JP2018070752A - Method for producing tire rubber composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a tire rubber composition with its fuel economy, fracture characteristics and workability improved in a balanced manner.SOLUTION: This invention relates to a method for producing a tire rubber composition that includes a first step of inputting a rubber component, silica and a silane coupling agent for kneading, to obtain a first kneaded product; a second step for further kneading the first kneaded product, to obtain a second kneaded product; and a third step for inputting the second kneaded product and a vulcanization agent for kneading, to obtain an unvulcanized rubber composition. In the first step, a reaction treatment for kneading the rubber component, the silica and the silane coupling agent while maintaining a reaction temperature set in a range of 140-155°C, is performed until the following formulas (1) and (2) are satisfied: formula (1) ΔG*t/ΔG*0×100<80 and formula (2) Vt/V0×100<80.SELECTED DRAWING: None

Description

The present invention relates to a method for producing a tire rubber composition.

In recent years, in response to increasing environmental awareness, there is a demand for reducing rolling resistance of tires in order to improve the fuel efficiency of automobiles.

Generally, in order to reduce rolling resistance, a method of blending silica with tread rubber is used. However, when silica is blended, there is a problem that Mooney viscosity after kneading increases and processability decreases. . Silica is a hydrophilic material whose surface is covered with silanol groups, and it is difficult to mix with diene rubber used in tire rubber compositions, but when used in combination with a silane coupling agent, silica and silane cups are used. Since the ring agent is bonded by polycondensation and the surface of the silica is hydrophobized, it can be easily dispersed in a diene rubber (see, for example, Patent Document 1).

Also, recently, with the enforcement of tire labeling systems in each country, tread rubber is required to have not only low fuel consumption but also high level of compatibility with fracture characteristics that are contrary to low fuel consumption. The current technology is insufficient to achieve this requirement.

JP 2002-363346 A

An object of the present invention is to solve the above-mentioned problems and to provide a method for producing a rubber composition for tires with improved fuel economy, fracture characteristics and processability in a well-balanced manner.

The present invention includes a first step in which a rubber component, silica and a silane coupling agent are added and kneaded to obtain a first kneaded product, and a second step in which the first kneaded product is further kneaded to obtain a second kneaded product. And a third step of adding the second kneaded product and the vulcanized chemical to knead to obtain an unvulcanized rubber composition, and in the first step, the temperature was set within the range of 140 to 155 ° C. It is related with the manufacturing method of the rubber composition for tires which implements the reaction process which knead | mixes the said rubber component, the said silica, and the said silane coupling agent, satisfy | filling following formula (1) and (2), maintaining reaction temperature.
Expression (1) ΔG * t / ΔG * 0 × 100 <80
(In the formula, ΔG * 0 represents G * of 100 ° C., 0.5% strain and G of 100 ° C., 64% strain of the unreacted kneaded product obtained by finishing kneading when the reaction temperature is reached. * G * t is the difference between G * and 100% of the first kneaded product obtained by kneading for a predetermined time after reaching the same reaction temperature as ΔG * 0 and 100% at 0.5% strain. It is the difference from G * at 64 ° C. and 64% strain.)
Formula (2) Vt / V0 × 100 <80
(In the formula, V0 is the Mooney viscosity at 130 ° C. of the unreacted kneaded product obtained by finishing kneading when the reaction temperature is reached, and Vt reaches a predetermined reaction temperature after reaching the same reaction temperature as V0. (The Mooney viscosity at 130 ° C. of the first kneaded product obtained by kneading for a period of time.)

（式中、Ｒ^１０１〜Ｒ^１０３は、分岐若しくは非分岐の炭素数１〜１２のアルキル基、分岐若しくは非分岐の炭素数１〜１２のアルコキシ基、又は−Ｏ−（Ｒ^１１１−Ｏ）_ｂ−Ｒ^１１２（ｂ個のＲ^１１１は、分岐若しくは非分岐の炭素数１〜３０の２価の炭化水素基を表す。ｂ個のＲ^１１１はそれぞれ同一でも異なっていてもよい。Ｒ^１１２は、分岐若しくは非分岐の炭素数１〜３０のアルキル基、分岐若しくは非分岐の炭素数２〜３０のアルケニル基、炭素数６〜３０のアリール基、又は炭素数７〜３０のアラルキル基を表す。ｂは１〜３０の整数を表す。）で表される基を表す。Ｒ^１０１〜Ｒ^１０３はそれぞれ同一でも異なっていてもよい。Ｒ^１０４は、分岐若しくは非分岐の炭素数１〜６のアルキレン基を表す。） The silane coupling agent is preferably a mercapto silane coupling agent represented by the following formula (I).

(Wherein R ^{101 to} R ¹⁰³ are branched or unbranched alkyl groups having 1 to 12 carbon atoms, branched or unbranched alkoxy groups having 1 to 12 carbon atoms, or —O— (R ¹¹¹ —O) _b. -R ¹¹² (b pieces ^{by R 111} are .b pieces ^{by R 111} are optionally each be the same or different ^{.R 112} representing a divalent hydrocarbon group of branched or unbranched C1-30 is 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; Represents an integer of 1 to 30.) R ^{101 to} R ¹⁰³ may be the same or different, and R ¹⁰⁴ is a branched or unbranched alkylene group having 1 to 6 carbon atoms. Represents.)

In the method for producing the rubber composition for a tire, it is preferable to perform a deaeration process in the first step.

In the method for producing the rubber composition for a tire, it is preferable that the first kneaded material and the modified rubber are added and kneaded in the second step.

