JP2013047329A - Rubber composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a rubber composition for improving viscoelastic characteristics possessed by vulcanized rubber used for tire production.SOLUTION: This rubber composition includes a compound expressed by formula (I), a rubber component and a filler. In formula (I), Arepresents an alkanediyl group which may have a substituent, cycloalkanediyl group which may have a substituent, or *-B-Ar-B- group, where -CH- contained in the alkanediyl group may be replaced by -NH-, -O- or -S-; Band Beach represents a single bond or an alkanediyl group; Ar represents a divalent aromatic hydrocarbon group which may have a substituent; Xrepresents -CO-NH-*, -CO-O-*, -CO-* or a single bond; Rand Reach represents H, a halogen atom, alkyl, aryl, hydroxy or alkoxy group, or mutually bonded to form an alkanediyl group.

Description

  The present invention relates to a rubber composition and the like.

  In recent years, there has been a demand for improvement in fuel consumption (that is, reduction in fuel consumption) of automobiles due to a demand for environmental protection. In the field of tires for automobiles, it is known that the fuel efficiency of automobiles is improved by improving the viscoelastic properties of vulcanized rubber used for tire manufacture (see Non-Patent Document 1).

Edited by Japan Rubber Association “Introduction to Rubber Technology” Maruzen Co., Ltd., p. 124

  In the conventional rubber composition, the viscoelastic property of the vulcanized rubber obtained from the rubber composition may not always be sufficiently satisfied.

［式（Ｉ）中、
Ａ^１は、置換基を有していてもよい炭素数２〜１２のアルカンジイル基、置換基を有していてもよい炭素数３〜１２のシクロアルカンジイル基、又は、^＊−Ｂ^１−Ａｒ−Ｂ^２−基を表し、炭素数２〜１２のアルカンジイル基に含まれる−ＣＨ_２−は−ＮＨ−、−Ｏ−又は−Ｓ−で置き換わっていてもよく、＊はＸ^１との結合手を表す。
Ｂ^１は、単結合又は炭素数１〜６のアルカンジイル基を表す。
Ｂ^２は、単結合又は炭素数１〜６のアルカンジイル基を表す。
Ａｒは、置換基を有していてもよい炭素数６〜１２の２価の芳香族炭化水素基を表す。
Ｘ^１は、−ＣＯ−ＮＨ−^＊、−ＣＯ−Ｏ−^＊、−ＣＯ−^＊又は単結合を表し、＊はＡ^１との結合手を表す。
Ｒ^１及びＲ^２は、それぞれ独立に、水素原子、ハロゲン原子、炭素数１〜６のアルキル基、炭素数６〜１２のアリール基、ヒドロキシ基又は炭素数１〜６のアルコキシ基を表すか、互いに結合して炭素数１〜１２のアルカンジイル基を形成する。］ The present invention includes the following inventions.
[1] A rubber composition comprising a compound represented by formula (I), a rubber component, and a filler.

[In the formula (I),
A ¹ is an alkanediyl group having 2 to 12 carbon atoms which may have a substituent, a cycloalkanediyl group having 3 to 12 carbon atoms which may have a substituent, or ^* -B ^1-. Represents an Ar—B ² — group, —CH ₂ — contained in the alkanediyl group having 2 to 12 carbon atoms may be replaced by —NH—, —O— or —S—, and * represents X ¹ Represents a bond.
B ¹ represents a single bond or an alkanediyl group having 1 to 6 carbon atoms.
B ² represents a single bond or alkanediyl group having 1 to 6 carbon atoms.
Ar represents a C6-C12 divalent aromatic hydrocarbon group which may have a substituent.
X ¹ represents —CO—NH— ^* , —CO—O— ^* , —CO— ^* or a single bond, and * represents a bond to A ¹ .
R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a hydroxy group, or an alkoxy group having 1 to 6 carbon atoms, Bond to each other to form an alkanediyl group having 1 to 12 carbon atoms. ]

[2] The rubber composition according to [1], wherein R ¹ and R ² are hydrogen atoms.

[3] The rubber composition according to [1] or [2], wherein A ¹ is an optionally substituted divalent aromatic hydrocarbon group having 6 to 12 carbon atoms.

[4] X ¹ represents a single bond, A ¹ represents a ^* —B ¹ —Ar—B ² — group (B ¹ represents a single bond, and B ² represents a single bond or an alkylene group) [1. ] The rubber composition in any one of [3].

[5] The rubber composition according to any one of [1] to [4], wherein the rubber component is natural rubber.

[6] The rubber composition according to any one of [1] to [5], further including a sulfur component.

[7] A vulcanized rubber obtained by heat-treating the rubber composition according to [6].

[8] A tire produced by processing the rubber composition according to [6].

[9] A tire belt comprising a steel cord coated with the vulcanized rubber according to [7].

[10] A tire carcass including a carcass fiber cord coated with the vulcanized rubber according to [7].

[11] A tire sidewall including the vulcanized rubber according to [7], a tire inner liner, a tire cap tread, or a tire under tread.

[12] A tire comprising the vulcanized rubber according to [7].

［式（Ｉ）中、
Ａ^１は、置換基を有していてもよい炭素数２〜１２のアルカンジイル基、置換基を有していてもよい炭素数３〜１２のシクロアルカンジイル基、又は、^＊−Ｂ^１−Ａｒ−Ｂ^２−基を表し、炭素数２〜１２のアルカンジイル基に含まれる−ＣＨ_２−は−ＮＨ−、−Ｏ−又は−Ｓ−で置き換わっていてもよく、＊はＸ^１との結合手を表す。
Ｂ^１は、単結合又は炭素数１〜６のアルカンジイル基を表す。
Ｂ^２は、単結合又は炭素数１〜６のアルカンジイル基を表す。
Ａｒは、置換基を有していてもよい炭素数６〜１２の２価の芳香族炭化水素基を表す。
Ｘ^１は、−ＣＯ−ＮＨ−^＊、−ＣＯ−Ｏ−^＊、−ＣＯ−^＊又は単結合を表し、＊はＡ^１との結合手を表す。
Ｒ^１及びＲ^２は、それぞれ独立に、水素原子、ハロゲン原子、炭素数１〜６のアルキル基、炭素数６〜１２のアリール基、ヒドロキシ基又は炭素数１〜６のアルコキシ基を表すか、互いに結合して炭素数１〜１２のアルカンジイル基を形成する。］ [13] Viscoelasticity of a vulcanized rubber having a step of kneading a compound represented by formula (I), a rubber component, a filler, and a sulfur component, and a step of heat-treating the kneaded product obtained in the previous step How to improve characteristics.

[In the formula (I),
A ¹ is an alkanediyl group having 2 to 12 carbon atoms which may have a substituent, a cycloalkanediyl group having 3 to 12 carbon atoms which may have a substituent, or ^* -B ^1-. Represents an Ar—B ² — group, —CH ₂ — contained in the alkanediyl group having 2 to 12 carbon atoms may be replaced by —NH—, —O— or —S—, and * represents X ¹ Represents a bond.
B ¹ represents a single bond or an alkanediyl group having 1 to 6 carbon atoms.
B ² represents a single bond or alkanediyl group having 1 to 6 carbon atoms.
Ar represents a C6-C12 divalent aromatic hydrocarbon group which may have a substituent.
X ¹ represents —CO—NH— ^* , —CO—O— ^* , —CO— ^* or a single bond, and * represents a bond to A ¹ .
R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a hydroxy group, or an alkoxy group having 1 to 6 carbon atoms, Bond to each other to form an alkanediyl group having 1 to 12 carbon atoms. ]

［式（Ｉ）中、
Ａ^１は、置換基を有していてもよい炭素数２〜１２のアルカンジイル基、置換基を有していてもよい炭素数３〜１２のシクロアルカンジイル基、又は、^＊−Ｂ^１−Ａｒ−Ｂ^２−基を表し、炭素数２〜１２のアルカンジイル基に含まれる−ＣＨ_２−は−ＮＨ−、−Ｏ−又は−Ｓ−で置き換わっていてもよく、＊はＸ^１との結合手を表す。
Ｂ^１は、単結合又は炭素数１〜６のアルカンジイル基を表す。
Ｂ^２は、単結合又は炭素数１〜６のアルカンジイル基を表す。
Ａｒは、置換基を有していてもよい炭素数６〜１２の２価の芳香族炭化水素基を表す。
Ｘ^１は、−ＣＯ−ＮＨ−^＊、−ＣＯ−Ｏ−^＊、−ＣＯ−^＊又は単結合を表し、＊はＡ^１との結合手を表す。
Ｒ^１及びＲ^２は、それぞれ独立に、水素原子、ハロゲン原子、炭素数１〜６のアルキル基、炭素数６〜１２のアリール基、ヒドロキシ基又は炭素数１〜６のアルコキシ基を表すか、互いに結合して炭素数１〜１２のアルカンジイル基を形成する。］ [14] Use of a compound represented by the formula (I) for improving viscoelastic properties of a vulcanized rubber.

