RUBBER COMPOSITION FOR TIRE, AND PNEUMATIC TIRE

The present invention provides a rubber composition for a tire, which has an increased rate of reaction between a silane coupling agent and silica so that its performances including fuel economy and abrasion resistance can be enhanced; and a pneumatic tire formed from the rubber composition. The present invention relates to a rubber composition for a tire, containing: diene rubber; silica; a silane coupling agent; and a carbonate salt and/or a hydrogen carbonate salt, wherein the rubber composition has a total content of the carbonate salt and the hydrogen carbonate salt of 0.3 to 25 parts by mass relative to 100 parts by mass of the silica.

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Description
TECHNICAL FIELD

The present invention relates to a rubber composition for a tire, and a pneumatic tire formed from the rubber composition.

BACKGROUND ART

Conventionally, silica has been used as a reinforcing filler in order to enhance the performances of tires such as durability (abrasion resistance) and fuel economy. Also, because a satisfactory effect cannot be achieved by using silica alone, silica has been used in combination with a silane coupling agent that bonds silica to the rubber component.

In order for a silane coupling agent to react with silica, it is necessary for an alkoxy group or the like bonded to the silicon atom in the silane coupling agent to be hydrolyzed to form a silanol group. However, because hydrolysis reaction of an alkoxy group or the like will not proceed in a short period of time, it has been difficult to bring about sufficient hydrolysis of an alkoxy group or the like in a rubber kneading step. Conventionally, therefore, the rate of reaction between a silane coupling agent and silica is low and the performance of silica cannot be maximized.

As the method for solving the above-mentioned problem, Patent Literatures 1 to 3 disclose adding boric acid or the like in a rubber composition. Still, further improvement in terms of the rate of reaction and the like is desired.

CITATION LIST Patent Literature

  • Patent Literature 1: JP-A 2007-77322
  • Patent Literature 2: JP-A 2001-247718
  • Patent Literature 3: JP-A 2005-232295

SUMMARY OF INVENTION Technical Problem

An object of the present invention is to solve the aforementioned problem and provide a rubber composition for a tire, which has an increased rate of reaction between a silane coupling agent and silica so that its performances including fuel economy and abrasion resistance can be enhanced; and a pneumatic tire formed from the rubber composition.

Solution to Problem

As a result of diligent research into how to solve the aforementioned problem, the inventor of the present invention has found that a carbonate salt, a hydrogen carbonate salt or carbon dioxide, which is generated by the decomposition of these salts, promotes a hydrolysis reaction of an alkoxy group or the like, thereby improving the rate of reaction between a silane coupling agent and silica, and has thereby completed the present invention.

The present invention relates to a rubber composition for a tire, containing: diene rubber; silica; a silane coupling agent; and at least one of a carbonate salt and a hydrogen carbonate salt, wherein the rubber composition has a total content of the carbonate salt and the hydrogen carbonate salt of 0.3 to 25 parts by mass relative to 100 parts by mass of the silica.

Preferably, the carbonate salt is at least one selected from the group consisting of sodium carbonate, potassium carbonate, ammonium carbonate, lithium carbonate, calcium carbonate and magnesium carbonate, and the hydrogen carbonate salt is at least one selected from the group consisting of sodium hydrogen carbonate, potassium hydrogen carbonate and ammonium hydrogen carbonate.

Preferably, the carbonate salt is at least one selected from the group consisting of sodium carbonate, ammonium carbonate, lithium carbonate, calcium carbonate and magnesium carbonate, and the hydrogen carbonate salt is ammonium hydrogen carbonate.

Preferably, the potassium carbonate has an average particle size of 40 μm or smaller.

Preferably, the silane coupling agent is at least one selected from the group consisting of a sulfide-type silane coupling agent, a silane coupling agent represented by formula (1):

wherein R1 is a group represented by —O—(R5—O)m—R6 in which m pieces of R5 are the same or different and each denote a branched or unbranched divalent hydrocarbon group having 1 to 30 carbon atoms, R6 denotes a branched or unbranched alkyl group having 1 to 30 carbon atoms, a branched or unbranched alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms, and m is an integer between 1 and 30; R2 and R3 are the same or different and each denote a group as defined for R1, a branched or unbranched alkyl group having 1 to 12 carbon atoms, or a group represented by —O—R7 in which R7 denotes a hydrogen atom, a branched or unbranched alkyl group having 1 to 30 carbon atoms, a branched or unbranched alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms; and R4 denotes a branched or unbranched alkylene group having 1 to 30 carbon atoms, and

a silane coupling agent containing linking units A and B respectively represented by formulae (2) and (3):

wherein x is an integer of 0 or higher; y is an integer of 1 or higher; R8 denotes a hydrogen atom, a halogen atom, a branched or unbranched alkyl or alkylene group having 1 to 30 carbon atoms, a branched or unbranched alkenyl or alkenylene group having 2 to 30 carbon atoms, a branched or unbranched alkynyl or alkynylene group having 2 to 30 carbon atoms, or a group in which a terminal of the alkyl or alkenyl group is substituted with a hydroxyl or carboxyl group; R9 denotes a hydrogen atom, a branched or unbranched alkylene or alkyl group having 1 to 30 carbon atoms, a branched or unbranched alkenylene or alkenyl group having 2 to 30 carbon atoms, or a branched or unbranched alkynylene or alkynyl group having 2 to 30 carbon atoms; and R8 and R9 may together form a ring structure.

Preferably, 5 to 150 parts by mass of the silica is contained relative to 100 parts by mass of the diene rubber, and 2 to 20 parts by mass of the silane coupling agent is contained relative to 100 parts by mass of the silica.

Preferably, the rubber composition for a tire is obtained by a production method including: a step (A) of kneading diene rubber, silica, a silane coupling agent, and at least one of a carbonate salt and a hydrogen carbonate salt, and discharging the resulting kneaded mixture A; a step (B) of kneading the kneaded mixture A discharged in the step (A), stearic acid and zinc oxide, and discharging the resulting kneaded mixture B; and a step (C) of kneading the kneaded mixture B discharged in the step (B), a vulcanizing agent and a vulcanization accelerator.

Preferably, the rubber composition for a tire is obtained by a production method including: a step (a) of kneading diene rubber, silica, a silane coupling agent, and at least one of a carbonate salt and a hydrogen carbonate salt, adding thereto stearic acid and zinc oxide, further kneading them, and discharging the resulting kneaded mixture a; and a step (b) of kneading the kneaded mixture a discharged in the step (a), a vulcanizing agent and a vulcanization accelerator.

The present invention also relates to a pneumatic tire formed from the rubber composition.

Advantageous Effects of Invention

According to the present invention, the rubber composition for a tire contains: diene rubber; silica; a silane coupling agent; and a predetermined amount of a carbonate salt and/or a hydrogen carbonate salt, and therefore has an increased rate of reaction between the silane coupling agent and silica so that its performances including fuel economy and abrasion resistance can be enhanced. Therefore, by using this rubber composition in various tire components, it is possible to provide pneumatic tires having excellent fuel economy and abrasion resistance.

DESCRIPTION OF EMBODIMENTS

The rubber composition for a tire of the present invention contains: diene rubber; silica; a silane coupling agent; and a predetermined amount of a carbonate salt and/or a hydrogen carbonate salt.

Rubbers able to be used as the diene rubber in the present invention are not particularly limited, and include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), styrene-isoprene-butadiene rubber (SIBR), styrene-isoprene rubber (SIR) and isoprene-butadiene rubber. It is possible to use one type of diene rubber or a combination of two or more types thereof. Of these, SBR, NR, IR and BR are preferred because they can enhance the abrasion resistance so that good abrasion resistance, fuel economy and wet grip performance can be obtained. Also, using oil-free SBR (non-oil-extended SBR) can also lead to such an effect.

Examples of SBR able to be used include emulsion polymerized styrene-butadiene rubber (E-SBR) and solution polymerized styrene-butadiene rubber (S-SBR). Of these, S-SBR is preferred because it can enhance the abrasion resistance so that both this performance and fuel economy can be satisfied.

The bound styrene content in SBR is preferably 40% by mass or lower, more preferably 35% by mass or lower, further preferably 30% by mass or lower, and particularly preferably 28% by mass or lower. If the bound styrene content exceeds 40% by mass, the glass transition temperature (Tg) tends to increase and the abrasion resistance tends to deteriorate. Also, the bound styrene content in SBR is preferably 10% by mass or higher, more preferably 20% by mass or higher, and further preferably 24% by mass or higher. If the bound styrene content is less than 10% by mass, the Tg value may be too low and it may not be possible to achieve satisfactory wet grip performance.

Here, the styrene content can be calculated by 1H-NMR measurement.

The content of SBR is preferably 50% by mass or higher, and more preferably 60% by mass or higher, based on 100% by mass of the diene rubber. If the content is lower than 50% by mass, it may not be possible to achieve satisfactory wet grip performance. The content may be 100% by mass, but is preferably 90% by mass or lower, and more preferably 70% by mass or lower. If the content exceeds 90% by mass, the fuel economy may deteriorate.

Examples of NR able to be used include those commonly used in the tire industry, such as SIR20, RSS#3 and TSR20.

The content of NR is preferably 20% by mass or higher, and more preferably 30% by mass or higher, based on 100% by mass of the diene rubber. If the content is lower than 20% by mass, the rubber strength may deteriorate, which may cause separation of rubber pieces. The content is preferably 85% by mass or lower, more preferably 70% by mass or lower, further preferably 50% by mass or lower, and particularly preferably 40% by mass or lower. If the content exceeds 85% by mass, the wet grip performance may deteriorate.

Silica is used in the present invention. Compounding silica can lead to enhancement in wet grip performance and fuel economy and also improvement of abrasion resistance due to its reinforcing effect. The type of silica used is not particularly limited, and may be, for example, dry silica (silicic anhydride) or wet silica (hydrous silicic acid), but wet silica is preferred because it has a large amount of silanol groups.