The modified rubber is preferably a modified styrene butadiene rubber.

The method for producing the tire rubber composition preferably produces a cap tread rubber composition.

According to the present invention, by carrying out the reaction treatment for kneading the rubber component, silica and the silane coupling agent at a predetermined temperature until the formulas (1) and (2) are satisfied, fuel efficiency, fracture characteristics and processing are improved. A tire rubber composition having improved properties in a well-balanced manner can be produced.

The present invention includes a first step in which a rubber component, silica and a silane coupling agent are added and kneaded to obtain a first kneaded product, and a second step in which the first kneaded product is further kneaded to obtain a second kneaded product. And a third step of adding the second kneaded product and the vulcanized chemical to knead to obtain an unvulcanized rubber composition, and in the first step, the temperature was set within the range of 140 to 155 ° C. It is related with the manufacturing method of the rubber composition for tires which implements the reaction process which knead | mixes the said rubber component, the said silica, and the said silane coupling agent, satisfy | filling following formula (1) and (2), maintaining reaction temperature.
Expression (1) ΔG * t / ΔG * 0 × 100 <80
(In the formula, ΔG * 0 represents G * of 100 ° C., 0.5% strain and G of 100 ° C., 64% strain of the unreacted kneaded product obtained by finishing kneading when the reaction temperature is reached. * G * t is the difference between G * and 100% of the first kneaded product obtained by kneading for a predetermined time after reaching the same reaction temperature as ΔG * 0 and 100% at 0.5% strain. It is the difference from G * at 64 ° C. and 64% strain.)
Formula (2) Vt / V0 × 100 <80
(In the formula, V0 is the Mooney viscosity at 130 ° C. of the unreacted kneaded product obtained by finishing kneading when the reaction temperature is reached, and Vt reaches a predetermined reaction temperature after reaching the same reaction temperature as V0. (The Mooney viscosity at 130 ° C. of the first kneaded product obtained by kneading for a period of time.)

When the polycondensation reaction between silica and silane coupling agent is promoted and the dispersibility of silica is improved, ΔG * (Pain effect) defined by the difference between G * in the low strain region and G * in the high strain region , Mooney viscosity decreases. ΔG * t / ΔG * 0 × 100 in the formula (1) is an index indicating how much ΔG * of the example in which the reaction treatment is performed has decreased with respect to ΔG * in the example in which the reaction treatment is not performed. Yes, Vt / V0 × 100 in the formula (2) is an index indicating how much the Mooney viscosity of the example in which the reaction treatment is performed is lowered with respect to the Mooney viscosity in the example in which the reaction treatment is not performed. Therefore, the degree of dispersion of silica can be determined from these indices. Utilizing this, in the present invention, in the first step, silica is good by carrying out the reaction treatment for kneading the rubber component, silica and silane coupling agent until the formulas (1) and (2) are satisfied. Thus, it is possible to produce a rubber composition for tires that is dispersed in the above and has improved fuel economy, fracture characteristics and processability in a well-balanced manner.

The measurement of G * (complex elastic modulus in shear mode) is usually carried out in a state where the rubber is vulcanized, but in the present invention, the first kneaded material in which the rubber is in an unvulcanized state is used. carry out. Thereby, since the influence of the dispersion of pure silica can be extracted, it is possible to accurately estimate the dispersibility of silica.

First, each component used in the present invention will be described.

(Rubber component)
As the rubber component, diene rubber is preferably used. As the diene rubber, natural rubber (NR) or diene synthetic rubber can be used. Examples of the diene synthetic rubber include isoprene rubber (IR), butadiene rubber (BR), styrene butadiene rubber (SBR), and acrylonitrile butadiene rubber. (NBR), chloroprene rubber (CR), butyl rubber (IIR) and the like. These may be used alone or in combination of two or more. Of these, NR, BR, and SBR are preferable, and BR and SBR are more preferable because they exhibit low fuel consumption, fracture characteristics, and processability in a well-balanced manner.

The rubber component may be a modified rubber modified with a modifier. Examples of the modified rubber include modified SBR and modified BR, and modified SBR is preferable. Examples of the modifier include 3-aminopropyldimethylmethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylethyldimethoxysilane, 3-aminopropyltrimethoxysilane, and 3- (2-aminoethylamino). Examples include propyltrimethoxysilane, tin tetrachloride, butyltin trichloride, and N-methylpyrrolidone, with N-methylpyrrolidone being preferred.

In the rubber composition obtained by the production method of the present invention, the BR content in 100% by mass of the rubber component is preferably 5% by mass or more because the fuel efficiency, fracture characteristics and processability can be obtained in a good balance. More preferably, it is 15 mass% or more, preferably 70 mass% or less, more preferably 50 mass% or less.

In the rubber composition obtained by the production method of the present invention, the SBR content in 100% by mass of the rubber component is preferably 30% by mass or more because the fuel efficiency, fracture characteristics, and processability can be obtained in a good balance. More preferably, it is 50 mass% or more, preferably 95 mass% or less, more preferably 85 mass% or less.
Moreover, when using modified | denatured SBR, the content is 30-60 mass% of the whole quantity of SBR, and 15-45 mass% in 100 mass% of rubber components is preferable.

(silica)
Silica is not particularly limited, but includes silica prepared by a dry process (anhydrous silica) and silica prepared by a wet process (hydrous silica), and has many silanol groups on the surface. Silica prepared by a wet method is preferred because it has many reactive sites with the ring agent. Silica may be used alone or in combination of two or more. Examples of commercially available silica include Ultrasil VN3 manufactured by Evonik.