[In the formula (I),
A ¹ is an alkanediyl group having 2 to 12 carbon atoms which may have a substituent, a cycloalkanediyl group having 3 to 12 carbon atoms which may have a substituent, or ^* -B ^1-. Represents an Ar—B ² — group, —CH ₂ — contained in the alkanediyl group having 2 to 12 carbon atoms may be replaced by —NH—, —O— or —S—, and * represents X ¹ Represents a bond.
B ¹ represents a single bond or an alkanediyl group having 1 to 6 carbon atoms.
B ² represents a single bond or alkanediyl group having 1 to 6 carbon atoms.
Ar represents a C6-C12 divalent aromatic hydrocarbon group which may have a substituent.
X ¹ represents —CO—NH— ^* , —CO—O— ^* , —CO— ^* or a single bond, and * represents a bond to A ¹ .
R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a hydroxy group, or an alkoxy group having 1 to 6 carbon atoms, Bond to each other to form an alkanediyl group having 1 to 12 carbon atoms. ]

［式（Ｉ）中、
Ａ^１は、置換基を有していてもよい炭素数２〜１２のアルカンジイル基、置換基を有していてもよい炭素数３〜１２のシクロアルカンジイル基、又は、^＊−Ｂ^１−Ａｒ−Ｂ^２−基を表し、炭素数２〜１２のアルカンジイル基に含まれる−ＣＨ_２−は−ＮＨ−、−Ｏ−又は−Ｓ−で置き換わっていてもよく、＊はＸ^１との結合手を表す。
Ｂ^１は、単結合又は炭素数１〜６のアルカンジイル基を表す。
Ｂ^２は、単結合又は炭素数１〜６のアルカンジイル基を表す。
Ａｒは、置換基を有していてもよい炭素数６〜１２の２価の芳香族炭化水素基を表す。
Ｘ^１は、−ＣＯ−ＮＨ−^＊、−ＣＯ−Ｏ−^＊、−ＣＯ−^＊又は単結合を表し、＊はＡ^１との結合手を表す。
Ｒ^１及びＲ^２は、それぞれ独立に、水素原子、ハロゲン原子、炭素数１〜６のアルキル基、炭素数６〜１２のアリール基、ヒドロキシ基又は炭素数１〜６のアルコキシ基を表すか、互いに結合して炭素数１〜１２のアルカンジイル基を形成する。］ [15] A vulcanized rubber viscoelastic property improver containing a compound represented by the formula (I) as an active ingredient.

[In the formula (I),
A ¹ is an alkanediyl group having 2 to 12 carbon atoms which may have a substituent, a cycloalkanediyl group having 3 to 12 carbon atoms which may have a substituent, or ^* -B ^1-. Represents an Ar—B ² — group, —CH ₂ — contained in the alkanediyl group having 2 to 12 carbon atoms may be replaced by —NH—, —O— or —S—, and * represents X ¹ Represents a bond.
B ¹ represents a single bond or an alkanediyl group having 1 to 6 carbon atoms.
B ² represents a single bond or alkanediyl group having 1 to 6 carbon atoms.
Ar represents a C6-C12 divalent aromatic hydrocarbon group which may have a substituent.
X ¹ represents —CO—NH— ^* , —CO—O— ^* , —CO— ^* or a single bond, and * represents a bond to A ¹ .
R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a hydroxy group, or an alkoxy group having 1 to 6 carbon atoms, Bond to each other to form an alkanediyl group having 1 to 12 carbon atoms. ]

  According to the rubber composition of the present invention, the viscoelastic properties of the vulcanized rubber obtained from the rubber composition can be improved.

  In the present invention, “improving viscoelastic properties” means, for example, modifying a loss factor (tan δ) of a vulcanized rubber described later.

<Compound represented by formula (I) (hereinafter sometimes referred to as “compound (I)”)>
Compound Two ^-X 1 ^-A 1 -NH ₂ group contained in the (I) represent the same group.
Examples of the alkanediyl group having 2 to 12 carbon atoms in A ¹ include linear alkanediyl groups such as ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group; isopropylene group and isobutylene group , Branched alkanediyl groups such as 2-methyltrimethylene group, isopentylene group, isohexylene group, isooctylene group, 2-ethylhexylene group, and isodecylene group. Especially, 3-12 are preferable and, as for carbon number of an alkanediyl group, 3-6 are more preferable. Moreover, a linear alkanediyl group (polymethylene group) is preferable.

Examples of the substituent that the alkanediyl group may have include, for example, a C1-C4 alkoxy group such as a methoxy group, an ethoxy group, and a butoxy group, a halogen atom such as a hydroxyl group, chlorine, bromine, iodine, and fluorine, C6-C12 aryl groups, such as a phenyl group, a naphthyl group, a biphenyl group, are mentioned. Examples of the alkanediyl group having a substituent include the following groups. * Represents a bond.

—CH ₂ — contained in the alkanediyl group having 2 to 12 carbon atoms may be replaced by —NH—, —O— or —S—. When —CH ₂ — contained in the alkanediyl group is replaced by —NH—, —O— or —S—, the alkanediyl preferably has 3 to 12 carbon atoms, and the —NH ₂ group, —X ¹ — -CH ₂ that bind to a group - is, -NH -, - not Okikawara in O- or -S-. When —CH ₂ — contained in the alkanediyl group is replaced with —NH—, —O— or —S—, the heteroatoms are not adjacent to each other.
Examples of the alkanediyl group containing —NH—, —O— or —S— include the following groups. * Represents a bond.

The cycloalkanediyl group having 3 to 12 carbon atoms in A ^1, e.g., cyclopropylene group, cyclopentylene group, cyclohexylene group, cyclododecylene group, and the like.
Examples of the substituent that the C3-C12 cycloalkanediyl group may have include, for example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, a t-butyl group, etc. 4 alkyl group; aryl group having 6 to 10 carbon atoms such as phenyl group, 4-methylphenyl group and naphthyl group; alkoxy group having 1 to 4 carbon atoms such as methoxy group, ethoxy group and butoxy group; acetyl group and benzoyl group Group, formyl group, pivaloyl group and other acyl groups having 1 to 7 carbon atoms; methoxycarbonyl group, ethoxycarbonyl group and other C3-C4 alkoxycarbonyl groups; phenoxycarbonyl group, naphthyloxycarbonyl group and other carbon atoms 7 -11 aryloxycarbonyl group; C2-C7 acyloxy groups such as acetoxy group and benzoyloxy group; and the like.
The cycloalkanediyl group having 3 to 12 carbon atoms which may have a substituent is preferably a cyclopentylene group, a cyclohexylene group, a methylcyclohexylene group or a t-butylcyclohexylene group.

Examples of the alkanediyl group having 1 to 6 carbon atoms in B ¹ and B ² include the same ones as the alkanediyl group having 2 to 6 carbon atoms in the above alkanediyl group having 2 to 12 carbon atoms and a methylene group. It is done.
Examples of the divalent aromatic hydrocarbon group having 6 to 12 carbon atoms in Ar include a phenylene group, a naphthylene group, and a biphenylene group.

Examples of the substituent that the divalent aromatic hydrocarbon group having 6 to 12 carbon atoms may have include an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a nitro group, and cyano. group, a carboxy group, a sulfo group, a halogen _atom, -CO 2 M, (in M, an alkali metal such as Na,. represents a cation of an organic base such as NH _{4) -SO} 3 M, and the like.

The A ^1, alkanediyl group or ^* -B ^{1 -Ar-B 2} having 2 to 12 carbon atoms - preferably a ^{group, * -B 1 '-Ar'-B} 2' - group ^{(B 1} 'is a single bond Ar ′ represents a phenylene group, B ² ′ represents a single bond or a methylene group, and * represents a bond to X ¹ ), more preferably a phenylene group.
X ¹ represents —CO—NH— ^* , —CO—O— ^* , —CO— ^* or a single bond, and * represents a bond to A ¹ . X ¹ is preferably —CO—NH— ^* or a single bond.

Examples of the halogen atom for R ¹ and R ² include fluorine, chlorine, bromine and iodine.
Examples of the alkyl group having 1 to 6 carbon atoms in R ¹ and R ² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, An n-pentyl group, an isopentyl group, an n-hexyl group, and the like can be given.
The aryl group having 6 to 12 carbon atoms in R ¹ and R ² represents a monocyclic or condensed polycyclic aromatic hydrocarbon having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and a biphenyl group. Can be mentioned.
Examples of the alkoxy group having 1 to 6 carbon atoms in R ¹ and R ² include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert. -Butyloxy group, n-pentyloxy group, isopentyloxy group, n-hexyloxy group and the like.
Examples of the alkanediyl group having 1 to 12 carbon atoms which R ¹ and R ² are bonded to each other include the same groups as described above, and are preferably alkanediyl groups having 3 or 4 carbon atoms. Examples of the cyclic structure formed by combining R ¹ and R ² together with the carbon atom to which they are bonded include a cyclopentene ring and a cyclohexene ring.
R ¹ is a hydrogen atom, it is preferred that R ² is an alkyl group having 1 to 6 carbon hydrogen or C, and more preferably R ¹ and R ² are hydrogen atoms.

Specific examples of compound (I) are shown below.

（式中、Ａ^１、Ａｒ、Ｂ^１、Ｒ^１及びＲ^２は上記と同じ意味を表す。
Ｐ^１、Ｐ^２及びＰ^３は、それぞれ独立に、ｔｅｒｔ-ブトキシカルボニル基等の保護基を表す。
ＷＳＣＩ ＨＣｌは、１−エチル−3−(3−ジメチルアミノプロピル)−カルボジイミド塩酸塩を表す。）
上記の製造方法において、製造の便宜上、保護基を使用してもよい。保護基を使用した場合には、その保護基を汎用される方法にて除去することができる。 Compound (I) may form a solvate with a lower alcohol such as methanol or ethanol or water.
Compound (I) can be produced, for example, by the method represented by the following formula.

(Wherein A ¹ , Ar, B ¹ , R ¹ and R ² represent the same meaning as described above.
P ¹ , P ² and P ³ each independently represent a protecting group such as a tert-butoxycarbonyl group.
WSCI HCl represents 1-ethyl-3- (3-dimethylaminopropyl) -carbodiimide hydrochloride. )
In the above production method, a protective group may be used for the convenience of production. When a protecting group is used, the protecting group can be removed by a commonly used method.

  The rubber composition of the present invention contains compound (I), a rubber component, and a filler. The rubber composition of the present invention is preferably a rubber composition obtained by kneading compound (I), a rubber component and a filler. The rubber composition of the present invention preferably further contains a sulfur component, and more preferably further contains a vulcanization accelerator and zinc oxide.

  Rubber components include natural rubber, epoxidized natural rubber, deproteinized natural rubber and other modified natural rubber, as well as polyisoprene rubber (IR), styrene / butadiene copolymer rubber (SBR), polybutadiene rubber (BR), and acrylonitrile. -Various synthetic rubbers such as butadiene copolymer rubber (NBR), isoprene / isobutylene copolymer rubber (IIR), ethylene / propylene-diene copolymer rubber (EPDM), halogenated butyl rubber (HR), etc., natural rubber, Highly unsaturated rubbers such as styrene / butadiene copolymer rubber and polybutadiene rubber are preferably used. Particularly preferred is natural rubber. It is also effective to combine several rubber components such as a combination of natural rubber and styrene / butadiene copolymer rubber, a combination of natural rubber and polybutadiene rubber.