The nitrogen adsorption specific surface area (N2SA) of silica is preferably 40 m2/g or higher, more preferably 50 m2/g or higher, further preferably 100 m2/g or higher, and particularly preferably 150 m2/g or higher. If the nitrogen adsorption specific surface area is lower than 40 m2/g, it may not be possible to achieve satisfactory abrasion resistance. Also, the N2SA of silica is preferably 220 m2/g or lower, and more preferably 200 m2/g or lower. If the N2SA exceeds 220 m2/g, dispersion of the silica may be difficult so that dispersion problems may occur.

Here, the nitrogen adsorption specific surface area of silica is a value measured using the BET method in accordance with ASTM D3037-81.

The content of silica is preferably 5 parts by mass or higher, and more preferably 15 parts by mass or higher, relative to 100 parts by mass of the diene rubber. If the content is lower than 5 parts by mass, satisfactory rubber strength may not be obtained and the abrasion resistance may deteriorate. The content of silica is preferably 150 parts by mass or lower, and more preferably 120 parts by mass or lower. If the content exceeds 150 parts by mass, the silica dispersibility tends to deteriorate and the abrasion resistance tends to deteriorate.

A silane coupling agent is used in the present invention. Compounding a silane coupling agent brings about bonding between rubber and silica, thereby enhancing performance such as abrasion resistance.

The silane coupling agent is not particularly limited, and examples thereof include sulfide-type silane coupling agents such as bis(3-triethoxysilylpropyl)tetrasulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(4-triethoxysilylbutyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, bis(4-trimethoxysilylbutyl)tetrasulfide, bis(3-triethoxysilylpropyl)trisulfide, bis(2-triethoxysilylethyl)trisulfide, bis(4-triethoxysilylbutyl)trisulfide, bis(3-trimethoxysilylpropyl)trisulfide, bis(2-trimethoxysilylethyl)trisulfide, bis(4-trimethoxysilylbutyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, bis(2-triethoxysilylethyl)disulfide, bis(4-triethoxysilylbutyl)disulfide, bis(3-trimethoxysilylpropyl)disulfide, bis(2-trimethoxysilylethyl)disulfide, bis(4-trimethoxysilylbutyl)disulfide, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyl tetrasulfide, 2-trimethoxysilylethyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropyl benzothiazolyl tetrasulfide, 3-triethoxysilylpropyl benzothiazole tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide and 3-trimethoxysilylpropyl methacrylate monosulfide; mercapto-type silane coupling agents such as 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane and 2-mercaptoethyltriethoxysilane; vinyl-type silane coupling agents such as vinyltriethoxysilane and vinyltrimethoxysilane; amino-type silane coupling agents such as 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltriethoxysilane and 3-(2-aminoethyl)aminopropyltrimethoxysilane; glycidoxy-type silane coupling agents such as γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane and γ-glycidoxypropylmethyldimethoxysilane; nitro-type silane coupling agents such as 3-nitropropyltrimethoxysilane and 3-nitropropyltriethoxysilane; and chlorine-type silane coupling agents such as 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 2-chloroethyltrimethoxysilane and 2-chloroethyltriethoxysilane.

Of these, preferred are sulfide-type silane coupling agents (especially, bis(3-triethoxysilylpropyl)disulfide and bis(3-triethoxysilylpropyl)tetrasulfide), silane coupling agents represented by the following formula (1) and silane coupling agents containing linking units A represented by the following formula (2) and linking units B represented by the following formula (3) because they exhibit high rates of reaction with silica so that excellent abrasion resistance can be obtained.

In formula (1), R1 is a group represented by —O—(R5—O)m—R6 in which m pieces of R5 are the same or different and each denote a branched or unbranched divalent hydrocarbon group having 1 to 30 carbon atoms, R6 denotes a branched or unbranched alkyl group having 1 to 30 carbon atoms, a branched or unbranched alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms, and m is an integer between 1 and 30; R2 and R3 are the same or different and each denote a group as defined for R1, a branched or unbranched alkyl group having 1 to 12 carbon atoms, or a group represented by —O—R7 in which R7 denotes a hydrogen atom, a branched or unbranched alkyl group having 1 to 30 carbon atoms, a branched or unbranched alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms; and R4 denotes a branched or unbranched alkylene group having 1 to 30 carbon atoms.

In formulae (2) and (3), x is an integer of 0 or higher; y is an integer of 1 or higher; R8 denotes a hydrogen atom, a halogen atom, a branched or unbranched alkyl or alkylene group having 1 to 30 carbon atoms, a branched or unbranched alkenyl or alkenylene group having 2 to 30 carbon atoms, a branched or unbranched alkynyl or alkynylene group having 2 to 30 carbon atoms, or a group in which a terminal of the alkyl or alkenyl group is substituted with a hydroxyl or carboxyl group; R9 denotes a hydrogen atom, a branched or unbranched alkylene or alkyl group having 1 to 30 carbon atoms, a branched or unbranched alkenylene or alkenyl group having 2 to 30 carbon atoms, or a branched or unbranched alkynylene or alkynyl group having 2 to 30 carbon atoms; and R8 and R9 may together form a ring structure.

By compounding the silane coupling agent represented by formula (1) above, it is possible to achieve excellent fuel economy and abrasion resistance.

In formula (1) above, R1 is a group represented by —O—(R5—O)m—R6 in which m pieces of R5 are the same or different and each denote a branched or unbranched divalent hydrocarbon group having 1 to 30 carbon atoms, R6 denotes a branched or unbranched alkyl group having 1 to 30 carbon atoms, a branched or unbranched alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms, and m is an integer between 1 and 30.

The R5 groups are the same or different and each denote a branched or unbranched divalent hydrocarbon group having 1 to 30 carbon atoms (preferably 1 to 15 carbon atoms, and more preferably 1 to 3 carbon atoms).

Examples of this hydrocarbon group include branched or unbranched alkylene groups having 1 to 30 carbon atoms, branched or unbranched alkenylene groups having 2 to 30 carbon atoms, branched or unbranched alkynylene groups having 2 to 30 carbon atoms and arylene groups having 6 to 30 carbon atoms. Of these, the alkylene groups are preferred because they can bond (react) readily with silica so that the fuel economy and abrasion resistance can be satisfactorily enhanced.

The branched or unbranched alkylene groups having 1 to 30 carbon atoms (preferably 1 to 15 carbon atoms, and more preferably 1 to 3 carbon atoms) of R5 include, for example, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, a tridecylene group, a tetradecylene group, a pentadecylene group, a hexadecylene group, a heptadecylene group and an octadecylene group.

The branched or unbranched alkenylene groups having 2 to 30 carbon atoms (preferably 2 to 15 carbon atoms, and more preferably 2 to 3 carbon atoms) of R5 include, for example, a vinylene group, a 1-propenylene group, a 2-propenylene group, a 1-butenylene group, a 2-butenylene group, a 1-pentenylene group, a 2-pentenylene group, a 1-hexenylene group, a 2-hexenylene group and a 1-octenylene group.

The branched or unbranched alkynylene groups having 2 to 30 carbon atoms (preferably 2 to 15 carbon atoms, and more preferably 2 to 3 carbon atoms) of R5 include, for example, an ethynylene group, a propynylene group, a butynylene group, a pentynylene group, a hexynylene group, a heptynylene group, an octynylene group, a nonynylene group, a decynylene group, an undecynylene group and a dodecynylene group.

The arylene groups having 6 to 30 carbon atoms (preferably 6 to 15 carbon atoms) of R5 include, for example, a phenylene group, a tolylene group, a xylylene group and a naphthylene group.

The m denotes an integer between 1 and 30 (preferably between 2 and 20, more preferably between 3 and 7, and further preferably between 5 and 6). If m is 0, the bonding (reaction) with silica is adversely affected, whereas if m is 31 or higher, the reactivity with silica decreases, which is disadvantageous from the perspective of the process.

R6 denotes a branched or unbranched alkyl group having 1 to 30 carbon atoms, a branched or unbranched alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms. Among these, R6 is preferably a branched or unbranched alkyl group having 1 to 30 carbon atoms because it leads to good reactivity with silica.

Examples of the branched or unbranched alkyl group having 1 to 30 carbon atoms (preferably 3 to 25 carbon atoms, and more preferably 10 to 15 carbon atoms) of R6 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group and an octadecyl group.

Examples of the branched or unbranched alkenyl group having 2 to 30 carbon atoms (preferably 3 to 25 carbon atoms, and more preferably 10 to 15 carbon atoms) of R6 include a vinyl group, a 1-propenyl group, a 2-propenyl group, a 1-butenyl group, a 2-butenyl group, a 1-pentenyl group, a 2-pentenyl group, a 1-hexenyl group, a 2-hexenyl group, a 1-octenyl group, a decenyl group, an undecenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group and an octadecenyl group.

Examples of the aryl group having 6 to 30 carbon atoms (preferably 10 to 20 carbon atoms) of R6 include a phenyl group, a tolyl group, a xylyl group, a naphthyl group and a biphenyl group.

Examples of the aralkyl group having 7 to 30 carbon atoms (preferably 10 to 20 carbon atoms) of R6 include a benzyl group and a phenethyl group.

Specific examples of R1 in formula (1) above include —O—(C2H4—O)5—C11H23, —O—(C2H4—O)5—C12H25, —O—(C2H4—O)5—C13H27, —O—(C2H4—O)5—C14H29, —O—(C2H4—O)5—C15H31, —O—(C2H4—O)3—C13H27, —O—(C2H4—O)4—C13H27, —O—(C2H4—O)6—C13H27 and —O—(C2H4—O)7—C13H27. Of these, —O—(C2H4—O)5—C11H23, —O—(C2H4—O)5—C13H27, —O—(C2H4—O)5—C15H31 and —O—(C2H4—O)6—C13H27 are preferred.