Nitrogen adsorption specific surface area _(N 2 SA) of silica is preferably ^90m 2 / g or more, more preferably ^{95 m} 2 / g or more, further preferably 100 m ² / g or more. If it is less than 90 m ² / g, sufficient fracture characteristics may not be obtained. The N ₂ SA of silica is preferably 300 m ² / g or less, more preferably 240 m ² / g or less. If it exceeds 300 m ² / g, it is difficult to disperse in rubber, which may cause poor dispersion.
The nitrogen adsorption specific surface area of silica is a value measured by the BET method according to ASTM D3037-81.

In the rubber composition obtained by the production method of the present invention, the content of silica is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and further preferably 50 parts by mass or more with respect to 100 parts by mass of the rubber component. It is. If it is less than 5 mass parts, there exists a possibility that the reinforcement required for a tire cannot be obtained. The silica content is preferably 200 parts by mass or less, more preferably 180 parts by mass or less, and still more preferably 100 parts by mass or less. When it exceeds 200 mass parts, workability may deteriorate and processing may become difficult.

（式中、Ｒ^１０１〜Ｒ^１０３は、分岐若しくは非分岐の炭素数１〜１２のアルキル基、分岐若しくは非分岐の炭素数１〜１２のアルコキシ基、又は−Ｏ−（Ｒ^１１１−Ｏ）_ｂ−Ｒ^１１２（ｂ個のＲ^１１１は、分岐若しくは非分岐の炭素数１〜３０の２価の炭化水素基を表す。ｂ個のＲ^１１１はそれぞれ同一でも異なっていてもよい。Ｒ^１１２は、分岐若しくは非分岐の炭素数１〜３０のアルキル基、分岐若しくは非分岐の炭素数２〜３０のアルケニル基、炭素数６〜３０のアリール基、又は炭素数７〜３０のアラルキル基を表す。ｂは１〜３０の整数を表す。）で表される基を表す。Ｒ^１０１〜Ｒ^１０３はそれぞれ同一でも異なっていてもよい。Ｒ^１０４は、分岐若しくは非分岐の炭素数１〜６のアルキレン基を表す。） (Silane coupling agent)
As the silane coupling agent, a mercapto-based silane coupling agent represented by the following formula (I) can be preferably used from the viewpoint of excellent reinforcing effect of the rubber composition. The mercapto-based silane coupling agent has an advantage of excellent reactivity with silica and rubber components, but tends to deteriorate processability. On the other hand, in this invention, the deterioration of workability can be suppressed by implementing reaction processing until it satisfy | fills Formula (1), (2).

(Wherein R ^{101 to} R ¹⁰³ are branched or unbranched alkyl groups having 1 to 12 carbon atoms, branched or unbranched alkoxy groups having 1 to 12 carbon atoms, or —O— (R ¹¹¹ —O) _b. -R ¹¹² (b pieces ^{by R 111} are .b pieces ^{by R 111} are optionally each be the same or different ^{.R 112} representing a divalent hydrocarbon group of branched or unbranched C1-30 is 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; Represents an integer of 1 to 30.) R ^{101 to} R ¹⁰³ may be the same or different, and R ¹⁰⁴ is a branched or unbranched alkylene group having 1 to 6 carbon atoms. Represents.)

R ^{101 to} R ¹⁰³ are branched or unbranched alkyl groups having 1 to 12 carbon atoms, branched or unbranched alkoxy groups having 1 to 12 carbon atoms, or —O— (R ¹¹¹ —O) _b —R ¹¹² . Represents the group represented. From the viewpoint that the effects of the present invention can be obtained satisfactorily, at least one of R ^{101 to} R ¹⁰³ is preferably a group represented by —O— (R ¹¹¹ —O) _b —R ¹¹² , and two are — More preferably, it is a group represented by O— (R ¹¹¹ —O) _b —R ¹¹² , and one is a branched or unbranched C 1-12 alkoxy group.

Examples of the branched or unbranched alkyl group having 1 to 12 carbon atoms (preferably 1 to 5 carbon atoms) represented by R ^{101 to} R ¹⁰³ include, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and n-butyl. Group, iso-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, nonyl group and the like.

Examples of the branched or unbranched alkoxy group having 1 to 12 carbon atoms (preferably 1 to 5 carbon atoms) of R ^{101 to} R ¹⁰³ include, for example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, n- Examples include butoxy, iso-butoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy, heptyloxy, 2-ethylhexyloxy, octyloxy, nonyloxy and the like.

In —O— (R ¹¹¹ —O) _b —R ¹¹² of R ^{101 to} R ¹⁰³ , R ¹¹¹ represents branched or unbranched carbon atoms of 1 to 30 (preferably having 1 to 15 carbon atoms, more preferably 1 carbon atom). To 3) a divalent hydrocarbon group.
Examples of the hydrocarbon group include a branched or unbranched alkylene group having 1 to 30 carbon atoms, a branched or unbranched alkenylene group having 2 to 30 carbon atoms, and a branched or unbranched alkynylene group having 2 to 30 carbon atoms. And an arylene group having 6 to 30 carbon atoms. Of these, a branched or unbranched alkylene group having 1 to 30 carbon atoms is preferable.

Examples of the branched or unbranched alkylene group having 1 to 30 carbon atoms (preferably 1 to 15 carbon atoms, more preferably 1 to 3 carbon atoms) of R ¹¹¹ include, for example, a methylene group, an ethylene group, a propylene group, and a butylene group. Pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group, octadecylene group and the like.

