD *7
1.0
1.0
1.0
1.0
1.0


Second Stage of Kneading







1,3-Diphenylguanidine *9
1.0
—
—
—
—


Tetrakis(2-ethylhexyl)thiuram Disulfide *22
—
1.0
—
—
—


Tetrakis(benzyl)thiuram Disulfide *23
—
—
1.0
—
—


Zinc Dibenzyldithiocarbamate *26
—
—
—
1.0
—


Final Stage of Kneading







Stearic Acid *5
2.0
2.0
2.0
2.0
—


Antiaging Agent TMDQ *8
1.0
1.0
1.0
1.0
1.0


Zinc Flower
2.5
2.5
2.5
2.5
2.5


1,3-Diphenylguanidine *9
1.0
1.0
1.0
1.0
1.0


Vulcanization Promoter MBTS *10
1.0
1.0
1.0
1.0
1.0


Vulcanization Promoter TBBS *11
0.6
0.6
0.6
0.6
0.6


Sulfur
1.5
1.5
1.5
1.5
1.5


Highest Temperature of Rubber Composition in Final Stage of Kneading
105
85
85
115
105


(° C.)







Type of Acid Compound Added in First Stage of Kneading
—
—
—
—
*5


*5: Stearic Acid







Kneading Stage of Acid Compound Addition
Final Stage
Final Stage
Final Stage
Final Stage
First stage


Vulcanizate Physical Property: Low-Heat-Generation Property (tanδ index)
126
126
126
131
100
















TABLE 9







Table 8










Example
Comparative Example




















part by mass
1
71
72
73
74
75
76
77
1
26
27
28
29























Formulation















First Stage of Kneading















Solution-Polymerized SBR-1 *1
100
75
50
60
90
50
60
90
100
75
50
60
90


Emulsion-Polymerized SBR-2 *34
—
25
50
40
10
50
40
10
—
25
50
40
10


Carbon Black-1 N220 *2
10
10
10
10
10
10
10
10
10
10
10
10
10


Silica *3
50
50
50
50
50
50
50
50
50
50
50
50
50


Silane Coupling Agent Si75 *4
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0


Aromatic Oil
30
30
30
30
30
30
30
30
30
30
30
30
30


Stearic Acid *5
—
—
—
—
—
—
—
—
2.0
2.0
2.0
2.0
2.0


1,3-Diphenylguanidine *9
—
—
—
—
—
1.0
1.0
1.0
—
—
—
—
—


Antiaging Agent 6PPD *7
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0


Final Stage of Kneading















Stearic Acid *5
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
—
—
—
—
—


Antiaging Agent TMDQ *8
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0


Zinc Flower
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


1,3-Diphenylguanidine *9
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0


Vulcanization Promoter MBTS *10
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0


Vulcanization Promoter TBBS *11
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6


Sulfur
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


Highest Temperature of Rubber Composition in Final Stage 
105
115
115
105
105
85
85
115
105
105
75
75
85


of Kneading (° C.)















Type of Acid Compound Added in First Stage of Kneading
—
—
—
—
—
—
—
—
*5
*5
*5
*5
*5


*5: Stearic Acid















Kneading Stage of Acid Compound Addition
Final
Final
Final
Final
Final
Final
First
First
First
First
First
First
First



Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage


Vulcanizate Physical Property: 
115
114
109
111
115
110
115
126
100
100
100
100
100


Low-Heat-Generation Property (tanδ index)
















TABLE 10







Table 9










Example
Comparative Example























part by mass
78
79
80
81
82
83
84
85
30
31
32
33
34
35
36
37


























Formaulation


















First Stage of Kneading 


















Solution-Polymerized
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100


SBR-1 *1


















Carbon Black-1 
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10


N220 *2


















Silica *35
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50


Silane Coupling 
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0


Agent Si75 *4


















Aromatic Oil
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30


Stearic Acid *5
—
—
—
—
—
—
—
—
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0


