JP2012153771A - Thiosulfonate compound, and rubber composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an additive for improving a viscoelastic characteristics of a vulcanized rubber used for producing tires.SOLUTION: The thiosulfonate compound represented by formula (I) (wherein, Ris 1C-12C alkanediyl; Ris 1C-12C alkyl which may have a substituent, 3C-12C cycloalkyl which may have a substituent, or 6-10C aryl which may have a substituent; n is 1 or 2).

Description

  The present invention relates to a thiosulfonate compound and a rubber composition containing the thiosulfonate compound.

  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

  There has been a demand for an additive for improving the viscoelastic properties of vulcanized rubber used in tire manufacture.

［式（Ｉ）中、Ｒ^１は炭素数１〜１２のアルカンジイル基を表し、Ｒ^２は置換基を有していてもよい炭素数１〜１２のアルキル基、置換基を有していてもよい炭素数３〜１２のシクロアルキル基、置換基を有していてもよい炭素数６〜１０のアリール基を表し、ｎは１又は２を表す。］
〔２〕Ｒ^２が、炭素数１〜１２のアルキル基である、〔１〕記載の化合物。 As a result of intensive studies under such circumstances, the present inventor has reached the present invention. That is, the present invention includes the following [1] to [12] inventions.
[1] A thiosulfonate compound represented by the formula (I).

[In Formula (I), R ¹ represents an alkanediyl group having 1 to 12 carbon atoms, and R ² has an optionally substituted alkyl group having 1 to 12 carbon atoms and a substituent. A cycloalkyl group having 3 to 12 carbon atoms, or an aryl group having 6 to 10 carbon atoms which may have a substituent, and n represents 1 or 2. ]
[2] The compound according to [1], wherein R ² is an alkyl group having 1 to 12 carbon atoms.

[3] A rubber composition obtained by kneading the thiosulfonate compound according to the above [1] or [2], a rubber component, and a filler.
[4] The rubber composition according to the above [3], wherein the rubber component is natural rubber.
[5] The rubber composition according to the above [3] or [4], further obtained by kneading a sulfur component.

[6] A vulcanized rubber obtained by heat-treating the rubber composition described in [5] above.
[7] A pneumatic tire produced by processing the rubber composition according to the above [5].

[8] A tire belt comprising a steel cord coated with the vulcanized rubber according to the above [6].
[9] A tire carcass comprising a carcass fiber cord coated with the vulcanized rubber according to [6] above.
[10] A tire sidewall, a tire inner liner, a tire cap tread or a tire undertread comprising the vulcanized rubber according to [6] above.
[11] A pneumatic tire comprising the vulcanized rubber according to the above [6].

[12] Use of the thiosulfonate compound according to the above [1] or [2] for improving the viscoelastic properties of the vulcanized rubber.

  When the thiosulfonate compound of the present invention is added to a rubber composition for tires, the viscoelastic properties of the vulcanized rubber obtained by vulcanizing it can be improved. That is, the thiosulfonate compound of the present invention is useful as a viscoelastic property improving agent for vulcanized rubber.

Hereinafter, the present invention will be described in detail.
In the present invention, “improving viscoelastic properties” includes, for example, modifying a loss factor (tan δ) of a vulcanized rubber as described below.

  First, the thiosulfonate compound represented by the above formula (I) (hereinafter sometimes referred to as “compound (I)”) will be described.

In the above formula (I), examples of the alkanediyl group having 1 to 12 carbon atoms represented by R ¹ include a straight chain such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group. Chain alkanediyl group; branched alkane such as propylene group, isopropylene group, isobutylene group, 2-methyltrimethylene group, isopentylene group, isohexylene group, isooctylene group, 2-ethylhexylene group, and isodecylene group A diyl group; Among these, a linear alkanediyl group (polymethylene group) is preferable, and the number of carbon atoms is more preferably 2 or 3.