Examples of the branched or unbranched carbon atoms 2-30 alkenylene group (preferably 2 to 15 carbon atoms, more preferably 2 to 3 carbon atoms) of R ^111, for example, vinylene group, propenylene group, 2-propenylene Group, 1-butenylene group, 2-butenylene group, 1-pentenylene group, 2-pentenylene group, 1-hexenylene group, 2-hexenylene group, 1-octenylene group and the like.

Examples of the branched or unbranched carbon atoms 2-30 alkynylene group (preferably 2 to 15 carbon atoms, more preferably 2 to 3 carbon atoms) of R ^111, for example, ethynylene group, propynylene group, butynylene group, pentynylene group Hexynylene group, heptynylene group, octynylene group, noninylene group, decynylene group, undecynylene group, dodecynylene group and the like.

Examples of the arylene group having 6 to 30 carbon atoms (preferably 6 to 15 carbon atoms) of R ¹¹¹ include a phenylene group, a tolylene group, a xylylene group, and a naphthylene group.

b represents an integer of 1 to 30 (preferably 2 to 20, more preferably 3 to 7, still more preferably 5 to 6).

R ¹¹² represents 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. Represent. Of these, a branched or unbranched alkyl group having 1 to 30 carbon atoms is preferable.

Examples of the branched or unbranched alkyl group having 1 to 30 carbon atoms (preferably 3 to 25 carbon atoms, more preferably 10 to 15 carbon atoms) of R ¹¹² include, for example, a methyl group, an ethyl group, an n-propyl group, Isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl , Dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, octadecyl group and the like.

Examples of the branched or unbranched alkenyl group having 2 to 30 carbon atoms (preferably 3 to 25 carbon atoms, more preferably 10 to 15 carbon atoms) for R ¹¹² include, for example, a vinyl group, a 1-propenyl group, and 2-propenyl. Group, 1-butenyl group, 2-butenyl group, 1-pentenyl group, 2-pentenyl group, 1-hexenyl group, 2-hexenyl group, 1-octenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group Group, pentadecenyl group, octadecenyl group and the like.

Examples of the aryl group having 6 to 30 carbon atoms (preferably 10 to 20 carbon atoms) of R ¹¹² 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 R ¹¹² include a benzyl group and a phenethyl group.

Specific examples of the group represented by —O— (R ¹¹¹ —O) _b —R ¹¹² include, for example, —O— (C ₂ H ₄ —O) ₅ —C ₁₁ H ₂₃ , —O— (C _{2 H 4 -O) 5 -C 12 H} 25, -O- (C 2 H 4 -O) 5 -C 13 H 27, -O- (C 2 H 4 -O) 5 -C 14 H 29, -O _{- (C 2 H 4 -O)} 5 -C 15 H 31, -O- (C 2 H 4 -O) 3 -C 13 H 27, -O- (C 2 H 4 -O) 4 -C 13 H _{27, -O- (C 2 H 4} -O) 6 -C 13 H 27, such as _{-O- (C 2 H 4 -O)} 7 -C 13 H 27 and the like. Among _{these, -O- (C 2 H 4 -O} ) 5 -C 11 H 23, -O- (C 2 H 4 -O) 5 -C 13 H 27, -O- (C 2 H 4 -O) 5 _{-C 15 H 31, -O- (C} 2 H 4 -O) 6 -C 13 H 27 are preferable.

Examples of the branched or unbranched alkylene group having 1 to 6 carbon atoms (preferably 1 to 5 carbon atoms) of R ¹⁰⁴ include the same groups as the branched or unbranched alkylene group having 1 to 30 carbon atoms of R ^111. Can give.

Examples of the mercapto silane coupling agent represented by the formula (I) include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, and 2-mercaptoethyltriethoxysilane. And a compound represented by the following formula (Si363 manufactured by Evonik) and the like, and a compound represented by the following formula can be preferably used. These may be used alone or in combination of two or more.

In the rubber composition obtained by the production method of the present invention, the content of the silane coupling agent is preferably 1 part by mass or more, more preferably 2 parts by mass or more with respect to 100 parts by mass of silica. If it is less than 1 part by mass, good workability may not be obtained. Further, the content of the silane coupling agent is preferably 20 parts by mass or less, more preferably 15 parts by mass or less. When it exceeds 20 parts by mass, there is a tendency that an effect commensurate with the increase in cost cannot be obtained.

(Vulcanized chemicals)
Examples of vulcanizing chemicals include vulcanizing agents and vulcanization accelerators, and it is preferable to use vulcanizing agents and vulcanization accelerators in combination.

As the vulcanizing agent, organic peroxides, sulfur-based vulcanizing agents and the like can be used. Examples of the organic peroxide include benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, t-butyl cumyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, 2,5-dimethyl-2, 5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne- Examples include 3,1,3-bis (t-butylperoxypropyl) benzene. Examples of the sulfur vulcanizing agent include sulfur and morpholine disulfide. These may be used alone or in combination of two or more. Especially, since the effect of this invention is acquired favorably, a sulfur type vulcanizing agent is preferable and sulfur is more preferable.

In the rubber composition obtained by the production method of the present invention, the content of the vulcanizing agent is preferably based on 100 parts by mass of the rubber component, because low fuel consumption, destructive properties and processability can be obtained in a good balance. It is 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and preferably 8 parts by mass or less, more preferably 5 parts by mass or less.