R2 and R3 are the same or different and each denote a group as defined for R1 (that is, a group represented by —O—(R5—O)m—R6), a branched or unbranched alkyl group having 1 to 12 carbon atoms, or a group represented by —O—R7 in which R7 denotes a hydrogen atom, a branched or unbranched alkyl group having 1 to 30 carbon atoms, a branched or unbranched alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms. Among these, R2 and R3 each are preferably a group as defined for R1 or a group represented by —O—R7 in which R7 denotes a branched or unbranched alkyl group having 1 to 30 carbon atoms because they exhibit good reactivity with silica.

Examples of the branched or unbranched alkyl group having 1 to 12 carbon atoms (preferably 1 to 8 carbon atoms, and more preferably 1 to 5 carbon atoms) for R2 and R3 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, an octyl group and a nonyl group.

Examples of the branched or unbranched alkyl group having 1 to 30 carbon atoms (preferably 1 to 15 carbon atoms, and more preferably 1 to 3 carbon atoms) of R7 include the same groups as mentioned as the branched or unbranched alkyl group having 1 to 30 carbon atoms of R6.

Examples of the branched or unbranched alkenyl group having 2 to 30 carbon atoms of R7 include the same groups as mentioned as the branched or unbranched alkenyl group having 2 to 30 carbon atoms of R6.

Examples of the aryl group having 6 to 30 carbon atoms of R7 include the same groups as mentioned as the aryl group having 6 to 30 carbon atoms of R6.

Examples of the aralkyl group having 7 to 30 carbon atoms of R7 include the same groups as mentioned as the aralkyl group having 7 to 30 carbon atoms of R6.

Specific examples of R2 and R3 in formula (1) above include —O—(C2H4—O)5—C11H23, —O—(C2H4—O)5—C12H25, —O—(C2H4—O)5—C13H27, —O—(C2H4—O)5—C14H29, —O—(C2H4—O)5—C15H31, —O—(C2H4—O)3—C13H27, —O—(C2H4—O)4C13H27, —O—(C2H4—O)6—C13H27, —O—(C2H4—O)7—C13H27, C2H5—O—, CH3—O— and C3H7—O—. Of these, —O—(C2H4—O)5—C11H23, —O—(C2H4—O)5—C13H27, —O—(C2H4—O)5—C15H31, —O—(C2H4—O)6—C13H27 and C2H5—O— are preferred.

Examples of the branched or unbranched alkylene group having 1 to 30 carbon atoms (preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms) of R4 include the same groups as mentioned as the branched or unbranched alkylene group having 1 to 30 carbon atoms of R5.

The silane coupling agent represented by formula (1) above may be, for example, Si363 produced by Degussa. It is possible to use one of such silane coupling agents or a combination of two or more thereof.

Also, by compounding a silane coupling agent containing linking units B represented by formula (3) above and optionally linking units A represented by formula (2) above, it is possible to enhance the fuel economy and abrasion resistance compared with a case in which a conventional silane coupling agent, such as bis(3-triethoxysilylpropyl)tetrasulfide, is used.

The silane coupling agent containing linking units A and B is preferably a copolymer in which the proportion of linking units B is 1 to 70 mol % of the total molar amount of linking units A and B.

If the molar ratio of linking units A and B satisfies this condition, an increase in viscosity during processing can be suppressed compared with cases in which polysulfide silanes such as bis(3-triethoxysilylpropyl)tetrasulfide are used. This is thought to be because the sulfide moiety in linking unit A is a C—S—C bond and is therefore more thermally stable than tetrasulfide or disulfide, which leads to less increase in Mooney viscosity.

Also, if the molar ratio of linking units A and B satisfies the condition, a reduction in scorch time can be suppressed compared with cases in which mercaptosilanes such as 3-mercaptopropyltrimethoxysilane are used. This is thought to be because although linking unit B has a mercaptosilane structure, the —C7H15 moiety in linking unit A covers the —SH group in linking unit B, and the silane coupling agent is therefore less likely to react with the polymer, which leads to less scorching.

The halogen atom of R8 may be chlorine, bromine, fluorine or the like.

Examples of the branched or unbranched alkyl groups having 1 to 30 carbon atoms (preferably 1 to 12 carbon atoms, and more preferably 1 to 5 carbon atoms) for R8 and R9 include the same groups as mentioned as the branched or unbranched alkyl group having 1 to 30 carbon atoms of R6.

Examples of the branched or unbranched alkylene groups having 1 to 30 carbon atoms (preferably 1 to 12 carbon atoms) for R8 and R9 include the same groups as mentioned as the branched or unbranched alkylene group having 1 to 30 carbon atoms of R5.

Examples of the branched or unbranched alkenyl groups having 2 to 30 carbon atoms (preferably 2 to 12 carbon atoms) for R8 and R9 include the same groups as mentioned as the branched or unbranched alkenyl group having 2 to 30 carbon atoms of R6.

Examples of the branched or unbranched alkenylene groups having 2 to 30 carbon atoms (preferably 2 to 12 carbon atoms) for R8 and R9 include the same groups as mentioned as the branched or unbranched alkenylene group having 2 to 30 carbon atoms of R5.

Examples of the branched or unbranched alkynyl groups having 2 to 30 carbon atoms (preferably 2 to 12 carbon atoms) for R8 and R9 include an ethynyl group, a propynyl group, a butynyl group, a pentynyl group, a hexynyl group, a heptynyl group, an octynyl group, a nonynyl group, a decynyl group, an undecynyl group and a dodecynyl group.

Examples of the branched or unbranched alkynylene groups having 2 to 30 carbon atoms (preferably 2 to 12 carbon atoms) for R8 and R9 include the same groups as mentioned as the branched or unbranched alkynylene group having 2 to 30 carbon atoms of R5.

In the silane coupling agent containing linking units A and B, the total number of repetitions (x+y) of the number of repetitions (x) of linking unit A and the number of repetitions (y) of linking unit B is preferably in the range of 3 to 300. If x+y is in this range and x is 1 or higher, the —C7H15 moiety in linking unit A covers the mercaptosilane in linking unit B, and it is therefore possible to suppress a reduction in scorch time and to ensure good reactivity with silica and with the rubber component.

Examples of the silane coupling agent containing linking units A and B include NXT-Z30, NXT-Z45, NXT-Z60 and NXT-Z100 all of which are produced by Momentive. It is possible to use one of such silane coupling agents or a combination of two or more thereof.

The content of the silane coupling agent is preferably 2 parts by mass or higher, more preferably 4 parts by mass or higher, and further preferably 6 parts by mass or higher, relative to 100 parts by mass of the silica. If the content is lower than 2 parts by mass, it tends not be possible to produce a satisfactory effect to enhance the fuel economy. Also, the content of the silane coupling agent is preferably 20 parts by mass or lower, more preferably 15 parts by mass or lower, and further preferably 10 parts by mass or lower. If the content exceeds 20 parts by mass, the fuel economy and abrasion resistance tend to fail to be improved with increase in the content and therefore costs tend to increase.

In cases where two or more silane coupling agents are used in combination, the content means the total content of the silane coupling agents.

At least one compound selected from the group consisting of carbonate salts and hydrogen carbonate salts is compounded in the present invention. This promotes a hydrolysis reaction of an alkoxy group or the like in the silane coupling agent and therefore a hydrolysis reaction of an alkoxy group or the like will proceed sufficiently (that is, silanol groups will be sufficiently produced) in the rubber composition kneading step, which can lead to an increased rate of reaction between the silane coupling agent and silica. Therefore, the fuel economy and abrasion resistance of the resulting rubber composition (pneumatic tire) can be enhanced.

Suitable carbonate salts and hydrogen carbonate salts are inorganic carbonate salts and inorganic hydrogen carbonate salts from the perspective of increasing the rate of reaction between the silane coupling agent and silica. Examples of the inorganic carbonate salts include alkali metal carbonates such as sodium carbonate, potassium carbonate and lithium carbonate; ammonium carbonate; and alkaline earth metal carbonates such as calcium carbonate and magnesium carbonate. Examples of the inorganic hydrogen carbonate salts include alkali metal hydrogen carbonates such as sodium hydrogen carbonate, potassium hydrogen carbonate and lithium hydrogen carbonate; ammonium hydrogen carbonate; and alkaline earth metal hydrogen carbonates such as calcium hydrogen carbonate and magnesium hydrogen carbonate. Of these, sodium carbonate, potassium carbonate, ammonium carbonate, lithium carbonate, calcium carbonate, magnesium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and ammonium hydrogen carbonate are preferred, and sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and ammonium hydrogen carbonate are more preferred, in terms of effectively increasing the reaction rate. In particular, ammonium hydrogen carbonate is very suitable because it has a lower melting temperature than metal salts and will decompose into carbon dioxide, ammonia and water, which will then vaporize, in a base kneading step, so that no adverse effect is caused on vulcanization in a final kneading step and therefore good vulcanization is ensured. Here, because ammonium hydrogen carbonate has a low decomposition temperature and some amount will vaporize in the step, it needs to be added in an amount somewhat larger than those of other inorganic carbonate salts and inorganic hydrogen carbonate salts.

Meanwhile, potassium carbonate having an average particle size of 40 μm or smaller is preferably used. The average particle size is more preferably 30 μm or smaller, and further preferably 20 μm or smaller. If the average particle size exceeds 40 μm, fracture nuclei tend to be formed due to poor dispersion of the potassium carbonate, in other words, foreign matter contaminates the rubber composition, and therefore breakage of the rubber composition tends to occur around foreign matter particles, thereby leading to poor abrasion resistance. Also, the lower limit of the average particle size is not particularly limited, but is preferably 3 μm or greater, and more preferably 5 μm or greater.