In the above formula (I), examples of the alkyl group having 1 to 12 carbon atoms represented by R ² include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group. A linear alkyl group such as a group or dodecyl group; a branched chain such as isopropyl group, isobutyl group, t-butyl group, isopentyl group, neopentyl group, t-pentyl group, 1-methylbutyl group or 1-methylheptyl group An alkyl group; Examples of the substituent that the alkyl group having 1 to 12 carbon atoms may have include an aryl group having 6 to 10 carbon atoms such as a phenyl group, a 4-methylphenyl group, and a naphthyl group; a methoxy group and an ethoxy group. An alkoxy group having 1 to 4 carbon atoms such as butoxy group; an acyl group having 1 to 7 carbon atoms such as acetyl group, benzoyl group, formyl group and pivaloyl group; 3 to 4 carbon atoms such as methoxycarbonyl group and ethoxycarbonyl group Alkoxycarbonyl groups such as: phenoxycarbonyl groups, naphthyloxycarbonyl groups, etc., aryloxycarbonyl groups having 7-11 carbon atoms; acetoxy groups, benzoyloxy groups, etc., C2-C7 acyloxy groups; Among these, a linear alkyl group is preferable, and the number of carbon atoms is more preferably 2-8.

In the above formula (I), examples of the cycloalkyl group having 3 to 12 carbon atoms represented by R ² include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and a cyclododecyl group. Examples of the substituent that the cycloalkyl group having 3 to 12 carbon atoms may have include 1 to 1 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and a t-butyl group. 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.
Of these, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, and a t-butylcyclohexyl group are preferable.

The formula (I), the aryl group having 6 to 10 carbon atoms represented by R ^2, for example, a phenyl group, a naphthyl group, and the like. Examples of the substituent that the aryl group having 6 to 10 carbon atoms may have include 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and a t-butyl group. A cycloalkyl group having 3 to 6 carbon atoms such as cyclopropyl group, cyclopentyl group and cyclohexyl group; an aryl group having 6 to 10 carbon atoms such as phenyl group, 4-methylphenyl group and naphthyl group; An alkoxy group having 1 to 4 carbon atoms such as ethoxy group and butoxy group; an acyl group having 1 to 7 carbon atoms such as acetyl group, benzoyl group, formyl group and pivaloyl group; 3 carbon atoms such as methoxycarbonyl group and ethoxycarbonyl group An alkoxycarbonyl group having ˜4; an aryloxycarbonyl group having 7 to 11 carbon atoms such as a phenoxycarbonyl group and a naphthyloxycarbonyl group; , An acyloxy group having 2 to 7 carbon atoms such as benzoyloxy group; and the like.
Of these, a phenyl group and a 4-methylphenyl group are preferable.

R ² is preferably an alkyl group having 1 to 12 carbon atoms, more preferably a linear alkyl group, and more preferably 2 to 8 carbon atoms.