Examples of the vulcanization accelerator include sulfenamide, thiazole, thiuram, thiourea, guanidine, dithiocarbamic acid, aldehyde-amine, aldehyde-ammonia, imidazoline, and xanthate vulcanization accelerators. Is mentioned. These may be used alone or in combination of two or more. Of these, sulfenamide-based and guanidine-based are preferable, and the combined use of sulfenamide-based and guanidine-based is more preferable because the effects of the present invention can be obtained satisfactorily.

In the rubber composition obtained by the production method of the present invention, the content of the vulcanization accelerator is preferably based on 100 parts by mass of the rubber component because the fuel efficiency, fracture characteristics and processability can be obtained in a good balance. Is 0.5 parts by mass or more, more preferably 1.5 parts by mass or more, and preferably 10 parts by mass or less, more preferably 8 parts by mass or less.

(Other ingredients)
In addition to the above components, the rubber composition obtained by the production method of the present invention includes a compounding agent generally used in the production of a rubber composition, such as carbon black; an anti-aging agent; a softening agent such as oil; and stearic acid. Vulcanization aids such as zinc oxide; and the like can be blended.

Next, each kneading step in the production method of the present invention will be described.

(First step)
The first step is a step in which a rubber component, silica and a silane coupling agent are added and kneaded to obtain a first kneaded product.

In this step, while maintaining the reaction temperature set within the range of 140 to 155 ° C., the reaction treatment for kneading the rubber component, silica and silane coupling agent is performed until the following formulas (1) and (2) are satisfied. carry out. Thereby, reaction of a silica and a silane coupling agent can fully be accelerated | stimulated.
Expression (1) ΔG * t / ΔG * 0 × 100 <80
(In the formula, ΔG * 0 represents G * of 100 ° C., 0.5% strain and G of 100 ° C., 64% strain of the unreacted kneaded product obtained by finishing kneading when the reaction temperature is reached. * G * t is the difference between G * and 100% of the first kneaded product obtained by kneading for a predetermined time after reaching the same reaction temperature as ΔG * 0 and 100% at 0.5% strain. It is the difference from G * at 64 ° C. and 64% strain.)
Formula (2) Vt / V0 × 100 <80
(In the formula, V0 is the Mooney viscosity at 130 ° C. of the unreacted kneaded product obtained by finishing kneading when the reaction temperature is reached, and Vt reaches a predetermined reaction temperature after reaching the same reaction temperature as V0. (The Mooney viscosity at 130 ° C. of the first kneaded product obtained by kneading for a period of time.)

When the reaction temperature is less than 140 ° C, the reaction rate of silica and silane coupling agent is slow, and silica cannot be sufficiently hydrophobized, making it impossible to ensure the necessary dispersion of silica and the bond between silica and polymer, resulting in low fuel consumption. Or the breaking strength may not be improved or deteriorated. When the reaction temperature exceeds 155 ° C., the reaction rate between the silica and the silane coupling agent becomes too fast, and the reaction between the coupling agent and the polymer occurs during the kneading, so that the dispersibility of the silica is deteriorated. There is a risk that fuel efficiency and breaking strength will not be improved or deteriorated.

Hereinafter, the procedure of the first step will be described. For example, when the reaction temperature is set to 150 ° C., when the rubber temperature reaches 150 ° C. during kneading, the number of revolutions of the mixer, the ram pressure drop, the temperature in the chamber, etc. are adjusted so as to maintain 150 ° C. Kneading is carried out (reaction treatment). This reaction treatment is performed for a predetermined time until the first kneaded material satisfies the formulas (1) and (2). When the time necessary for the first kneaded material to satisfy the expressions (1) and (2) has elapsed, the kneading is finished and the first kneaded material is discharged from the kneader. G * and Mooney viscosity of the first kneaded product thus obtained are measured, and ΔG * t and Vt are calculated.
In this example, ΔG * 0 and V0 are unreacted kneaded materials obtained by finishing kneading when the rubber temperature reaches 150 ° C. (the first step is finished without carrying out the reaction treatment). Determined based on the measurement result of the kneaded material obtained in the above. Since ΔG * 0 and V0 are different for each reaction temperature, when changing the reaction temperature, it is necessary to determine ΔG * 0 and V0 at the changed reaction temperature.

The reaction time required for the first kneaded product to satisfy the formulas (1) and (2) depends on the type of kneader used for kneading, the blending content of the first kneaded product, the set reaction temperature, and the like. Usually, 80 to 800 seconds are preferable.

The rubber temperature (temperature of the kneaded product) during the reaction treatment affects the reaction between silica and the silane coupling agent and the reaction between the silane coupling agent and the rubber component. Therefore, from the viewpoint of stabilizing the quality of the resulting rubber composition, the rubber temperature during the reaction treatment is preferably as constant as possible, specifically, within a range of ± 3 ° C. of the set reaction temperature. It is preferable.

The kneading machine used in the first step is preferably a closed Banbury mixer. The shape of the rotor of the Banbury mixer may be tangential or meshing.

The reaction between silica and the silane coupling agent is accompanied by the generation of by-products such as ethanol. However, when the amount of by-products in the reaction system is increased, an equilibrium state is reached and the reaction does not proceed. Therefore, in the first step, by performing a deaeration treatment, the by-product generated by the reaction between silica and the silane coupling agent is removed, so that the reaction can be further accelerated.

The deaeration process may be performed after the reaction between the silica and the silane coupling agent occurs by kneading, but it is performed simultaneously with the reaction process because the by-products such as ethanol can be efficiently removed. Or it is preferable to implement alternately with reaction processing, and it is more preferable to implement alternately with reaction processing.
In addition, when performing a reaction process and a deaeration process alternately, the processing time of a reaction process and a deaeration process is although it does not specifically limit, Usually, 40 to 80 second is preferable respectively.