The average particle size of potassium carbonate herein is a value measured using a laser diffraction/scattering particle size distribution analyzer (LA-910 manufactured by Horiba, Ltd.).

The total content of the carbonate salt and the hydrogen carbonate salt is 0.3 parts by mass or higher, preferably 0.5 parts by mass or higher, more preferably 1 part by mass or higher, and further preferably 2 parts by mass or higher, relative to 100 parts by mass of the silica. If the total content is lower than 0.3 parts by mass, the rate of reaction between the silane coupling agent and silica tends not to be increased sufficiently, thereby failing to enhance the fuel economy and abrasion resistance. The total content is 25 parts by mass or lower, preferably 20 parts by mass or lower, more preferably 10 parts by mass or lower, and further preferably 6 parts by mass or lower. If the total content exceeds 25 parts by mass, the content of the carbonate salt and hydrogen carbonate salt is so high that the rolling resistance tends to increase to reduce the fuel economy.

In addition to the aforementioned components, compounding ingredients commonly used in the production of rubber compositions, such as carbon black, stearic acid, antioxidants, antiozonants, oil, wax, vulcanizing agents and vulcanization accelerators, may be compounded as appropriate in the rubber composition of the present invention.

Usable antioxidants include amine antioxidants, for example, diphenylamine derivatives such as p-(p-toluenesulfonylamide)-diphenylamine; and p-phenylenediamine derivatives such as N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine (6PPD) and N-phenyl-N′-isopropyl-p-phenylenediamine (IPPD).

In the rubber composition of the present invention, the content of the antioxidant is preferably 5 parts by mass or lower, more preferably 4 parts by mass or lower, and further preferably 3 parts by mass or lower, relative to 100 parts by mass of the diene rubber.

The rubber composition of the present invention can be produced using an ordinary method. Specifically, the rubber composition can be produced by, for example, kneading the aforementioned components in a Banbury mixer, a kneader, an open roll mill or the like, and then vulcanizing the mixture.

In particular, Production Methods 1 and 2 mentioned below are preferred and Production Method 1 is more preferred because firstly kneading the rubber component, the silica, the silane coupling agent and the carbonate salt and/or hydrogen carbonate salt can lead to an increased rate of reaction between the silane coupling agent and silica and therefore excellent fuel economy and abrasion resistance.

(Production Method 1)

A production method that includes: a step (A) of kneading diene rubber, silica, a silane coupling agent, and a carbonate salt and/or a hydrogen carbonate salt, and discharging the resulting kneaded mixture A; a step (B) of kneading the kneaded mixture A discharged in the step (A), stearic acid and zinc oxide, and discharging the resulting kneaded mixture B; and a step (C) of kneading the kneaded mixture B discharged in the step (B), a vulcanizing agent and a vulcanization accelerator.

(Production Method 2)

A production method that includes: a step (a) of kneading diene rubber, silica, a silane coupling agent, and a carbonate salt and/or a hydrogen carbonate salt, adding thereto stearic acid and zinc oxide, further kneading them, and discharging the resulting kneaded mixture a; and a step (b) of kneading the kneaded mixture a discharged in the step (a), a vulcanizing agent and a vulcanization accelerator.

The kneading processes in the steps in Production Methods 1 and 2 can be carried out using a conventionally known kneading machine and the kneading temperature and time may be set as appropriate. With regard to the kneading temperature in particular, the kneading temperature in the steps (A) and (B) and the kneading temperature in the step (a) (the temperature at which diene rubber, silica, a silane coupling agent, and a carbonate salt and/or a hydrogen carbonate salt are kneaded and the temperature at which stearic acid and zinc oxide are added and further kneaded) each are preferably in the range of 120 to 160° C. Also, the kneading temperature in the steps (C) and (b) is preferably in the range of 70 to 120° C.

Oil, carbon black, an antioxidant, wax and the like may also be kneaded in the kneading process in the step (A) of Production Method 1. Here, it is preferable to knead oil together in this kneading process because the load on the kneading machine can be reduced. Also, an antioxidant, wax and the like may also be kneaded in the kneading process in the step (B).

Meanwhile, oil, carbon black, an antioxidant, wax and the like may also be kneaded in the kneading process in the step (a) of Production Method 2. Also, it is preferable to knead oil together in this kneading process for the same reason as that given above.

The kneading process in the steps (C) and (b) in Production Methods 1 and 2 is carried out, and then the resulting kneaded mixture (unvulcanized rubber composition) is vulcanized for 5 to 40 minutes at 140 to 185° C., whereby a vulcanized rubber composition can be obtained.

By using Production Method 1 or 2, it is possible to increase the rate of reaction between the silica and the silane coupling agent and thereby reduce the amount of unreacted silane coupling agent to 15% by mass or lower (preferably to 10% by mass or lower).

The amount of unreacted silane coupling agent can be measured using the method mentioned in examples given below.

The rubber composition of the present invention can be suitably used in various tire components. In particular, the rubber composition of the present invention is preferably used in treads (cap treads and base treads), sidewalls and clinches for which fuel economy, abrasion resistance and other performances are required.

The pneumatic tire of the present invention can be produced from the rubber composition by an ordinary method.

Specifically, an unvulcanized rubber composition with the aforementioned components compounded therein is extruded and processed into the shape of a tread or the like and then molded with other tire components in a tire building machine by an ordinary method to form an unvulcanized tire. A tire is obtained by heating and pressurizing this unvulcanized tire in a vulcanizer.

The pneumatic tire of the present invention can be suitably used as automotive tires, bus tires, truck tires and the like.

EXAMPLES

The present invention will now be explained in greater detail, referring to examples, but is in no way limited to these examples.

An explanation of the various chemicals used in the examples will now be given.

SBR: SBR Nipol NS210 produced by Zeon Corporation (bound styrene content: 25% by mass, Mooney viscosity (ML1+4, 100° C.): 56) NR: RSS#3
Carbon black: Diablack I produced by Mitsubishi Chemical Corporation
Silica: Ultrasil VN3 produced by Degussa (N2SA: 175 m2/g)
Silane coupling agent (1): Si266
(bis(3-triethoxysilylpropyl)disulfide) produced by Degussa
Silane coupling agent (2): Si363 produced by Degussa (silane coupling agent represented by formula below (in formula (1) above, R1═—O—(C2H4—O)5—C13H27, R2═C2H5—O—, R3═—O—(C2H4—O)5—C13H27, R4═—C3H6—))

Silane coupling agent (3): NXT-Z45 produced by Momentive (copolymer of linking units A and B, linking unit A: 55 mol %, linking unit B: 45 mol %)
Aromatic oil: X140 produced by Jomo
Stearic acid: stearic acid beads “Tsubaki” produced by NOF Corporation
Zinc oxide: zinc oxide #2 produced by Mitsui Mining & Smelting Co., Ltd.
Sulfur: sulfur (200 meshes) produced by Tsurumi Chemical Industry Co., Ltd.
Vulcanization accelerator TBBS: Nocceler NS produced by Ouchi Shinko Chemical Industrial Co., Ltd.
Vulcanization accelerator DPG: Nocceler D produced by Ouchi Shinko Chemical Industrial Co., Ltd.
Sodium carbonate: produced by Wako Pure Chemical Industries, Ltd.
Potassium carbonate (1): produced by Wako Pure Chemical Industries, Ltd. (average particle size: 340 μm as measured using a laser diffraction/scattering particle size distribution analyzer (LA-910 manufactured by Horiba, Ltd.))
Potassium carbonate (2): produced by Asahi Glass Co., Ltd. (average particle size: 21 μm as measured described above)
Ammonium carbonate: produced by Wako Pure Chemical Industries, Ltd.
Lithium carbonate: produced by Wako Pure Chemical Industries, Ltd.
Calcium carbonate: produced by Wako Pure Chemical Industries, Ltd.
Magnesium carbonate: produced by Wako Pure Chemical Industries, Ltd.
Potassium hydrogen carbonate: produced by Wako Pure Chemical Industries, Ltd.
Sodium hydrogen carbonate: produced by Wako Pure Chemical Industries, Ltd.
Ammonium hydrogen carbonate: produced by Nissei Corporation

Examples and Comparative Examples (Preparation of Rubber Test Pieces) Production Example 1 Examples 1 to 50 and Comparative Examples 1 to 21 (Production Method 1)

100 parts by mass of SBR, 55 parts by mass of silica, 20 parts by mass of carbon black, 10 parts by mass of aromatic oil, and 4.4 parts by mass of silane coupling agent (1) were kneaded with various amounts of carbonate or hydrogen carbonate salts (relative to 100 parts by mass of the silica) shown in Table 1 in a 1.7 L Banbury mixer, followed by discharging when the kneading temperature was 150° C. Thus kneaded mixtures 1 were obtained.

Next, 2 parts by mass of stearic acid and 3 parts by mass of zinc oxide were kneaded with each kneaded mixture 1 in a 1.7 L Banbury mixer, followed by discharging when the kneading temperature was 130° C. Thus kneaded mixtures 2 were obtained.

Further, 1.5 parts by mass of sulfur, 1 part by mass of vulcanization accelerator TBBS and 0.5 parts by mass of vulcanization accelerator DPG were kneaded with each kneaded mixture 2 by a roller to give an unvulcanized rubber sheet (unvulcanized rubber composition).

The obtained unvulcanized rubber composition was press-vulcanized for 20 minutes at 170° C. to give a vulcanized rubber composition.