  Examples of the compound (I) include S-[(4-aminophenyl) methyl] methanethiosulfonate, S- [2- (4-aminophenyl) ethyl] methanethiosulfonate, and S- [3- (4 -Aminophenyl) propyl] methanethiosulfonate, S-[(4-aminophenyl) methyl] ethanethiosulfonate, S- [2- (4-aminophenyl) ethyl] ethanethiosulfonate, S- [3- (4-aminophenyl) propyl] ethanethiosulfonate, S-[(4-aminophenyl) methyl] propanethiosulfonate, S- [2- (4-aminophenyl) ethyl] propanethiosulfonate, S- [ 3- (4-aminophenyl) propyl] propanethiosulfonate, S-[(4-aminophenyl) methyl] 2-propanethiosulfonate S- [2- (4-aminophenyl) ethyl] 2-propanethiosulfonate, S- [3- (4-aminophenyl) propyl] 2-propanethiosulfonate, S-[(4-aminophenyl) ) Methyl] butanethiosulfonate, S- [2- (4-aminophenyl) ethyl] butanethiosulfonate, S- [3- (4-aminophenyl) propyl] butanethiosulfonate, S-[(4- Aminophenyl) methyl] hexanethiosulfonate, S- [2- (4-aminophenyl) ethyl] hexanethiosulfonate, S- [3- (4-aminophenyl) propyl] hexanethiosulfonate, S-[( 4-aminophenyl) methyl] octanethiosulfonate, S- [2- (4-aminophenyl) ethyl] octanethiosulfonate, S- 3- (4-aminophenyl) propyl] octanethiosulfonate, S-[(4-aminophenyl) methyl] benzenethiosulfonate, S- [2- (4-aminophenyl) ethyl] benzenethiosulfonate, S -[3- (4-aminophenyl) propyl] benzenethiosulfonate, S-[(4-aminophenyl) methyl] 4-methylbenzenethiosulfonate, S- [2- (4-aminophenyl) ethyl] 4 -Methylbenzenethiosulfonate, S- [3- (4-aminophenyl) propyl] 4-methylbenzenethiosulfonate, S-[(4-aminophenyl) methyl] phenylmethanethiosulfonate, S- [2- (4-Aminophenyl) ethyl] phenylmethanethiosulfonate, S- [3- (4-aminophenyl) propyl] Phenylmethanethiosulfonate, S-[(4-aminophenyl) methyl] 4-methoxybenzenethiosulfonate, S- [2- (4-aminophenyl) ethyl] 4-methoxybenzenethiosulfonate, S- [3 -(4-aminophenyl) propyl] 4-methoxybenzenethiosulfonate, and the like. Among them, S- [2- (4-aminophenyl) ethyl] 4-methylbenzenethiosulfonate and S- [2- (4-aminophenyl) ethyl] ethanethiosulfonate are preferable, and S- [2- (4 -Aminophenyl) ethyl] ethanethiosulfonate is more preferred. Each of the above compounds may form a salt with any acid (an inorganic acid such as hydrochloride or sulfate, or an organic acid such as acetic acid or methanesulfonic acid).

（式中、Ｒ^１及びＲ^２は上記と同じ意味を表し、Ｒ^３はｔ−ブトキシカルボニル等のアルコキシカルボニル基を表し、Ｒ^４はメチル基、エチル基等のアルキル基、又は、フェニル基、４−メチルフェニル基等のアリール基を表し、Ｍはアルカリ金属原子を表す。） Compound (I) can be produced, for example, by the method represented by the following formula.

(Wherein R ¹ and R ² represent the same meaning as described above, R ³ represents an alkoxycarbonyl group such as t-butoxycarbonyl, R ⁴ represents an alkyl group such as a methyl group or an ethyl group, or a phenyl group, Represents an aryl group such as a 4-methylphenyl group, and M represents an alkali metal atom.)

  The rubber composition of the present invention is obtained by kneading compound (I), a rubber component and a filler. Along with them, it is preferable to knead a sulfur component, and it is more preferable to knead 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. are exemplified. Highly unsaturated rubbers such as rubber, 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 preferable. Preferably used. 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), 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) 360", "Ultrasil (registered trademark) 7000", Rhodia "Zeosil (registered trademark) 115GR", "Zeosil (registered trademark)" Commercially available products such as “1115MP”, “Zeosil (registered trademark) 1205MP”, “Zeosil (registered trademark) Z85MP”, “Nippal (registered trademark) AQ” manufactured by Nippon Silica Co., Ltd. are 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 silica is preferably used in the rubber composition for a tread for passenger cars, and the range of 10 to 120 parts by weight per 100 parts by weight of the rubber component is preferable. 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).

  It is also possible to mix and knead an agent for improving the viscoelastic properties conventionally 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.

  Various compounding agents conventionally used in the rubber field can be blended and kneaded. Examples of such compounding agents include anti-aging agents; oils; fatty acids such as stearic acid; Coumarone resin NG4 (softening point 81 to 100 ° C.) of Nittsu Chemical Co., Ltd., process resin of Kobe Oil Chemical Co., Ltd. Coumarone-indene resin such as AC5 (softening point 75 ° C.); Terpene resin such as terpene resin, terpene / phenol resin, aromatic modified terpene resin; Mitsubishi Gas Chemical Co., Ltd. “Nikanol (registered trademark) A70” Rosin derivatives such as 70 to 90 ° C .; hydrogenated rosin derivatives; novolac alkylphenol resins; resole alkylphenol resins; C5 petroleum resins; liquid polybutadienes. 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, and aromatic process oil.