The deaeration treatment is not particularly limited as long as it can remove a by-product such as ethanol, but air blow treatment is preferable because the by-product can be removed in a short time.

The rubber component, silica, and silane coupling agent to be added in the first step may be all or part of them, but the total amount is preferable. However, when a modified rubber is used as the rubber component, it is preferable to add a rubber component other than the modified rubber in the first step and to add the modified rubber in the second step.

In the first step, in addition to the rubber component, silica, and silane coupling agent, other components may be added and kneaded. Other components are not particularly limited as long as they are components other than vulcanized chemicals, and examples thereof include carbon black, oil, anti-aging agent, wax, stearic acid, and zinc oxide.

(Second step)
The second step is a step of further kneading the first kneaded product obtained in the first step to obtain a second kneaded product. By providing the second step, dispersion of silica is further promoted.
In the second step, only the first kneaded product may be kneaded, or other components may be added and kneaded together with the first kneaded product.

The kneading in the second step is preferably performed under the same conditions as in the first step. That is, it is preferable to carry out the same reaction treatment as in the first step also in the second step. Moreover, it is preferable to implement a deaeration process on the same conditions as a 1st process. Further, the kneading machine to be used is preferably a closed Banbury mixer as in the first step.

(Third process)
The third step is a step in which the second kneaded product and vulcanized chemical obtained in the second step are added and kneaded to obtain an unvulcanized rubber composition.

In the third step, the kneading is terminated when the rubber temperature reaches a predetermined temperature (preferably 60 to 120 ° C.) in order to prevent scorching from occurring due to an increase in the rubber temperature during the kneading. The rubber composition is preferably discharged from the kneader. The kneading time in the third step is not particularly limited, but is preferably about 1 to 15 minutes.

As in the first step, the kneader used in the third step may be a closed Banbury mixer or an open roll.

(Other processes)
The unvulcanized rubber composition obtained in the third step is extruded according to the shape of the tire member (preferably cap tread), molded by a normal method on a tire molding machine, and other tire members The tire can be manufactured by pasting together and forming an unvulcanized tire, followed by heating and pressing in a vulcanizer.

The present invention will be specifically described based on examples, but the present invention is not limited to these examples.

老化防止剤：住友化学（株）製のアンチゲン６Ｃ（Ｎ−（１，３−ジメチルブチル）−Ｎ’−フェニル−ｐ−フェニレンジアミン）
ワックス：大内新興化学工業（株）製のサンノックＮ
ステアリン酸：日油（株）製のステアリン酸「椿」
酸化亜鉛：三井金属鉱業（株）製の亜鉛華１号
硫黄：軽井沢硫黄（株）製の粉末硫黄
加硫促進剤（１）：大内新興化学工業（株）製のノクセラーＣＺ（Ｎ−シクロヘキシル−２−ベンゾチアゾリルスルフェンアミド）
加硫促進剤（２）：大内新興化学工業（株）製のノクセラーＤ（Ｎ，Ｎ’−ジフェニルグアニジン） Hereinafter, various chemicals used in Examples and Comparative Examples will be described together.
SBR: NS616 manufactured by Nippon Zeon Co., Ltd.
Modified SBR: NS116R manufactured by Nippon Zeon Co., Ltd. (S-SBR modified at one end with N-methylpyrrolidone)
BR: BR1220 manufactured by Nippon Zeon Co., Ltd. (cis 1, 4 content: 96% by mass)
Carbon black: Seast N220 manufactured by Mitsubishi Chemical Corporation
Silica: Ultrasil VN3 manufactured by Evonik (average primary particle size: 15 nm, N ₂ SA: 175 m ² / g)
Oil: Process X-140 manufactured by Japan Energy Co., Ltd.
Silane coupling agent: Si363 manufactured by Evonik (silane coupling agent represented by the following formula (R ¹⁰¹ = -O- (C ₂ H ₄ -O) in the above formula (I) ₅ -C ₁₃ H ₂₇ , R ^{_{102 = C 2 H 5 -O-,}} R 103 = -O- (C 2 H 4 -O) 5 -C 13 H 27, R 104 = -C 3 H 6 -))

Anti-aging agent: Antigen 6C (N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine) manufactured by Sumitomo Chemical Co., Ltd.
Wax: Sunnock N manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
Stearic acid: Stearic acid “椿” manufactured by NOF Corporation
Zinc oxide: Zinc Hua No. 1 manufactured by Mitsui Mining & Smelting Co., Ltd. Sulfur: Powder sulfur vulcanization accelerator manufactured by Karuizawa Sulfur Co., Ltd. (1): Noxeller CZ (N-cyclohexyl manufactured by Ouchi Shinsei Chemical Co., Ltd.) -2-Benzothiazolylsulfenamide)
Vulcanization accelerator (2): Noxeller D (N, N'-diphenylguanidine) manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.

