# 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, a filler containing an inorganic filler (B), a silane coupling agent (C) and at least one vulcanization promoter (D) selected from thiurams, dithiocarbamate salts, thioureas and xanthate salts, wherein the rubber composition is kneaded in multiple stages, and in the first stage of kneading, the rubber component (A), all or a part of the inorganic filler (B), all or apart of the silane coupling agent (C) and the vulcanization promoter (D) are kneaded. The production method enables production of a rubber composition having a low-heat-generation property while successfully enhancing the coupling function activity of the silane coupling agent.

## 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
For solving the above-mentioned problems, the present inventors have made various investigations of a method of kneading a rubber component, all or a part of an inorganic filler, all or a part of a silane coupling agent and at least one vulcanization promoter selected from thiurams, dithiocarbamate salts, thioureas and xanthate salts in the first stage of the kneading step therein, and, as a result, have experimentally found that, in order to enhance the activity of the coupling function, it is good to optimize the kneading stage in which at least one vulcanization promoter selected from thiurams, dithiocarbamate salts, thioureas and xanthate salts is added to the rubber composition, 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, a filler containing an inorganic filler (B), a silane coupling agent (C) and at least one vulcanization promoter (D) selected from thiurams, dithiocarbamate salts, thioureas and xanthate salts, wherein the rubber composition is kneaded in multiple stages, and in the first stage of kneading, the rubber component (A), all or a part of the inorganic filler (B), all or apart of the silane coupling agent (C) and the vulcanization promoter (D) are kneaded.
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.



BRIEF DESCRIPTION OF THE DRAWINGS
[FIG. 1] This is a graph showing the critical regression formula [1] for low-heat-generation property in the present invention where the vulcanization promoter (D) is tetrakis(2-ethylhexyl)thiuram disulfide.
[FIG. 2] This is a graph showing the critical regression formula [1] for low-heat-generation property in the present invention where the vulcanization promoter (D) is N,N′-diethylthiourea.
[FIG. 3] This is a graph showing the critical regression formula [1] for low-heat-generation property in the present invention where the vulcanization promoter (D) is zinc dibenzyldithiocarbamate.
[FIG. 4] This is a graph showing the critical regression formula [1] for low-heat-generation property in the present invention where the vulcanization promoter (D) is zinc isopropylxanthate.



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, a filler containing an inorganic filler (B), a silane coupling agent (C) and at least one vulcanization promoter (D) selected from thiurams, dithiocarbamate salts, thioureas and xanthate salts, wherein the rubber composition is kneaded in multiple stages, and in the first stage of kneading, the rubber component (A), all or a part of the inorganic filler (B), all or a part of the silane coupling agent (C) and the vulcanization promoter (D) are kneaded.
In the present invention, at least one vulcanization promoter (D) selected from thiurams, dithiocarbamate salts, thioureas and xanthate salts is added and kneaded in the first stage of kneading, and this is for increasing the activity of the coupling function of the silane coupling agent (C).
The present inventors have made various experiments of blending the rubber component (A), all or a part of the inorganic filler (B), all or a part of the silane coupling agent (C) and the vulcanization promoter (D) in the first stage of kneading, and as a result, have found that, when the vulcanization promoter (D) is added in the first stage of kneading, the effect of increasing the activity of the coupling function is high in some cases but is low in some other cases. With that, the present inventors have variously and experimentally analyzed the factors of increasing the effect and, as a result, have obtained an experimental finding that, in order to increase the activity of coupling function, the mixing amount of an organic acid compound (E) and the mixing amount of the vulcanization promoter (D) are to be in a specific relationship. We, the present inventors have plotted a part of our experiments on graphs in which X is on the vertical axis and Y is on the horizontal axis, and derived the following formula [1] that is a critical regression formula for low-heat-generation property, from the graphs, and have found out further preferred embodiments of the present invention. FIG. 1 shows the critical regression formula [1] for low-heat-generation property in the present invention where the vulcanization promoter (D) is tetrakis(2-ethylhexyl)thiuram disulfide, as mentioned below; FIG. 2 shows the critical regression formula [1] for low-heat-generation property in the present invention where the vulcanization promoter (D) is N,N′-diethylthiourea; FIG. 3 shows the critical regression formula [1] for low-heat-generation property in the present invention where the vulcanization promoter (D) is zinc dibenzyldithiocarbamate; and FIG. 4 shows the critical regression formula [1] for low-heat-generation property in the present invention where the vulcanization promoter (D) is zinc isopropylxanthate. As obvious from the critical regression formulae for low-heat-generation property shown in these FIGS. 1 to 4, the present inventors have found that, in any case where the vulcanization promoter (D) is selected from thiurams, dithiocarbamate salts, thioureas and xanthate salts, it is desirable that an organic acid compound (E) is added and kneaded in the first stage of kneading in the rubber production method of the present invention, and the number of molecules X of the organic acid compound (E) in the rubber composition in the first stage satisfies the following relational formula [1] relative to the number of molecules Y of the vulcanization promoter (D):

0≦X≦1.5×Y  [1]

For more successfully increasing the activity of the coupling function of the silane coupling agent (C), preferably, the highest temperature of the rubber composition in the first stage of kneading is from 120 to 190° C.
The kneading step for the rubber composition in the present invention includes at least two stages of the first stage of kneading the others than vulcanization-related chemicals except the vulcanization promoter (D) and the final stage of kneading those including vulcanization-related chemicals, and may optionally include an intermediate stage of kneading the others than vulcanization-related chemicals except the vulcanization promoter (D). Here the vulcanization-related chemicals are chemicals relevant to vulcanization concretely including a vulcanizing agent and a vulcanization promoter.
The first stage of kneading in the present invention is the first stage of kneading the rubber component (A), the inorganic filler (B) and 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.
In the present invention, the kneading stage before the final stage such as the first stage, the intermediate stage and others is a step of mixing the other starting materials than vulcanization-related chemicals (vulcanizing agent and vulcanization promoter), such as the rubber component, the inorganic filler, the coupling agent and others and kneading them, and this is a step of dispersing the inorganic filler in the rubber composition and reinforcing the rubber component. One characteristic feature of the present invention is that the vulcanization promoter (D) is incorporated in the first stage to thereby better the dispersion of the inorganic filler in the rubber composition. As the case may be, the rubber component, the filler and others may be incorporated and kneaded in the intermediate stage.
In case where the method of the present invention includes an intermediate stage after the first stage of kneading and before the final stage, preferably, the highest temperature of the rubber composition in the intermediate kneading stage is from 120 to 190° C., more preferably from 130 to 175° C., even more preferably from 140 to 170° C. The kneading time is preferably from 10 seconds to 20 minutes, more preferably from 10 seconds to 10 minutes, even more preferably from 30 seconds to 5 minutes. When the method includes the intermediate stage, it is desirable that after the first kneading stage, the temperature of the rubber composition is lowered by at least 10° C. than the temperature thereof after the kneading of the first stage and thereafter the composition is processed in the subsequent stage.
The final stage of kneading is a step of incorporating vulcanization-related chemicals (vulcanizing agent, vulcanization promoter) and kneading the ingredients. Preferably, the highest temperature of the rubber composition in the final stage is from 60 to 140° C., more preferably from 80 to 120° C., even more preferably from 100 to 120° C. The kneading time is preferably 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 rubber composition is processed sequentially from the first kneading stage, the intermediate stage to the final stage, it is desirable that the temperature of the rubber composition is lowered by at least 10° C. than the temperature thereof after the first kneading stage and thereafter the composition is processed in the subsequent stage.
[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 may be the same or different, each representing 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—S3—(CH2)3—Si(OCH2CH3)3, an average compositional formula (CH3CH2O)3Si—(CH2)3—S4—(CH2)6—S4—(CH2)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)3Si—(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 is 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.
Of the compounds represented by the general formulae (I) to (IV), those represented by the above-mentioned general formula (I) are especially preferred as the silane coupling agent (C) for use in the present invention. The vulcanization promoter (D) can readily activate the polysulfide bond that reacts with the rubber component (A).
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 (D)]
Thiurams, dithiocarbamate salts, thioureas and xanthate salts that are for the vulcanization promoter (D) for use in the rubber composition production method of the present invention are described in detail.
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, tetraoctylthiuram monosulfide, 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 first stage of kneading in the present invention, preferably, the number of molecules (molar number) of the vulcanization promoter (D) in the rubber composition is from 0.1 to 1.0 time the number of molecules (molar number) of the silane coupling agent (C) therein. 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 (D) is from 0.2 to 0.6 times the number of molecules (molar number) of the silane coupling agent (C).
The vulcanization promoter (D) 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 (D) 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.
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, M1 in the general formula (VIII) 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 filler 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.
[Organic Acid Compound (E)]
The organic acid compound (E) to be incorporated in the rubber composition in the present invention includes organic acids, for example, 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 acid, modified rosin acid, etc.; and esters of the above-mentioned saturated fatty acids, unsaturated fatty acids and resin acids, etc.
In the present invention, preferably, at least 50 mol % of the organic acid compound (E) in the rubber composition in the first stage of kneading is stearic acid, in order that the compound must fully exhibit the function as a vulcanization promoter aid.
In case the rubber component (A) contains at least one selected from emulsion-polymerized styrene-butadiene copolymer and natural rubber, preferably, at least 50 mol % of the organic acid compound (E) in the rubber composition in the first stage of kneading is at least one compound selected from rosin acids and fatty acids which are contained in at least one selected from emulsion-polymerized styrene-butadiene copolymer and natural rubber. The rosin acids (including modified rosin acids) and the fatty acids contained in the emulsion-polymerized styrene-butadiene copolymer are derived from the emulsifying agent necessary in producing the styrene-butadiene copolymer through emulsion polymerization. Natural rubbers generally contain minor fatty acids.
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, 2, 14, 17, 18, 19 or 20, 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, 2, 14, 17, 18, 19 or 20)/(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 244 and Comparative Examples 1 to 20
According to the compositional formulation and the kneading method shown in Table 1 to Table 17, the rubber component, silica, the silane coupling agent and others were kneaded for 0 second, 60 seconds or 90 seconds in the first stage of kneading, then the vulcanization promoter (D) shown in Table 1 to Table 17 was added and further kneaded, and at the highest temperature of the rubber composition in the first stage of kneading as shown in Table 1 to Table 17, the mixture was taken out of the kneader to prepare the rubber composition of Examples 1 to 244. Here, “0 second” means that the vulcanization promoter (D) was added simultaneously with silica and the silane coupling agent. On the other hand, in the same manner as that for the rubber compositions of Examples 1 to 244 except that the vulcanization promoter (D) was not added in the first stage of kneading, the rubber compositions of Comparative Examples 1 to 20 each having the formulation shown in Table 1 to Table 17 were prepared. As the kneader, used was a Banbury mixer.
The obtained 264 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 17.