Production Example 2 Examples 51 to 70 and Comparative Examples 22 to 30 (Production Method 2)

100 parts by mass of SBR, 55 parts by mass of silica, 20 parts by mass of carbon black, 10 parts by mass of aromatic oil, and 4.4 parts by mass of silane coupling agent (1) were kneaded with various amounts of carbonate or hydrogen carbonate salts (relative to 100 parts by mass of the silica) shown in Table 2 in a 1.7 L Banbury mixer, and then 2 parts by mass of stearic acid and 3 parts by mass of zinc oxide were kneaded therewith, followed by discharging when the kneading temperature was 150° C. Thus kneaded mixtures 1 were obtained.

Further, 1.5 parts by mass of sulfur, 1 part by mass of vulcanization accelerator TBBS and 0.5 parts by mass of vulcanization accelerator DPG were kneaded with each kneaded mixture 1 by a roller to give an unvulcanized rubber sheet (unvulcanized rubber composition).

The obtained unvulcanized rubber composition was press-vulcanized for 20 minutes at 170° C. to give a vulcanized rubber composition.

Production Example 3 Examples 71 to 90 and Comparative Examples 31 to 39 (Production Method 3)

100 parts by mass of SBR, 55 parts by mass of silica, 20 parts by mass of carbon black, 10 parts by mass of aromatic oil, 4.4 parts by mass of silane coupling agent (1), 2 parts by mass of stearic acid, and 3 parts by mass of zinc oxide were kneaded with various amounts of carbonate or hydrogen carbonate salts (relative to 100 parts by mass of the silica) shown in Table 3 in a 1.7 L Banbury mixer, followed by discharging when the kneading temperature was 150° C. Thus kneaded mixtures 1 were obtained.

Further, 1.5 parts by mass of sulfur, 1 part by mass of vulcanization accelerator TBBS and 0.5 parts by mass of vulcanization accelerator DPG were kneaded with each kneaded mixture 1 by a roller to give an unvulcanized rubber sheet (unvulcanized rubber composition).

The obtained unvulcanized rubber composition was press-vulcanized for 20 minutes at 170° C. to give a vulcanized rubber composition.

Production Example 4 Examples 91 to 110 and Comparative Examples 40 to 48 (Production Method 1)

Unvulcanized rubber compositions and vulcanized rubber compositions were obtained in the same way as in Production Example 1, except that 6.6 parts by mass of silane coupling agent (2) was used instead of 4.4 parts by mass of silane coupling agent (1) and various carbonate or hydrogen carbonate salts were used in amounts shown in Table 4.

Production Example 5 Examples 111 to 130 and Comparative Examples 49 to 57 (Production Method 2)

Unvulcanized rubber compositions and vulcanized rubber compositions were obtained in the same way as in Production Example 2, except that 6.6 parts by mass of silane coupling agent (2) was used instead of 4.4 parts by mass of silane coupling agent (1) and various carbonate or hydrogen carbonate salts were used in amounts shown in Table 5.

Production Example 6 Examples 131 to 150 and Comparative Examples 58 to 66 (Production Method 1)

Unvulcanized rubber compositions and vulcanized rubber compositions were obtained in the same way as in Production Example 1, except that 4.4 parts by mass of silane coupling agent (3) was used instead of 4.4 parts by mass of silane coupling agent (1) and various carbonate or hydrogen carbonate salts were used in amounts shown in Table 6.

Production Example 7 Examples 151 to 170 and Comparative Examples 67 to 75 (Production Method 2)

Unvulcanized rubber compositions and vulcanized rubber compositions were obtained in the same way as in Production Example 2, except that 4.4 parts by mass of silane coupling agent (3) was used instead of 4.4 parts by mass of silane coupling agent (1) and various carbonate or hydrogen carbonate salts were used in amounts shown in Table 7.

Production Example 8 Examples 171 to 220 and Comparative Examples 76 to 96 (Production Method 1)

Unvulcanized rubber compositions and vulcanized rubber compositions were obtained in the same way as in Production Example 1, except that the rubber component was changed to include 70 parts by mass of SBR and 30 parts by mass of NR and various carbonate or hydrogen carbonate salts were used in amounts shown in Table 8.

Production Example 9 Examples 221 to 240 and Comparative Examples 97 to 105 (Production Method 1)

Unvulcanized rubber compositions and vulcanized rubber compositions were obtained in the same way as in Production Example 1, except that the rubber component was changed to include 70 parts by mass of SBR and 30 parts by mass of NR, 6.6 parts by mass of silane coupling agent (2) was used instead of 4.4 parts by mass of silane coupling agent (1), and various carbonate or hydrogen carbonate salts were used in amounts shown in Table 9.

Production Example 10 Examples 241 to 260 and Comparative Examples 106 to 114 (Production Method 1)

Unvulcanized rubber compositions and vulcanized rubber compositions were obtained in the same way as in Production Example 1, except that the rubber component was changed to include 70 parts by mass of SBR and 30 parts by mass of NR, 4.4 parts by mass of silane coupling agent (3) was used instead of 4.4 parts by mass of silane coupling agent (1), and various carbonate or hydrogen carbonate salts were used in amounts shown in Table 10.

Production Example 11 Examples 261 to 310 and Comparative Examples 115 to 135 (Production Method 2)

Unvulcanized rubber compositions and vulcanized rubber compositions were obtained in the same way as in Production Example 2, except that the rubber component was changed to include 70 parts by mass of SBR and 30 parts by mass of NR and various carbonate or hydrogen carbonate salts were used in amounts shown in Table 11.

Production Example 12 Examples 311 to 330 and Comparative Examples 136 to 144 (Production Method 2)

Unvulcanized rubber compositions and vulcanized rubber compositions were obtained in the same way as in Production Example 2, except that the rubber component was changed to include 70 parts by mass of SBR and 30 parts by mass of NR, 6.6 parts by mass of silane coupling agent (2) was used instead of 4.4 parts by mass of silane coupling agent (1), and various carbonate or hydrogen carbonate salts were used in amounts shown in Table 12.

Production Example 13 Examples 331 to 350 and Comparative Examples 145 to 153 (Production Method 2)

Unvulcanized rubber compositions and vulcanized rubber compositions were obtained in the same way as in Production Example 2, except that the rubber component was changed to include 70 parts by mass of SBR and 30 parts by mass of NR, 4.4 parts by mass of silane coupling agent (3) was used instead of 4.4 parts by mass of silane coupling agent (1), and various carbonate or hydrogen carbonate salts were used in amounts shown in Table 13.

The obtained unvulcanized rubber compositions and vulcanized rubber compositions were evaluated as follows. The results are shown in Tables 1 to 13.

(Amount of Unreacted Coupling Agent)

An unvulcanized rubber sheet was finely cut and subjected to extraction with ethanol for 24 hours. The amount of unreacted silane coupling agent in the resultant extract was measured by gas chromatography, and the amount (wt %) of unreacted silane coupling agent was calculated based on the charged amount of the silane coupling agent.

A smaller value for this content means that a smaller amount of the silane coupling agent exists in an unreacted state in the unvulcanized rubber composition after completion of kneading. In other words, this indicates that a composition in which the silane coupling agent has reacted sufficiently during the kneading has a small amount of unreacted silane coupling agent and is therefore good.

(Abrasion Index)

Using a Lambourn abrasion tester, the loss in volume of each vulcanized rubber composition was measured for a test period of 3 minutes under a load of 2.5 kgf at a slip ratio of 40%. With the loss in volume of Comparative Example 1 deemed to be 100 (abrasion index), abrasion indices of the examples were calculated using the following calculation formula. A higher abrasion index means better abrasion resistance.


(Abrasion index of each example)=(loss in volume of Comparative Example 1)/(loss in volume of each example)×100

(Rolling Resistance Index)

Using a VES viscoelasticity spectrometer manufactured by Iwamoto Seisakusho Co., Ltd., the tan δ of each vulcanized rubber composition was measured at 70° C. under conditions of initial strain 10% and dynamic strain 2%. With the tan δ value of Comparative Example 1 deemed to be 100 (rolling resistance index), rolling resistance indices of the examples were calculated using the following calculation formula. A higher index means better performance in terms of rolling resistance.


(Rolling resistance index of each example)=(tan δ value of Comparative Example 1)/(tan δ value of each example)×100

TABLE 1 Rubber component: SBR 100 parts by mass (Production Example 1: Production Method 1 (Si266)) Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 1 Example 2 ple 1 ple 2 ple 3 ple 4 ple 5 Example 3 Formulation Sodium carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 18.4 14.6 5.5 0.5 0 0 0 0 coupling agent Abrasion index 100 99 102 105 108 106 104 95 Rolling resistance index 100 100 102 106 112 108 105 100 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 1 Example 4 ple 6 ple 7 ple 8 ple 9 ple 10 Example 5 Formulation Potassium carbonate (2) — 0.2 0.5 1 2 5 10 30 Evaluation Amount of unreacted 18.4 14.3 0.7 0 0 0 0 0 coupling agent Abrasion index 100 100 103 105 110 108 106 98 Rolling resistance index 100 100 108 112 114 111 108 101 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 1 Example 6 ple 11 ple 12 ple 13 ple 14 ple 15 Example 7 Formulation Ammonium carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 18.4 16.8 8.1 2.5 0 0 0 0 coupling agent Abrasion index 100 99 106 108 112 110 105 94 Rolling resistance index 100 101 105 112 114 110 104 101 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 1 Example 8 ple 16 ple 17 ple 18 ple 19 ple 20 Example 9 Formulation Lithium carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 18.4 15.3 3.7 0.5 0 0 0 0 coupling agent Abrasion index 100 99 103 105 108 103 102 97 Rolling resistance index 100 101 102 105 110 106 105 102 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 1 Example 10 ple 21 ple 22 ple 23 ple 24 ple 25 Example 11 Formulation Calcium carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 18.4 17.8 8.8 4.3 2 0 0 0 coupling agent Abrasion index 100 100 102 104 105 106 105 97 Rolling resistance index 100 99 101 102 108 112 105 102 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 1 Example 12 ple 26 ple 27 ple 28 ple 29 ple 30 Example 13 Formulation Magnesium carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 18.4 16.9 8.4 3.6 0.2 0 0 0 coupling agent Abrasion index 100 100 102 105 105 104 104 97 Rolling resistance index 100 99 102 104 110 108 102 100 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 1 Example 14 ple 31 ple 32 ple 33 ple 34 ple 35 Example 15 Formulation Potassium hydrogen carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 18.4 14.3 2 0 0 0 0 0 coupling agent Abrasion index 100 100 102 106 109 108 103 97 Rolling resistance index 100 99 101 101 105 107 104 101 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 1 Example 16 ple 36 ple 37 ple 38 ple 39 ple 40 Example 17 Formulation Sodium hydrogen carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 18.4 14 1.7 0 0 0 0 0 coupling agent Abrasion index 100 100 102 104 107 105 103 97 Rolling resistance index 100 99 101 102 105 108 102 100 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 1 Example 18 ple 41 ple 42 ple 43 ple 44 ple 45 Example 19 Formulation Ammonium hydrogen carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 18.4 16.5 8.5 4.2 0 0 0 0 coupling agent Abrasion index 100 100 101 104 110 108 103 97 Rolling resistance index 100 99 103 108 113 110 108 101 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 1 Example 20 ple 46 ple 47 ple 48 ple 49 ple 50 Example 21 Formulation Potassium carbonate (1) — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 18.4 15.6 1.2 0.4 0 0 0 0 coupling agent Abrasion index 100 99 101 102 103 103 100 98 Rolling resistance index 100 100 107 112 113 110 108 101