Maleic Acid 
—
—
—
—
—
—
—
—
—
2.0
—
2.0
—
2.0
—
2.0


Monoester *6


















Antiaging 
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0


Agent 6PPD *7


















Final Stage of Kneading 


















Stearic Acid *5
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
—
—
—
—
—
—
—
—


Maleic Acid 
—
2.0
—
2.0
—
2.0
—
2.0
—
—
—
—
—
—
—
—


Monoester *6


















Antiaging Agent 
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0


TMDQ *8


















Zinc Flower
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
2.5
2.5
2.5


1,3-Diphenylguanidine *9
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0


Vulcanization 
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0


Promoter MBTS *10


















Vulcanization 
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6


Promoter TBBS *11


















Sulfur
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
1.5
1.5
1.5


Highest Temperature of Rubber 
105
105
75
75
85
85
115
115
105
105
75
75
85
85
115
115


Composition in 


















Final Stage of Kneading (° C.)


















Type of Acid Compound Added in 
—
—
—
—
—
—
—
—
*5
*5
*5
*5
*5
*5
*5
*5


First Stage of Kneading









*6

*6

*6

*6


*5: Stearic Acid


















*6: Maleic Acid Monoester


















Kneading Stage of Acid 
Final
Final
Final
Final
Final
Final
Final
Final
First
First
First
First
First
First
First
First


Compound Addition
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage


Vulcanizate Physical Property: 
117
117
107
106
110
110
117
118
100
98
99
98
99
99
100
100


Low-Heat-Generation 


















Property (tanδ index)
















TABLE 11







Table 10










Example
Comparative Example























part by mass
86
87
88
89
90
91
92
93
38
39
40
41
42
43
44
45


























Formulation 


















First Stage of Kneading 


















SolutionPolymerized 
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100


SBR-1 *1


















Carbon Black-1 
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10


N220 *2


















Silica *36
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50


Silane Coupling 
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0


Agent Si75 *4


















Aromatic Oil
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30


Stearic Acid *5
—
—
—
—
—
—
—
—
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0


Maleic Acid 
—
—
—
—
—
—
—
—
—
2.0
—
2.0
—
2.0
—
2.0


Monoester *6


















Antiaging Agent
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0


6PPD *7


















Final Stage of Kneading


















Stearic Acid *5
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
—
—
—
—
—
—
—
—


Maleic Acid 
—
2.0
—
2.0
—
2.0
—
2.0
—
—
—
—
—
—
—
—


Monoester *6


















Antiaging Agent 
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0


TMDQ *8


















Zinc Flower
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
2.5
2.5
2.5


1,3-Diphenylguanidine *9
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0


Vulcanization 
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0


Promoter 


















MBTS *10


















Vulcanization Promoter 
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6


TBBS *11


















Sulfur
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
1.5
1.5
1.5


Highest Temperature of 
105
105
75
75
85
85
115
115
105
105
75
75
85
85
115
115


Rubber Composition in


















Final Stage of Kneading (° C.)


















Type of Acid Compound Added in 
—
—
—
—
—
—
—
—
*5
*5
*5
*5
*5
*5
*5
*5


First Stage of Kneading









*6

*6

*6

*6


*5: Stearic Acid


















*6: Maleic Acid Monoester


















Kneading Stage of 
Final
Final
Final
Final
Final
Final
Final
Final
First
First
First
First
First
First
First
First


Acid Compound Addition
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage


Vulcanizate Physical Property: 
112
112
105
105
110
110
114
114
100
100
98
98
99
100
100
100


Low-Heat-Generation 


















Property (tanδ index)
















TABLE 12







Table 11










Example
Comparative Example























part by mass
94
95
96
97
98
99
100
101
46
47
48
49
50
51
52
53


























Formulation


















First Stage of Kneading


















Solution-Polymerized SBR-1 *1
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100


Carbon Black-1 N220 *2
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
—


Silica *37
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
—


Silane Coupling Agent Si75 *4
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0


Aromatic Oil
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30


Stearic Acid *5
—
—
—
—
—
—
—
—
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0