TABLE 1









Example




















part by mass
1
2
3
4
5
6
7
8
9
10
11
12
13

























Formu-
First
Solution-Polymerized SBR-A *1
100
100
100
100
100
100
100
100
100
100
100
100
100


lation
Stage of
Carbon Black 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
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 6PPD *5
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




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




Disulfide *6




Tetrabenzylthiuram Disulfide *7
—
1.0
—
—
—
—
—
—
—
—
—
1.0
—




N,N′-diethylthiourea *8
—
—
1.0
—
—
—
—
—
—
—
—
—
1.0




Trimethylthiourea *9
—
—
—
1.0
—
—
—
—
—
—
—
—
—




N,N′-diphenylthiourea *10
—
—
—
—
1.0
—
—
—
—
—
—
—
—




Zinc Dibenzyldithiocarbamate
—
—
—
—
—
1.0
—
—
—
—
—
—
—




*11




Zinc N-ethyl-N-phenyldithio-
—
—
—
—
—
—
1.0
—
—
—
—
—
—




carbamate *12




Zinc Dimethyldithio-
—
—
—
—
—
—
—
1.0
—
—
—
—
—




carbamate *13




Copper Dimethyldithio-
—
—
—
—
—
—
—
—
1.0
—
—
—
—




carbamate *14




Zinc Isopropylxanthate *15
—
—
—
—
—
—
—
—
—
1.0
—
—
—



Final
Antiaging Agent TMDQ *16
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



Stage of
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



Kneading
1,3-Diphenylguanidine *17
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
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




MBTS *18




Vulcanization Promoter TBBS
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




*19




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
150
150
150
150
150
150
150
150
150
150
170
170
170


in First Stage of Kneading (° C.)


Time of Adding Vulcanization Promoter (D)
0
0
0
0
0
0
0
0
0
0
90
90
90


in First Stage of Kneading (Note 1





















Vulcanizate
Low-Heat-Generation
105
106
106
105
106
107
106
106
105
104
126
128
121


Physical Property
Property (tanδ index)













Example
Comparative


















part by mass

14
15
16
17
18
19
20
Example 1























Formu-
First
Solution-Polymerized SBR-A *1
100
100
100
100
100
100
100
100



lation
Stage of
Carbon Black N220 *2
10
10
10
10
10
10
10
10




Kneading
Silica *3
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





Aromatic Oil
30
30
30
30
30
30
30
30





Stearic Acid
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0





Antiaging Agent 6PPD *5
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0





Tetrakis(2-ethylhexyl)thiuram
—
—
—
—
—
—
—
—





Disulfide *6





Tetrabenzylthiuram Disulfide *7
—
—
—
—
—
—
—
—





N,N′-diethylthiourea *8
—
—
—
—
—
—
—
—





Trimethylthiourea *9
1.0
—
—
—
—
—
—
—





N,N′-diphenylthiourea *10
—
1.0
—
—
—
—
—
—





Zinc Dibenzyldithiocarbamate
—
—
1.0
—
—
—
—
—





*11





Zinc N-ethyl-N-phenyldithio-
—
—
—
1.0
—
—
—
—





carbamate *12





Zinc Dimethyldithio-
—
—
—
—
1.0
—
—
—





carbamate *13





Copper Dimethyldithio-
—
—
—
—
—
1.0
—
—





carbamate *14





Zinc Isopropylxanthate *15
—
—
—
—
—
—
1.0
—




Final
Antiaging Agent TMDQ *16
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0




Stage of
Zinc Flower
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5




Kneading
1,3-Diphenylguanidine *17
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6





Vulcanization Promoter
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0





MBTS *18





Vulcanization Promoter TBBS
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6





*19





Sulfur
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5

















Highest Temperature of Rubber Composition
170
170
170
170
170
170
170
150



in First Stage of Kneading (° C.)



Time of Adding Vulcanization Promoter (D)
90
90
90
90
90
90
90
—



in First Stage of Kneading (Note 1


















Vulcanizate
Low-Heat-Generation
124
120
129
129
127
122
124
100



Physical Property
Property (tanδ index)



















TABLE 2









Example



















part by mass
21
22
23
24
25
26
27
28
29
30
31
32
























Formu-
First
Solution-Polymerized SBR-A *1
100
100
90
80
70
70
50
40
90
80
70
70


lation
Stage of
Emulsion-Polymerized SBR-A *20
—
—
10
20
30
30
50
60
10
20
30
30



Kneading
Carbon Black N220 *2
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




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




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




Stearic Acid
—
—
—
—
—
0.5
—
—
—
—
—
0.5




Antiaging Agent 6PPD *5
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0




Tetrakis(2-ethylhexyl)thiuram
2.0
0.5
1.4
2.6
3.8
5.0
6.4
7.8
0.5
1.0
2.0
3.0




Disulfide *6



Final
Stearic Acid
2.0
2.0
2.0
2.0
2.0
1.5
2.0
2.0
2.0
2.0
2.0
1.5



Stage of
Antiaging Agent TMDQ *16
1.0
1.0
1.0
1.0
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
2.5
2.5
2.5
2.5




1,3-Diphenylguanidine *17
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 *18
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 *19
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



















Highest Temperature of Rubber Composition in First
150
150
150
150
150
150
150
150
150
150
150
150


Stage of Kneading (° C.)


Time of Adding Vulcanization Promoter (D) in First
0
0
0
0
0
0
0
0
0
0
0
0


Stage of Kneading (Note 1


Number of Molecules of Organic Acid Compound (E)
0
0
2.0
4.0
6.0
7.7
9.9
11.9
2.0
4.0
6.0
7.7


in First Stage of Kneading (mol × 10−3)


Number of Molecules of Vulcanization Promoter (D)
2.1
0.53
1.5
2.7
4.0
5.3
6.7
8.2
0.53
1.1
2.1
3.2


in First Stage of Kneading (mol × 10−3)


Number of Molecules of Silane Coupling Agent in First
8.1
8.1
8.1
8.1
8.1
8.1
8.1
8.1
8.1
8.1
8.1
8.1


Stage of Kneading (mol × 10−3)




















Vulcanizate
Low-Heat-Generation
116
112
114
113
115
118
121
126
106
106
108
108


Physical Property
Property (tanδ index)












Example
















part by mass
33
34
35
36
37
38
39
40
41





















Formu-
First
Solution-Polymerized SBR-A *1
50
40
90
90
90
90
90
90
90


lation
Stage of
Emulsion-Polymerized SBR-A *20
50
60
10
10
10
10
10
10
10



Kneading
Carbon Black N220 *2
10
10
10
10
10
10
10
10
10




Silica *3
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




Aromatic Oil
30
30
30
30
30
30
30
30
30




Stearic Acid
—
—
—
—
—
—
—
1.1
0.6




Antiaging Agent 6PPD *5
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0




Tetrakis(2-ethylhexyl)thiuram
4.0
5.0
1.6
2.0
2.4
3.0
4.5
3.8
2.6




Disulfide *6



Final
Stearic Acid
2.0
2.0
2.0
2.0
2.0
2.0
2.0
0.9
1.4



Stage of
Antiaging Agent TMDQ *16
1.0
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
2.5




1,3-Diphenylguanidine *17
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6




Vulcanization Promoter MBTS *18
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0




Vulcanization Promoter TBBS *19
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
















Highest Temperature of Rubber Composition in First
150
150
150
150
150
150
150
150
150


Stage of Kneading (° C.)