(Examples A1 to A12 and Comparative Examples A1 to A18)
(First step)
In accordance with the formulation shown in Table 1, materials other than sulfur and a vulcanization accelerator were put into a Banbury mixer and kneaded to obtain a first kneaded product or an unreacted kneaded product. The kneading was carried out while adjusting the rubber temperature to be ± 3 ° C. of the reaction temperature after the rubber temperature reached the set reaction temperature, and finished when a predetermined time (reaction time) had elapsed. . The reaction temperature and reaction time in each example are as shown in Tables 2-6.
(Second step)
The obtained first kneaded material or unreacted kneaded material was put into a Banbury mixer and further kneaded to obtain a second kneaded material. The kneading conditions are the same as in the first step.
(Third process)
The obtained second kneaded product, sulfur and vulcanization accelerator were put into an open roll and kneaded to obtain an unvulcanized rubber composition. The kneading was finished when the rubber temperature reached 110 ° C. The kneading time was 2 minutes.
(Vulcanization process)
The obtained unvulcanized rubber composition was vulcanized at 170 ° C. for 12 minutes to obtain a vulcanized rubber composition.

(Examples B1 to B12 and Comparative Examples B1 to B18)
(First step)
In accordance with the formulation shown in Table 1, materials other than sulfur and a vulcanization accelerator were put into a Banbury mixer and kneaded to obtain a first kneaded product or an unreacted kneaded product. The kneading was carried out while adjusting the rubber temperature to be ± 3 ° C. of the reaction temperature after the rubber temperature reached the set reaction temperature, and finished when a predetermined time (reaction time) had elapsed. . The reaction temperature and reaction time in each example are as shown in Tables 7-11.
Further, in the first step, every 60 seconds of reaction time, the ban of the Banbury mixer was opened, and the air blowing process of blowing air toward the inside was performed for 60 seconds. For example, in an example where the reaction time is 240 seconds, the reaction process of 60 seconds and the air blow process of 60 seconds were alternately performed four times in this order.
(Second step)
The obtained first kneaded material or unreacted kneaded material was put into a Banbury mixer and further kneaded to obtain a second kneaded material. The conditions for kneading and air blowing are the same as in the first step.
(Third process)
The obtained second kneaded product, sulfur and vulcanization accelerator were put into an open roll and kneaded to obtain an unvulcanized rubber composition. The kneading was finished when the rubber temperature reached 110 ° C. The kneading time was 2 minutes.
(Vulcanization process)
The obtained unvulcanized rubber composition was vulcanized at 170 ° C. for 12 minutes to obtain a vulcanized rubber composition.

(Examples C1 to C12 and Comparative Examples C1 to C24)
(First step)
In accordance with the formulation shown in Table 12, materials other than modified SBR, sulfur and vulcanization accelerator were charged into a Banbury mixer and kneaded to obtain a first kneaded product or an unreacted kneaded product. The kneading was carried out while adjusting the rubber temperature to be ± 3 ° C. of the reaction temperature after the rubber temperature reached the set reaction temperature, and finished when a predetermined time (reaction time) had elapsed. . The reaction temperature and reaction time in each example are as shown in Tables 12-18.
(Second step)
The obtained first kneaded material or unreacted kneaded material was put into a Banbury mixer and further kneaded to obtain a second kneaded material. The kneading conditions are the same as in the first step.
(Third process)
The obtained second kneaded product, sulfur and vulcanization accelerator were put into an open roll and kneaded to obtain an unvulcanized rubber composition. The kneading was finished when the rubber temperature reached 110 ° C. The kneading time was 2 minutes.
(Vulcanization process)
The obtained unvulcanized rubber composition was vulcanized at 170 ° C. for 12 minutes to obtain a vulcanized rubber composition.

The following evaluation was performed about the 1st kneaded material obtained above, the unreacted kneaded material, the unvulcanized rubber composition, and the vulcanized rubber composition. The results are shown in Tables 2-11 and 13-18.
In the following evaluation, the reference comparative examples in Tables 2 to 6 were Comparative Example A1, the reference comparative examples in Tables 7 to 11 were Comparative Example B1, and the reference comparative examples in Tables 13 to 18 were Comparative Example C1.

(Mooney viscosity)
According to JIS K6300, the Mooney viscosity of the first kneaded material or the unreacted kneaded material was measured at 130 ° C. The results are shown as an index with the reference comparative example being 100 (VIS index after the first step). The smaller the index, the better the workability.
Moreover, Vt / V0 * 100 of Formula (2) was calculated for every set reaction temperature (VIS reduction rate).

(Pain effect)
Using RPA2000 (manufactured by Alpha Technologies), G * of 100 ° C. and 0.5% strain and G * of 100 ° C. and 64% strain of the first kneaded product or unreacted kneaded product are measured, and ΔG * Was calculated. The results are displayed as an index with the reference comparative example being 100 (ΔG * index after the first step).
In addition, ΔG * t / ΔG * 0 × 100 of Equation (1) was calculated for each reaction temperature that was set (ΔG * decrease rate).

(Tan δ)
Using a spectrometer manufactured by Ueshima Seisakusho, tan δ of the vulcanized rubber composition was measured at a dynamic strain amplitude of 1%, a frequency of 10 Hz, and a temperature of 50 ° C. The results were expressed as an index with the reference comparative example being 100 (tan δ index). The smaller the index, the lower the rolling resistance and the better the fuel efficiency.

(Destructive energy)
In accordance with JIS K 6251 “Vulcanized Rubber and Thermoplastic Rubber-Determination of Tensile Properties”, a tensile test was conducted using a No. 3 dumbbell with a thickness of 2 mm formed from the above vulcanized rubber composition. And elongation at break (EB) were measured. Then, the breaking energy defined by the product of TB and EB was displayed as an index (breaking energy index) with the reference comparative example being 100. The larger the index, the better the fracture characteristics.

