JP5889017B2 - Method for producing vulcanized rubber - Google Patents

Description

  The present invention relates to a method for producing vulcanized rubber and the like.

  Patent Document 1 includes a process kneading natural rubber, a filler, stearic acid, zinc oxide and a sodium salt of S- (3-aminopropyl) thiosulfuric acid, a kneaded product obtained in the process a, sulfur and A method for producing a vulcanized rubber is described which includes a step b for kneading a vulcanization accelerator and a step for heat-treating the kneaded product obtained in step b.

International Publication No. 2011/001990

  There has been a demand for a method for producing a vulcanized rubber capable of improving the viscoelastic properties of the vulcanized rubber.

The present invention includes the following inventions.
[1] A first step of kneading one component of the group consisting of stearic acid and zinc oxide, a rubber component, and a filler;
A second step of kneading the other component of the group consisting of stearic acid and zinc oxide, a kneaded product obtained in the first step, a sulfur component and a vulcanization accelerator;
A third step of heat treating the kneaded product obtained in the second step;
A method for producing a vulcanized rubber.

（式（Ｉ）中、Ｍ^ｎ＋は、Ｈ^＋又はｎ価の金属イオンを表す。
ｎは、１又は２の整数を表す。
Ｒ^１及びＲ^２は、それぞれ独立に、水素原子又は炭素数１〜６のアルキル基を表すか、或いは、Ｒ^１とＲ^２とが互いに結合して、それらが結合している窒素原子とともに環を形成する。
ｍは、２〜９の整数を表す。） [2] The vulcanized rubber according to [1], wherein the first step is a step of kneading one component of the group consisting of stearic acid and zinc oxide, a rubber component, a filler, and a compound represented by formula (I) Manufacturing method.

(In formula (I), M ^{n +} represents H ⁺ or an n-valent metal ion.
n represents an integer of 1 or 2.
R ¹ and R ² each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, or R ¹ and R ² are bonded to each other, and a ring together with the nitrogen atom to which they are bonded Form.
m represents an integer of 2 to 9. )

[3] The second step is a step of simultaneously kneading the kneaded product obtained in the first step with the other component of the group consisting of stearic acid and zinc oxide, a sulfur component, and a vulcanization accelerator. The method for producing a vulcanized rubber according to [1] or [2].

[4] A vulcanized rubber obtained by the method for producing a vulcanized rubber according to any one of [1] to [3].

[5] A tire belt including a steel cord covered with a vulcanized rubber obtained by the method for producing a vulcanized rubber according to any one of [1] to [3].

[6] A tire carcass including a carcass fiber cord covered with a vulcanized rubber obtained by the method for producing a vulcanized rubber according to any one of [1] to [3].

[7] A tire sidewall, a tire inner liner, a tire cap tread, or a tire undertread including the vulcanized rubber obtained by the method for producing a vulcanized rubber according to any one of [1] to [3].

[8] A tire including a vulcanized rubber obtained by the method for producing a vulcanized rubber according to any one of [1] to [3].

  According to the method for producing a vulcanized rubber of the present invention, the viscoelastic properties of the obtained vulcanized rubber can be improved.

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

<First step>
In the first step, one component of the group consisting of stearic acid and zinc oxide, a rubber component, and a filler are kneaded. In the first step, it is preferable to knead one component of the group consisting of stearic acid and zinc oxide, a rubber component, a filler, and a compound represented by formula (I), and zinc oxide, rubber component, filler and formula It is more preferable to knead the compound represented by (I).
The first step is preferably performed at 80 to 200 ° C, more preferably 110 to 180 ° C.
The first step is preferably performed for 1 to 10 minutes, more preferably 2 to 7 minutes.

<Stearic acid>
The amount of stearic acid used is preferably 0.5 to 5 parts by weight, more preferably 0.5 to 3 parts by weight per 100 parts by weight of the rubber component.
<Zinc oxide>
The amount of zinc oxide used is preferably 0.5 to 10 parts by weight and more preferably 2 to 7 parts by weight per 100 parts by weight of the rubber component.

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

  Examples of natural rubber include natural rubber of grades such as RSS # 1, RSS # 3, TSR20, SIR20 and the like. As the epoxidized natural rubber, those having a degree of epoxidation of 10 to 60 mol% are preferable, and examples thereof include ENR25 and ENR50 manufactured by Kumpoulan 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. In addition, oil-added SBR obtained by adding oil such as post-polymerization process oil and aroma oil 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 high cis BR is preferably used. Further, 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 It is 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 40 to 0% by weight for BR relative to the total rubber weight. 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.