Time of Adding Vulcanization Promoter (D) in First
0
0
0
0
0
0
0
0
0


Stage of Kneading (Note 1


Number of Molecules of Organic Acid Compound (E)
9.9
11.9
2.0
2.0
2.0
2.0
2.0
5.9
4.1


in First Stage of Kneading (mol × 10−3)


Number of Molecules of Vulcanization Promoter (D)
4.2
5.3
1.7
2.1
2.5
3.2
4.7
4.0
2.8


in First Stage of Kneading (mol × 10−3)


Number of Molecules of Silane Coupling Agent in First
8.1
8.1
8.1
8.1
8.1
8.1
8.1
8.1
8.1


Stage of Kneading (mol × 10−3)

















Vulcanizate
Low-Heat-Generation
108
109
116
116
117
119
120
117
115


Physical Property
Property (tanδ index)












Comparative Example

















part by mass
2
3
4
5
6
7
8
9























Formu-
First
Solution-Polymerized SBR-A *1
100
—
90
80
70
70
50
40



lation
Stage of
Emulsion-Polymerized SBR-A *20
—
100
10
20
30
30
50
60




Kneading
Carbon Black N220 *2
10
10
10
10
10
10
10
10





Silica *3
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





Aromatic Oil
30
30
30
30
30
30
30
30





Stearic Acid
—
—
—
—
—
0.5
—
—





Antiaging Agent 6PPD *5
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0





Tetrakis(2-ethylhexyl)thiuram
—
—
—
—
—
—
—
—





Disulfide *6




Final
Stearic Acid
2.0
2.0
2.0
2.0
2.0
1.5
2.0
2.0




Stage of
Antiaging Agent TMDQ *16
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 *17
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6





Vulcanization Promoter MBTS *18
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0





Vulcanization Promoter TBBS *19
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 Composition in First
150
150
150
150
150
150
150
150



Stage of Kneading (° C.)



Time of Adding Vulcanization Promoter (D) in First
—
—
—
—
—
—
—
—



Stage of Kneading (Note 1



Number of Molecules of Organic Acid Compound (E)
0
2.0
2.0
4.0
6.0
7.7
9.9
11.9



in First Stage of Kneading (mol × 10−3)



Number of Molecules of Vulcanization Promoter (D)
0
0
0
0
0
0
0
0



in First Stage of Kneading (mol × 10−3)



Number of Molecules of Silane Coupling Agent in First
8.1
8.1
8.1
8.1
8.1
8.1
8.1
8.1



Stage of Kneading (mol × 10−3)


















Vulcanizate
Low-Heat-Generation
100
100
99
99
98
99
99
99



Physical Property
Property (tanδ index)



















TABLE 3









Example















part by mass
42
43
44
45
46
47
48
49




















Formu-
First
Solution-Polymerized SBR-A *1
100
100
100
100
100
100
100
100


lation
Stage of
Carbon Black N220 *2
10
10
10
10
10
10
10
10



Kneading
Silica *3
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




Aromatic Oil
30
30
30
30
30
30
30
30




Antiaging Agent 6PPD *5
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0




Tetrakis(2-ethylhexyl)thiuram Disulfide *6
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0



Final
Stearic Acid
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0



Stage of
Antiaging Agent TMDQ *16
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 *17
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6




Vulcanization Promoter MBTS *18
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0




Vulcanization Promoter TBBS *19
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 Composition in First Stage of Kneading (° C.)
150
115
125
140
170
150
115
125


Time of Adding Vulcanization Promoter (D) in First Stage of Kneading (Note 1
0
0
0
0
0
60
60
60
















Vulcanizate Physical Property
Low-Heat-Generation Property (tanδ index)
114
108
111
113
115
120
108
116













Example
Comparative Example
















part by mass
50
51
2
10
11
12
13






















Formu-
First
Solution-Polymerized SBR-A *1
100
100
100
100
100
100
100



lation
Stage of
Carbon Black N220 *2
10
10
10
10
10
10
10




Kneading
Silica *3
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





Aromatic Oil
30
30
30
30
30
30
30





Antiaging Agent 6PPD *5
1.0
1.0
1.0
1.0
1.0
1.0
1.0





Tetrakis(2-ethylhexyl)thiuram Disulfide *6
1.0
1.0
—
—
—
—
—




Final
Stearic Acid
2.0
2.0
2.0
2.0
2.0
2.0
2.0




Stage of
Antiaging Agent TMDQ *16
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





1,3-Diphenylguanidine *17
0.6
0.6
0.6
0.6
0.6
0.6
0.6





Vulcanization Promoter MBTS *18
1.0
1.0
1.0
1.0
1.0
1.0
1.0





Vulcanization Promoter TBBS *19
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
















Highest Temperature of Rubber Composition in First Stage of Kneading (° C.)
140
170
150
115
125
140
170



Time of Adding Vulcanization Promoter (D) in First Stage of Kneading (Note 1
60
60
—
—
—
—
—

















Vulcanizate Physical Property
Low-Heat-Generation Property (tanδ index)
118
124
100
92
95
99
105




















TABLE 4









Example
Comparative Example
















part by mass
52
53
54
55
56
57
14
15
16





















Formu-
First
Solution-Polymerized SBR-A *1
100
100
100
100
100
100
100
100
100


lation
Stage of
Carbon Black N220 *2
10
10
10
10
10
10
10
10
10



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




Silane Coupling Agent NXT *21
4.0
—
—
4.0
—
—
4.0
—
—




Silane Coupling Agent NXT-Z *22
—
4.0
—
—
4.0
—
—
4.0
—




Silane Coupling Agent *23
—
—
4.0
—
—
4.0
—
—
4.0




Aromatic Oil
30
30
30
30
30
30
30
30
30




Antiaging Agent 6PPD *5
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0




Tetrakis(2-ethylhexyl)thiuram Disulfide *6
1.0
1.0
1.0
2.0
2.0
2.0
—
—
—



Final
Stearic Acid
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0



Stage of
Antiaging Agent TMDQ *16
1.0
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
2.5




1,3-Diphenylguanidine *17
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6




Vulcanization Promoter MBTS *18
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0




Vulcanization Promoter TBBS *19
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
















Highest Temperature of Rubber Composition in First Stage of Kneading (° C.)
150
150
150
150
150
150
150
150
150


Time of Adding Vulcanization Promoter (D) in First Stage of Kneading (Note 1
0
0
0
60
60
60
—
—
—

















Vulcanizate Physical Property
Low-Heat-Generation Property (tanδ index)
112
113
116
115
118
121
100
98
98


















TABLE 5









Example


















part by mass
58
59
60
61
62
63
64
65
66
67
68























Formu-
First
Solution-Polymerized SBR-A *1
100
100
90
80
70
70
50
40
90
80
70


lation
Stage of
Emulsion-Polymerized SBR-A *20
—
—
10
20
30
30
50
60
10
20
30



Kneading
Carbon Black 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
—
—
—
—
—
0.5
—
—
—
—
—




Antiaging Agent 6PPD *5
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0




N,N′-Diethylthiourea *8
0.5
0.8
0.2
0.4
0.6
0.7
1.0
1.2
0.1
0.3
0.5



Final
Stearic Acid
2.0
2.0
2.0
2.0
2.0
1.5
2.0
2.0
2.0
2.0
2.0



Stage of
Antiaging Agent TMDQ *16
1.0
1.0
1.0
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
2.5
2.5
2.5




1,3-Diphenylguanidine *17
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 *18
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 *19
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
150
150
150
150
150
150
150
150
150
150
150


Stage of Kneading (° C.)


Time of Adding Vulcanization Promoter (D) in First
0
0
0
0
0
0
0
0
0
0
0


Stage of Kneading (Note 1


Number of Molecules of Organic Acid Compound (E)
0
0
2.0
4.0
6.0
7.7
9.9
11.9
2.0
4.0
6.0


in First Stage of Kneading (mol × 10−3)


Number of Molecules of Vulcanization Promoter (D)
3.8
6.1
1.5
3.0
4.5
5.3
7.6
9.1
0.76
2.3
3.8


in First Stage of Kneading (mol × 10−3)


Number of Molecules of Silane Coupling Agent in First
8.1
8.1
8.1
8.1
8.1
8.1
8.1
8.1
8.1
8.1
8.1


Stage of Kneading (mol × 10−3)



















Vulcanizate
Low-Heat-Generation
112
116
111
111
112
112
114
113
105
106
107


Physical Property
Property (tanδ index)












Example

















part by mass
69
70
71
72
73
74
75
76
77
78






















Formu-
First
Solution-Polymerized SBR-A *1
70
50
40
90
90
90
90
90
90
90


lation
Stage of
Emulsion-Polymerized SBR-A *20
30
50
60
10
10
10
10
10
10
10



Kneading
Carbon Black 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
0.5
—
—
—
—
—
—
—
1.1
0.6




Antiaging Agent 6PPD *5
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0




N,N′-Diethylthiourea *8
0.6
0.8
1.0
0.4
0.6
0.8
1.0
1.4
0.6
0.4



Final
Stearic Acid
1.5
2.0
2.0
2.0
2.0
2.0
2.0
2.0
0.9
1.4



Stage of
Antiaging Agent TMDQ *16
1.0
1.0
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
2.5
2.5




1,3-Diphenylguanidine *17
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6




Vulcanization Promoter MBTS *18
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0




Vulcanization Promoter TBBS *19
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

















Highest Temperature of Rubber Composition in First
150
150
150
150
150
150
150
150
150
150


Stage of Kneading (° C.)