Maleic Acid Monoester *6
—
—
—
—
—
—
—
—
—
2.0
—
2.0
—
2.0
—
2.0


Antiaging Agent 6PPD *7
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0


Final Stage of Kneading


















Stearic Acid *5
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
—
—
—
—
—
—
—
—


Maleic Acid Monoester *6
—
2.0
—
2.0
—
2.0
—
2.0
—
—
—
—
—
—
—
—


Antiaging Agent TMDQ *8
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0


Zinc Flower
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
2.5
2.5
2.5


1,3-Diphenylguanidine *9
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0


Vulcanization Promoter MBTS *10
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0


Vulcanization Promoter TBBS *11
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6


Sulfur
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
1.5
1.5
1.5


Highest Temperature of Rubber 
105
105
75
75
85
85
115
115
105
105
75
75
85
85
115
115


Composition in Final


















Stage of Kneading (° C.)


















Type of Acid Compound Added
—
—
—
—
—
—
—
—
*5
*5
*5
*5
*5
*5
*5
*5


in First Stage of Kneading 









*6

*6

*6

*6


*5: Stearic Acid


















*6: Maleic Acid Monoester


















Kneading Stage of Acid 
Final
Final
Final
Final
Final
Final
Final
Final
First
First
First
First
First
First
First
First


Compound Addition
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage


Vulcanizate Physical Property: 
108
109
105
105
106
107
109
111
100
99
97
98
98
99
100
100


Low-Heat-Generation Property


















(tanδ index)
















TABLE 13







Table 12










Example
Comparative Example























part by mass
102
103
104
105
106
107
108
109
54
55
56
57
58
59
60
61


























Formulation


















First Stage of Kneading 


















Solution-Polymerized SBR-1 *1
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100


Carbon Black-1 N220 *2
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10
10


Silica *38
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50
50


Silane Coupling Agent Si75 *4
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0
4.0


Aromatic Oil
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30
30


Stearic Acid *5
—
—
—
—
—
—
—
—
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0


Maleic Acid Monoester *6
—
—
—
—
—
—
—
—
—
2.0
—
2.0
—
2.0
—
2.0


Antiaging Agent 6PPD *7
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0


Final Stage of Kneading


















Stearic Acid *5
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
—
—
—
—
—
—
—
—


Maleic Acid Monoester *6
—
2.0
—
2.0
—
2.0
—
2.0
—
—
—
—
—
—
—
—


Antiaging Agent TMDQ *8
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0


Zinc Flower
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
2.5
2.5
2.5


1,3-Diphenylguanidine *9
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0


Vulcanization Promoter MBTS *10
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0


Vulcanization Promoter TBBS *11
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6


Sulfur
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
1.5
1.5
1.5


Highest Temperature of 
105
105
75
75
85
85
115
115
105
105
75
75
85
85
115
115


Rubber Composition in 


















Final Stage of Kneading (° C.)


















Type of Acid Compound Added 
—
—
—
—
—
—
—
—
*5
*5
*5
*5
*5
*5
*5
*5


in First Stage of Kneading









*6

*6

*6

*6


*5: Stearic Acid


















*6: Maleic Acid Monoester


















Kneading Stage of Acid 
Final
Final
Final
Final
Final
Final
Final
Final
First
First
First
First
First
First
First
First


Compound Addition
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage
Stage


Vulcanizate Physical Property: 
105
105
102
102
104
104
106
105
100
100
97
97
98
98
99
100


Low-Heat-Generation Property 


















(tanδ index)





[Notes] 


*1: Asahi Kasei's solution-polymerized styrene-butadiene copolymer rubber (SBR), trade name “Toughden 2000”


*2: N220 (ISAF), Asahi Carbon's trade name “#80” 


*3: Tosoh Silica's trade name “Nipseal AQ”, BET specific surface area 205 m2/g


*4: Bis(3-triethoxysilylpropyl) disulfide (mean sulfur chain length: 2.35), Evonik's silane coupling agent, trade name “Si75” (registered trademark)