TABLE 2 Rubber component: SBR 100 parts by mass (Production Example 2: Production Method 2 (Si266)) Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 22 Example 23 ple 51 ple 52 ple 53 ple 54 ple 55 Example 24 Formulation Sodium carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 18.6 15.6 7.2 2.5 0.7 0 0 0 coupling agent Abrasion index 100 100 101 104 106 105 103 94 Rolling resistance index 100 99 102 105 110 107 103 98 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 22 Example 25 ple 56 ple 57 ple 58 ple 59 ple 60 Example 26 Formulation Potassium carbonate (2) — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 18.6 14.8 1.5 0.2 0 0 0 0 coupling agent Abrasion index 100 100 102 103 107 106 104 96 Rolling resistance index 100 98 108 110 112 109 106 98 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 22 Example 27 ple 61 ple 62 ple 63 ple 64 ple 65 Example 28 Formulation Potassium carbonate (1) — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 18.6 15.8 2.9 1.5 0.6 0.1 0 0 coupling agent Abrasion index 100 100 101 101 102 102 101 97 Rolling resistance index 100 99 105 108 110 107 104 96 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 22 Example 29 ple 66 ple 67 ple 68 ple 69 ple 70 Example 30 Formulation Ammonium hydrogen carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 18.6 16.9 9.2 5.2 2.5 0.8 0 0 coupling agent Abrasion index 100 100 101 103 107 106 102 97 Rolling resistance index 100 99 102 106 110 106 104 96

TABLE 3 Rubber component: SBR 100 parts by mass (Production Example 3: Production Method 3 (Si266)) Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 31 Example 32 ple 71 ple 72 ple 73 ple 74 ple 75 Example 33 Formulation Sodium carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 19.2 16.4 8.2 4.8 2.1 0.6 0 0 coupling agent Abrasion index 100 99 101 103 104 103 102 93 Rolling resistance index 100 98 101 104 107 105 102 97 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 31 Example 34 ple 76 ple 77 ple 78 ple 79 ple 80 Example 35 Formulation Potassium carbonate (2) — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 19.2 15.6 3.5 0.9 0.1 0 0 0 coupling agent Abrasion index 100 99 101 102 105 104 102 95 Rolling resistance index 100 98 105 107 109 106 104 96 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 31 Example 36 ple 81 ple 82 ple 83 ple 84 ple 85 Example 37 Formulation Potassium carbonate (1) — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 19.2 16.2 3.8 1.9 0.8 0.4 0 0 coupling agent Abrasion index 100 100 101 101 101 102 101 97 Rolling resistance index 100 100 103 106 107 105 102 95 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 31 Example 38 ple 86 ple 87 ple 88 ple 89 ple 90 Example 39 Formulation Ammonium hydrogen carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 19.2 17.6 9.9 6.4 3.5 1.6 0.5 0 coupling agent Abrasion index 100 100 101 102 105 105 102 96 Rolling resistance index 100 99 102 105 107 105 103 94

TABLE 4 Rubber component: SBR 100 parts by mass (Production Example 4: Production Method 1 (Si363)) Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 40 Example 41 ple 91 ple 92 ple 93 ple 94 ple 95 Example 42 Formulation Sodium carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 14.2 11.8 4.6 0.4 0 0 0 0 coupling agent Abrasion index 101 101 103 106 110 108 105 100 Rolling resistance index 102 102 104 106 114 112 108 102 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 40 Example 43 ple 96 ple 97 ple 98 ple 99 ple 100 Example 44 Formulation Potassium carbonate (2) — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 14.2 11.3 0.6 0 0 0 0 0 coupling agent Abrasion index 101 102 104 106 114 110 108 100 Rolling resistance index 102 101 109 114 117 113 110 102 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 40 Example 45 ple 101 ple 102 ple 103 ple 104 ple 105 Example 46 Formulation Potassium carbonate (1) — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 14.2 12.1 1.5 0.1 0 0 0 0 coupling agent Abrasion index 101 101 103 104 105 104 103 101 Rolling resistance index 102 101 108 113 115 112 108 101 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 40 Example 47 ple 106 ple 107 ple 108 ple 109 ple 110 Example 48 Formulation Ammonium hydrogen carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 14.2 12.8 7.4 3.0 0 0 0 0 coupling agent Abrasion index 101 101 102 108 114 109 104 100 Rolling resistance index 102 101 104 110 115 111 109 101

TABLE 5 Rubber component: SBR 100 parts by mass (Production Example 5: Production Method 2 (Si363)) Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 49 Example 50 ple 111 ple 112 ple 113 ple 114 ple 115 Example 51 Formulation Sodium carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 14.8 12.5 7.0 2.5 0.8 0.2 0 0 coupling agent Abrasion index 101 101 102 104 107 106 102 100 Rolling resistance index 101 101 103 106 112 109 105 101 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 49 Example 52 ple 116 ple 117 ple 118 ple 119 ple 120 Example 53 Formulation Potassium carbonate (2) — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 14.8 11.7 2.5 0.8 0.2 0 0 0 coupling agent Abrasion index 101 101 103 105 112 107 105 101 Rolling resistance index 101 101 109 112 114 110 106 101 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 49 Example 54 ple 121 ple 122 ple 123 ple 124 ple 125 Example 55 Formulation Potassium carbonate (1) — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 14.8 13.2 3.5 1.5 0.5 0 0 0 coupling agent Abrasion index 101 101 102 103 104 104 102 101 Rolling resistance index 101 101 105 108 111 106 104 101 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 49 Example 56 ple 126 ple 127 ple 128 ple 129 ple 130 Example 57 Formulation Ammonium hydrogen carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 14.8 13.4 8.4 4.0 0.8 0 0 0 coupling agent Abrasion index 101 101 101 106 110 106 103 100 Rolling resistance index 101 101 103 108 114 107 105 101

TABLE 6 Rubber component: SBR 100 parts by mass (Production Example 6: Production Method 1 (NXT-Z45)) Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 58 Example 59 ple 131 ple 132 ple 133 ple 134 ple 135 Example 60 Formulation Sodium carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 11.2 10.8 2.5 0 0 0 0 0 coupling agent Abrasion index 103 102 105 107 113 110 108 102 Rolling resistance index 102 102 106 108 116 114 112 102 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 58 Example 61 ple 136 ple 137 ple 138 ple 139 ple 140 Example 62 Formulation Potassium carbonate (2) — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 11.2 10.4 0.6 0 0 0 0 0 coupling agent Abrasion index 103 103 106 110 117 114 110 101 Rolling resistance index 102 102 112 115 118 116 113 103 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 58 Example 63 ple 141 ple 142 ple 143 ple 144 ple 145 Example 64 Formulation Potassium carbonate (1) — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 11.2 10.6 1.3 0.1 0 0 0 0 coupling agent Abrasion index 103 103 104 106 108 107 105 101 Rolling resistance index 102 102 110 114 116 113 109 102 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 58 Example 65 ple 146 ple 147 ple 148 ple 149 ple 150 Example 66 Formulation Ammonium hydrogen carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 11.2 10.5 6.4 2.5 0.4 0 0 0 coupling agent Abrasion index 103 102 104 109 115 112 106 101 Rolling resistance index 102 102 104 112 117 112 110 102

TABLE 7 Rubber component: SBR 100 parts by mass (Production Example 7: Production Method 2 (NXT-Z45)) Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 67 Example 68 ple 151 ple 152 ple 153 ple 154 ple 155 Example 69 Formulation Sodium carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 12.0 11.0 5.9 2.4 0.5 0 0 0 coupling agent Abrasion index 102 102 103 105 109 106 104 101 Rolling resistance index 102 102 105 107 113 111 106 101 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 67 Example 70 ple 156 ple 157 ple 158 ple 159 ple 160 Example 71 Formulation Potassium carbonate (2) — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 12.0 10.4 2.0 0.5 0.1 0 0 0 coupling agent Abrasion index 102 102 105 108 114 112 106 101 Rolling resistance index 102 102 108 112 115 113 108 102 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 67 Example 72 ple 161 ple 162 ple 163 ple 164 ple 165 Example 73 Formulation Potassium carbonate (1) — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 12.0 10.9 2.4 0.9 0.6 0.1 0 0 coupling agent Abrasion index 102 102 103 104 105 105 104 101 Rolling resistance index 102 102 106 110 108 107 104 102 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 67 Example 74 ple 166 ple 167 ple 168 ple 169 ple 170 Example 75 Formulation Ammonium hydrogen carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 12.0 10.8 7.8 3.5 1.8 0.6 0 0 coupling agent Abrasion index 102 102 104 105 108 104 103 101 Rolling resistance index 102 102 103 108 115 109 104 102