  Examples of natural rubber include natural rubber of grades such as RSS # 1, RSS # 3, TSR20, SIR20 and the like. As the epoxidized natural rubber, those having a degree of epoxidation of 10 to 60 mol% are preferable, and examples thereof include ENR25 and ENR50 manufactured by Kumpoulan Gasly. As the deproteinized natural rubber, a deproteinized natural rubber having a total nitrogen content of 0.3% by weight or less is preferable. The modified natural rubber contains a polar group obtained by reacting natural rubber with 4-vinylpyridine, N, N, -dialkylaminoethyl acrylate (for example, N, N, -diethylaminoethyl acrylate), 2-hydroxyacrylate, or the like in advance. Natural rubber is preferably used.

  Examples of the SBR include emulsion polymerization SBR and solution polymerization SBR described in pages 210 to 211 of “Rubber Industry Handbook <Fourth Edition>” edited by the Japan Rubber Association. In particular, solution-polymerized SBR is preferably used as a rubber composition for a tread, and further, the molecular terminal is terminated by using 4,4′-bis- (dialkylamino) benzophenone such as “Nippol (registered trademark) NS116” manufactured by Nippon Zeon Co., Ltd. Modified polymerized SBR, solution polymerized SBR modified with molecular halides using tin halide compounds such as “SL574” manufactured by JSR, commercially available silane-modified solution polymerized SBR such as “E10” and “E15” manufactured by Asahi Kasei , Lactam compounds, amide compounds, urea compounds, N, N-dialkylacrylamide compounds, isocyanate compounds, imide compounds, silane compounds having an alkoxy group (trialkoxysilane compounds, etc.), and aminosilane compounds alone, Or a silane compound having a tin compound and an alkoxy group, Using two or more different compounds as described above, such as an alkylacrylamide compound and a silane compound having an alkoxy group, each of the molecular ends obtained by modifying the molecular ends is either nitrogen, tin, or silicon, or those Solution polymerization SBR having a plurality of elements is particularly preferably used. Oil-extended SBR in which oil such as post-polymerization process oil and aroma oil is added to emulsion polymerization SBR and solution polymerization SBR can be preferably used as a rubber composition for treads.

  Examples of BR include solution polymerization BR such as high cis BR having 90% or more of cis 1,4 bond and low cis BR having cis bond of around 35%, and low cis BR having a high vinyl content is preferably used. . Furthermore, tin-modified BR such as “Nipol (registered trademark) BR 1250H” manufactured by Nippon Zeon, 4,4′-bis- (dialkylamino) benzophenone, tin halide compound, lactam compound, amide compound, urea compound, N, An N-dialkylacrylamide compound, an isocyanate compound, an imide compound, a silane compound having an alkoxy group (trialkoxysilane compound, etc.), an aminosilane compound alone, or a silane compound having a tin compound and an alkoxy group, Using two or more different compounds as described above, such as an alkylacrylamide compound and a silane compound having an alkoxy group, each of the molecular ends obtained by modifying the molecular ends is either nitrogen, tin, or silicon, or those Solution polymerization B with multiple elements But particularly preferably used. These BRs can be preferably used as a rubber composition for a tread or a rubber composition for a sidewall, and are usually used in a blend with SBR and / or natural rubber. In the rubber composition for treads, the blend ratio is preferably 60 to 100% by weight for SBR and / or natural rubber and 0 to 40% by weight for BR relative to the total rubber weight. In the rubber composition for sidewalls, The SBR and / or natural rubber is preferably 10 to 70% by weight and the BR is preferably 90 to 30% by weight based on the total rubber weight, and further the natural rubber is 40 to 60% by weight and BR 60 to 40% based on the total rubber weight. Weight percent blends are particularly preferred. In this case, a blend of modified SBR and non-modified SBR or a blend of modified BR and non-modified BR is also preferable.

Examples of the filler include carbon black, silica, talc, clay, aluminum hydroxide, titanium oxide and the like that are usually used in the rubber field. Carbon black and silica are preferably used, and carbon black is particularly preferably used. Is done. Examples of the carbon black include those described on page 494 of “Rubber Industry Handbook <Fourth Edition>” edited by the Japan Rubber Association. HAF (High Abrasion Furnace), SAF (Super Abrasion Furnace), ISAF (Intermediate). Carbon blacks such as SAF), ISAF-HM (Intermediate SAF-High Modulus), FEF (Fast Extrusion Furnace), MAF, GPF (General Purpose Furnace), and SRF (Semi-Reinforcing Furnace) are preferred. The rubber composition for a tire tread CTAB surface 40~250m ² / g, nitrogen adsorption specific surface area 20 to 200 m ² / g, carbon black having a particle diameter 10~50nm is preferably used, with CTAB surface 70~180m ² / g A certain carbon black is more preferable, and examples thereof include N110, N220, N234, N299, N326, N330, N330T, N339, N343, N351 and the like in the ASTM standard. A surface-treated carbon black in which 0.1 to 50% by weight of silica is attached to the surface of the carbon black is also preferable. Furthermore, it is also effective to combine several kinds of fillers such as the combined use of carbon black and silica. In the rubber composition for a tire tread, it is preferable to use carbon black alone or both carbon black and silica. In the rubber composition for carcass and sidewall, carbon black having a CTAB surface area of 20 to 60 m ² / g and a particle diameter of 40 to 100 nm is preferably used. Examples thereof include N330, N339, N343, N351, N550 in the ASTM standard. N568, N582, N630, N642, N660, N662, N754, N762, and the like. The amount of the filler used is not particularly limited, but is preferably in the range of 5 to 100 parts by weight per 100 parts by weight of the rubber component. Particularly preferably, the amount is 30 to 80 parts by weight when only carbon black is used as a filler, and 5 to 50 parts by weight when used in combination with silica in a tread member application.

Examples of the silica include CTAB specific surface area of 50 to 180 m ² / g and nitrogen adsorption specific surface area of 50 to 300 m ² / g. “AQ”, “AQ-N”, Degussa manufactured by Tosoh Silica Co., Ltd. "Ultrasil (registered trademark) VN3", "Ultrasil (registered trademark) VN3-G", "Ultrasil (registered trademark) 360", "Ultrasil (registered trademark) 7000", Rhodia Commercially available products such as “registered trademark” 115GR, “zeosyl (registered trademark) 1115MP”, “zeosyl (registered trademark) 1205MP”, “zeosyl (registered trademark) Z85MP”, “NIPSEAL (registered trademark) AQ” manufactured by Nippon Silica Preferably used. Further, silica having a pH of 6 to 8, silica containing 0.2 to 1.5% by weight of sodium, true spherical silica having a roundness of 1 to 1.3, silicone oil such as dimethyl silicone oil, and ethoxysilyl group It is also preferable to use an organosilicon compound containing silane, silica surface-treated with an alcohol such as ethanol or polyethylene glycol, and silica having two or more different nitrogen adsorption specific surface areas.

  The amount of the filler used is not particularly limited, but is preferably in the range of 10 to 120 parts by weight per 100 parts by weight of the rubber component. Moreover, when mix | blending a silica, it is preferable to mix | blend 5-50 weight part of carbon black, and the blend ratio of silica / carbon black is especially preferable 0.7 / 1-1 / 0.1. When silica is usually used as a filler, bis (3-triethoxysilylpropyl) tetrasulfide ("Si-69" manufactured by Degussa) or bis (3-triethoxysilylpropyl) disulfide ("Si-" manufactured by Degussa) 75 "), bis (3-diethoxymethylsilylpropyl) tetrasulfide, bis (3-diethoxymethylsilylpropyl) disulfide, octanethioic acid S- [3- (triethoxysilyl) propyl] ester (General Electronic Silicones) "NXT silane"), octanethioic acid S- [3-{(2-methyl-1,3-propanedialkoxy) ethoxysilyl} propyl] ester and octanethioic acid S- [3-{(2-methyl-1, 3-propanedialkoxy) methylsilyl} propyl] ester Rutriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, n-octyltrimethoxysilane , N-octyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (methoxyethoxy) silane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, 3-methacryloxypropyltrimethoxysilane, 3 -Methacryloxypropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) ) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxy Silane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyl It is preferable to add a compound having a functional group such as an element such as silicon or alkoxysilane that can be bonded to silica, such as one or more silane coupling agents selected from the group consisting of triethoxysilane, and bis (3 -Triethoxysilylpropyl) tetrasulfide (Degussa "Si-69 ), Bis (3-triethoxysilylpropyl) disulfide (manufactured by Degussa, "Si-75"), 3-octanoylthiopropyl aminopropyltriethoxysilane (General Electronic Silicon Inc. Ltd. "NXT silane") is particularly preferred. Although the addition time of these compounds is not particularly limited, it is preferably compounded into rubber at the same time as silica, and the compounding amount is preferably 2 to 10% by weight, more preferably 7 to 9% by weight, based on silica. is there. In the case of blending, the blending temperature is preferably 80 to 200 ° C, more preferably 110 to 180 ° C. Furthermore, when silica is used as the filler, in addition to silica, an element such as silicon that can be bonded to silica or a compound having a functional group such as alkoxysilane, monohydric alcohol such as ethanol, butanol, octanol, or ethylene Glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, pentaerythritol, polyether polyol and other dihydric alcohols, N-alkylamines, amino acids, liquid polybutadienes whose molecular ends are carboxyl-modified or amine-modified, etc. It is also preferable to mix.

Examples of the aluminum hydroxide include aluminum hydroxide having a nitrogen adsorption specific surface area of 5 to 250 m ² / g and a DOP oil supply amount of 50 to 100 ml / 100 g.

  Examples of the sulfur component include powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur. Usually, powdered sulfur is preferred, and insoluble sulfur is preferred when used for tire members having a large amount of sulfur such as belt members.