  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.

  It is also possible to blend and knead a vulcanizing agent such as morpholine disulfide conventionally 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 (that is, the rubber composition obtained by kneading the compound (I), the rubber component, the filler and the sulfur component, and may be hereinafter referred to as “the rubber composition”. )) 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 the rubber composition processed into a specific state.

  Here, “the rubber composition processed into a specific state” means, for example, in the field of tires, “the rubber composition coated with a steel cord” “the rubber composition coated with a carcass fiber cord” "" The rubber composition processed into the shape of a tread member "and the like. 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 a 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.

  Using the vulcanized rubber thus obtained, a pneumatic tire is produced by a usual method. That is, the rubber composition in the stage before the vulcanization treatment is extruded into a tread member, and is pasted and molded by a usual method on a tire molding machine to form a green tire. A tire can be obtained by heating and pressurizing.

  The fuel efficiency of the automobile equipped with the tire thus obtained is improved, and a reduction in fuel consumption can be achieved.

  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.

Production Example 1: Production of 2- [4- (tert-butoxycarbonylamino) phenyl] ethanol In a nitrogen atmosphere, 25.61 g (0.187 mol) of 2- (4-aminophenyl) ethanol and N-ethyldiisopropyl were placed in a reaction vessel. 32 ml (0.187 mol) of amine and 300 ml of tetrahydrofuran were charged, and 38.90 g (0.178 mol) of di-t-butyl dicarbonate was added dropwise under cooling with ice water. After stirring overnight at room temperature, 100 ml of water and 300 ml of ethyl acetate were added to the white residue obtained by concentrating the reaction solution, followed by liquid separation. The obtained organic layer was washed successively with 0.3N hydrochloric acid (100 ml), water (100 ml × 2), saturated brine (100 ml), dried over anhydrous magnesium sulfate and concentrated to 2- [4- (tert-butoxycarbonylamino) phenyl. 41.38 g of ethanol was obtained as a white solid. Yield 98%.

Production Example 2: Production of methanesulfonic acid 2- (4-tert-butoxycarbonylaminophenyl) ethyl ester 2- [4- (tert-butoxycarbonylamino) phenyl] obtained in Production Example 1 in a reactor under a nitrogen atmosphere Ethanol (41.38 g, 0.174 mol), triethylamine (25 ml, 0.183 mol) and dichloromethane (400 ml) were charged. Under cooling with ice water, 20.9 g (0.183 mol) of methanesulfonyl chloride was added dropwise, and the mixture was stirred overnight at room temperature. 200 ml of water was added to the reaction solution, and after separation, the aqueous layer was extracted with 200 ml of chloroform. The obtained organic layers were combined, washed successively with 200 ml of water and 200 ml of saturated brine, dried over anhydrous magnesium sulfate and concentrated to give methanesulfonic acid 2- (4-tert-butoxycarbonylaminophenyl). 55.0 g of ethyl ester was obtained as a pale yellow viscous liquid. Yield 100%.

Production Example 3 Production of S- {2- [4- (tert-butoxycarbonylamino) phenyl] ethyl} ethanethiosulfonate Methanesulfonic acid 2- (4- tert-Butoxycarbonylaminophenyl) ethyl ester 20.81 g (66 mmol), ethanethiosulfonic acid S-sodium 9.78 g (66 mmol) and ethanol 150 ml were charged and heated to reflux for 9.5 hours. After cooling, the reaction mixture was concentrated, 200 ml of water was added to the yellow residue, and then extracted twice with 200 ml of ethyl acetate. The organic layers were combined, washed with water, dried over anhydrous magnesium sulfate, concentrated, and 21.58 g of the orange viscous liquid obtained was subjected to silica gel column chromatography (chloroform) to give S- {2- [4- (tert 14.33 g of -butoxycarbonylamino) phenyl] ethyl} ethanethiosulfonate was obtained as a pale yellow solid. Yield 62.8%