*5: Stearic Acid


*6: Monomalate of maleic acid


*7: N-(1,3-dimehtylbutyl)-N′-phenyl-p-phenylenediamine, Ouchi Shinko Chemical's trade name “Noclac 6C” 


*8: 2,2,4-Trimethyl-1,2-dihydroquinoline polymer, Ouchi Shinko Chemical's trade name “Noclac 224” 


*9: 1,3-Diphenylguanidine, Sanshin Chemical's trade name “Sanceler D” 


*10: Di-2-benzothiazolyl disulfide, Sanshin Chemical's trade name “Sanceler DM” 


*11: N-tert-butyl-2-benzothiazolylsulfenamide, Sanshin Chemical's trade name “Sanceler NS”


*12: Valeric acid, Kanto Chemical's reagent


*13: Ascorbic acid, Kanto Chemical's reagent


*14: Catechol, Kanto Chemical's reagent


*15: Phenol, Kanto Chemical's reagent


*16: Phthalic acid, Kanto Chemical's reagent


*17: O-nitrophenol, Kanto Chemical's reagent


*18: M-nitrophenol, Kanto Chemical's reagent


*19: P-nitrophenol, Kanto Chemical's reagent


*20: N-cyclohexyl-2-benzothiazolylsulfenamide, Ouchi Shinko Chemical's trade name “Nocceler CZ” 


*21: Ouchi Shinko Chemical's trade name “Nocceler M-P” 


*22: Ouchi Shinko Chemical's trade name “Nocceler TOT-N” 


*23: Sanshin Chemical's trade name “Sanceler TBZTD” 


*24: Sanshin Chemical's trade name “Sanceler TMU” 


*25: Ouchi Shinko Chemical's trade name “Nocceler EUR” 


*26: Ouchi Shinko Chemical's trade name “Nocceler ZTC” 


*27: Sanshin Chemical's trade name “Sanceler PX” 


*28: Sanshin Chemical's trade name “Sanceler PZ” 


*29: Sanshin Chemical's trade name “Sanceler TT-CU” 


*30: Ouchi Shinko Chemical's trade name “Nocceler ZIX-O” 


*31: 3-Octanoylthiopropyltriethoxysilane, Momentive Performance Materials' trade name “NXT Silane” (registered trademark)


*32: Silane coupling agent represented by the chemical formula (VII), Momentive Performance Materials' trade name “NXT-Z” (registered trademark)


*33: Silane coupling agent represented by the following average compositional formula and obtained in Production






Example 1


(CH3CH2O)3Si—(CH2)3—S—(CH2)6—S2.5—(CH2)6—S—(CH2)3—Si(OCH2CH3)3 

    *34: JSR's emulsion-polymerized styrene-butadiene copolymer rubber (SBR), trade name “#1500”
    *35: Tosoh Silica's trade name “Nipseal KQ”, BET specific surface area 240 m2/g
    *36: Tosoh Silica's trade name “Nipseal NS”, BET specific surface area 160 m2/g
    *37: Tosoh Silica's trade name “Nipseal NA”, BET specific surface area 135 m2/g
    *38: Tosoh Silica's trade name “Nipseal ER”, BET specific surface area 95 m2/g


As obvious from Table 1 to Table 13, the rubber compositions of Examples 1 to 109 are all better than the comparative rubber compositions of Comparative Examples 1 to 61 in point of the low-heat-generation property (tan δ index).
INDUSTRIAL APPLICABILITY
According to the production method for a rubber composition of the present invention, it is possible to obtain a rubber composition excellent in low-heat-generation property with successfully inhibiting the coupling function activity of the silane coupling agent used from lowering and with further increasing the coupling function activity thereof, and is therefore favorably used as a production method for constitutive members of various types of pneumatic tires for passenger cars, small-size trucks, minivans, pickup trucks and big-size vehicles (trucks, buses, construction vehicles, etc.) and others, especially for tread members of pneumatic radial tires.