(Performance index)
In order to comprehensively evaluate the performance of each example, a performance index was calculated by the following formula.
Performance index = ((100 / VIS index after first step) × 100 + (100 / tan δ index) × 100 + fracture energy index) / 3

As shown in Tables 2 to 6, Example A1 in which the reaction temperature was set in the range of 140 to 155 ° C. in the first step and the reaction treatment was performed until the formulas (1) and (2) were satisfied. Although -A12 has the same reaction temperature, compared with Comparative Examples A1-A6 in which the reaction treatment was not carried out until the formulas (1) and (2) were satisfied, the fuel economy, fracture characteristics, and processability were higher. Remarkably improved.
In Comparative Examples A7 to A18 in which the reaction temperature was set outside the range of 140 to 155 ° C., even if the reaction time was increased, the formulas (1) and (2) could not be satisfied, and sufficient performance improvement was observed. There wasn't.
From these results, it has been clarified that the dispersibility of silica can be improved by a simple technique of adjusting the kneading method using the formulas (1) and (2) as an index without changing the kind of the compounding chemical. .

As shown in Tables 7 to 11, in the first step, the reaction temperature was set within the range of 140 to 155 ° C., and the reaction treatment was carried out until the formulas (1) and (2) were satisfied. Example B1 -B12 has the same reaction temperature, but has low fuel consumption, fracture characteristics and processability compared to Comparative Examples B1 to B6 in which the reaction treatment was not performed until the formulas (1) and (2) were satisfied. Remarkably improved.
In Comparative Examples B7 to B18 where the reaction temperature was set outside the range of 140 to 155 ° C., even if the reaction time was increased, the formulas (1) and (2) could not be satisfied, and sufficient performance improvement was observed. There wasn't.
From these results, it has been clarified that the dispersibility of silica can be improved by a simple technique of adjusting the kneading method using the formulas (1) and (2) as an index without changing the kind of the compounding chemical. .
Moreover, it became clear from the comparison with Example B1-B12 and Example A1-A12 that performance improves further by implementing a deaeration process.

As shown in Tables 13 to 18, Example C1 in which the reaction temperature was set in the range of 140 to 155 ° C. in the first step and the reaction treatment was performed until Expressions (1) and (2) were satisfied. Although -C12 has the same reaction temperature, compared with Comparative Examples C1-C6 which did not carry out reaction treatment until Formula (1) and (2) were satisfy | filled, fuel-consumption property, a fracture characteristic, and workability are Remarkably improved.
In Comparative Examples C7 to C18 in which the reaction temperature was set outside the range of 140 to 155 ° C., even if the reaction time was increased, the formulas (1) and (2) could not be satisfied, and sufficient performance improvement was observed. There wasn't. Comparative examples C19 to C24 in which the modified rubber was added in the first step had the same tendency.
From these results, it has been clarified that the dispersibility of silica can be improved by a simple technique of adjusting the kneading method using the formulas (1) and (2) as an index without changing the kind of the compounding chemical. .

Claims (6)

A rubber component, silica and a silane coupling agent are added and kneaded to obtain a first kneaded product;
A second step of further kneading the first kneaded product to obtain a second kneaded product;
Adding the second kneaded product and the vulcanized chemical and kneading to obtain a non-vulcanized rubber composition,
In the first step, a reaction treatment for kneading the rubber component, the silica and the silane coupling agent while maintaining a reaction temperature set within a range of 140 to 155 ° C. is represented by the following formulas (1) and ( The manufacturing method of the rubber composition for tires implemented until 2) is satisfy | filled.
Expression (1) ΔG * t / ΔG * 0 × 100 <80
(In the formula, ΔG * 0 represents G * of 100 ° C., 0.5% strain and G of 100 ° C., 64% strain of the unreacted kneaded product obtained by finishing kneading when the reaction temperature is reached. * G * t is the difference between G * and 100% of the first kneaded product obtained by kneading for a predetermined time after reaching the same reaction temperature as ΔG * 0 and 100% at 0.5% strain. It is the difference from G * at 64 ° C. and 64% strain.)
Formula (2) Vt / V0 × 100 <80
(In the formula, V0 is the Mooney viscosity at 130 ° C. of the unreacted kneaded product obtained by finishing kneading when the reaction temperature is reached, and Vt reaches a predetermined reaction temperature after reaching the same reaction temperature as V0. (The Mooney viscosity at 130 ° C. of the first kneaded product obtained by kneading for a period of time.) The method for producing a rubber composition for a tire according to claim 1, wherein the silane coupling agent is a mercapto silane coupling agent represented by the following formula (I).

(Wherein R ^{101 to} R ¹⁰³ are branched or unbranched alkyl groups having 1 to 12 carbon atoms, branched or unbranched alkoxy groups having 1 to 12 carbon atoms, or —O— (R ¹¹¹ —O) _b. -R ¹¹² (b pieces ^{by R 111} are .b pieces ^{by R 111} are optionally each be the same or different ^{.R 112} representing a divalent hydrocarbon group of branched or unbranched C1-30 is 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; Represents an integer of 1 to 30.) R ^{101 to} R ¹⁰³ may be the same or different, and R ¹⁰⁴ is a branched or unbranched alkylene group having 1 to 6 carbon atoms. Represents.) The method for producing a tire rubber composition according to claim 1 or 2, wherein a deaeration treatment is performed in the first step. The method for producing a rubber composition for a tire according to any one of claims 1 to 3, wherein in the second step, the first kneaded product and the modified rubber are added and kneaded. The method for producing a rubber composition for a tire according to claim 4, wherein the modified rubber is a modified styrene butadiene rubber. The manufacturing method of the rubber composition for tires in any one of Claims 1-5 which manufactures the rubber composition for cap treads.