Example 1: Production of S- [2- (4-aminophenyl) ethyl] ethanethiosulfonate S- {2- [4- (tert-butoxycarbonylamino) phenyl] ethyl obtained in Production Example 3 in a reaction vessel } 13.88 g (40.2 mmol) of ethanethiosulfonate was charged, and 15 ml (60.3 mmol) of 4N hydrogen chloride / dioxane solution was added while cooling with ice water. After stirring at room temperature overnight, 15 ml of isopropanol was added to the reaction mixture, and the precipitate was collected by filtration and dried to obtain 8.40 g of crude hydrochloride as a white solid. 15 ml of isopropanol was added to 8.4 g of the crude crystals, and the mixture was kept warm at around 60 ° C. for 30 minutes. After cooling, the crystals were collected by filtration and dried to obtain 7.11 g of S- [2- (4-aminophenyl) ethyl] ethanethiosulfonate hydrochloride as a white powder.
The reaction vessel was charged with 6.7 g (23.8 mmol) of S- [2- (4-aminophenyl) ethyl] ethanethiosulfonate hydrochloride obtained above and 130 ml of tetrahydrofuran, and 3.32 ml (23.8 mmol) of triethylamine was added. In addition, the mixture was stirred at room temperature for 3 hours. Insoluble matters were filtered off, and the obtained filtrate was concentrated to obtain 6.65 g of a pale yellow liquid. To this was added 80 ml of ethyl acetate to form a solution, washed with 30 ml of water, dried over anhydrous magnesium sulfate, and concentrated to give S- [2- (4-aminophenyl) ethyl] ethanethiosulfonate as a yellow liquid. As a result, 5.92 g was obtained. Yield 58.7%
¹ H-NMR (300.13 MHz, CDCl 3 + D 2 O) δ _ppm : 7.00 (2H, d, J = 8.4 Hz), 6.64 (2H, d, J = 8.4 Hz), 3.33 (2H, t, J = 7.2 Hz), 3.17 (2H, q, J = 14.7, 7.2 Hz), 2.92 (2H, t, J = 7.8 Hz), 1.40 (3H, t , J = 7.5Hz)

Example 2: 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 S- [2- (4-aminophenyl) ethyl] ethanethiosulfonate obtained in Example 1 was kneaded and mixed to obtain a rubber composition. This procedure 1 was carried out by kneading at a rotational speed of a mixer of 50 rpm for 5 minutes after charging various chemicals and fillers, 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-benzothiazolesulfenamide) and 2 parts by weight of sulfur at a temperature of 60 to 80 ° C. in an open roll machine. The rubber composition was obtained by kneading and mixing the parts.

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

Reference example 1
In Example 3, a rubber composition was obtained in the same manner as in Example 2 except that S- [2- (4-aminophenyl) ethyl] ethanethiosulfonate 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.

Test example 1
The rebound resilience and viscoelastic properties were measured as follows.
(1) Rebound resilience The resilience was measured using a Lupke type testing machine.
(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

  When the vulcanized rubber obtained in Reference Example 2 was used as a control, the vulcanized rubber obtained in Example 3 had a 5% improvement in resilience and a 31% decrease in viscoelastic properties (tan δ at 60 ° C.). In various tests, improvements in various physical properties were confirmed.

Example 4
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 2. 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 5
The rubber composition obtained in the procedure 2 of Example 2 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 6
The rubber composition obtained in the procedure 2 of Example 2 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 7
In the procedure 2 of Example 2, a rubber composition is obtained in the same manner as in Example 3 except that 0.2 parts by weight of N- (cyclohexylthio) -phthalimide (CTP) is further kneaded and blended.

Example 8
The rubber composition obtained in the procedure 2 of Example 7 is vulcanized at 145 ° C. to obtain a vulcanized rubber.