## Claims

1. A method for producing a rubber composition containing a rubber component (A) of at least one selected from natural rubbers and synthetic dienic rubbers, an inorganic filler (B), a silane coupling agent (C) and an acidic compound (D),
wherein the rubber composition is kneaded in multiple stages, and in the final stage of kneading, the acidic compound (D) is added, and the highest temperature of the rubber composition in the final stage of kneading is from 60 to 120° C.,
wherein the highest temperature of the rubber composition in the first stage of kneading is from 140 to 190° C., and
wherein the rubber component (A), all or a part of the inorganic filler (B) and all or a part of the silane coupling agent (C) are kneaded in the first stage of kneading, and on the way of the first stage, a vulcanization promoter (E) is added after an elapsed time of 60 to 90 seconds from adding the silane coupling agent (C) and further kneaded.

2. The method for producing a rubber composition according to claim 1, wherein the highest temperature of the rubber composition in the final stage of kneading is from 100 to 120° C.

3. The method for producing a rubber composition according to claim 1, wherein the acidic compound (D) is a fatty acid.

4. The method for producing a rubber composition according to claim 3, wherein the fatty acid is stearic acid.

5. The method for producing a rubber composition according to claim 1, wherein in the stage before the final stage of kneading, at least one vulcanization promoter (E) selected from guanidines, sulfenamides, thiazoles, thiurams, dithiocarbamate salts, thioureas and xanthate salts is added.

6. The method for producing a rubber composition according to claim 1, wherein the silane coupling agent (C) is at least one compound selected from a group of compounds represented by the following general formulae (I) to (IV):


(R1O)3-p(R2)pSi—R3—Sa—R3—Si(OR1)3-r(R2)r  (I)

(wherein multiple R1's may be the same or different, each representing a linear, cyclic or branched alkyl group having from 1 to 8 carbon atoms, a linear or branched alkoxylalkyl group having from 2 to 8 carbon atoms, or a hydrogen atom; multiple R2's may be the same or different, each representing a linear, cyclic or branched alkyl group having from 1 to 8 carbon atoms; multiple R3's may be the same or different, each representing a linear or branched alkylene group having from 1 to 8 carbon atoms; a indicates from 2 to 6 as a mean value; p and r may be the same or different, each indicating from 0 to 3 as a mean value, provided that both p and r are not 3 at the same time);




(wherein R4 represents a monovalent group selected from —Cl, —Br, R9O—, R9C(—O)O—, R9R10C—NO—, R9R10CNO—, R9R10N—, and —(OSi R9R10)h(OSi R9R10R11) (where R9, R10 and R11 each represents a hydrogen atom or a monovalent hydrocarbon group having from 1 to 18 carbon atoms; and h indicates from 1 to 4 as a mean value); R5 represents R4, a hydrogen atom, or a hydrocarbon group having from 1 to 18 carbon atoms; R6 represents R4, R5, a hydrogen atom, or a group —[O(R12O)j]0.5 (where R12 represents an alkylene group having from 1 to 18 carbon atoms; and j indicates an integer of from 1 to 4); R7 represents a divalent hydrocarbon group having from 1 to 18 carbon atoms; R8 represents a monovalent hydrocarbon group having from 1 to 18 carbon atoms; x, y and z each indicates a number satisfying the relationship of x+y+2z=3, 0≦x≦3, 0≦y≦2, 0≦z≦1);


(R13O)3-s(R14)sSi—R15—Sk—R16—Sk—R15—Si(OR13)3-t(R14)t  (III)


(wherein multiple R13's may be the same or different, each representing a linear, cyclic or branched alkyl group having from 1 to 8 carbon atoms, a linear or branched alkoxylalkyl group having from 2 to 8 carbon atoms, or a hydrogen atom; multiple R14's may be the same or different, each representing a linear, cyclic or branched alkyl group having from 1 to 8 carbon atoms; multiple R15's may be the same or different, each representing a linear or branched alkylene group having from 1 to 8 carbon atoms; R16 represents a divalent group of a general formula (—S—R17—S—), (—R18—Sm1—R19—) or (—R20—Sm2—R21—Sm3—R22—) (where R17 to R22 each represents a divalent hydrocarbon group, a divalent aromatic group or a divalent organic group containing a hetero element except sulfur and oxygen, having from 1 to 20 carbon atoms; m1, m2 and m3 may be the same or different, each indicating from 1 to less than 4 as a mean value); multiple k's may be the same or different, each indicating from 1 to 6 as a mean value; s and t each indicates from 0 to 3 as a mean value, provided that both s and t are not 3 at the same time);