TABLE 8 Rubber component: SBR 70 parts by mass, NR 30 parts by mass (Production Example 8: Production Method 1 (Si266)) Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 76 Example 77 ple 171 ple 172 ple 173 ple 174 ple 175 Example 78 Formulation Sodium carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 19.7 17.8 7.6 4.5 2.1 0.5 0 0 coupling agent Abrasion index 112 111 116 122 123 118 116 106 Rolling resistance index 108 108 111 114 120 116 114 108 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 76 Example 79 ple 176 ple 177 ple 178 ple 179 ple 180 Example 80 Formulation Potassium carbonate (2) — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 19.7 16.8 5.5 2.4 1.1 0 0 0 coupling agent Abrasion index 112 111 115 116 123 121 117 110 Rolling resistance index 108 108 116 121 125 120 115 109 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 76 Example 81 ple 181 ple 182 ple 183 ple 184 ple 185 Example 82 Formulation Ammonium carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 19.7 16.8 8.1 2.5 0 0 0 0 coupling agent Abrasion index 112 111 118 120 122 122 117 106 Rolling resistance index 108 108 113 121 121 118 109 107 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 76 Example 83 ple 186 ple 187 ple 188 ple 189 ple 190 Example 84 Formulation Lithium carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 19.7 16.3 6.5 3.4 1.5 0 0 0 coupling agent Abrasion index 112 112 115 118 120 114 114 109 Rolling resistance index 108 110 112 114 119 114 112 109 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 76 Example 85 ple 191 ple 192 ple 193 ple 194 ple 195 Example 86 Formulation Calcium carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 19.7 17.8 8.8 4.3 2 0 0 0 coupling agent Abrasion index 112 111 114 116 118 117 116 109 Rolling resistance index 108 107 110 111 116 121 113 109 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 76 Example 87 ple 196 ple 197 ple 198 ple 199 ple 200 Example 88 Formulation Magnesium carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 19.7 17.6 8.8 4.6 2.5 1.0 0 0 coupling agent Abrasion index 112 112 115 116 116 116 115 109 Rolling resistance index 108 108 111 112 119 117 113 107 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 76 Example 89 ple 201 ple 202 ple 203 ple 204 ple 205 Example 90 Formulation Potassium hydrogen carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 19.7 16.8 4.0 1.8 0 0 0 0 coupling agent Abrasion index 112 111 114 118 121 119 116 109 Rolling resistance index 108 107 110 110 114 115 112 109 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 76 Example 91 ple 206 ple 207 ple 208 ple 209 ple 210 Example 92 Formulation Sodium hydrogen carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 19.7 17.2 6.4 3.0 1.0 0 0 0 coupling agent Abrasion index 112 111 114 117 120 115 114 109 Rolling resistance index 108 109 111 112 114 116 111 109 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 76 Example 93 ple 211 ple 212 ple 213 ple 214 ple 215 Example 94 Formulation Ammonium hydrogen carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 19.7 17.6 8.9 5.6 2.4 0.8 0 0 coupling agent Abrasion index 112 112 114 116 122 121 115 109 Rolling resistance index 108 108 112 116 121 119 117 110 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 76 Example 95 ple 216 ple 217 ple 218 ple 219 ple 220 Example 96 Formulation Potassium carbonate (1) — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 19.7 18.2 9.6 6.5 3.2 2.6 0 0 coupling agent Abrasion index 112 111 114 115 115 115 113 108 Rolling resistance index 108 109 114 121 121 120 116 110

TABLE 9 Rubber component: SBR 70 parts by mass, NR 30 parts by mass (Production Example 9: Production Method 1 (Si363)) Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 97 Example 98 ple 221 ple 222 ple 223 ple 224 ple 225 Example 99 Formulation Sodium carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 15.4 12.6 6.0 2.9 0.8 0 0 0 coupling agent Abrasion index 113 113 116 124 124 122 118 112 Rolling resistance index 109 110 113 116 127 124 120 110 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 97 Example 100 ple 226 ple 227 ple 228 ple 229 ple 230 Example 101 Formulation Potassium carbonate (2) — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 15.4 12.7 2.6 0.8 0 0 0 0 coupling agent Abrasion index 113 112 115 120 126 123 119 113 Rolling resistance index 109 109 116 124 126 122 119 108 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 97 Example 102 ple 231 ple 232 ple 233 ple 234 ple 235 Example 103 Formulation Potassium carbonate (1) — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 15.4 12.8 4.5 1.6 0.5 0 0 0 coupling agent Abrasion index 113 112 115 117 119 117 116 110 Rolling resistance index 109 110 114 125 124 124 120 108 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 97 Example 104 ple 236 ple 237 ple 238 ple 239 ple 240 Example 105 Formulation Ammonium hydrogen carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 15.4 12.8 7.4 3.0 0 0 0 0 coupling agent Abrasion index 113 113 116 121 126 122 117 113 Rolling resistance index 109 108 113 120 124 119 117 109

TABLE 10 Rubber component: SBR 70 parts by mass, NR 30 parts by mass (Production Example 10: Production Method 1 (NXT-Z45)) Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 106 Example 107 ple 241 ple 242 ple 243 ple 244 ple 245 Example 108 Formulation Sodium carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 12.5 11.2 6.5 3.1 1.2 0 0 0 coupling agent Abrasion index 114 114 120 124 126 126 123 113 Rolling resistance index 110 110 114 118 128 125 122 111 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 106 Example 109 ple 246 ple 247 ple 248 ple 249 ple 250 Example 110 Formulation Potassium carbonate (2) — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 12.5 11.0 5.6 2.3 0.6 0 0 0 coupling agent Abrasion index 114 113 120 125 130 126 124 114 Rolling resistance index 110 110 116 125 127 126 123 109 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 106 Example 111 ple 251 ple 252 ple 253 ple 254 ple 255 Example 112 Formulation Potassium carbonate (1) — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 12.5 11.5 7.8 4.6 2.0 0.9 0 0 coupling agent Abrasion index 114 115 120 122 123 122 120 114 Rolling resistance index 110 110 115 123 124 122 118 111 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 106 Example 113 ple 256 ple 257 ple 258 ple 259 ple 260 Example 114 Formulation Ammonium hydrogen carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 12.5 12.0 8.9 6.1 3.6 0.8 0 0 coupling agent Abrasion index 114 115 118 124 127 123 120 113 Rolling resistance index 110 111 115 124 129 125 120 111

TABLE 11 Rubber component: SBR 70 parts by mass, NR 30 parts by mass (Production Example 11: Production Method 2 (Si266)) Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 115 Example 116 ple 261 ple 262 ple 263 ple 264 ple 265 Example 117 Formulation Sodium carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 20.7 18.4 8.6 5.3 2.8 1.5 0.8 0 coupling agent Abrasion index 110 109 113 120 121 114 114 107 Rolling resistance index 106 106 110 113 115 114 113 107 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 115 Example 118 ple 266 ple 267 ple 268 ple 269 ple 270 Example 119 Formulation Potassium carbonate (2) — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 20.7 17.8 6.9 3.2 1.2 0.1 0 0 coupling agent Abrasion index 110 109 114 114 120 117 114 107 Rolling resistance index 106 106 112 116 117 115 114 106 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 115 Example 120 ple 271 ple 272 ple 273 ple 274 ple 275 Example 121 Formulation Ammonium carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 20.7 17.6 9.6 5.6 2.5 1.0 0 0 coupling agent Abrasion index 110 110 116 118 121 118 115 108 Rolling resistance index 106 105 112 118 117 116 109 105 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 115 Example 122 ple 276 ple 277 ple 278 ple 279 ple 280 Example 123 Formulation Lithium carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 20.7 18.3 7.9 4.6 2.5 1.2 0 0 coupling agent Abrasion index 110 108 114 116 118 114 113 108 Rolling resistance index 106 105 110 112 116 113 111 106 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 115 Example 124 ple 281 ple 282 ple 283 ple 284 ple 285 Example 125 Formulation Calcium carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 20.7 18.4 9.2 5.3 2.8 1.4 0.1 0 coupling agent Abrasion index 110 110 112 114 116 114 113 109 Rolling resistance index 106 105 110 111 114 116 110 104 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 115 Example 126 ple 286 ple 287 ple 288 ple 289 ple 290 Example 127 Formulation Magnesium carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 20.7 19.4 9.8 5.4 3.1 1.4 0.5 0 coupling agent Abrasion index 110 109 113 114 115 114 113 109 Rolling resistance index 106 106 110 111 117 115 114 104 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 115 Example 128 ple 291 ple 292 ple 293 ple 294 ple 295 Example 129 Formulation Potassium hydrogen carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 20.7 18.4 6.5 2.7 1.1 0 0 0 coupling agent Abrasion index 110 109 113 115 118 115 113 110 Rolling resistance index 106 105 110 110 113 114 112 106 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 115 Example 130 ple 296 ple 297 ple 298 ple 299 ple 300 Example 131 Formulation Sodium hydrogen carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 20.7 18.4 7.4 4.2 2.0 0.6 0 0 coupling agent Abrasion index 110 108 113 116 118 114 113 109 Rolling resistance index 106 106 111 111 113 114 111 104 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 115 Example 132 ple 301 ple 302 ple 303 ple 304 ple 305 Example 133 Formulation Ammonium hydrogen carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 20.7 19.3 9.9 6.2 4.1 2.2 0.6 0 coupling agent Abrasion index 110 108 113 115 120 119 114 107 Rolling resistance index 106 105 111 114 118 116 114 105 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 115 Example 134 ple 306 ple 307 ple 308 ple 309 ple 310 Example 135 Formulation Potassium carbonate (1) — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 20.7 19.9 9.9 6.9 4.0 2.7 1.2 0.2 coupling agent Abrasion index 110 109 113 114 114 114 112 107 Rolling resistance index 106 106 112 116 114 115 112 105