  Examples of vulcanization accelerators include thiazole-based vulcanization accelerators and sulfur compounds described on pages 412 to 413 of Rubber Industry Handbook <Fourth Edition> (issued by the Japan Rubber Association on January 20, 1994). Examples thereof include phenamide vulcanization accelerators and guanidine vulcanization accelerators.

  Specifically, for example, N-cyclohexyl-2-benzothiazolylsulfenamide (CBS), N-tert-butyl-2-benzothiazolylsulfenamide (BBS), N, N-dicyclohexyl-2 -Benzothiazolylsulfenamide (DCBS), 2-mercaptobenzothiazole (MBT), dibenzothiazyl disulfide (MBTS), diphenylguanidine (DPG). When carbon black is used as the filler, N-cyclohexyl-2-benzothiazolylsulfenamide (CBS), N-tert-butyl-2-benzothiazolylsulfenamide (BBS), N, N-dicyclo Hexyl-2-benzothiazolylsulfenamide (DCBS) or dibenzothiazyl disulfide (MBTS) and diphenylguanidine (DPG) are preferably used in combination, and when silica and carbon black are used in combination as fillers N-cyclohexyl-2-benzothiazolylsulfenamide (CBS), N-tert-butyl-2-benzothiazolylsulfenamide (BBS), N, N-dicyclohexyl-2-benzothiazolylsulfate Fenamide (DCBS), dibenzothiazyl disulfide It is preferable that either of MBTS) in combination with diphenyl guanidine (DPG).

  The ratio of sulfur to the vulcanization accelerator is not particularly limited, but is preferably in the range of sulfur / vulcanization accelerator = 2/1 to 1/2 by weight ratio. Further, EV vulcanization in which the ratio of sulfur / vulcanization accelerator, which is a method for improving heat resistance in rubber members mainly composed of natural rubber, is 1 or less is used in the present invention in applications that particularly require improvement in heat resistance. Preferably used.

  As a procedure for kneading each component, a rubber component and a filler are kneaded (hereinafter sometimes referred to as “procedure 1”), and then the composition obtained in procedure 1 and a sulfur component are kneaded. (Hereinafter also referred to as “procedure 2”). Both the kneaded product obtained in Procedure 1 and the kneaded product obtained in Procedure 2 are rubber compositions of the present invention.

  Compound (I) may be blended in Procedure 2, but is preferably blended in Procedure 1 together with a filler and zinc oxide. The amount of compound (I) used is preferably in the range of 0.1 to 10 parts by weight per 100 parts by weight of the rubber component. More preferably, it is the range of 0.3-3 weight part. The blending temperature when blended in Procedure 1 is preferably 80 to 200 ° C, more preferably 110 to 180 ° C. The blending temperature when blended in Procedure 2 is preferably 50 to 100 ° C.

Compound (I) can be blended in advance with a carrier. Examples of such a carrier include the fillers exemplified above and “inorganic fillers and reinforcing agents” described on pages 510 to 513 of “Rubber Industry Handbook <Fourth Edition>” edited by the Japan Rubber Association. Carbon black, silica, calcined clay and aluminum hydroxide are preferred. The amount of the carrier used is not particularly limited, but is preferably in the range of 10 to 1000 parts by weight per 100 parts by weight of compound (I).
When the melting point of compound (I) is high, it is preferable to pulverize compound (I) into particles having a particle size of 100 μm or less in order to ensure sufficient dispersibility during kneading.
For example, the compound (I) is mixed with carbon black, silica, calcined clay or aluminum hydroxide, and the resulting mixture is pulverized to produce particles having a particle size of 100 μm or less composed of the compound (I). .

  It is also possible to mix and knead an agent for improving viscoelastic properties usually used in the rubber field. Examples of such an agent include N, N′-bis (2-methyl-2-nitropropyl) -1,6-hexanediamine (“SUMIFINE (registered trademark) 1162” manufactured by Sumitomo Chemical Co., Ltd.), JP-A-63. Dithiouracil compound described in JP-A No. 233942, nitrosoquinoline compounds such as 5-nitroso-8-hydroxyquinoline (NQ-58) described in JP-A-60-82406, “Tactrol (registered trademark) AP, manufactured by Taoka Chemical Co., Ltd.” V-200 ”, alkylphenol / sulfur chloride condensates described in JP-A No. 2009-138148 such as“ BALTAC 2, 3, 4, 5, 7, 710 ”manufactured by Penwald, and bis (3-triethoxysilyl) Propyl) tetrasulfide (“Si-69” manufactured by Degussa), bis (3-triethoxysilylpropyl) disulfide (Degussa) “Si-75”), bis (3-diethoxymethylsilylpropyl) tetrasulfide, bis (3-diethoxymethylsilylpropyl) disulfide, octanethioic acid S- [3- (triethoxysilyl) propyl] ester, octanethio Acid S- [3-{(2-methyl-1,3-propanedialkoxy) ethoxysilyl} propyl] ester and octanethioic acid S- [3-{(2-methyl-1,3-propanedialkoxy) methylsilyl} Propyl] ester phenyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, n- Oh Tiltrimethoxysilane, n-octyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (methoxyethoxy) silane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, 3-methacryloxypropyltri Methoxysilane, 3-methacryloxypropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2- Aminoethyl) -3-aminopropyltriethoxysilane, (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Silane coupling agents such as rutrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 1,6-bis (N, N′-dibenzylthiocarbamoyldithio) hexane (“BA9188” manufactured by Bayer), 1,6-hexamethylenedithiosulfate disodium salt dihydrate, 1,3-bis (citraconimidomethyl) benzene ( “Perkalink 900” manufactured by Flexis Co., Ltd.), 1-benzoyl-2-phenylhydrazide, 1- or 3-hydroxy-N ′-(1-methylethylidene) -2-naphthoic acid hydrazide, described in JP-A No. 2004-91505 1- or 3-hydroxy-N ′-(1-methylpropylidene 2-naphthoic acid hydrazide, 1- or 3-hydroxy-N ′-(1,3-dimethylbutylidene) -2-naphthoic acid hydrazide and 1- or 3-hydroxy-N ′-(2-furylmethylene)- Carboxylic acid hydrazide derivatives such as 2-naphthoic acid hydrazide, 3-hydroxy-N ′-(1,3-dimethylbutylidene) -2-naphthoic acid hydrazide and 3-hydroxy-N ′ described in JP-A No. 2000-190704 -(1,3-diphenylethylidene) -2-naphthoic acid hydrazide and 3-hydroxy-N '-(1-methylethylidene) -2-naphthoic acid hydrazide, bismercaptooxadiazole described in JP-A-2006-328310 Compound, pyrithione salt compound described in JP-A-2009-40898, JP-A-2006-249361 Cobalt hydroxide compound of publication and the like.

  Among them, N, N′-bis (2-methyl-2-nitropropyl) -1,6-hexanediamine (“Sumifine (registered trademark) 1162” manufactured by Sumitomo Chemical Co., Ltd.), 5-nitroso-8-hydroxyquinoline ( NQ-58), bis (3-triethoxysilylpropyl) tetrasulfide (“Si-69” manufactured by Degussa), bis (3-triethoxysilylpropyl) disulfide (“Si-75” manufactured by Degussa), 1, 6-bis (N, N′-dibenzylthiocarbamoyldithio) -hexane (“KA9188” manufactured by Bayer), hexamethylenebisthiosulfate disodium salt dihydrate, 1,3-bis (citraconimidomethyl) benzene (Flexera's “Parka Link 900”), Taoka Chemical's “Tacquiroll (registered trademark) AP, V-200”, etc. Le phenol-sulfur chloride condensate is preferred.

  When blending zinc oxide, blending in Procedure 1 is preferable, and when blending a vulcanization accelerator, blending in Procedure 2 is preferable.

  It is also possible to mix and knead various compounding agents usually used in the rubber field. As such a compounding agent, for example, an anti-aging agent such as “Antigen (registered trademark) 6C” manufactured by Sumitomo Chemical Co., Ltd .; oil; fatty acids such as stearic acid; Coumarone resin NG4 (softening point 81) manufactured by Nippon Steel Chemical Co., Ltd. ~ 100 ° C), process resin AC5 (softening point 75 ° C) of Kobe Oil Chemical Co., Ltd .; terpene resins such as terpene resin, terpene / phenol resin, aromatic modified terpene resin; Mitsubishi Gas Rosin derivatives such as Chemical Co., Ltd. “Nikanol (registered trademark) A70” (softening point 70-90 ° C.); Hydrogenated rosin derivatives; Novolac alkylphenol resins; Resole alkylphenol resins; C5 petroleum resins; Liquid polybutadienes; Is mentioned. These compounding agents can be blended in either Procedure 1 or Procedure 2.

  Examples of the oil include process oil and vegetable oil. Examples of the process oil include paraffinic process oil, naphthenic process oil, aromatic process oil, and the like. For example, aromatic oil (“NC-140” manufactured by Cosmo Oil Co., Ltd.), process oil (produced by Idemitsu Kosan Co., Ltd. “ And Diana process PS32 ").

Examples of the anti-aging agent include those described in pages 436 to 443 of “Rubber Industry Handbook <Fourth Edition>” edited by the Japan Rubber Association. Among them, N-phenyl-N′-1,3-dimethylbutyl-p-phenylenediamine (6PPD), reaction product of aniline and acetone (TMDQ), poly (2,2,4-trimethyl-1,2-) dihydro Quinoline) (“Antioxidant FR” manufactured by Matsubara Sangyo Co., Ltd.), synthetic wax (paraffin wax, etc.) and vegetable wax are preferably used.
Examples of the wax include “Sannok (registered trademark) wax” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd. and “OZOACE-0355” manufactured by Nippon Seiwa Co., Ltd.

  It is also possible to blend and knead a vulcanizing agent such as morpholine disulfide which is usually used in the rubber field. These are preferably blended in Procedure 2.

  Further, a peptizer and a retarder may be blended and kneaded, and various general rubber chemicals and softeners may be blended and kneaded as necessary.