Time of Adding Vulcanization Promoter (D) in First
0
0
0
0
0
0
0
0
0
0


Stage of Kneading (Note 1


Number of Molecules of Organic Acid Compound (E)
7.7
9.9
11.9
2.0
2.0
2.0
2.0
2.0
5.9
4.1


in First Stage of Kneading (mol × 10−3)


Number of Molecules of Vulcanization Promoter (D)
4.5
6.1
7.7
3.0
4.5
6.1
7.6
10.6
4.5
3.0


in First Stage of Kneading (mol × 10−3)


Number of Molecules of Silane Coupling Agent in First
8.1
8.1
8.1
8.1
8.1
8.1
8.1
8.1
8.1
8.1


Stage of Kneading (mol × 10−3)


















Vulcanizate
Low-Heat-Generation
107
108
108
112
112
113
114
115
114
113


Physical Property
Property (tanδ index)












Comparative Example

















part by mass
2
3
4
5
6
7
8
9























Formu-
First
Solution-Polymerized SBR-A *1
100
—
90
80
70
70
50
40



lation
Stage of
Emulsion-Polymerized SBR-A *20
—
100
10
20
30
30
50
60




Kneading
Carbon Black N220 *2
10
10
10
10
10
10
10
10





Silica *3
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





Aromatic Oil
30
30
30
30
30
30
30
30





Stearic Acid
—
—
—
—
—
0.5
—
—





Antiaging Agent 6PPD *5
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0





N,N′-Diethylthiourea *8
—
—
—
—
—
—
—
—




Final
Stearic Acid
2.0
2.0
2.0
2.0
2.0
1.5
2.0
2.0




Stage of
Antiaging Agent TMDQ *16
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 *17
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6





Vulcanization Promoter MBTS *18
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0





Vulcanization Promoter TBBS *19
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 Composition in First
150
150
150
150
150
150
150
150



Stage of Kneading (° C.)



Time of Adding Vulcanization Promoter (D) in First
—
—
—
—
—
—
—
—



Stage of Kneading (Note 1



Number of Molecules of Organic Acid Compound (E)
0
2.0
2.0
4.0
6.0
7.7
9.9
11.9



in First Stage of Kneading (mol × 10−3)



Number of Molecules of Vulcanization Promoter (D)
0
0
0
0
0
0
0
0



in First Stage of Kneading (mol × 10−3)



Number of Molecules of Silane Coupling Agent in First
8.1
8.1
8.1
8.1
8.1
8.1
8.1
8.1



Stage of Kneading (mol × 10−3)


















Vulcanizate
Low-Heat-Generation
100
100
99
99
98
99
99
99



Physical Property
Property (tanδ index)



















TABLE 6









Example















part by mass
58
79
80
81
82
83
84
85




















Formu-
First
Solution-Polymerized SBR-A *1
100
100
100
100
100
100
100
100


lation
Stage of
Carbon Black N220 *2
10
10
10
10
10
10
10
10



Kneading
Silica *3
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




Aromatic Oil
30
30
30
30
30
30
30
30




Antiaging Agent 6PPD *5
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0




N,N′-Diethylthiourea *8
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5



Final
Stearic Acid
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0



Stage of
Antiaging Agent TMDQ *16
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 *17
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6




Vulcanization Promoter MBTS *18
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0




Vulcanization Promoter TBBS *19
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 Composition in First Stage of Kneading (° C.)
150
115
125
140
170
150
115
125


Time of Adding Vulcanization Promoter (D) in First Stage of Kneading (Note 1
0
0
0
0
0
60
60
60
















Vulcanizate Physical Property
Low-Heat-Generation Property (tanδ index)
110
105
109
111
113
117
107
113













Example
Comparative Example
















part by mass
86
87
2
10
11
12
13






















Formu-
First
Solution-Polymerized SBR-A *1
100
100
100
100
100
100
100



lation
Stage of
Carbon Black N220 *2
10
10
10
10
10
10
10




Kneading
Silica *3
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





Aromatic Oil
30
30
30
30
30
30
30





Antiaging Agent 6PPD *5
1.0
1.0
1.0
1.0
1.0
1.0
1.0





N,N′-Diethylthiourea *8
0.5
0.5
—
—
—
—
—




Final
Stearic Acid
2.0
2.0
2.0
2.0
2.0
2.0
2.0




Stage of
Antiaging Agent TMDQ *16
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





1,3-Diphenylguanidine *17
0.6
0.6
0.6
0.6
0.6
0.6
0.6





Vulcanization Promoter MBTS *18
1.0
1.0
1.0
1.0
1.0
1.0
1.0





Vulcanization Promoter TBBS *19
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
















Highest Temperature of Rubber Composition in First Stage of Kneading (° C.)
140
170
150
115
125
140
170



Time of Adding Vulcanization Promoter (D) in First Stage of Kneading (Note 1
60
60
—
—
—
—
—

















Vulcanizate Physical Property
Low-Heat-Generation Property (tanδ index)
115
118
100
92
95
99
105




















TABLE 7









Example
Comparative Example
















part by mass
58
88
89
90
91
92
14
15
16





















Formu-
First
Solution-Polymerized SBR-A *1
100
100
100
100
100
100
100
100
100


lation
Stage of
Carbon Black N220 *2
10
10
10
10
10
10
10
10
10



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




Silane Coupling Agent NXT *21
4.0
—
—
4.0
—
—
4.0
—
—




Silane Coupling Agent NXT-Z *22
—
4.0
—
—
4.0
—
—
4.0
—




Silane Coupling Agent *23
—
—
4.0
—
—
4.0
—
—
4.0




Aromatic Oil
30
30
30
30
30
30
30
30
30




Antiaging Agent 6PPD *5
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0




N,N′-Diethylthiourea *8
0.5
0.5
0.5
0.5
0.5
0.5
—
—
—



Final
Stearic Acid
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0



Stage of
Antiaging Agent TMDQ *16
1.0
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
2.5




1,3-Diphenylguanidine *17
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6




Vulcanization Promoter MBTS *18
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0




Vulcanization Promoter TBBS *19
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
















Highest Temperature of Rubber Composition in First Stage of Kneading (° C.)
150
150
150
150
150
150
150
150
150


Time of Adding Vulcanization Promoter (D) in First Stage of Kneading (Note 1
0
0
0
60
60
60
—
—
—

















Vulcanizate Physical Property
Low-Heat-Generation Property (tanδ index)
110
109
114
114
116
119
100
98
98


















TABLE 8









Example


















part by mass
93
94
95
96
97
98
99
100
101
102
103























Formu-
First
Solution-Polymerized SBR-A *1
100
100
90
80
70
70
50
40
90
80
70


lation
Stage of
Emulsion-Polymerized SBR-A *20
—
—
10
20
30
30
50
60
10
20
30



Kneading
Carbon Black 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
—
—
—
—
—
0.5
—
—
—
—
—




Antiaging Agent 6PPD *5
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0




Zinc Dibenzyldithiocarbamate *11
2.0
0.4
1.0
1.8
2.5
3.4
4.4
5.0
0.5
1.0
1.5



Final
Stearic Acid
2.0
2.0
2.0
2.0
2.0
1.5
2.0
2.0
2.0
2.0
2.0



Stage of
Antiaging Agent TMDQ *16
1.0
1.0
1.0
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
2.5
2.5
2.5




1,3-Diphenylguanidine *17
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 *18
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 *19
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
150
150
150
150
150
150
150
150
150
150
150


Stage of Kneading (° C.)


Time of Adding Vulcanization Promoter (D) in First
0
0
0
0
0
0
0
0
0
0
0


Stage of Kneading (Note 1


Number of Molecules of Organic Acid Compound (E)
0
0
2.0
4.0
6.0
7.7
9.9
11.9
2.0
4.0
6.0


in First Stage of Kneading (mol × 10−3)


Number of Molecules of Vulcanization Promoter (D)
3.3
0.66
1.6
3.0
4.1
5.6
7.2
8.2
0.82
1.6
2.5


in First Stage of Kneading (mol × 10−3)


Number of Molecules of Silane Coupling Agent in First
8.1
8.1
8.1
8.1
8.1
8.1
8.1
8.1
8.1
8.1
8.1


Stage of Kneading (mol × 10−3)



















Vulcanizate
Low-Heat-Generation
118
115
115
116
116
117
117
118
108
108
109


Physical Property
Property (tanδ index)












Example

















part by mass
104
105
106
107
108
109
110
111
112
113






















Formu-
First
Solution-Polymerized SBR-A *1
70
50
40
90
90
90
90
90
90
90


lation
Stage of
Emulsion-Polymerized SBR-A *20
30
50
60
10
10
10
10
10
10
10



Kneading
Carbon Black 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
0.5
—
—
—
—
—
—
—
1.1
0.6




Antiaging Agent 6PPD *5
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0




Zinc Dibenzyldithiocarbamate *11
2.0
3.0
4.0
1.2
1.6
2.4
2.8
3.4
2.5
1.8



Final
Stearic Acid
1.5
2.0
2.0
2.0
2.0
2.0
2.0
2.0
0.9
1.4



Stage of
Antiaging Agent TMDQ *16
1.0
1.0
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
2.5
2.5




1,3-Diphenylguanidine *17
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6




Vulcanization Promoter MBTS *18
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0




Vulcanization Promoter TBBS *19
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

















Highest Temperature of Rubber Composition in First
150
150
150
150
150
150
150
150
150
150


Stage of Kneading (° C.)