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

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

  Although the usage-amount of a filler is not specifically limited, The range of 10-120 weight part per 100 weight part of rubber components 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.

（式（Ｉ）中、Ｍ^ｎ＋は、Ｈ^＋又はｎ価の金属イオンを表す。
ｎは、１又は２の整数を表す。
Ｒ^１及びＲ^２は、それぞれ独立に、水素原子又は炭素数１〜６のアルキル基を表すか、或いは、Ｒ^１とＲ^２とが互いに結合して、それらが結合している窒素原子とともに環を形成する。
ｍは、２〜９の整数を表す。） <Compound represented by formula (I) (hereinafter sometimes referred to as “compound (I)”)>

(In formula (I), M ^{n +} represents H ⁺ or an n-valent metal ion.
n represents an integer of 1 or 2.
R ¹ and R ² each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, or R ¹ and R ² are bonded to each other, and a ring together with the nitrogen atom to which they are bonded Form.
m represents an integer of 2 to 9. )

Examples of the alkyl group having 1 to 6 carbon atoms in R ¹ and R ² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, heptyl Group and hexyl group.
When R ¹ and R ² are bonded to each other to form a ring together with the nitrogen atom to which they are bonded, the polymethylene group formed by combining R ¹ and R ² with each other is an ethylene group ( Dimethylene group), trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group and the like. R ¹ and R ² are preferably a hydrogen atom.

Examples of M ^{n +} include H ⁺ , lithium ions, sodium ions, potassium ions, cesium ions, magnesium ions, calcium ions, strontium ions, barium ions, mangaion ions, iron ions, copper ions, zinc ions, and the like. Is H ⁺ , an alkali metal ion, more preferably H ⁺ , a sodium ion.

  Compound (I) includes S- (aminoalkyl) thiosulfuric acid, S- (aminoalkyl) thiosulfate, S- (N, N-dialkylaminoalkyl) thiosulfuric acid, S- (N, N-dialkylaminoalkyl). ) Thiosulfate, S- (N-monoalkylaminoalkyl) thiosulfuric acid, S- (N-monoalkylaminoalkyl) thiosulfate and the like, preferably S- (aminoalkyl) thiosulfuric acid, S- ( Aminoalkyl) thiosulfate.

Examples of S- (aminoalkyl) thiosulfuric acid include S- (aminoethyl) thiosulfuric acid, S- (aminopropyl) thiosulfuric acid, S- (aminobutyl) thiosulfuric acid, S- (aminopentyl) thiosulfuric acid, S- ( Aminohexyl) thiosulfuric acid, S- (aminoheptyl) thiosulfuric acid, S- (aminooctyl) thiosulfuric acid, S- (aminononyl) thiosulfuric acid and the like.
Examples of S- (aminoalkyl) thiosulfate include sodium S- (aminoethyl) thiosulfate, sodium S- (aminopropyl) thiosulfate, sodium S- (aminobutyl) thiosulfate, and S- (aminopentyl) thiosulfate. Examples include sodium, sodium S- (aminohexyl) thiosulfate, sodium S- (aminoheptyl) thiosulfate, sodium S- (aminooctyl) thiosulfate, and sodium S- (aminononyl) thiosulfate.
Examples of S- (N, N-dialkylaminoalkyl) thiosulfuric acid include S- (N, N-dimethylaminoethyl) thiosulfuric acid, S- (N, N-dimethylaminopropyl) thiosulfuric acid, S- (N, N -Dimethylaminobutyl) thiosulfuric acid, S- (N, N-dimethylaminopentyl) thiosulfuric acid, S- (N, N-dimethylaminohexyl) thiosulfuric acid, S- (N, N-dimethylaminoheptyl) thiosulfuric acid, S- (N, N-dimethylaminooctyl) thiosulfuric acid, S- (N, N-dimethylaminononyl) thiosulfuric acid and the like can be mentioned.
Examples of S- (N, N-dialkylaminoalkyl) thiosulfate include sodium S- (N, N-dimethylaminoethyl) thiosulfate, sodium S- (N, N-dimethylaminopropyl) thiosulfate, S- ( N, N-dimethylaminobutyl) sodium thiosulfate, S- (N, N-dimethylaminopentyl) sodium thiosulfate, S- (N, N-dimethylaminohexyl) sodium thiosulfate, S- (N, N-dimethyl) Aminoheptyl) sodium thiosulfate, S- (N, N-dimethylaminooctyl) sodium thiosulfate, sodium S- (N, N-dimethylaminononyl) thiosulfate and the like.
Examples of S- (N-monoalkylaminoalkyl) thiosulfuric acid include S- (N-methylaminoethyl) thiosulfuric acid, S- (N-methylaminopropyl) thiosulfuric acid, S- (N-methylaminobutyl) thiosulfuric acid. S- (N-methylaminopentyl) thiosulfuric acid, S- (N-methylaminohexyl) thiosulfuric acid, S- (N-methylaminoheptyl) thiosulfuric acid, S- (N-methylaminooctyl) thiosulfuric acid, S -(N-methylaminononyl) thiosulfuric acid and the like.
Examples of S- (N-monoalkylaminoalkyl) thiosulfate include sodium S- (N-methylaminoethyl) thiosulfate, sodium S- (N-methylaminopropyl) thiosulfate, and S- (N-methylaminobutyl). ) Sodium thiosulfate, S- (N-methylaminopentyl) sodium thiosulfate, S- (N-methylaminohexyl) sodium thiosulfate, S- (N-methylaminoheptyl) sodium thiosulfate, S- (N-methyl) Aminooctyl) sodium thiosulfate, S- (N-methylaminononyl) sodium thiosulfate and the like.