Example 9: 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, S- [2- (4-aminophenyl) ethyl] ethanethiosulfonate 1 part by weight, anti-aging agent (N-phenyl-N′-1) , 3-dimethylbutyl-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) The rubber composition is obtained by kneading and blending. This process is carried out by kneading at a rotational speed of a mixer of 50 rpm for 5 minutes after charging various chemicals and fillers, and the rubber temperature at that time is 160 to 175 ° C.
<Procedure 2>
The rubber composition obtained by the procedure 1, 3 parts by weight of vulcanization accelerator N-cyclohexyl-2-benzothiazolesulfenamide (CBS) and sulfur 2 at a temperature of 60 to 80 ° C. in an open roll machine. A rubber composition is obtained by kneading and blending with parts by weight.

Example 10 Production of Vulcanized Rubber A vulcanized rubber is obtained by heat-treating the rubber composition obtained in Procedure 2 of Example 9 at 145 ° C. Such vulcanized rubber is suitable for cap treads.

Example 11: 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, S- [2- (4-aminophenyl) ethyl] ethanethiosulfonate 1 part by weight, anti-aging agent (N-phenyl-N′-1) , 3-dimethylbutyl-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) The rubber composition is obtained by kneading and blending. This process is carried out by kneading at a rotational speed of a mixer of 50 rpm for 5 minutes after charging various chemicals and fillers, 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-cyclohexyl-2-benzothiazolesulfenamide (CBS) 2 parts by weight at a temperature of 60 to 80 ° C. in an open roll machine, vulcanization A rubber composition is obtained by kneading 0.5 parts by weight of the accelerator diphenylguanidine (DPG), 0.8 parts by weight of the vulcanization accelerator dibenzothiazyl disulfide (MBTS) and 1 part by weight of sulfur.

Example 12: Production of vulcanized rubber For undertread A vulcanized rubber is obtained by heat-treating the rubber composition obtained in the procedure 2 of Example 11 at 145 ° C. Such vulcanized rubber is suitable for undertread.

Example 13: 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 S- [2- (4-aminophenyl) ethyl] ethanethiosulfonate, 10 parts by weight of hydrous silica (“Nipsil (registered trademark) AQ” manufactured by Tosoh Silica Co., Ltd.) 2 parts by weight of anti-aging agent 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. It is carried out by kneading at a rotation speed of a mixer of 50 rpm for 5 minutes after charging the agent, and the rubber temperature at that time is 160 to 175 ° C.
<Procedure 2>
Rubber composition obtained by procedure 1 at a temperature of 60-80 ° C. in an open roll machine, and 1 part by weight of vulcanization accelerator N, N-dicyclohexyl-2-benzothiazolesulfenamide (DCBS), 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 14 Production of Vulcanized Rubber A vulcanized rubber is obtained by heat-treating the rubber composition obtained in Procedure 2 of Example 13 at 145 ° C. Such vulcanized rubber is suitable for a belt.

Example 15: 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 S- [2- (4-aminophenyl) ethyl] ethanethiosulfonate 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 process is carried out by kneading at a rotational speed of a mixer of 50 rpm for 5 minutes after charging various chemicals and fillers, 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 16: Production of vulcanized rubber The rubber composition obtained in the procedure 2 of Example 15 is heat-treated at 145 ° C to obtain a vulcanized rubber. Such vulcanized rubber is suitable for an inner liner.

Example 17: 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, S- [2- (4-aminophenyl) ethyl] ethanethiosulfonate 1 part by weight, anti-aging agent (N-phenyl-N′-1,3-dimethylbutyl-p-phenylene Diamine (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 (Ouchi Shinsei Chemical Industry) 2 parts by weight of “Sannok (registered trademark) wax” manufactured by the company is kneaded and mixed to obtain a rubber composition. This process is carried out by kneading at a rotational speed of a mixer of 50 rpm for 5 minutes after charging various chemicals and fillers, 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 18: Production of vulcanized rubber A vulcanized rubber is obtained by heat-treating the rubber composition obtained in the procedure 2 of Example 17 at 145 ° C. Such vulcanized rubber is suitable for side walls.