Time of Adding Vulcanization Promoter (D) in First
0
0
0
0
0
0
0
0
0
0


Stage of Kneading (Note 1


Number of Molecules of Organic Acid Compound (E)
7.7
9.9
11.9
2.0
2.0
2.0
2.0
2.0
5.9
4.1


in First Stage of Kneading (mol × 10−3)


Number of Molecules of Vulcanization Promoter (D)
3.3
4.9
6.6
2.0
2.6
3.9
4.6
5.6
4.1
3.0


in First Stage of Kneading (mol × 10−3)


Number of Molecules of Silane Coupling Agent in First
8.1
8.1
8.1
8.1
8.1
8.1
8.1
8.1
8.1
8.1


Stage of Kneading (mol × 10−3)


















Vulcanizate
Low-Heat-Generation
109
110
112
117
117
118
118
119
118
118


Physical Property
Property (tanδ index)












Comparative Example

















part by mass
2
3
4
5
6
7
8
9























Formu-
First
Solution-Polymerized SBR-A *1
100
—
90
80
70
70
50
40



lation
Stage of
Emulsion-Polymerized SBR-A *20
—
100
10
20
30
30
50
60




Kneading
Carbon Black N220 *2
10
10
10
10
10
10
10
10





Silica *3
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





Aromatic Oil
30
30
30
30
30
30
30
30





Stearic Acid
—
—
—
—
—
0.5
—
—





Antiaging Agent 6PPD *5
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0





Zinc Dibenzyldithiocarbamate *11
—
—
—
—
—
—
—
—




Final
Stearic Acid
2.0
2.0
2.0
2.0
2.0
1.5
2.0
2.0




Stage of
Antiaging Agent TMDQ *16
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 *17
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6





Vulcanization Promoter MBTS *18
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0





Vulcanization Promoter TBBS *19
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 Composition in First
150
150
150
150
150
150
150
150



Stage of Kneading (° C.)



Time of Adding Vulcanization Promoter (D) in First
—
—
—
—
—
—
—
—



Stage of Kneading (Note 1



Number of Molecules of Organic Acid Compound (E)
0
2.0
2.0
4.0
6.0
7.7
9.9
11.9



in First Stage of Kneading (mol × 10−3)



Number of Molecules of Vulcanization Promoter (D)
0
0
0
0
0
0
0
0



in First Stage of Kneading (mol × 10−3)



Number of Molecules of Silane Coupling Agent in First
8.1
8.1
8.1
8.1
8.1
8.1
8.1
8.1



Stage of Kneading (mol × 10−3)


















Vulcanizate
Low-Heat-Generation
100
100
99
99
98
99
99
99



Physical Property
Property (tanδ index)



















TABLE 9









Example















part by mass
93
114
115
116
117
118
119
120




















Formu-
First
Solution-Polymerized SBR-A *1
100
100
100
100
100
100
100
100


lation
Stage of
Carbon Black N220 *2
10
10
10
10
10
10
10
10



Kneading
Silica *3
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




Aromatic Oil
30
30
30
30
30
30
30
30




Antiaging Agent 6PPD *5
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0




Zinc Dibenzyldithiocarbamate *11
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0



Final
Stearic Acid
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0



Stage of
Antiaging Agent TMDQ *16
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 *17
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6




Vulcanization Promoter MBTS *18
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0




Vulcanization Promoter TBBS *19
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 Composition in First Stage of Kneading (° C.)
150
115
125
140
170
150
115
125


Time of Adding Vulcanization Promoter (D) in First Stage of Kneading (Note 1
0
0
0
0
0
60
60
60
















Vulcanizate Physical Property
Low-Heat-Generation Property (tanδ index)
118
108
113
116
123
123
109
118













Example
Comparative Example
















part by mass
121
122
2
10
11
12
13






















Formu-
First
Solution-Polymerized SBR-A *1
100
100
100
100
100
100
100



lation
Stage of
Carbon Black N220 *2
10
10
10
10
10
10
10




Kneading
Silica *3
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





Aromatic Oil
30
30
30
30
30
30
30





Antiaging Agent 6PPD *5
1.0
1.0
1.0
1.0
1.0
1.0
1.0





Zinc Dibenzyldithiocarbamate *11
2.0
2.0
—
—
—
—
—




Final
Stearic Acid
2.0
2.0
2.0
2.0
2.0
2.0
2.0




Stage of
Antiaging Agent TMDQ *16
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





1,3-Diphenylguanidine *17
0.6
0.6
0.6
0.6
0.6
0.6
0.6





Vulcanization Promoter MBTS *18
1.0
1.0
1.0
1.0
1.0
1.0
1.0





Vulcanization Promoter TBBS *19
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
















Highest Temperature of Rubber Composition in First Stage of Kneading (° C.)
140
170
150
115
125
140
170



Time of Adding Vulcanization Promoter (D) in First Stage of Kneading (Note 1
60
60
—
—
—
—
—

















Vulcanizate Physical Property
Low-Heat-Generation Property (tanδ index)
120
126
100
92
95
99
105




















TABLE 10









Example
Comparative Example
















part by mass
123
124
125
126
127
128
14
15
16





















Formu-
First
Solution-Polymerized SBR-A *1
100
100
100
100
100
100
100
100
100


lation
Stage of
Carbon Black N220 *2
10
10
10
10
10
10
10
10
10



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




Silane Coupling Agent NXT *21
4.0
—
—
4.0
—
—
4.0
—
—




Silane Coupling Agent NXT-Z *22
—
4.0
—
—
4.0
—
—
4.0
—




Silane Coupling Agent *23
—
—
4.0
—
—
4.0
—
—
4.0




Aromatic Oil
30
30
30
30
30
30
30
30
30




Antiaging Agent 6PPD *5
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0




Zinc Dibenzyldithiocarbamate *11
2.0
2.0
2.0
2.0
2.0
2.0
—
—
—



Final
Stearic Acid
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0



Stage of
Antiaging Agent TMDQ *16
1.0
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
2.5




1,3-Diphenylguanidine *17
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6




Vulcanization Promoter MBTS *18
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0




Vulcanization Promoter TBBS *19
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
















Highest Temperature of Rubber Composition in First Stage of Kneading (° C.)
150
150
150
150
150
150
150
150
150


Time of Adding Vulcanization Promoter (D) in First Stage of Kneading (Note 1
0
0
0
60
60
60
—
—
—

















Vulcanizate Physical Property
Low-Heat-Generation Property (tanδ index)
113
112
112
115
117
120
100
98
98


















TABLE 11









Example


















part by mass
129
130
131
132
133
134
135
136
137
138
139























Formu-
First
Solution-Polymerized SBR-A *1
100
100
90
80
70
70
50
40
90
80
70


lation
Stage of
Emulsion-Polymerized SBR-A *20
—
—
10
20
30
30
50
60
10
20
30



Kneading
Carbon Black 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
—
—
—
—
—
0.5
—
—
—
—
—




Antiaging Agent 6PPD *5
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0




Zinc Isopropylxanthate *15
1.5
0.25
0.5
1.0
1.5
1.8
2.4
2.8
0.2
0.5
1.0



Final
Stearic Acid
2.0
2.0
2.0
2.0
2.0
1.5
2.0
2.0
2.0
2.0
2.0



Stage of
Antiaging Agent TMDQ *16
1.0
1.0
1.0
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
2.5
2.5
2.5




1,3-Diphenylguanidine *17
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 *18
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 *19
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
150
150
150
150
150
150
150
150
150
150
150


Stage of Kneading (° C.)


Time of Adding Vulcanization Promoter (D) in First
0
0
0
0
0
0
0
0
0
0
0


Stage of Kneading (Note 1


Number of Molecules of Organic Acid Compound (E)
0
0
2.0
4.0
6.0
7.7
9.9
11.9
2.0
4.0
6.0


in First Stage of Kneading (mol × 10−3)


Number of Molecules of Vulcanization Promoter (D)
4.5
0.74
1.5
3.0
4.5
5.4
7.1
8.3
0.60
1.5
3.0


in First Stage of Kneading (mol × 10−3)


Number of Molecules of Silane Coupling Agent in First
8.1
8.1
8.1
8.1
8.1
8.1
8.1
8.1
8.1
8.1
8.1


Stage of Kneading (mol × 10−3)



















Vulcanizate Physical
Low-Heat-Generation
117
113
113
114
115
115
116
116
106
106
107


Property
Property (tanδ index)












Example

















part by mass
140
141
142
143
144
145
146
147
148
149






















Formu-
First
Solution-Polymerized SBR-A *1
70
50
40
90
90
90
90
90
90
90


lation
Stage of
Emulsion-Polymerized SBR-A *20
30
50
60
10
10
10
10
10
10
10



Kneading
Carbon Black 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
0.5
—
—
—
—
—
—
—
1.1
0.6




Antiaging Agent 6PPD *5
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0




Zinc Isopropylxanthate *15
1.5
2.0
2.5
1.0
1.5
2.0
2.4
2.8
1.5
1.0



Final
Stearic Acid
1.5
2.0
2.0
2.0
2.0
2.0
2.0
2.0
0.9
1.4



Stage of
Antiaging Agent TMDQ *16
1.0
1.0
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
2.5
2.5




1,3-Diphenylguanidine *17
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6




Vulcanization Promoter MBTS *18
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0




Vulcanization Promoter TBBS *19
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

















Highest Temperature of Rubber Composition in First
150
150
150
150
150
150
150
150
150
150


Stage of Kneading (° C.)