(wherein R23 represents a linear, branched or cyclic alkyl group having from 1 to 20 carbon atoms; multiple G's may be the same or different, each representing an alkanediyl group or an alkenediyl group having from 1 to 9 carbon atoms; multiple Za's may be the same or different, each representing a functional group capable of bonding to the two silicon atoms and selected from [—O—]0.5, [—O-G-]0.5 and [—O-G-O—]0.5; multiple Zb's may be the same or different, each representing a functional group capable of bonding to the two silicon atoms and represented by [—O-G-O-]0.5; multiple Zc's may be the same or different, each representing a functional group selected from —Cl, —Br, —ORa, RaC(═O)O—, RaRbC═NO—, RaRbN—, Ra— and HO-G-O— (where G is the same as above); Ra and Rb each represents a linear, branched or cyclic alkyl group having from 1 to 20 carbon atoms; m, n, u, v and w each are 1≦m≦20, 0≦n≦20, 0≦u≦3, 0≦v≦2, 0≦w≦1, and (u/2)+v+2w is 2 or 3; in case where the formula has multiple A's, then Zau, Zbv and Zcw may be the same or different in those multiple A's; in case where the formula has multiple B's, then Zau, Zbv and Zcw may be the same or different in those multiple B's).

7. The method for producing a rubber composition according to claim 5, wherein the guanidine is at least one compound selected from 1,3-diphenylguanidine, 1,3-di-o-tolylguanidine and 1-o-tolylbiguanide.

8. The method for producing a rubber composition according to claim 5, wherein the sulfenamide is N-cyclohexyl-2-benzothiazolylsulfenamide and/or N-tert-butyl-2-benzothiazolylsulfenamide.

9. The method for producing a rubber composition according to claim 5, wherein the thiazol is at least one compound selected from 2-mercaptobenzothiazole and di-2-benzothiazolyl disulfide.

10. The method for producing a rubber composition according to claim 5, wherein the thiuram is at least one compound selected from tetrakis(2-ethylhexyl)thiuram disulfide and tetrabenzylthiuram disulfide.

11. The method for producing a rubber composition according to claim 5, wherein the thiourea is at least one compound selected from N,N′-diethylthiourea, trimethylthiourea, N,N′-diphenylthiourea and N,N′-dimethylthiourea.

12. The method for producing a rubber composition according to claim 5, wherein the dithiocarbamate salt is at least one compound selected from zinc dibenzyldithiocarbamate, zinc N-ethyl-N-phenyldithiocarbamate, zinc dimethyldithiocarbamate and copper dimethyldithiocarbamate.

13. The method for producing a rubber composition according to claim 5, wherein the xanthate salt is zinc isopropylxanthate.

14. A rubber composition produced according to the rubber composition production method of claim 1.

15. A tire using the rubber composition of claim 14.

16. The method for producing a rubber composition according to claim 1, wherein a synthetic rubber produced according to a solution polymerization method accounts for at least 70% by mass of the rubber component (A).

17. The method for producing a rubber composition according to claim 1, wherein the vulcanization promoter (E) is at least one compound selected from tetrakis(2-ethylhexyl)thiuram disulfide and tetrabenzylthiuram disulfide.

18. The method for producing a rubber composition according to claim 1, wherein the vulcanization promoter (E) is at least one compound selected from zinc dibenzyldithiocarbamate, zinc N-ethyl-N-phenyldithiocarbamate, zinc dimethyldithiocarbamate and copper dimethyldithiocarbamate.

19. The method for producing a rubber composition according to claim 18, wherein the vulcanization promoter (E) is zinc dibenzyldithiocarbamate.