  Compound (I) can be produced, for example, by reacting 3-chloropropylamine hydrochloride with sodium thiosulfate. Compound (I) may be obtained by neutralizing the metal salt of compound (I) with a protonic acid such as hydrochloric acid or sulfuric acid. Examples of the metal salt of compound (I) include a method of reacting 3-halopropylamine and sodium thiosulfate, a reaction of phthalimide potassium salt and 1,3-dihalopropane, and the resulting compound and thiosulfuric acid. It can be produced by any known method such as a method of reacting with sodium and then hydrolyzing the obtained compound.

The compound (I) obtained as described above can be isolated as a solid by an operation such as concentration and crystallization. The isolated compound (I) may contain about 0.1% to 5% water.
The amount of compound (I) used is preferably 0.1 to 10 parts by weight, more preferably 0.3 to 3 parts by weight per 100 parts by weight of the rubber component.

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 support 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).
By adding the compound (I), the viscoelastic properties of the resulting vulcanized rubber can be further improved.

<Second step>
In the second step, the other component of the group consisting of stearic acid and zinc oxide, the kneaded product obtained in the first step, the sulfur component and the vulcanization accelerator are kneaded.
The second step is preferably a step of simultaneously kneading the kneaded product obtained in the first step with the other component of the group consisting of stearic acid and zinc oxide, a sulfur component and a vulcanization accelerator. .
The second step is preferably performed at 50 to 100 ° C, more preferably 60 to 90 ° C.
The second step is preferably performed for 1 to 10 minutes, more preferably 2 to 8 minutes.
<Sulfur component>
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.
The amount of the sulfur component used is preferably 0.1 to 10 parts by weight, more preferably 0.3 to 3 parts by weight per 100 parts by weight of the rubber component.

<Vulcanization accelerator>
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.

  In the first step and / or the second step, an agent for improving viscoelastic properties usually used in the rubber field can be blended and kneaded. 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.

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

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

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

  It is also possible to mix and knead a vulcanizing agent such as morpholine disulfide which is usually used in the rubber field in the first step and / or the second step.

  Further, in the first step and / or the second step, a peptizer or a retarder may be blended and kneaded. Furthermore, general rubber chemicals or softeners may be blended and kneaded as necessary. May be.

  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.

  Although the usage-amount of a retarder is not specifically limited, The range of 0.01-1 weight part per 100 weight part of rubber components is preferable. Particularly preferred is 0.05 to 0.5 parts by weight.

<Third step>
In the third step, the kneaded material obtained in the second step is heat-treated.
The temperature in the heat treatment is preferably 120 to 180 ° C. The heat treatment is usually performed at normal pressure or under pressure.
The processing time of the third step is, for example, 90% vulcanization time (t _c (90)) of the kneaded product obtained in the second step in accordance with JIS K 6300-2. It is preferable to set a time longer by 10 minutes.

  The production method of the present invention preferably includes a step of processing the kneaded product obtained in the second step into a specific state before subjecting the kneaded product obtained in the second step to the third step.

