JP2012116813A - Thiosulfuric acid compound or salt thereof, and rubber composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an additive for improving viscoelastic characteristics possessed by a vulcanized rubber usable for tire production.SOLUTION: There are provided the thiosulfuric acid compound represented by formula (I) [wherein, R is 3-12C alkanediyl; and n is an integer of 2-5], or a salt thereof, and a rubber composition obtained by kneading the compound or a salt thereof, a rubber component and a filler. The thiosulfuric acid compound represented by formula (I) and used for improving the viscoelastic characteristics possessed by the vulcanized rubber is preferably an alkali metal salt, and more preferably a sodium salt.

Description

  The present invention relates to a thiosulfuric acid compound or a salt thereof and a rubber composition containing the same.

  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は炭素数３〜１２のアルカンジイル基を表し、ｎは２〜５の整数を表す。］
〔２〕式（Ｉ）で示されるチオ硫酸化合物又はそのアルカリ金属塩。

［式（Ｉ）中、Ｒは炭素数３〜１２のアルカンジイル基を表し、ｎは２〜５の整数を表す。］
〔３〕式（Ｉ）で示されるチオ硫酸化合物のナトリウム塩。

［式（Ｉ）中、Ｒは炭素数３〜１２のアルカンジイル基を表し、ｎは２〜５の整数を表す。］ 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 thiosulfuric acid compound represented by the formula (I) or a salt thereof.

[In formula (I), R represents an alkanediyl group having 3 to 12 carbon atoms, and n represents an integer of 2 to 5. ]
[2] A thiosulfuric acid compound represented by the formula (I) or an alkali metal salt thereof.

[In formula (I), R represents an alkanediyl group having 3 to 12 carbon atoms, and n represents an integer of 2 to 5. ]
[3] A sodium salt of a thiosulfuric acid compound represented by the formula (I).

[In formula (I), R represents an alkanediyl group having 3 to 12 carbon atoms, and n represents an integer of 2 to 5. ]

[4] A rubber composition obtained by kneading the thiosulfuric acid compound or salt thereof according to any one of [1] to [3] above, a rubber component and a filler.
[5] The rubber composition according to the above [4], wherein the rubber component is natural rubber.
[6] The rubber composition according to the above [4] or [5], further obtained by kneading a sulfur component.

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

[9] A tire belt comprising a steel cord coated with the vulcanized rubber according to the above [7].
[10] A tire carcass comprising the carcass fiber cord covered with the vulcanized rubber according to [7].
[11] A tire sidewall, a tire inner liner, a tire cap tread, or a tire undertread comprising the vulcanized rubber according to [7] above.
[12] A pneumatic tire comprising the vulcanized rubber according to the above [7].

[13] Use of the thiosulfuric acid compound or a salt thereof according to any one of [1] to [3] above for improving the viscoelastic properties of the vulcanized rubber.

  When the thiosulfuric acid compound of the present invention is added to a rubber composition for tires, viscoelastic properties of a vulcanized rubber obtained by vulcanizing the rubber composition can be improved. That is, the thiosulfuric acid 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 thiosulfuric acid compound represented by the above formula (I) or a salt thereof (hereinafter sometimes referred to as “compound (I)”) will be described.

  In the above formula (I), examples of the alkanediyl group having 3 to 12 carbon atoms represented by R include linear alkanediyl groups such as trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group; And branched alkanediyl groups such as propylene group, isopropylene group, isobutylene group, 2-methyltrimethylene group, isopentylene group, isohexylene group, isooctylene group, 2-ethylhexylene group, and isodecylene group. Among these, a linear alkanediyl group (polymethylene group) is preferable, and the number of carbon atoms is more preferably 3-6.

  In said formula (I), n is an integer of 2-5, Preferably it is 4 or 5, More preferably, it is 5.

  Examples of the salt of the thiosulfate compound represented by the above formula (I) include alkali metal salts such as lithium salt, sodium salt, potassium salt and cesium salt; transition metal salts such as cobalt salt and copper salt; zinc salt and the like Typical metal salts; substituted or unsubstituted ammonium salts such as ammonium salts and trimethylammonium salts; Alkali metal salts are preferred, and sodium salts are more preferred.