Example 19: 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 S- [2- (4-aminophenyl) ethyl] ethanethiosulfonate 1 part by weight is kneaded and mixed to obtain a rubber composition. This process is carried out by kneading at a rotational speed of a mixer of 50 rpm for 5 minutes after charging various chemicals and fillers, 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 20: Production of vulcanized rubber The rubber composition obtained in the procedure 2 of Example 19 is heat-treated at 145 ° C to obtain a vulcanized rubber. Such vulcanized rubber is suitable for carcass.

Example 21: Production of rubber composition <Procedure 1>
Using a Banbury mixer (600 ml Laboplast 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 S- [2- (4-aminophenyl) ethyl] ethanethiosulfonate are kneaded and mixed to obtain a rubber composition. The process is operated in a temperature range of 70 ° C. to 120 ° C., kneaded at 80 rpm mixer speed for 5 minutes after charging various chemicals and fillers, and then kneaded at 100 rpm mixer speed for 5 minutes. To implement.
<Procedure 2>
The rubber composition obtained by the procedure 1 and the vulcanization accelerator N-cyclohexyl-2-benzothiazole sulfenamide (CBS) 1 part by weight in an open roll machine at a temperature of 30 to 80 ° C., vulcanization acceleration 1 parts by weight of diphenylguanidine (DPG), 1.5 parts by weight of wax (trade name “Sannok (registered trademark) N” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.) and 1.4 parts by weight of sulfur are kneaded and blended. Get things.

Example 22 Production of Vulcanized Rubber A vulcanized rubber is obtained by heat-treating the rubber composition obtained in the procedure 2 of Example 21 at 160 ° C. Such vulcanized rubber is suitable for cap treads.

Example 23: Production of rubber composition In Example 21, a solution-polymerized SBR ("Asaprene (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 21 except for the above.

Example 24: Production of vulcanized rubber A vulcanized rubber is obtained by heat-treating the rubber composition obtained in the procedure 2 of Example 23 at 160 ° C. Such vulcanized rubber is suitable for cap treads.

Example 25: Production of rubber composition In Example 21, 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 21 except that the timing of charging the zinc oxide is changed to the procedure 2 in the procedure 2.

Example 26: Production of vulcanized rubber A vulcanized rubber is obtained by heat-treating the rubber composition obtained in the procedure 2 of Example 25 at 160 ° C. Such vulcanized rubber is suitable for cap treads.

  When the thiosulfonate compound of the present invention is added to a rubber composition for tires, the viscoelastic properties of the vulcanized rubber obtained by vulcanizing it can be improved.

Claims (12)

A thiosulfonate compound represented by the formula (I):

[In Formula (I), R ¹ represents an alkanediyl group having 1 to 12 carbon atoms, and R ² has an optionally substituted alkyl group having 1 to 12 carbon atoms and a substituent. A cycloalkyl group having 3 to 12 carbon atoms, or an aryl group having 6 to 10 carbon atoms which may have a substituent, and n represents 1 or 2. ] The compound of Claim 1 whose R < ² > is a C1-C12 alkyl group. A rubber composition obtained by kneading the thiosulfonate compound according to claim 1 or 2, a rubber component, and a filler. The rubber composition according to claim 3, wherein the rubber component is natural rubber. Furthermore, the rubber composition of Claim 3 or 4 obtained by knead | mixing a sulfur component. A vulcanized rubber obtained by heat-treating the rubber composition according to claim 5. A pneumatic tire produced by processing the rubber composition according to claim 5. A tire belt comprising a steel cord coated with the vulcanized rubber according to claim 6. A tire carcass comprising the carcass fiber cord coated with the vulcanized rubber according to claim 6. A tire sidewall comprising the vulcanized rubber according to claim 6, a tire inner liner, a tire cap tread, or a tire under tread. A pneumatic tire comprising the vulcanized rubber according to claim 6. Use of the thiosulfonate compound according to claim 1 or 2 for improving viscoelastic properties of vulcanized rubber.