  Here, “processing to a specific state” includes, for example, in the field of tires, covering with a steel cord, covering with a carcass fiber cord, processing into the shape of a tread member, and the like. . The kneaded material processed into a specific state is heat-treated to obtain a member such as a belt, carcass, inner liner, sidewall, tread (cap tread or under tread).

  When vulcanized rubber is used 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 natural rubber and SBR and / or BR. The filler is preferably carbon black alone or a blend of silica and carbon black. 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.

  When the vulcanized rubber is used for tread members suitable for passenger car tires, the rubber component is a solution-polymerized SBR having a molecular end modified with a silicon compound alone, or the terminal-modified solution-polymerized SBR and non-modified solution-polymerized SBR, emulsified A blend with at least one rubber selected from the group consisting of polymerized SBR, natural rubber and BR is preferred. The filler is preferably a blend of silica and carbon black. 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.

  When vulcanized rubber is used for a side wall member, the rubber component is preferably a blend of BR and at least one rubber selected from the group consisting of non-modified solution polymerization SBR, emulsion polymerization SBR and natural rubber. The filler is preferably carbon black alone or a blend of carbon black and silica. 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.

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

A tire is manufactured by a normal method using the vulcanized rubber obtained by the manufacturing method of the present invention. 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.
Examples of the tire include a pneumatic tire and a solid tire.

The fuel consumption of an automobile equipped with a tire containing a vulcanized rubber obtained by the production method of the present invention is improved, and a reduction in fuel consumption can be achieved.
The vulcanized rubber obtained by the production method of the present invention can be used not only for tires but also for various anti-vibration rubbers, various rubber belts, damping materials, and seismic isolation rubbers. Examples of the anti-vibration rubber include anti-vibration rubbers for automobiles such as engine mounts, strut mounts, bushes, and exhaust hangers. The anti-vibration rubber is usually obtained by processing the kneaded product obtained in the second step into a shape possessed by the anti-vibration rubber and then subjecting it to a heat treatment in the third step. Moreover, as a rubber belt use, a power transmission belt, a conveyor belt, a V belt etc. are mentioned, for example.

  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: S- (3-aminopropyl) thiosulfuric acid 100 g (0.77 mol) of 3-chloropropylamine hydrochloride, 180 mL of water and 200.4 g of sodium thiosulfate pentahydrate (0 .81 mol), and the resulting mixture was stirred at a bath temperature of 70 to 80 ° C. for 5 hours. The reaction mixture was allowed to cool overnight, and the crystals were collected by filtration and washed with water and methanol. The obtained crystals were dried at 50 ° C. for 4 hours to obtain S- (3-aminopropyl) thiosulfuric acid. The amount of crystals obtained was 97.8 g.
¹ H-NMR (270.05 MHz, D ₂ O) δ _ppm : 3.0-3.1 (4H, m), 2.0-2.1 (2H, m)

Example 1
<First step>
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 ISAF (Asahi Carbon Co., Ltd., trade name “Asahi # 80”), 3 parts by weight of stearic acid And 0.5 part by weight of S- (3-aminopropyl) thiosulfuric acid obtained in Production Example 1 was kneaded to obtain a kneaded product. In this step, kneading was performed at a mixer set temperature of 120 ° C. and a mixer rotation speed of 50 rpm for 5 minutes after charging various chemicals and fillers. The temperature of the kneaded product at the end of kneading was 166 ° C.
<Second step>
Kneaded product obtained in the first step, zinc oxide 5 parts 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., 1 part by weight of vulcanization accelerator N-cyclohexyl-2-benzothiazolesulfenamide (CBS), sulfur 2 parts by weight were kneaded and blended to obtain an unvulcanized rubber composition.
<Third step>
The unvulcanized rubber composition obtained in the second step was heat-treated at 145 ° C. to obtain a vulcanized rubber composition.

Reference example 1
In Example 1, a rubber composition was obtained in the same manner as in Example 1 except that S- (3-aminopropyl) thiosulfuric acid was not used and zinc oxide and an antioxidant were kneaded in the first step.

Test example 1
The dynamic viscoelastic properties of the vulcanized rubber composition obtained in the third step of Example 1 were measured as follows.
(1) Dynamic viscoelastic properties (tan δ)
Measurement was performed using a viscoelasticity analyzer manufactured by Ueshima Seisakusho.
Condition: Temperature 60 ° C
Initial strain 10%, dynamic strain 2.5%, frequency 10Hz

  Using the vulcanized rubber obtained in Reference Example 1 as a control, the decrease rate (%) of the viscoelastic properties (tan δ at 60 ° C.) of the vulcanized rubber obtained in Example 1 with respect to the vulcanized rubber obtained in Reference Example 1. As a result, the reduction rate was 21%.