Time of Adding Vulcanization Promoter (D) in First
0
0
0
0
0
0
0
0
0
0


Stage of Kneading (Note 1


Number of Molecules of Organic Acid Compound (E)
7.7
9.9
11.9
2.0
2.0
2.0
2.0
2.0
5.9
4.1


in First Stage of Kneading (mol × 10−3)


Number of Molecules of Vulcanization Promoter (D)
4.5
6.0
7.4
3.0
4.5
6.0
7.1
8.3
4.5
3.0


in First Stage of Kneading (mol × 10−3)


Number of Molecules of Silane Coupling Agent in First
8.1
8.1
8.1
8.1
8.1
8.1
8.1
8.1
8.1
8.1


Stage of Kneading (mol × 10−3)


















Vulcanizate Physical
Low-Heat-Generation
107
108
108
115
116
118
120
119
118
116


Property
Property (tanδ index)












Comparative Example

















part by mass
2
3
4
5
6
7
8
9























Formu-
First
Solution-Polymerized SBR-A *1
100
—
90
80
70
70
50
40



lation
Stage of
Emulsion-Polymerized SBR-A *20
—
100
10
20
30
30
50
60




Kneading
Carbon Black N220 *2
10
10
10
10
10
10
10
10





Silica *3
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





Aromatic Oil
30
30
30
30
30
30
30
30





Stearic Acid
—
—
—
—
—
0.5
—
—





Antiaging Agent 6PPD *5
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0





Zinc Isopropylxanthate *15
—
—
—
—
—
—
—
—




Final
Stearic Acid
2.0
2.0
2.0
2.0
2.0
1.5
2.0
2.0




Stage of
Antiaging Agent TMDQ *16
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 *17
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6





Vulcanization Promoter MBTS *18
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0





Vulcanization Promoter TBBS *19
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 Composition in First
150
150
150
150
150
150
150
150



Stage of Kneading (° C.)



Time of Adding Vulcanization Promoter (D) in First
—
—
—
—
—
—
—
—



Stage of Kneading (Note 1



Number of Molecules of Organic Acid Compound (E)
0
2.0
2.0
4.0
6.0
7.7
9.9
11.9



in First Stage of Kneading (mol × 10−3)



Number of Molecules of Vulcanization Promoter (D)
0
0
0
0
0
0
0
0



in First Stage of Kneading (mol × 10−3)



Number of Molecules of Silane Coupling Agent in First
8.1
8.1
8.1
8.1
8.1
8.1
8.1
8.1



Stage of Kneading (mol × 10−3)


















Vulcanizate Physical
Low-Heat-Generation
100
100
99
99
98
99
99
99



Property
Property (tanδ index)



















TABLE 12









Example















part by mass
129
150
151
152
153
154
155
156




















Formu-
First
Solution-Polymerized SBR-A *1
100
100
100
100
100
100
100
100


lation
Stage of
Carbon Black N220 *2
10
10
10
10
10
10
10
10



Kneading
Silica *3
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




Aromatic Oil
30
30
30
30
30
30
30
30




Antiaging Agent 6PPD *5
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0




Zinc Isopropylxanthate *15
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5



Final
Stearic Acid
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0



Stage of
Antiaging Agent TMDQ *16
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 *17
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6




Vulcanization Promoter MBTS *18
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0




Vulcanization Promoter TBBS *19
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 Composition in First Stage of Kneading (° C.)
150
115
125
140
170
150
115
125


Time of Adding Vulcanization Promoter (D) in First Stage of Kneading (Note 1
0
0
0
0
0
60
60
60
















Vulcanizate Physical Property
Low-Heat-Generation Property (tanδ index)
117
106
113
115
118
123
108
119













Example
Comparative Example
















part by mass
157
158
2
10
11
12
13






















Formu-
First
Solution-Polymerized SBR-A *1
100
100
100
100
100
100
100



lation
Stage of
Carbon Black N220 *2
10
10
10
10
10
10
10




Kneading
Silica *3
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





Aromatic Oil
30
30
30
30
30
30
30





Antiaging Agent 6PPD *5
1.0
1.0
1.0
1.0
1.0
1.0
1.0





Zinc Isopropylxanthate *15
1.5
1.5
—
—
—
—
—




Final
Stearic Acid
2.0
2.0
2.0
2.0
2.0
2.0
2.0




Stage of
Antiaging Agent TMDQ *16
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





1,3-Diphenylguanidine *17
0.6
0.6
0.6
0.6
0.6
0.6
0.6





Vulcanization Promoter MBTS *18
1.0
1.0
1.0
1.0
1.0
1.0
1.0





Vulcanization Promoter TBBS *19
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
















Highest Temperature of Rubber Composition in First Stage of Kneading (° C.)
140
170
150
115
125
140
170



Time of Adding Vulcanization Promoter (D) in First Stage of Kneading (Note 1
60
60
—
—
—
—
—

















Vulcanizate Physical Property
Low-Heat-Generation Property (tanδ index)
121
124
100
92
95
99
105




















TABLE 13









Example
Comparative Example
















part by mass
159
160
161
162
163
164
14
15
16





















Formu-
First
Solution-Polymerized SBR-A *1
100
100
100
100
100
100
100
100
100


lation
Stage of
Carbon Black N220 *2
10
10
10
10
10
10
10
10
10



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




Silane Coupling Agent NXT *21
4.0
—
—
4.0
—
—
4.0
—
—




Silane Coupling Agent NXT-Z *22
—
4.0
—
—
4.0
—
—
4.0
—




Silane Coupling Agent *23
—
—
4.0
—
—
4.0
—
—
4.0




Aromatic Oil
30
30
30
30
30
30
30
30
30




Antiaging Agent 6PPD *5
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0




Zinc Isopropylxanthate *15
2.0
2.0
2.0
2.0
2.0
2.0
—
—
—



Final
Stearic Acid
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0



Stage of
Antiaging Agent TMDQ *16
1.0
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
2.5




1,3-Diphenylguanidine *17
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6




Vulcanization Promoter MBTS *18
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0




Vulcanization Promoter TBBS *19
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
















Highest Temperature of Rubber Composition in First Stage of Kneading (° C.)
150
150
150
150
150
150
150
150
150


Time of Adding Vulcanization Promoter (D) in First Stage of Kneading (Note 1
0
0
0
60
60
60
—
—
—

















Vulcanizate Physical Property
Low-Heat-Generation Property (tanδ index)
110
111
115
114
114
122
100
98
98


















TABLE 14









Example




















part by mass
165
166
167
168
169
170
171
172
173
174
175
176
177

























Formu-
First
Solution-Polymerized SBR-A *1
100
100
100
100
100
100
100
100
100
100
100
100
100


lation
Stage of
Carbon Black N220 *2
10
10
10
10
10
10
10
10
10
10
10
10
10



Kneading
Silica *24
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
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 6PPD *5
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




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




Disulfide *6




Tetrabenzylthiuram Disulfide *7
—
1.0
—
—
—
—
—
—
—
—
—
1.0
—




N,N′-diethylthiourea *8
—
—
1.0
—
—
—
—
—
—
—
—
—
1.0




Trimethylthiourea *9
—
—
—
1.0
—
—
—
—
—
—
—
—
—




N,N′-diphenylthiourea *10
—
—
—
—
1.0
—
—
—
—
—
—
—
—




Zinc Dibenzyldithiocarbamate
—
—
—
—
—
1.0
—
—
—
—
—
—
—




*11




Zinc N-ethyl-N-phenyldithio-
—
—
—
—
—
—
1.0
—
—
—
—
—
—




carbamate *12




Zinc Dimethyldithio-
—
—
—
—
—
—
—
1.0
—
—
—
—
—




carbamate *13




Copper Dimethyldithio-
—
—
—
—
—
—
—
—
1.0
—
—
—
—




carbamate *14




Zinc Isopropylxanthate *15
—
—
—
—
—
—
—
—
—
1.0
—
—
—



Final
Antiaging Agent TMDQ *16
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



Stage of
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



Kneading
1,3-Diphenylguanidine *17
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
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




MBTS *18




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




TBBS *19




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
150
150
150
150
150
150
150
150
150
150
170
170
170


in First Stage of Kneading (° C.)