  Examples of the retarder include phthalic anhydride, benzoic acid, salicylic acid, N-nitrosodiphenylamine, N- (cyclohexylthio) -phthalimide (CTP), sulfonamide derivatives, diphenylurea, bis (tridecyl) pentaerythritol-diphosphite, etc. N- (cyclohexylthio) -phthalimide (CTP) is preferably used.

  The retarder may be blended and kneaded in Procedure 1, but is preferably blended and kneaded in Procedure 2.

  The amount of the retarder used is not particularly limited, but is preferably in the range of 0.01 to 1 part by weight per 100 parts by weight of the rubber component. Particularly preferred is 0.05 to 0.5 parts by weight.

  The temperature condition in Procedure 1 is preferably 200 ° C. or lower. More preferably, it is 120-180 degreeC. The temperature condition in Procedure 2 is preferably 60 to 120 ° C.

  The rubber composition obtained in the procedure 2 is heat-treated to obtain the vulcanized rubber of the present invention.

  The temperature condition in the heat treatment is preferably 120 to 180 ° C. The heat treatment is usually performed at normal pressure or under pressure.

  The vulcanized rubber of the present invention includes a vulcanized rubber obtained by heat-treating a rubber composition processed into a specific state.

  Here, the “rubber composition processed into a specific state” means, for example, in the field of tires, “a rubber composition coated with a steel cord”, “a rubber composition coated with a carcass fiber cord”, “tread”. Rubber composition processed into the shape of a member for use. " In addition, each member such as a belt, a carcass, an inner liner, a sidewall, and a tread (cap tread or under tread) obtained by heat treatment is usually combined with other members by a method usually performed in the field of tires. It is molded into the shape of a tire, that is, the rubber composition is incorporated into the tire and heat treated in the state of a raw tire containing the rubber composition. Such heat treatment is usually performed under pressure.

  Of the rubber blends suitable for tread members suitable for trucks, buses, light trucks, and large construction tires, the rubber component is preferably natural rubber alone or a blend of SBR and / or BR containing natural rubber as a main component. As the filler, carbon black alone or a blend with carbon black containing silica as a main component is preferably used. Further, N, N′-bis (2-methyl-2-nitropropyl) -1,6-hexanediamine (“Sumifine (registered trademark) 1162” manufactured by Sumitomo Chemical Co., Ltd.), 5-nitroso-8-hydroxyquinoline ( NQ-58), bis (3-triethoxysilylpropyl) tetrasulfide (Si-69), bis (3-triethoxysilylpropyl) disulfide (Si-75), 1,6-bis (N, N′-di) Benzylthiocarbamoyldithio) -hexane ("KA9188" manufactured by Bayer), hexamethylene bisthiosulfate disodium salt dihydrate, 1,3-bis (citraconimidomethyl) benzene ("Parkalink 900" manufactured by Flexis) Alkylphenol / sulfur chloride condensates such as “Tacchirol (registered trademark) AP, V-200” manufactured by Taoka Chemical Co., Ltd. It is preferable to use a viscoelastic improving agent.

  Among rubber blends suitable for tread members suitable for passenger car tires, the rubber component includes, as a main component, solution-polymerized SBR having a molecular end modified with a silicon compound alone or the above-mentioned terminal-modified solution-polymerized SBR, and non-modified solution polymerization. A blend with at least one rubber selected from the group consisting of SBR, emulsion polymerization SBR, natural rubber and BR is preferred. Moreover, as a filler, the blend with carbon black which has a silica as a main component is used preferably. Further, N, N′-bis (2-methyl-2-nitropropyl) -1,6-hexanediamine (“Sumifine (registered trademark) 1162” manufactured by Sumitomo Chemical Co., Ltd.), 5-nitroso-8-hydroxyquinoline ( NQ-58), bis (3-triethoxysilylpropyl) tetrasulfide (Si-69), bis (3-triethoxysilylpropyl) disulfide (Si-75), 1,6-bis (N, N′-di) Benzylthiocarbamoyldithio) -hexane ("KA9188" manufactured by Bayer), hexamethylene bisthiosulfate disodium salt dihydrate, 1,3-bis (citraconimidomethyl) benzene ("Parkalink 900" manufactured by Flexis) Alkylphenol / sulfur chloride condensates such as “Tacchirol (registered trademark) AP, V-200” manufactured by Taoka Chemical Co., Ltd. It is preferable to use a viscoelastic improving agent.

  Among the rubber blends suitable for the sidewall member, the rubber component includes a blend of at least one rubber selected from the group consisting of BR as a main component, non-modified solution polymerization SBR, emulsion polymerization SBR, and natural rubber. preferable. Further, as the filler, carbon black alone or a blend with silica containing carbon black as a main component is preferably used. Further, N, N′-bis (2-methyl-2-nitropropyl) -1,6-hexanediamine (“Sumifine (registered trademark) 1162” manufactured by Sumitomo Chemical Co., Ltd.), 5-nitroso-8-hydroxyquinoline ( NQ-58), bis (3-triethoxysilylpropyl) tetrasulfide (Si-69), bis (3-triethoxysilylpropyl) disulfide (Si-75), 1,6-bis (N, N′-di) Benzylthiocarbamoyldithio) -hexane ("KA9188" manufactured by Bayer), hexamethylene bisthiosulfate disodium salt dihydrate, 1,3-bis (citraconimidomethyl) benzene ("Parkalink 900" manufactured by Flexis) Alkylphenol / sulfur chloride condensates such as “Tacchirol (registered trademark) AP, V-200” manufactured by Taoka Chemical Co., Ltd. It is preferable to use a viscoelastic improving agent.

  Among rubber blends suitable for carcass and belt members, the rubber component is preferably natural rubber alone or a blend with BR containing natural rubber as a main component. Further, as the filler, carbon black alone or a blend with silica containing carbon black as a main component is preferably used. Further, N, N′-bis (2-methyl-2-nitropropyl) -1,6-hexanediamine (“Sumifine (registered trademark) 1162” manufactured by Sumitomo Chemical Co., Ltd.), 5-nitroso-8-hydroxyquinoline ( NQ-58), bis (3-triethoxysilylpropyl) tetrasulfide (Si-69), bis (3-triethoxysilylpropyl) disulfide (Si-75), 1,6-bis (N, N′-di) Benzylthiocarbamoyldithio) -hexane ("KA9188" manufactured by Bayer), hexamethylene bisthiosulfate disodium salt dihydrate, 1,3-bis (citraconimidomethyl) benzene ("Parkalink 900" manufactured by Flexis) Alkylphenol / sulfur chloride condensates such as “Tacchirol (registered trademark) AP, V-200” manufactured by Taoka Chemical Co., Ltd. It is preferable to use a viscoelastic improving agent.

A tire is manufactured by a usual method using the vulcanized rubber thus obtained. That is, the rubber composition in the stage before vulcanization is extruded into a tread member, and pasted and molded by a usual method on a tire molding machine to form a raw tire. A tire is obtained by applying heat and pressure.
Examples of the tire include a pneumatic tire and a solid tire.

The fuel efficiency of the automobile equipped with the tire thus obtained is improved, and a reduction in fuel consumption can be achieved.
When compound (I) is added to the rubber composition, the viscoelastic properties of the vulcanized rubber obtained by vulcanizing it can be improved. Further, the vulcanized rubber can be used not only for tires but also for anti-vibration rubbers, rubber belts, vibration damping agents and seismic isolation rubbers. Examples of such anti-vibration rubbers include anti-vibration rubbers for automobiles such as engine mounts, strut mounts, bushes, and exhaust hangers. The anti-vibration rubber is usually obtained by processing the kneaded product into a shape possessed by the anti-vibration rubber and then subjecting it to a heat treatment. Examples of the rubber belt use include a transmission belt, a conveyor belt, and a V belt.
Since compound (I) also has anti-aging performance, it can be used as an anti-aging agent for rubber. When compound (I) is added to a rubber composition as an anti-aging agent for rubber, compound (I) may be used in combination with an anti-aging agent usually used in the rubber field.
Vulcanized rubber obtained from a rubber composition containing compound (I) is excellent in anti-reversion performance.

  EXAMPLES Hereinafter, although an Example, a test example, a manufacture example, etc. are given and this invention is demonstrated concretely, this invention is not limited to these.

窒素雰囲気下、反応容器に１，４−フェニレンジアミン２５．１７ｇ（０．２３３ｍｏｌ）とテトラヒドロフラン２３０mlを仕込んだ。そこへ氷冷下、無水マレイン酸２２．８４ｇ（０．２３３ｍｏｌ）をテトラヒドロフラン５０ｍｌに溶解した溶液を約１時間で滴下した後、室温で一晩撹拌した。反応終了後、析出した結晶を濾取し、テトラヒドロフラン４０ｍｌで２回洗浄し、４０℃で５時間乾燥して粗製の（Z）−３−（４−アミノフェニルカルバモイル）アクリル酸を橙色の粉末として４６．９２ｇ得た。粗製の（Z）−３−（４−アミノフェニルカルバモイル）アクリル酸４６．９２ｇにメタノール２５０ｍｌを加えて５０℃で１時間撹拌し冷却後、ろ過しメタノール２０ｍｌで２回洗浄した。得られた結晶を乾燥して（Z）−３−（４−アミノフェニルカルバモイル）アクリル酸を黄橙色粉末として４２．６７ｇ得た。収率８８．８％ Production Example 1: Production of (Z) -3- (4-aminophenylcarbamoyl) acrylic acid

Under a nitrogen atmosphere, a reaction vessel was charged with 25.17 g (0.233 mol) of 1,4-phenylenediamine and 230 ml of tetrahydrofuran. A solution prepared by dissolving 22.84 g (0.233 mol) of maleic anhydride in 50 ml of tetrahydrofuran was added dropwise thereto in about 1 hour under ice cooling, and the mixture was stirred overnight at room temperature. After completion of the reaction, the precipitated crystals were collected by filtration, washed twice with 40 ml of tetrahydrofuran, and dried at 40 ° C. for 5 hours to give crude (Z) -3- (4-aminophenylcarbamoyl) acrylic acid as an orange powder. 46.92 g was obtained. To 46.92 g of crude (Z) -3- (4-aminophenylcarbamoyl) acrylic acid, 250 ml of methanol was added, stirred at 50 ° C. for 1 hour, cooled, filtered, and washed twice with 20 ml of methanol. The obtained crystals were dried to obtain 42.67 g of (Z) -3- (4-aminophenylcarbamoyl) acrylic acid as a yellow-orange powder. Yield 88.8%