TABLE 12 Rubber component: SBR 70 parts by mass, NR 30 parts by mass (Production Example 12: Production Method 2 (Si363)) Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 136 Example 137 ple 311 ple 312 ple 313 ple 314 ple 315 Example 138 Formulation Sodium carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 16.8 14.1 7.8 3.9 2.2 1.0 0.2 0 coupling agent Abrasion index 111 111 114 121 123 119 116 110 Rolling resistance index 107 108 112 114 123 119 115 106 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 136 Example 139 ple 316 ple 317 ple 318 ple 319 ple 320 Example 140 Formulation Potassium carbonate (2) — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 16.8 13.2 3.5 1.0 0.1 0 0 0 coupling agent Abrasion index 111 110 114 118 122 118 114 108 Rolling resistance index 107 106 112 120 118 116 115 106 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 136 Example 141 ple 321 ple 322 ple 323 ple 324 ple 325 Example 142 Formulation Potassium carbonate (1) — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 16.8 14.0 5.4 2.6 1.3 0.4 0 0 coupling agent Abrasion index 111 110 114 116 117 115 113 107 Rolling resistance index 107 106 113 115 115 116 113 103 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 136 Example 143 ple 326 ple 327 ple 328 ple 329 ple 330 Example 144 Formulation Ammonium hydrogen carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 16.8 15.4 8.4 5.0 2.5 1.1 0 0 coupling agent Abrasion index 111 109 114 118 120 118 114 108 Rolling resistance index 107 107 112 118 122 118 114 105

TABLE 13 Rubber component: SBR 70 parts by mass, NR 30 parts by mass (Production Example 13: Production Method 2 (NXT-Z45)) Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 145 Example 146 ple 331 ple 332 ple 333 ple 334 ple 335 Example 147 Formulation Sodium carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 13.8 11.9 7.6 3.8 1.8 0.5 0 0 coupling agent Abrasion index 112 112 116 122 123 121 117 111 Rolling resistance index 106 107 113 116 124 122 117 106 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 145 Example 148 ple 336 ple 337 ple 338 ple 339 ple 340 Example 149 Formulation Potassium carbonate (2) — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 13.8 11.7 7.4 3.4 1.6 0.1 0 0 coupling agent Abrasion index 112 111 116 120 124 121 118 111 Rolling resistance index 106 105 115 123 124 122 115 106 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 145 Example 150 ple 341 ple 342 ple 343 ple 344 ple 345 Example 151 Formulation Potassium carbonate (1) — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 13.8 12.5 8.5 5.2 2.5 1.3 0.5 0 coupling agent Abrasion index 112 111 115 118 120 118 116 111 Rolling resistance index 106 106 113 120 120 117 115 106 Comparative Comparative Exam- Exam- Exam- Exam- Exam- Comparative Example 145 Example 152 ple 346 ple 347 ple 348 ple 349 ple 350 Example 153 Formulation Ammonium hydrogen carbonate — 0.2 0.5 1 5 10 20 30 Evaluation Amount of unreacted 13.8 12.0 8.9 6.1 3.6 0.8 0 0 coupling agent Abrasion index 112 112 117 120 122 120 118 111 Rolling resistance index 106 106 114 122 125 121 116 105

In the examples in which silica, a silane coupling agent and a predetermined amount of a carbonate salt or hydrogen carbonate salt were contained, the amount of unreacted silane coupling agent was as small as at most 10% by mass, the rate of reaction between the silane coupling agent and the silica was increased, and the fuel economy and abrasion resistance were enhanced, as compared with the comparative examples. In addition, in the examples using silane coupling agent (2) or (3), excellent fuel economy and abrasion resistance were exhibited. In the examples using potassium carbonate (2) with an average particle size of 40 μm or smaller, an increased rate of reaction and superior abrasion resistance were exhibited compared with cases in which potassium carbonate (1) with an average particle size of 340 μm was used. With regard to Production Examples 1 to 3, in Examples 1 to 50 which were obtained by carrying out the first base kneading step, the second base kneading step and the final kneading step (Production Example 1 (Production Method 1)), good fuel economy and abrasion resistance were exhibited. Next to these examples, the improvement effect was large in the examples obtained according to Production Example 2 (Production Method 2) and Production Example 3 (Production Method 3). In contrast, in the comparative examples, the fuel economy and abrasion resistance could not be enhanced in a balanced manner.

In addition, if the content of the carbonate or hydrogen carbonate salt is increased too far, the abrasion resistance tends to deteriorate (for example, see Comparative Examples 3, 5, 7, 9, 11, 13, 15, 17 and 19).

Claims

1. A rubber composition for a tire, comprising: diene rubber; silica; a silane coupling agent; and at least one of a carbonate salt and a hydrogen carbonate salt,

wherein the rubber composition has a total content of the carbonate salt and the hydrogen carbonate salt of 0.3 to 25 parts by mass relative to 100 parts by mass of the silica.

2. The rubber composition for a tire according to claim 1, wherein the carbonate salt is at least one selected from the group consisting of sodium carbonate, potassium carbonate, ammonium carbonate, lithium carbonate, calcium carbonate and magnesium carbonate, and

the hydrogen carbonate salt is at least one selected from the group consisting of sodium hydrogen carbonate, potassium hydrogen carbonate and ammonium hydrogen carbonate.

3. The rubber composition for a tire according to claim 1, wherein the carbonate salt is at least one selected from the group consisting of sodium carbonate, ammonium carbonate, lithium carbonate, calcium carbonate and magnesium carbonate, and

the hydrogen carbonate salt is ammonium hydrogen carbonate.

4. The rubber composition for a tire according to claim 1 or 2, wherein the potassium carbonate has an average particle size of 40 μm or smaller.

5. The rubber composition for a tire according to claim 1, wherein the silane coupling agent is at least one selected from the group consisting of a sulfide-type silane coupling agent, a silane coupling agent represented by formula (1): wherein x is an integer of 0 or higher; y is an integer of 1 or higher; R8 denotes a hydrogen atom, a halogen atom, a branched or unbranched alkyl or alkylene group having 1 to 30 carbon atoms, a branched or unbranched alkenyl or alkenylene group having 2 to 30 carbon atoms, a branched or unbranched alkynyl or alkynylene group having 2 to 30 carbon atoms, or a group in which a terminal of the alkyl or alkenyl group is substituted with a hydroxyl or carboxyl group; R9 denotes a hydrogen atom, a branched or unbranched alkylene or alkyl group having 1 to 30 carbon atoms, a branched or unbranched alkenylene or alkenyl group having 2 to 30 carbon atoms, or a branched or unbranched alkynylene or alkynyl group having 2 to 30 carbon atoms; and R8 and R9 may together form a ring structure.

wherein R1 is a group represented by —O—(R5—O)m—R6 in which m pieces of R5 are the same or different and each denote a branched or unbranched divalent hydrocarbon group having 1 to 30 carbon atoms, R6 denotes a branched or unbranched alkyl group having 1 to 30 carbon atoms, a branched or unbranched alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms, and m is an integer between 1 and 30; R2 and R3 are the same or different and each denote a group as defined for R1, a branched or unbranched alkyl group having 1 to 12 carbon atoms, or a group represented by —O—R7 in which R7 denotes a hydrogen atom, a branched or unbranched alkyl group having 1 to 30 carbon atoms, a branched or unbranched alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms; and R4 denotes a branched or unbranched alkylene group having 1 to 30 carbon atoms, and
a silane coupling agent comprising linking units A and B respectively represented by formulae (2) and (3):

6. The rubber composition for a tire according to claim 1, wherein 5 to 150 parts by mass of the silica is contained relative to 100 parts by mass of the diene rubber, and

2 to 20 parts by mass of the silane coupling agent is contained relative to 100 parts by mass of the silica.

7. The rubber composition for a tire according to claim 1, which is obtained by a production method comprising:

a step (A) of kneading diene rubber, silica, a silane coupling agent, and at least one of a carbonate salt and a hydrogen carbonate salt, and discharging the resulting kneaded mixture A;
a step (B) of kneading the kneaded mixture A discharged in the step (A), stearic acid and zinc oxide, and discharging the resulting kneaded mixture B; and
a step (C) of kneading the kneaded mixture B discharged in the step (B), a vulcanizing agent and a vulcanization accelerator.

8. The rubber composition for a tire according to claim 1, which is obtained by a production method comprising:

a step (a) of kneading diene rubber, silica, a silane coupling agent, and at least one of a carbonate salt and a hydrogen carbonate salt, adding thereto stearic acid and zinc oxide, further kneading them, and discharging the resulting kneaded mixture a; and
a step (b) of kneading the kneaded mixture a discharged in the step (a), a vulcanizing agent and a vulcanization accelerator.

9. A pneumatic tire formed from the rubber composition according to claim 1.

Patent History
Publication number: 20130053491
Type: Application
Filed: Feb 28, 2011
Publication Date: Feb 28, 2013
Applicant: SUMITOMO RUBBER INDUSTRIES, LTD. (Kobe-shi, Hyogo)
Inventor: Yasuhisa Minagawa (Kobe-shi)
Application Number: 13/641,954
Classifications
Current U.S. Class: Atom Other Than Si, O, C, Or H (524/262)
International Classification: C08L 9/06 (20060101); C08K 5/548 (20060101); C08K 3/26 (20060101); C08K 3/36 (20060101);