Time of Adding Vulcanization Promoter (D)
0
0
0
0
0
0
0
0
0
0
90
90
90


in First Stage of Kneading (Note 1





















Vulcanizate
Low-Heat-Generation
107
109
109
106
108
112
108
109
106
105
130
135
124


Physical Property
Property (tanδ index)













Example
Comparative

















part by mass
178
179
180
181
182
183
184
Example 17























Formu-
First
Solution-Polymerized SBR-A *1
100
100
100
100
100
100
100
100



lation
Stage of
Carbon Black N220 *2
10
10
10
10
10
10
10
10




Kneading
Silica *24
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





Aromatic Oil
30
30
30
30
30
30
30
30





Stearic Acid
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0





Antiaging Agent 6PPD *5
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0





Tetrakis(2-ethylhexyl)thiuram
—
—
—
—
—
—
—
—





Disulfide *6





Tetrabenzylthiuram Disulfide *7
—
—
—
—
—
—
—
—





N,N′-diethylthiourea *8
—
—
—
—
—
—
—
—





Trimethylthiourea *9
1.0
—
—
—
—
—
—
—





N,N′-diphenylthiourea *10
—
1.0
—
—
—
—
—
—





Zinc Dibenzyldithiocarbamate
—
—
1.0
—
—
—
—
—





*11





Zinc N-ethyl-N-phenyldithio-
—
—
—
1.0
—
—
—
—





carbamate *12





Zinc Dimethyldithio-
—
—
—
—
1.0
—
—
—





carbamate *13





Copper Dimethyldithio-
—
—
—
—
—
1.0
—
—





carbamate *14





Zinc Isopropylxanthate *15
—
—
—
—
—
—
1.0
—




Final
Antiaging Agent TMDQ *16
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0




Stage of
Zinc Flower
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5




Kneading
1,3-Diphenylguanidine *17
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6





Vulcanization Promoter
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0





MBTS *18





Vulcanization Promoter
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6





TBBS *19





Sulfur
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5

















Highest Temperature of Rubber Composition
170
170
170
170
170
170
170
150



in First Stage of Kneading (° C.)



Time of Adding Vulcanization Promoter (D)
90
90
90
90
90
90
90
—



in First Stage of Kneading (Note 1


















Vulcanizate
Low-Heat-Generation
129
125
137
138
135
125
130
100



Physical Property
Property (tanδ index)



















TABLE 15









Example




















part by mass
185
186
187
188
189
190
191
192
193
194
195
196
197

























Formu-
First
Solution-Polymerized SBR-A *1
100
100
100
100
100
100
100
100
100
100
100
100
100


lation
Stage of
Carbon Black N220 *2
10
10
10
10
10
10
10
10
10
10
10
10
10



Kneading
Silica *25
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
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 6PPD *5
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




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




Disulfide *6




Tetrabenzylthiuram Disulfide *7
—
1.0
—
—
—
—
—
—
—
—
—
1.0
—




N,N′-diethylthiourea *8
—
—
1.0
—
—
—
—
—
—
—
—
—
1.0




Trimethylthiourea *9
—
—
—
1.0
—
—
—
—
—
—
—
—
—




N,N′-diphenylthiourea *10
—
—
—
—
1.0
—
—
—
—
—
—
—
—




Zinc Dibenzyldithiocarbamate
—
—
—
—
—
1.0
—
—
—
—
—
—
—




*11




Zinc N-ethyl-N-phenyldithio-
—
—
—
—
—
—
1.0
—
—
—
—
—
—




carbamate *12




Zinc Dimethyldithio-
—
—
—
—
—
—
—
1.0
—
—
—
—
—




carbamate *13




Copper Dimethyldithio-
—
—
—
—
—
—
—
—
1.0
—
—
—
—




carbamate *14




Zinc Isopropylxanthate *15
—
—
—
—
—
—
—
—
—
1.0
—
—
—



Final
Antiaging Agent TMDQ *16
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



Stage of
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



Kneading
1,3-Diphenylguanidine *17
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
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




MBTS *18




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




TBBS *19




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
150
150
150
150
150
150
150
150
150
150
170
170
170


in First Stage of Kneading (° C.)


Time of Adding Vulcanization Promoter (D)
0
0
0
0
0
0
0
0
0
0
90
90
90


in First Stage of Kneading (Note 1





















Vulcanizate
Low-Heat-Generation
104
104
105
104
104
105
105
104
105
104
121
120
116


Physical Property
Property (tanδ index)













Example
Comparative

















part by mass
198
199
200
201
202
203
204
Example 18























Formu-
First
Solution-Polymerized SBR-A *1
100
100
100
100
100
100
100
100



lation
Stage of
Carbon Black N220 *2
10
10
10
10
10
10
10
10




Kneading
Silica *25
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





Aromatic Oil
30
30
30
30
30
30
30
30





Stearic Acid
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0





Antiaging Agent 6PPD *5
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0





Tetrakis(2-ethylhexyl)thiuram
—
—
—
—
—
—
—
—





Disulfide *6





Tetrabenzylthiuram Disulfide *7
—
—
—
—
—
—
—
—





N,N′-diethylthiourea *8
—
—
—
—
—
—
—
—





Trimethylthiourea *9
1.0
—
—
—
—
—
—
—





N,N′-diphenylthiourea *10
—
1.0
—
—
—
—
—
—





Zinc Dibenzyldithiocarbamate
—
—
1.0
—
—
—
—
—





*11





Zinc N-ethyl-N-phenyldithio-
—
—
—
1.0
—
—
—
—





carbamate *12





Zinc Dimethyldithio-
—
—
—
—
1.0
—
—
—





carbamate *13





Copper Dimethyldithio-
—
—
—
—
—
1.0
—
—





carbamate *14





Zinc Isopropylxanthate *15
—
—
—
—
—
—
1.0
—




Final
Antiaging Agent TMDQ *16
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0




Stage of
Zinc Flower
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5




Kneading
1,3-Diphenylguanidine *17
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6





Vulcanization Promoter
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0





MBTS *18





Vulcanization Promoter
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6





TBBS *19





Sulfur
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5

















Highest Temperature of Rubber Composition
170
170
170
170
170
170
170
150



in First Stage of Kneading (° C.)



Time of Adding Vulcanization Promoter (D)
90
90
90
90
90
90
90
—



in First Stage of Kneading (Note 1


















Vulcanizate
Low-Heat-Generation
117
114
120
119
120
118
120
100



Physical Property
Property (tanδ index)



















TABLE 16









Example




















part by mass
205
206
207
208
209
210
211
212
213
214
215
216
217

























Formu-
First
Solution-Polymerized SBR-A *1
100
100
100
100
100
100
100
100
100
100
100
100
100


lation
Stage of
Carbon Black N220 *2
10
10
10
10
10
10
10
10
10
10
10
10
10



Kneading
Silica *26
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
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 6PPD *5
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




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




Disulfide *6




Tetrabenzylthiuram Disulfide *7
—
1.0
—
—
—
—
—
—
—
—
—
1.0
—




N,N′-diethylthiourea *8
—
—
1.0
—
—
—
—
—
—
—
—
—
1.0




Trimethylthiourea *9
—
—
—
1.0
—
—
—
—
—
—
—
—
—




N,N′-diphenylthiourea *10
—
—
—
—
1.0
—
—
—
—
—
—
—
—




Zinc Dibenzyldithiocarbamate
—
—
—
—
—
1.0
—
—
—
—
—
—
—




*11




Zinc N-ethyl-N-phenyldithio-
—
—
—
—
—
—
1.0
—
—
—
—
—
—




carbamate *12




Zinc Dimethyldithio-
—
—
—
—
—
—
—
1.0
—
—
—
—
—




carbamate *13




Copper Dimethyldithio-
—
—
—
—
—
—
—
—
1.0
—
—
—
—




carbamate *14




Zinc Isopropylxanthate *15
—
—
—
—
—
—
—
—
—
1.0
—
—
—



Final
Antiaging Agent TMDQ *16
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



Stage of
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



Kneading
1,3-Diphenylguanidine *17
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
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




MBTS *18




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




TBBS *19




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
150
150
150
150
150
150
150
150
150
150
170
170
170


in First Stage of Kneading (° C.)


Time of Adding Vulcanization Promoter (D)
0
0
0
0
0
0
0
0
0
0
90
90
90


in First Stage of Kneading (Note 1





















Vulcanizate
Low-Heat-Generation
103
102
103
102
103
102
103
103
104
102
115
112
109


Physical Property
Property (tanδ index)













Example
Comparative

















part by mass
218
219
220
221
222
223
224
Example 19























Formu-
First
Solution-Polymerized SBR-A *1
100
100
100
100
100
100
100
100



lation
Stage of
Carbon Black N220 *2
10
10
10
10
10
10
10
10




Kneading
Silica *26
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





Aromatic Oil
30
30
30
30
30
30
30
30





Stearic Acid
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0





Antiaging Agent 6PPD *5
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0





Tetrakis(2-ethylhexyl)thiuram
—
—
—
—
—
—
—
—





Disulfide *6





Tetrabenzylthiuram Disulfide *7
—
—
—
—
—
—
—
—





N,N′-diethylthiourea *8
—
—
—
—
—
—
—
—





Trimethylthiourea *9
1.0
—
—
—
—
—
—
—





N,N′-diphenylthiourea *10
—
1.0
—
—
—
—
—
—





Zinc Dibenzyldithiocarbamate
—
—
1.0
—
—
—
—
—





*11





Zinc N-ethyl-N-phenyldithio-
—
—
—
1.0
—
—
—
—





carbamate *12





Zinc Dimethyldithio-
—
—
—
—
1.0
—
—
—





carbamate *13





Copper Dimethyldithio-
—
—
—
—
—
1.0
—
—





carbamate *14





Zinc Isopropylxanthate *15
—
—
—
—
—
—
1.0
—




Final
Antiaging Agent TMDQ *16
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0




Stage of
Zinc Flower
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5




Kneading
1,3-Diphenylguanidine *17
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6





Vulcanization Promoter
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0





MBTS *18





Vulcanization Promoter
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6





TBBS *19





Sulfur
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5

















Highest Temperature of Rubber Composition
170
170
170
170
170
170
170
150



in First Stage of Kneading (° C.)