窒素雰囲気下、反応容器に製造例１で合成した（Z）−３−（４−アミノフェニルカルバモイル）アクリル酸１３．８５ｇ（６７．２ｍｍｏｌ）に、１，４−フェニレンジアミン６．９０ｇ（６７．２ｍｍｏｌ）、ジメチルアミノピリジン０．８２ｇとジメチルホルムアミド１３０ｍｌを仕込んだ。そこへ氷冷下、１−エチル−3−(3−ジメチルアミノプロピル)−カルボジイミド塩酸塩１２．８８ｇ（６７．２ｍｍｏｌ）を加え、室温で終夜撹拌した。反応終了後、水５６０ｍｌ加え、酢酸エチル５００ｍｌで４回抽出した。有機層を合一し、食塩水５００ｍｌで洗浄し、硫酸ナトリウムで乾燥後、減圧下に溶媒を留去し赤色粘性物１５．０ｇを得た。これにクロロホルム５０ｍｌを加えて減圧濃縮を３回繰り返し、得られた残留物にメタノール８０ｍｌを加えて析出した固体を濾別した。濾液を減圧濃縮後、シリカゲルカラムクロマトグラフィーに供し、Ｎ，Ｎ’−ビス（４−アミノフェニル）マレアミドを濃赤色固体として５．３０ｇ得た。収率２６．６％。
^１Ｈ−ＮＭＲ（３００．１３ＭＨｚ，ＤＭＳＯ−ｄ６）δ_ｐｐｍ：１０．７５（２Ｈ，ｓ），７．３０（４Ｈ，ｄ，Ｊ＝８．７Ｈｚ），６．５２（４Ｈ，ｄ，Ｊ＝８．７Ｈｚ），６．２９（２Ｈ，ｓ），４．９５（４Ｈ，ｓ） Production Example 2: Production of N, N′-bis (4-aminophenyl) maleamide

Under a nitrogen atmosphere, 13.90 g (67.2 mmol) of (Z) -3- (4-aminophenylcarbamoyl) acrylic acid synthesized in Production Example 1 in a reaction vessel was added to 6.90 g (67. 2 mmol), 0.82 g of dimethylaminopyridine and 130 ml of dimethylformamide were charged. Under ice cooling, 12.88 g (67.2 mmol) of 1-ethyl-3- (3-dimethylaminopropyl) -carbodiimide hydrochloride was added thereto, and the mixture was stirred at room temperature overnight. After completion of the reaction, 560 ml of water was added and extraction was performed 4 times with 500 ml of ethyl acetate. The organic layers were combined, washed with 500 ml of brine, dried over sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain 15.0 g of a red viscous product. 50 ml of chloroform was added thereto, and the concentration under reduced pressure was repeated three times. 80 ml of methanol was added to the obtained residue, and the precipitated solid was separated by filtration. The filtrate was concentrated under reduced pressure and subjected to silica gel column chromatography to obtain 5.30 g of N, N′-bis (4-aminophenyl) maleamide as a dark red solid. Yield 26.6%.
¹ H-NMR (300.13 MHz, DMSO-d6) δ _ppm : 10.75 (2H, s), 7.30 (4H, d, J = 8.7 Hz), 6.52 (4H, d, J = 8.7 Hz), 6.29 (2H, s), 4.95 (4H, s)

Example 1: Production of rubber composition <Procedure 1>
Using a Banbury mixer (600 ml Lab Plast Mill manufactured by Toyo Seiki Co., Ltd.), 100 parts by weight of natural rubber (RSS # 1), 45 parts by weight of HAF (Asahi Carbon Co., Ltd., trade name “Asahi # 70”), 3 parts by weight of stearic acid , 5 parts by weight of zinc oxide, 1 part by weight of an antioxidant (N-phenyl-N′-1,3-dimethylbutyl-p-phenylenediamine: trade name “Antigen (registered trademark) 6C” manufactured by Sumitomo Chemical Co., Ltd.) 1 part by weight of N, N′-bis (4-aminophenyl) maleamide obtained in Production Example 2 was kneaded and mixed to obtain a rubber composition. This procedure 1 was carried out by kneading for 5 minutes at a rotational speed of a mixer of 50 rpm for 5 minutes after charging various components, and the rubber temperature at that time was 160 to 170 ° C.
<Procedure 2>
The rubber composition obtained by the procedure 1, 1 part by weight of a vulcanization accelerator (N-cyclohexyl-2-benzothiazolylsulfenamide) and sulfur 2 at a temperature of 60 to 80 ° C. in an open roll machine. A rubber composition was obtained by kneading and blending with parts by weight.

Example 2: Production of vulcanized rubber The rubber composition obtained in the procedure 2 of Example 1 was vulcanized at 145 ° C to obtain a vulcanized rubber.

Example 3 Production of Rubber Composition In Example 1, instead of N, N′-bis (4-aminophenyl) maleamide, a commercially available 4,4′-diaminostilbene dihydrochloride (Tokyo Chemical Industry Co., Ltd.) A rubber composition was obtained in the same manner as in Example 1 except that the product manufactured by the company was used.

Example 4: Production of vulcanized rubber The rubber composition obtained in the procedure 2 of Example 3 was vulcanized at 145 ° C to obtain a vulcanized rubber.

Reference example 1
In Example 1, a rubber composition was obtained in the same manner as in Example 1, except that N, N′-bis (4-aminophenyl) maleamide was not used.

Reference example 2
The rubber composition obtained in Procedure 2 of Reference Example 1 was vulcanized at 145 ° C. to obtain a vulcanized rubber.

Scorch time and viscoelastic properties were measured as follows.
(1) Scorch time It measured at 125 degreeC based on JIS-K6300-1.
A larger scorch time value indicates that rubber scoring is less likely to occur and processing stability is better.

Test example 1
Using the rubber composition obtained in Reference Example 1 as a control, the scorch time of the rubber composition obtained in Reference Example 1 as 100, and the rubber composition obtained in Example 1 and Example 3 with respect to the scorch time relative values. When indicated by an index, they were 89 and 91, respectively.

(2) Viscoelastic property It measured using the viscoelasticity analyzer made by Ueshima Seisakusho.
Conditions: Temperature-5 ° C to 80 ° C (Temperature increase rate: 2 ° C / min)
Initial strain 10%, dynamic strain 2.5%, frequency 10Hz

  Using the vulcanized rubber obtained in Reference Example 2 as a control, the viscoelastic properties (tan δ at 60 ° C.) of the vulcanized rubber obtained in Example 2 and Example 4 with respect to the vulcanized rubber obtained in Reference Example 2 were reduced. When the rate (%) was measured, the rate of decrease was 33% and 17%, respectively.

Example 5
A belt is obtained by covering the steel cord subjected to the brass plating treatment with the rubber composition obtained in the procedure 2 of Example 1. A vulcanized tire is obtained by forming a green tire using the obtained belt according to a normal production method and heating and pressing the obtained green tire in a vulcanizer.

Example 6
The rubber composition obtained in the procedure 2 of Example 1 is extruded to obtain a tread member. Using the obtained tread member, a raw tire is formed according to a normal production method, and the obtained raw tire is heated and pressurized in a vulcanizer to obtain a vulcanized tire.

Example 7
The rubber composition obtained in the procedure 2 of Example 1 is extruded to prepare a rubber composition having a shape corresponding to the carcass shape, and a carcass is obtained by applying the rubber composition on top and bottom of a polyester carcass fiber cord. . Using the obtained carcass, a raw tire is formed according to a normal production method, and the obtained raw tire is heated and pressurized in a vulcanizer to obtain a vulcanized tire.

Example 8
In the procedure 2 of Example 1, a rubber composition is obtained in the same manner as in Example 1 except that 0.2 parts by weight of N- (cyclohexylthio) -phthalimide (CTP) is further kneaded and blended.

Example 9
The rubber composition obtained in the procedure 2 of Example 8 is vulcanized at 145 ° C. to obtain a vulcanized rubber.

Example 10: Production of rubber composition <Procedure 1>
Using a Banbury mixer (600 ml Lab Plast Mill manufactured by Toyo Seiki Co., Ltd.), 100 parts by weight of styrene / butadiene copolymer rubber SBR # 1502 (manufactured by Sumitomo Chemical Co., Ltd.), ISAF-HM (manufactured by Asahi Carbon Co., Ltd., trade name “Asahi # 80”) ) 45 parts by weight, stearic acid 2 parts by weight, zinc oxide 3 parts by weight, N, N′-bis (4-aminophenyl) maleamide 1 part by weight, anti-aging agent (N-phenyl-N′-1,3-dimethyl) Butyl-p-phenylenediamine (6PPD): 1 part by weight of trade name “Antigen (registered trademark) 6C” manufactured by Sumitomo Chemical Co., Ltd. and 2 parts by weight of wax (“OZOACE-0355” manufactured by Nippon Seiwa) were kneaded and mixed. A rubber composition is obtained. This step is carried out by kneading for 5 minutes at a rotational speed of a mixer of 50 rpm for 5 minutes after charging each component, and the rubber temperature at that time is 160 to 175 ° C.
<Procedure 2>
The rubber composition obtained by the procedure 1, the vulcanization accelerator N-cyclohexyl-2-benzothiazolylsulfenamide (CBS) 3 parts by weight and sulfur at a temperature of 60 to 80 ° C. in an open roll machine 2 parts by weight are kneaded and blended to obtain a rubber composition.

Example 11: Production of vulcanized rubber The rubber composition obtained in the procedure 2 of Example 10 is heat-treated at 145 ° C to obtain a vulcanized rubber. Such vulcanized rubber is suitable for cap treads.