  Examples of the compound (I) include S-3- (piperidin-1-yl) propylthiosulfuric acid, S-4- (piperidin-1-yl) butylthiosulfuric acid, and S-5- (piperidin-1-yl) pentylthiosulfuric acid. S-6- (piperidin-1-yl) hexylthiosulfuric acid, S-7- (piperidin-1-yl) heptylthiosulfuric acid, S-8- (piperidin-1-yl) octylthiosulfuric acid, S-10- (piperidine- 1-yl) decylthiosulfuric acid, S-12- (piperidin-1-yl) dodecylthiosulfuric acid, S-3- (pyrrolidin-1-yl) propylthiosulfuric acid, S-4- (pyrrolidin-1-yl) butylthiosulfuric acid, S -5- (Pyrrolidin-1-yl) pentylthiosulfate, S-6- (Pyrrolidin-1-yl) hexylthiosulfate, S-7- (Pyrrolidin-1-yl) heptyl Thiosulfuric acid, S-8- (pyrrolidin-1-yl) octylthiosulfuric acid, S-10- (pyrrolidin-1-yl) decylthiosulfuric acid, S-12- (pyrrolidin-1-yl) dodecylthiosulfuric acid, and lithium thereof Alkali metal salts such as salts, sodium salts, potassium salts and cesium salts; transition metal salts such as cobalt salts and copper salts; typical metal salts such as zinc salts; substituted or unsubstituted ammonium salts such as ammonium salts and trimethylammonium salts And the like. Among them, S-3- (piperidin-1-yl) propylthiosulfate, S-3- (piperidin-1-yl) propylthiosulfate sodium, S-6- (piperidin-1-yl) hexylthiosulfate or S-6- ( Piperidin-1-yl) hexylthiosulfate sodium is preferred, and S-3- (piperidin-1-yl) propylthiosulfate sodium is more preferred.

（式中、Ｒ及びｎは上記と同じ意味を表し、Ｘ_１及びＸ_２はそれぞれ独立に塩素原子、臭素原子又はヨウ素原子を表す。）
かかる製法によれば、通常、ナトリウム塩が得られるが、必要に応じてカチオン交換し、所望の化合物を製造できる。得られる化合物（Ｉ）は、通常０．１〜５質量％程度の水分を含む。 Compound (I) can be produced, for example, by the method represented by the following formula.

(In the formula, R and n represent the same meaning as described above, and X ₁ and X ₂ each independently represent a chlorine atom, a bromine atom or an iodine atom.)
According to such a production method, a sodium salt is usually obtained, but a desired compound can be produced by cation exchange if necessary. The obtained compound (I) usually contains about 0.1 to 5% by mass of water.

  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 chloride.

  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 Guthrie. 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 compounds 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 1- (3-bromopropyl) piperidine hydrobromide In a nitrogen-substituted reaction vessel, 16.0 g (187 mmol) of piperidine and 320 ml of tetrahydrofuran (hereinafter referred to as THF) were charged and dissolved. . Thereto, 41.7 g (69.6 mmol) of 1,3-dibromopropane was added dropwise at room temperature, and the resulting mixture was stirred at room temperature overnight. The precipitated crystals were collected by filtration and washed successively with 300 ml of THF and 300 ml of hexane. The obtained crystals were dried to obtain 21.87 g of 1- (3-bromopropyl) piperidine hydrobromide. Yield 40.7%.

Example 1: Production of sodium S-3- (piperidin-1-yl) propylthiosulfate 20.0 g of 1- (3-bromopropyl) piperidine hydrobromide obtained in Production Example 1 in a nitrogen-substituted reaction vessel (69.6 mmol), sodium thiosulfate pentahydrate 17.3 g (69.6 mmol), methanol 100 ml and water 100 ml were charged, and the resulting mixture was stirred at 70 ° C. for 4 hours. After the reaction was completed, the reaction mixture was allowed to cool, and 2.78 g (69.6 mmol) of sodium hydroxide was added to the liquid obtained by evaporating methanol under reduced pressure, followed by stirring at room temperature for 30 minutes. Thereafter, 200 ml of ethanol was added to the solid obtained by completely distilling off the solvent under reduced pressure and refluxed for 1 hour, and the insoluble matter was filtered while hot. The solvent was completely distilled off from the obtained filtrate under reduced pressure. . After the obtained solid was dissolved in 50 ml of ethanol, 150 ml of hexane and 50 ml of ethyl acetate were added to precipitate crystals, and the crystals were collected by filtration and washed with a mixed solvent of 30 ml of ethanol and 170 ml of hexane. The obtained crystals were vacuum-dried to obtain 13.3 g of sodium S-3- (piperidin-1-yl) propylthiosulfate. Yield 73.1%.
¹ H-NMR (270.05 MHz, CD ₃ OD) δ _ppm : 3.10 (2H, t, J = 6.2 Hz), 2.84-2.89 (6H, m), 2.09-2. 17 (2H, m), 1.69-1.77 (4H, m), 1.54-1.60 (2H, m)