Time of Adding Vulcanization Promoter (D)
90
90
90
90
90
90
90
—



in First Stage of Kneading (Note 1


















Vulcanizate
Low-Heat-Generation
110
109
113
109
114
112
112
100



Physical Property
Property (tanδ index)



















TABLE 17









Example




















part by mass
225
226
227
228
229
230
231
232
233
234
235
236
237

























Formu-
First
Solution-Polymerized SBR-A *1
100
100
100
100
100
100
100
100
100
100
100
100
100


lation
Stage of
Carbon Black N220 *2
10
10
10
10
10
10
10
10
10
10
10
10
10



Kneading
Silica *27
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
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 6PPD *5
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




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




Disulfide *6




Tetrabenzylthiuram Disulfide *7
—
1.0
—
—
—
—
—
—
—
—
—
1.0
—




N,N′-diethylthiourea *8
—
—
1.0
—
—
—
—
—
—
—
—
—
1.0




Trimethylthiourea *9
—
—
—
1.0
—
—
—
—
—
—
—
—
—




N,N′-diphenylthiourea *10
—
—
—
—
1.0
—
—
—
—
—
—
—
—




Zinc Dibenzyldithiocarbamate
—
—
—
—
—
1.0
—
—
—
—
—
—
—




*11




Zinc N-ethyl-N-phenyldithio-
—
—
—
—
—
—
1.0
—
—
—
—
—
—




carbamate *12




Zinc Dimethyldithio-
—
—
—
—
—
—
—
1.0
—
—
—
—
—




carbamate *13




Copper Dimethyldithio-
—
—
—
—
—
—
—
—
1.0
—
—
—
—




carbamate *14




Zinc Isopropylxanthate *15
—
—
—
—
—
—
—
—
—
1.0
—
—
—



Final
Antiaging Agent TMDQ *16
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



Stage of
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



Kneading
1,3-Diphenylguanidine *17
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
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




MBTS *18




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




TBBS *19




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
150
150
150
150
150
150
150
150
150
150
170
170
170


in First Stage of Kneading (° C.)


Time of Adding Vulcanization Promoter (D)
0
0
0
0
0
0
0
0
0
0
90
90
90


in First Stage of Kneading (Note 1





















Vulcanizate
Low-Heat-Generation
104
102
103
103
104
102
103
104
103
102
108
107
105


Physical Property
Property (tanδ index)













Example
Comparative

















part by mass
238
239
240
241
242
243
244
Example 20























Formu-
First
Solution-Polymerized SBR-A *1
100
100
100
100
100
100
100
100



lation
Stage of
Carbon Black N220 *2
10
10
10
10
10
10
10
10




Kneading
Silica *27
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





Aromatic Oil
30
30
30
30
30
30
30
30





Stearic Acid
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0





Antiaging Agent 6PPD *5
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0





Tetrakis(2-ethylhexyl)thiuram
—
—
—
—
—
—
—
—





Disulfide *6





Tetrabenzylthiuram Disulfide *7
—
—
—
—
—
—
—
—





N,N′-diethylthiourea *8
—
—
—
—
—
—
—
—





Trimethylthiourea *9
1.0
—
—
—
—
—
—
—





N,N′-diphenylthiourea *10
—
1.0
—
—
—
—
—
—





Zinc Dibenzyldithiocarbamate
—
—
1.0
—
—
—
—
—





*11





Zinc N-ethyl-N-phenyldithio-
—
—
—
1.0
—
—
—
—





carbamate *12





Zinc Dimethyldithio-
—
—
—
—
1.0
—
—
—





carbamate *13





Copper Dimethyldithio-
—
—
—
—
—
1.0
—
—





carbamate *14





Zinc Isopropylxanthate *15
—
—
—
—
—
—
1.0
—




Final
Antiaging Agent TMDQ *16
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0




Stage of
Zinc Flower
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5




Kneading
1,3-Diphenylguanidine *17
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6





Vulcanization Promoter
1.0
1.0
1.0
1.0
1.0
1.0
1.0
1.0





MBTS *18





Vulcanization Promoter
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6





TBBS *19





Sulfur
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5

















Highest Temperature of Rubber Composition
170
170
170
170
170
170
170
150



in First Stage of Kneading (° C.)



Time of Adding Vulcanization Promoter (D)
90
90
90
90
90
90
90
—



in First Stage of Kneading (Note 1


















Vulcanizate
Low-Heat-Generation
105
103
105
106
105
105
106
100



Physical Property
Property (tanδ index)







[Notes]



(Note 1:



This indicates how much time (second) was taken after the time, referred to as 0 second, of addition of silica, silane coupling agent and other chemicals added in the first stage.



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



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



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



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



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



*10: Ouchi Shinko Chemical's trade name “Nocceler C”



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



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



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



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



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



*16: 2, 2,4-Trimethyl-1,2-dihydroquinoline polymer, Ouchi Shinko Chemical's trade name “Noclac 224”



*17: Sanshin Chemical's trade name “Sanceler D”



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



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



*20: JSR's emulsion-polymerized styrene-butadiene copolymer rubber (SBR), trade name “#1500”



*21: 3-Octanoylthiopropyltriethoxysilane, Momentive Performance Materials' trade name “NXT Silane” (registered trademark)



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



*21: Silane coupling agent represented by the following average compositional formula obtained in Production Example 1: (CH3CH2O)3Si—(CH2)3—S—(CH2)6—S2.5—(CH2)6—S—(CH2)3—Si(OCH2CH3)3



*24: Tosoh Silica's trade name “Nipseal KQ”, BET specific surface area 240 m2/g



*25: Tosoh Silica's trade name “Nipseal NS”, BET specific surface area 160 m2/g



*26: Tosoh Silica's trade name “Nipseal NA”, BET specific surface area 135 m2/g



*27: Tosoh Silica's trade name “Nipseal ER”, BET specific surface area 95 m2/g






As obvious from Table 1 to Table 17, the rubber compositions of Examples 1 to 244 are all better than the comparative rubber compositions of Comparative Examples 1 to 20 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, a filler containing an inorganic filler (B), a silane coupling agent (C) and at least one vulcanization promoter (D) selected from thiurams, dithiocarbamate salts, thioureas and xanthate salts, wherein in a 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) are kneaded and then the vulcanization promoter (D) is added and further kneaded.

2. The method for producing a rubber composition according to claim 1, wherein an organic acid compound (E) is further kneaded in the first stage of kneading, and the number of molecules X of the organic acid compound (E) in the rubber composition in the first stage satisfies the following relational formula [1] relative to the number of molecules Y of the vulcanization promoter (D):


0<X<1.5×Y  [1].

3. The method for producing a rubber composition according to claim 1, wherein the highest temperature of the rubber composition in the first stage of kneading is from 120 to 190° C.

4. 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):
[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);



(wherein R4 represents a monovalent group selected from —Cl, —Br, R9O—, R9C(═O)O—, R9R10C═NO—, R9R10CNO—, R9R10 N—, 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);
[Chemical Formula 3]


(R13O)3-s(R14)sSi—R15—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 m3each indicates 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 is 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).

5. The method for producing a rubber composition according to claim 4, wherein the silane coupling agent (C) is a compound represented by the general formula (I).

6. The method for producing a rubber composition according to claim 1, wherein the inorganic filler (B) is silica.

7. The method for producing a rubber composition according to claim 1, wherein the inorganic filler (B) accounts for at least 30% by mass of the filler.

8. The method for producing a rubber composition according to claim 1, wherein the number of molecules of the vulcanization promoter (D) in the rubber composition in the first stage of kneading is from 0.1 to 1.0 time the number of molecules of the silane coupling agent (C) therein.

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

10. The method for producing a rubber composition according to claim 1, wherein the thiourea is at least one compound selected from N,N′-diethylthiourea, trimethylthiourea, N,N′-diphenylthiourea and N,N′-dimethylthiourea.

11. The method for producing a rubber composition according to claim 1, wherein the dithiocarbamate salt is at least one compound selected from zinc dibenzyldithiocarbamate, zinc N-ethyl-N-phenyldithiocarbamate, zinc dimethyldithiocarbamate and copper dimethyldithiocarbamate.

12. The method for producing a rubber composition according to claim 1, wherein the xanthate salt is zinc isopropylxanthate.

13. The method for producing a rubber composition according to claim 1, wherein the rubber composition contains an organic acid compound (E) in the first stage of kneading, and a stearic acid accounts for at least 50 mol % of the organic acid compound (E) in the rubber composition in the first stage of kneading.

14. The method for producing a rubber composition according to claim 1, wherein the rubber composition contains an organic acid compound (E) in the first stage of kneading, the rubber component (A) contains at least one selected from emulsion-polymerized styrene-butadiene copolymer and natural rubber, and at least 50 mol % of the organic acid compound (E) contained in the rubber composition in the first stage of kneading is at least one compound selected from rosin acids contained in the emulsion-polymerized styrene-butadiene copolymer and fatty acids contained in at least one selected from the emulsion-polymerized styrene butadiene copolymer and the natural rubber.