Example 12: Production of rubber composition <Procedure 1>
Using a Banbury mixer (600 ml Lab Plast Mill manufactured by Toyo Seiki Co., Ltd.), 100 parts by weight of styrene / butadiene copolymer rubber SBR # 1502 (manufactured by Sumitomo Chemical Co., Ltd.), ISAF-HM (manufactured by Asahi Carbon Co., Ltd., trade name “Asahi # 80”) ) 35 parts by weight, stearic acid 2 parts by weight, zinc oxide 3 parts by weight, N, N′-bis (4-aminophenyl) maleamide 1 part by weight, anti-aging agent (N-phenyl-N′-1,3-dimethyl) Butyl-p-phenylenediamine (6PPD): 1 part by weight of trade name “Antigen (registered trademark) 6C” manufactured by Sumitomo Chemical Co., Ltd. and 2 parts by weight of wax (“OZOACE-0355” manufactured by Nippon Seiwa) were kneaded and mixed. A rubber composition is obtained. This step is carried out by kneading for 5 minutes at a rotational speed of a mixer of 50 rpm for 5 minutes after charging each component, and the rubber temperature at that time is 160 to 175 ° C.
<Procedure 2>
The rubber composition obtained by the procedure 1 and 2 parts by weight of a vulcanization accelerator N-cyclohexyl-2-benzothiazolylsulfenamide (CBS) at a temperature of 60 to 80 ° C. in an open roll machine. A rubber composition is obtained by kneading 0.5 parts by weight of a sulfur accelerator diphenylguanidine (DPG), 0.8 parts by weight of a vulcanization accelerator dibenzothiazyl disulfide (MBTS) and 1 part by weight of sulfur.

Example 13: Production of vulcanized rubber For undertread A vulcanized rubber is obtained by heat-treating the rubber composition obtained in the procedure 2 of Example 12 at 145 ° C. Such vulcanized rubber is suitable for undertread.

Example 14: Production of rubber composition <Procedure 1>
Using a Banbury mixer (600 ml Lab Plast Mill manufactured by Toyo Seiki Co., Ltd.), 100 parts by weight of natural rubber (RSS # 1), 45 parts by weight of HAF (Asahi Carbon Co., Ltd., trade name “Asahi # 70”), 3 parts by weight of stearic acid , 5 parts by weight of zinc oxide, 1 part by weight of N, N′-bis (4-aminophenyl) maleamide, 10 parts by weight of water-containing silica (“Nipsil (registered trademark) AQ” manufactured by Tosoh Silica Co., Ltd.), anti-aging agent 2 parts by weight of FR (“Antioxidant FR” manufactured by Matsubara Sangyo Co., Ltd.), 2 parts by weight of resorcin and 2 parts by weight of cobalt naphthenate are kneaded and mixed to obtain a rubber composition, which is performed at 50 rpm for 5 minutes after each component is added. The rubber temperature at that time is 160 to 175 ° C.
<Procedure 2>
The rubber composition obtained by the procedure 1 and the vulcanization accelerator N, N-dicyclohexyl-2-benzothiazolylsulfenamide (DCBS) 1 part by weight in an open roll machine at a temperature of 60 to 80 ° C. Then, 6 parts by weight of sulfur and 3 parts by weight of methoxylated methylol melamine resin (“SUMIKANOL 507AP” manufactured by Sumitomo Chemical Co., Ltd.) are kneaded and mixed to obtain a rubber composition.

Example 15 Production of Vulcanized Rubber A vulcanized rubber is obtained by heat-treating the rubber composition obtained in Procedure 2 of Example 14 at 145 ° C. Such vulcanized rubber is suitable for a belt.

Example 16: Production of rubber composition <Procedure 1>
Using a Banbury mixer (600 ml Lab Plast Mill manufactured by Toyo Seiki), halogenated butyl rubber ("Br-IIR2255" manufactured by ExxonMobil) 100 parts by weight, GPF 60 parts by weight, stearic acid 1 part by weight, zinc oxide 3 parts by weight, 1 part by weight of N, N′-bis (4-aminophenyl) maleamide and 10 parts by weight of paraffin oil (“Diana Process Oil” manufactured by Idemitsu Kosan Co., Ltd.) are kneaded and mixed to obtain a rubber composition. This step is carried out by kneading for 5 minutes at a rotational speed of a mixer of 50 rpm for 5 minutes after charging each component, and the rubber temperature at that time is 160 to 175 ° C.
<Procedure 2>
The rubber composition obtained by the procedure 1 in an open roll machine at a temperature of 60 to 80 ° C., 1 part by weight of an antioxidant (condensation product of aniline and acetone (TMDQ)), a vulcanization accelerator dibenzothiazyl disulfide (MBTS) 1 part by weight and 2 parts by weight of sulfur are kneaded and mixed to obtain a rubber composition.

Example 17: Production of vulcanized rubber The rubber composition obtained in the procedure 2 of Example 16 is heat-treated at 145 ° C to obtain a vulcanized rubber. Such vulcanized rubber is suitable for an inner liner.

Example 18: Production of rubber composition <Procedure 1>
Using a Banbury mixer (600 ml Labo Plast Mill manufactured by Toyo Seiki Co., Ltd.), 40 parts by weight of natural rubber (RSS # 3), 60 parts of polybutadiene rubber (“BR150B” manufactured by Ube Industries), 50 parts by weight of FEF, and 2.5 parts by weight of stearic acid Parts, zinc oxide 3 parts by weight, N, N'-bis (4-aminophenyl) maleamide 1 part by weight, anti-aging agent (N-phenyl-N'-1,3-dimethylbutyl-p-phenylenediamine (6PPD) : 2 parts by weight of trade name “Antigen (registered trademark) 6C” manufactured by Sumitomo Chemical Co., Ltd., 10 parts by weight of aromatic oil (“NC-140” manufactured by Cosmo Oil Co., Ltd.) and wax (“ 2 parts by weight of “Sannok (registered trademark) wax”) are kneaded and mixed to obtain a rubber composition. This step is carried out by kneading for 5 minutes at a rotational speed of a mixer of 50 rpm for 5 minutes after charging each component, and the rubber temperature at that time is 160 to 175 ° C.
<Procedure 2>
The rubber composition obtained by the procedure 1 and the vulcanization accelerator N-tert-butyl-2-benzothiazolylsulfenamide (BBS) 0.75 parts by weight in an open roll machine at a temperature of 60 to 80 ° C. And 1.5 parts by weight of sulfur are kneaded and mixed to obtain a rubber composition.

Example 19: Production of vulcanized rubber The rubber composition obtained in the procedure 2 of Example 18 is heat-treated at 145 ° C to obtain a vulcanized rubber. Such vulcanized rubber is suitable for side walls.

Example 20: Production of rubber composition <Procedure 1>
Using a Banbury mixer (600 ml Labo Plast Mill manufactured by Toyo Seiki Co., Ltd.), 70 parts by weight of natural rubber (TSR20), 30 parts by weight of styrene / butadiene copolymer rubber SBR # 1502 (manufactured by Sumitomo Chemical), N339 (manufactured by Mitsubishi Chemical) 60 parts by weight, 2 parts by weight of stearic acid, 5 parts by weight of zinc oxide, 7 parts by weight of process oil (“Diana Process PS32” manufactured by Idemitsu Kosan Co., Ltd.) and 1 part by weight of N, N′-bis (4-aminophenyl) maleamide The rubber composition is obtained by kneading and blending. This step is carried out by kneading for 5 minutes at a rotational speed of a mixer of 50 rpm for 5 minutes after charging each component, and the rubber temperature at that time is 160 to 175 ° C.
<Procedure 2>
The rubber composition obtained by the procedure 1 at a temperature of 60 to 80 ° C. in an open roll machine, the vulcanization accelerator N-tert-butyl-2-benzothiazolylsulfenamide (BBS) 1 part by weight, sulfur 3 parts by weight, 1 part by weight of an antioxidant (N-phenyl-N′-1,3-dimethylbutyl-p-phenylenediamine (6PPD): trade name “Antigen (registered trademark) 6C” manufactured by Sumitomo Chemical Co., Ltd.) A rubber composition is obtained by kneading and blending 1 part by weight of an antioxidant (condensation product of aniline and acetone (TMDQ)).

Example 21: Production of vulcanized rubber A vulcanized rubber is obtained by heat-treating the rubber composition obtained in Procedure 2 of Example 20 at 145 ° C. Such vulcanized rubber is suitable for carcass.

Example 22: Production of rubber composition <Procedure 1>
Using a Banbury mixer (600 ml Labo Plast Mill manufactured by Toyo Seiki Co., Ltd.), 100 parts by weight of styrene / butadiene copolymer rubber SBR # 1500 (manufactured by JSR), silica (trade name: “Ultrasil (registered trademark) VN3-G” Degussa 78.4 parts by weight, carbon black (trade name “N-339” manufactured by Mitsubishi Chemical Corporation), 6.4 parts by weight, silane coupling agent (bis (3-triethoxysilylpropyl) tetrasulfide: trade name “ 6.4 parts by weight of Si-69 (manufactured by Degussa), 47.6 parts by weight of process oil (trade name “NC-140” manufactured by Cosmo Oil), anti-aging agent (N-phenyl-N′-1,3- Dimethylbutyl-p-phenylenediamine (6PPD): trade name “Antigen (registered trademark) 6C” manufactured by Sumitomo Chemical Co., Ltd.) 1.5 parts by weight, zinc oxide 2 parts by weight, 2 parts by weight of stearic acid and 3 parts by weight of N, N′-bis (4-aminophenyl) maleamide are kneaded and mixed to obtain a rubber composition. This step is operated in a temperature range of 70 ° C. to 120 ° C., and is carried out by kneading at a rotational speed of a mixer of 80 rpm for 5 minutes after charging each component, and subsequently kneading at a rotational speed of a mixer of 100 rpm for 5 minutes. .
<Procedure 2>
The rubber composition obtained by the procedure 1 and the vulcanization accelerator N-cyclohexyl-2-benzothiazolylsulfenamide (CBS) 1 part by weight at a temperature of 30 to 80 ° C. in an open roll machine, vulcanization 1 part by weight of accelerator diphenylguanidine (DPG), 1.5 parts by weight of wax (trade name “Sannok (registered trademark) N” manufactured by Ouchi Shinsei Chemical Co., Ltd.) and 1.4 parts by weight of sulfur are kneaded and blended. A composition is obtained.