Production Example 2: Production of 1- (6-bromohexyl) piperidine hydrobromide The reaction vessel was purged with nitrogen, and 26.1 g (307 mmol) of piperidine and 520 ml of THF were charged and dissolved. Thereto, 75.0 g (307 mmol) of 1,6-dibromohexane was added dropwise at room temperature, and the resulting mixture was stirred at room temperature overnight. The precipitated crystals were separated by filtration, and the obtained filtrate was concentrated to dryness to obtain 75.2 g of an oily substance.
72.5 g of the obtained oil and 350 ml of hexane were mixed, and 26.1 g (153.5 mmol) of 48% aqueous hydrobromic acid solution was added dropwise thereto, and the resulting mixture was stirred at room temperature overnight. After separating the hexane layer by decantation, the operation of adding 350 ml of hexane and decanting was repeated three times. After adding 100 ml of methanol to the obtained oily substance, 300 ml of hexane was added, and insoluble matter was separated by filtration. The filtrate was concentrated to dryness and dissolved in methanol. Ethyl acetate was added to precipitate crystals, which were collected by filtration. The obtained crystals were vacuum-dried to obtain 25.9 g of 1- (6-bromohexyl) piperidine hydrobromide. Yield 25.6%.

Example 2: Production of sodium S-6- (piperidin-1-yl) hexylthiosulfate 25.0 g of 1- (6-bromohexyl) piperidine hydrobromide obtained in Production Example 2 by replacing the reaction vessel with nitrogen. (76.0 mmol), sodium thiosulfate pentahydrate 18.9 g (76.0 mmol), methanol 125 ml and water 125 ml were charged, and the resulting mixture was stirred at 70 ° C. for 7 hours. After completion of the reaction, the mixture was allowed to cool and methanol was distilled off under reduced pressure. To the resulting residue was added 3.0 g (76.0 mmol) of sodium hydroxide, and the mixture was stirred at room temperature for 30 minutes, and then the solvent was completely removed under reduced pressure. After 200 ml of ethanol was added and refluxed for 1 hour, insoluble matters were removed by hot filtration. The filtrate was concentrated to completely remove the solvent, and then 200 ml of ethanol was added again and the same operation was repeated. The obtained filtrate was concentrated to completely remove the solvent, and then hexane was added to the solution obtained by adding chloroform and ethyl acetate to precipitate crystals. The crystals were collected by filtration, and the obtained crystals were vacuum-dried to obtain 22.9 g of sodium S-6- (piperidin-1-yl) hexylthiosulfate. Yield 99%.
¹ H-NMR (270.05 MHz, CD ₃ OD) δ _ppm : 3.05 (2H, t, J = 6.5 Hz), 2.35-2.50 (4H, m), 2.31 (2H, m), 1.70-1.82 (2H, m), 1.28-1.64 (12H, m)

Example 3: 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 sodium S-3- (piperidin-1-yl) propylthiosulfate obtained in Example 1 were 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), 2 parts by weight of sulfur at a temperature of 60 to 80 ° C. in an open roll machine. 1 part by weight and an antioxidant (N-phenyl-N′-1,3-dimethylbutyl-p-phenylenediamine: trade name “Antigen (registered trademark) 6C” manufactured by Sumitomo Chemical Co., Ltd.), A rubber composition was obtained.

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.

Example 5: Production of rubber composition In Example 3, S-6- (piperidin-1-yl) hexylthiosulfate obtained in Example 2 above instead of sodium S-3- (piperidin-1-yl) propylthiosulfate A rubber composition was obtained in the same manner as in Example 3 except that sodium was used.

Example 6: Production of vulcanized rubber The rubber composition obtained in the procedure 2 of Example 5 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 3 except that sodium S-3- (piperidin-1-yl) propylthiosulfate 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 4 had a 5% improvement in resilience and a 12% reduction in viscoelastic properties (tan δ at 60 ° C.). In various tests, improvements in various physical properties were confirmed.