Example 23: Production of vulcanized rubber A vulcanized rubber is obtained by heat-treating the rubber composition obtained in the procedure 2 of Example 22 at 160 ° C. Such vulcanized rubber is suitable for cap treads.

Example 24: Production of rubber composition In Example 22, a solution polymerization SBR ("ASPRENE (registered trademark)" manufactured by Asahi Kasei Chemicals Co., Ltd.) was used instead of the styrene-butadiene copolymer rubber SBR # 1500 (manufactured by JSR). A rubber composition is obtained in the same manner as in Example 22 except for the above.

Example 25: Production of vulcanized rubber The rubber composition obtained in the procedure 2 of Example 24 is heat-treated at 160 ° C to obtain a vulcanized rubber. Such vulcanized rubber is suitable for cap treads.

Example 26: Production of rubber composition In Example 22, SBR # 1712 (manufactured by JSR) was used instead of styrene-butadiene copolymer rubber SBR # 1500 (manufactured by JSR), and the amount of process oil used was 21 wt. The rubber composition is obtained in the same manner as in Example 22 except that the timing for charging zinc oxide is changed to the procedure 2 except that the timing is changed to the procedure 2.

Example 27: Production of vulcanized rubber A vulcanized rubber is obtained by heat-treating the rubber composition obtained in the procedure 2 of Example 26 at 160 ° C. Such vulcanized rubber is suitable for cap treads.

Example 28: Production of rubber composition <Procedure 1>
Using a Banbury mixer (600 ml Lab Plast Mill manufactured by Toyo Seiki Co., Ltd.), 100 parts by weight of natural rubber (RSS # 1), 45 parts by weight of HAF (Asahi Carbon Co., Ltd., trade name “Asahi # 70”), 3 parts by weight of stearic acid Then, 5 parts by weight of zinc oxide and 1 part by weight of 4,4′-diaminostilbene dihydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) are kneaded and mixed to obtain a rubber composition. This procedure 1 is carried out by kneading for 5 minutes at a rotational speed of a mixer of 50 rpm for 5 minutes after charging various components, and the rubber temperature at that time is 160 to 170 ° C.
<Procedure 2>
The rubber composition obtained by the procedure 1, 1 part by weight of a vulcanization accelerator (N-cyclohexyl-2-benzothiazolylsulfenamide) and 2 parts by weight of sulfur in an open roll machine at a temperature of 60 to 80 ° C. Are kneaded and mixed to obtain a rubber composition.
Example 29: Production of vulcanized rubber

  A vulcanized rubber is obtained by heat-treating the rubber composition obtained in Procedure 2 of Example 28 at 160 ° C. The resulting vulcanized rubber has improved viscoelastic properties and is excellent in anti-aging performance.

Example 30: Production of rubber composition <Procedure 1>
Using a Banbury mixer (600 ml Labo Plast Mill manufactured by Toyo Seiki Co., Ltd.), 100 parts by weight of natural rubber (RSS # 1), 50 parts by weight of HAF (Asahi Carbon Co., Ltd., trade name “Asahi # 70”), 3 parts by weight of stearic acid , 5 parts by weight of zinc oxide and an antioxidant (N-phenyl-N′-1,3-dimethylbutyl-p-phenylenediamine (6PPD): trade name “Antigen (registered trademark) 6C” manufactured by Sumitomo Chemical Co., Ltd.) 1 A rubber composition is obtained by kneading and blending parts by weight. This procedure 1 is carried out by kneading for 5 minutes at a rotational speed of a mixer of 50 rpm for 5 minutes after charging various components, and the rubber temperature at that time is 160 to 170 ° C.
<Procedure 2>
The rubber composition obtained by procedure 1 at a temperature of 60 to 80 ° C. in an open roll machine, 1 part by weight of 4,4′-diaminostilbene dihydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.), a vulcanization accelerator ( 1 part by weight of dibenzothiazyl disulfide) and 1 part by weight of sulfur are kneaded and mixed to obtain a rubber composition.

Example 31: Production of vulcanized rubber A vulcanized rubber is obtained by heat-treating the rubber composition obtained in the procedure 2 of Example 30 at 170 ° C. The resulting vulcanized rubber is excellent in anti-reversion performance.

  According to the rubber composition of the present invention, the viscoelastic properties of the vulcanized rubber obtained from the rubber composition can be improved.

Claims (15)

A rubber composition comprising a compound represented by formula (I), a rubber component, and a filler.

[In the formula (I),
A ¹ is an alkanediyl group having 2 to 12 carbon atoms which may have a substituent, a cycloalkanediyl group having 3 to 12 carbon atoms which may have a substituent, or ^* -B ^1-. Represents an Ar—B ² — group, —CH ₂ — contained in the alkanediyl group having 2 to 12 carbon atoms may be replaced by —NH—, —O— or —S—, and * represents X ¹ Represents a bond.
B ¹ represents a single bond or an alkanediyl group having 1 to 6 carbon atoms.
B ² represents a single bond or alkanediyl group having 1 to 6 carbon atoms.
Ar represents a C6-C12 divalent aromatic hydrocarbon group which may have a substituent.
X ¹ represents —CO—NH— ^* , —CO—O— ^* , —CO— ^* or a single bond, and * represents a bond to A ¹ .
R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a hydroxy group, or an alkoxy group having 1 to 6 carbon atoms, Bond to each other to form an alkanediyl group having 1 to 12 carbon atoms. ] The rubber composition according to claim 1, wherein R ¹ and R ² are hydrogen atoms. A ¹ is, according to claim 1 or 2 rubber composition wherein the divalent aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent. X ¹ represents a single bond, ^{A 1} is ^* -B ^{1 -Ar-B 2} - group ^{(B 1} represents a single bond, ^{B 2} represents a single bond or an alkylene group.) Claims 1 to 3, representing the The rubber composition according to any one of the above.   The rubber composition according to any one of claims 1 to 4, wherein the rubber component is natural rubber.   Furthermore, the rubber composition in any one of Claims 1-5 containing a sulfur component.   A vulcanized rubber obtained by heat-treating the rubber composition according to claim 6.   A tire manufactured by processing the rubber composition according to claim 6.   A tire belt comprising a steel cord coated with the vulcanized rubber according to claim 7.   A tire carcass comprising a carcass fiber cord coated with the vulcanized rubber according to claim 7.   A tire sidewall including the vulcanized rubber according to claim 7, a tire inner liner, a tire cap tread, or a tire undertread.   A tire comprising the vulcanized rubber according to claim 7. Improvement of viscoelastic properties of vulcanized rubber having a step of kneading a compound represented by formula (I), a rubber component, a filler, and a sulfur component, and a step of heat-treating the kneaded product obtained in the previous step Method.

[In the formula (I),
A ¹ is an alkanediyl group having 2 to 12 carbon atoms which may have a substituent, a cycloalkanediyl group having 3 to 12 carbon atoms which may have a substituent, or ^* -B ^1-. Represents an Ar—B ² — group, —CH ₂ — contained in the alkanediyl group having 2 to 12 carbon atoms may be replaced by —NH—, —O— or —S—, and * represents X ¹ Represents a bond.
B ¹ represents a single bond or an alkanediyl group having 1 to 6 carbon atoms.
B ² represents a single bond or alkanediyl group having 1 to 6 carbon atoms.
Ar represents a C6-C12 divalent aromatic hydrocarbon group which may have a substituent.
X ¹ represents —CO—NH— ^* , —CO—O— ^* , —CO— ^* or a single bond, and * represents a bond to A ¹ .
R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a hydroxy group, or an alkoxy group having 1 to 6 carbon atoms, Bond to each other to form an alkanediyl group having 1 to 12 carbon atoms. ] Use of a compound represented by formula (I) for improving viscoelastic properties of vulcanized rubber.

[In the formula (I),
A ¹ is an alkanediyl group having 2 to 12 carbon atoms which may have a substituent, a cycloalkanediyl group having 3 to 12 carbon atoms which may have a substituent, or ^* -B ^1-. Represents an Ar—B ² — group, —CH ₂ — contained in the alkanediyl group having 2 to 12 carbon atoms may be replaced by —NH—, —O— or —S—, and * represents X ¹ Represents a bond.
B ¹ represents a single bond or an alkanediyl group having 1 to 6 carbon atoms.
B ² represents a single bond or alkanediyl group having 1 to 6 carbon atoms.
Ar represents a C6-C12 divalent aromatic hydrocarbon group which may have a substituent.
X ¹ represents —CO—NH— ^* , —CO—O— ^* , —CO— ^* or a single bond, and * represents a bond to A ¹ .
R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a hydroxy group, or an alkoxy group having 1 to 6 carbon atoms, Bond to each other to form an alkanediyl group having 1 to 12 carbon atoms. ] A vulcanized rubber viscoelastic property improver containing a compound represented by formula (I) as an active ingredient.

[In the formula (I),
A ¹ is an alkanediyl group having 2 to 12 carbon atoms which may have a substituent, a cycloalkanediyl group having 3 to 12 carbon atoms which may have a substituent, or ^* -B ^1-. Represents an Ar—B ² — group, —CH ₂ — contained in the alkanediyl group having 2 to 12 carbon atoms may be replaced by —NH—, —O— or —S—, and * represents X ¹ Represents a bond.
B ¹ represents a single bond or an alkanediyl group having 1 to 6 carbon atoms.
B ² represents a single bond or alkanediyl group having 1 to 6 carbon atoms.
Ar represents a C6-C12 divalent aromatic hydrocarbon group which may have a substituent.
X ¹ represents —CO—NH— ^* , —CO—O— ^* , —CO— ^* or a single bond, and * represents a bond to A ¹ .
R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a hydroxy group, or an alkoxy group having 1 to 6 carbon atoms, Bond to each other to form an alkanediyl group having 1 to 12 carbon atoms. ]