Test example 2
When the impact resilience and viscoelastic properties were measured in the same manner as in Test Example 1, when the vulcanized rubber obtained in Reference Example 2 was used as a control, the vulcanized rubber obtained in Example 6 had a 5% increase in resilience. The viscoelastic properties (tan δ at 60 ° C.) were reduced by 15%, and improvements in various physical properties were confirmed in all tests.

Example 7
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 3. 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 8
The rubber composition obtained in the procedure 2 of Example 3 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 9
The rubber composition obtained in the procedure 2 of Example 3 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 10
In the procedure 2 of Example 3, 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 11
The rubber composition obtained in the procedure 2 of Example 10 is vulcanized at 145 ° C. to obtain a vulcanized rubber.

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”) ) 45 parts by weight, stearic acid 2 parts by weight, zinc oxide 3 parts by weight, S-3- (piperidin-1-yl) propylthiosulfate sodium 1 part by weight, anti-aging agent (N-phenyl-N′-1,3- 1 part by weight of dimethylbutyl-p-phenylenediamine (6PPD): 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) A rubber composition is obtained. 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 13: Production of vulcanized rubber 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 cap treads.

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 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-3- (piperidin-1-yl) propylthiosulfate sodium 1 part by weight, anti-aging agent (N-phenyl-N′-1,3- 1 part by weight of dimethylbutyl-p-phenylenediamine (6PPD): 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) A rubber composition is obtained. 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 15 Production of Vulcanized Rubber For Undertread 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 undertread.

Example 16: 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 sodium S-3- (piperidin-1-yl) propylthiosulfate, 10 parts by weight of hydrous silica (“Nipsil (registered trademark) AQ” manufactured by Tosoh Silica Co., Ltd.), anti-aging 2 parts by weight of an 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 for 5 minutes at a mixer speed of 50 rpm, 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 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 a belt.

Example 18: 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 sodium S-3- (piperidin-1-yl) propylthiosulfate 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 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 an inner liner.

Example 20: 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-3- (piperidin-1-yl) propyl sodium thiosulfate 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.) 2 parts by weight of “Sannok (registered trademark) wax”) 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 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 side walls.

Example 22: 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 sodium S-3- (piperidin-1-yl) propylthiosulfate 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 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 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 145 ° C. Such vulcanized rubber is suitable for carcass.

Example 24: 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 sodium S-3- (piperidin-1-yl) propylthiosulfate 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 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 24, solution-polymerized SBR ("Asaprene (registered trademark)" manufactured by Asahi Kasei Chemicals Co., Ltd.) was used instead of styrene-butadiene copolymer rubber SBR # 1500 (manufactured by JSR). A rubber composition is obtained in the same manner as in Example 24 except for the above.

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 In Example 24, 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 24 except that the timing of charging the zinc oxide is changed to the procedure 2.

Example 29: Production of vulcanized rubber A vulcanized rubber is obtained by heat-treating the rubber composition obtained in the procedure 2 of Example 28 at 160 ° C. Such vulcanized rubber is suitable for cap treads.

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

Claims (13)

A thiosulfuric acid compound represented by the formula (I) or a salt thereof.

[In formula (I), R represents an alkanediyl group having 3 to 12 carbon atoms, and n represents an integer of 2 to 5. ] A thiosulfuric acid compound represented by formula (I) or an alkali metal salt thereof.

[In formula (I), R represents an alkanediyl group having 3 to 12 carbon atoms, and n represents an integer of 2 to 5. ] Sodium salt of thiosulfate compound represented by formula (I).

[In formula (I), R represents an alkanediyl group having 3 to 12 carbon atoms, and n represents an integer of 2 to 5. ] A rubber composition obtained by kneading the thiosulfuric acid compound or salt thereof according to any one of claims 1 to 3, a rubber component, and a filler. The rubber composition according to claim 4, wherein the rubber component is natural rubber. Furthermore, the rubber composition of Claim 4 or 5 obtained by knead | mixing a sulfur component. A vulcanized rubber obtained by heat-treating the rubber composition according to claim 6. A pneumatic tire produced 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 carcass for a tire comprising a carcass fiber cord coated with the vulcanized rubber according to claim 7. A tire sidewall comprising the vulcanized rubber according to claim 7, a tire inner liner, a tire cap tread, or a tire under tread. A pneumatic tire comprising the vulcanized rubber according to claim 7. Use of the thiosulfuric acid compound or a salt thereof according to any one of claims 1 to 3, for improving the viscoelastic properties of the vulcanized rubber.