Example 2
A rubber composition was obtained in the same manner as in Example 1 except that stearic acid was kneaded in the second step and zinc oxide was kneaded in the first step.

Test example 2
Using the vulcanized rubber obtained in Reference Example 1 as a control, the reduction rate (%) of the viscoelastic properties (tan δ at 60 ° C.) of the vulcanized rubber obtained in Example 2 with respect to the vulcanized rubber obtained in Reference Example 1 As a result, the reduction rate was 24%.

Reference example 2
In Example 1, a vulcanized rubber composition was obtained in the same manner as in Example 1 except that the zinc oxide and the antioxidant were kneaded in the first step, and the vulcanized rubber obtained in Reference Example 1 was used as a control. When the reduction rate (%) of the viscoelastic property (tan δ at 60 ° C.) with respect to the vulcanized rubber obtained in Reference Example 1 was measured, the reduction rate was 14%.

Reference example 3
A belt is obtained by covering the steel cord subjected to the brass plating treatment with the rubber composition obtained in the second step of Example 1 or 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.

Reference example 4
The rubber composition obtained in the second step of Example 1 or 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.

Reference Example 5
By extruding the rubber composition obtained in the second step of Example 1 or Example 2 to prepare a rubber composition having a shape corresponding to the carcass shape, and pasting it on the upper and lower sides of a polyester carcass fiber cord Carcass is obtained. 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.

Reference Example 6
<First step>
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, 2 parts by weight of stearic acid, 1 part by weight of S- (3-aminopropyl) thiosulfuric acid, and 2 parts by weight of wax (“OZOACE-0355” manufactured by Nippon Seiwa) are kneaded and blended to obtain a rubber composition. obtain. This step is carried out by kneading for 5 minutes at a rotational speed of a mixer of 50 rpm for 5 minutes after charging each component, and the rubber temperature at that time is 160 to 175 ° C.
<Second step>
The rubber composition obtained by the first step, 3 parts by weight of zinc oxide, an anti-aging agent (N-phenyl-N′-1,3-dimethylbutyl-p at a temperature of 60 to 80 ° C. in an open roll machine -Phenylenediamine (6PPD): Trade name "Antigen (registered trademark) 6C" manufactured by Sumitomo Chemical Co., Ltd.) 1 part by weight Vulcanization accelerator N-cyclohexyl-2-benzothiazolylsulfenamide (CBS) 3 parts by weight And 2 parts by weight of sulfur are kneaded and mixed to obtain a rubber composition.

Reference Example 7
A vulcanized rubber is obtained by heat-treating the rubber composition obtained in the second step of Reference Example 6 at 145 ° C. Such vulcanized rubber is suitable for cap treads.

Reference Example 8
<First step>
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, 3 parts by weight of zinc oxide, 1 part by weight of S- (3-aminopropyl) thiosulfuric acid, and 2 parts by weight of wax (“OZOACE-0355” manufactured by Nippon Seiwa) are kneaded and blended to obtain a rubber composition. obtain. This step is carried out by kneading for 5 minutes at a rotational speed of a mixer of 50 rpm for 5 minutes after charging each component, and the rubber temperature at that time is 160 to 175 ° C.
<Second step>
The rubber composition obtained by the first step, 2 parts by weight of stearic acid, an anti-aging agent (N-phenyl-N′-1,3-dimethylbutyl-p at a temperature of 60 to 80 ° C. in an open roll machine -Phenylenediamine (6PPD): Trade name "Antigen (registered trademark) 6C" manufactured by Sumitomo Chemical Co., Ltd.) 1 part by weight Vulcanization accelerator N-cyclohexyl-2-benzothiazolylsulfenamide (CBS) 2 parts by weight Then, 0.5 part by weight of the vulcanization accelerator diphenylguanidine (DPG), 0.8 part by weight of the vulcanization accelerator dibenzothiazyl disulfide (MBTS) and 1 part by weight of sulfur are kneaded and mixed to obtain a rubber composition.

Reference Example 9
A vulcanized rubber is obtained by heat-treating the rubber composition obtained in the second step of Reference Example 8 at 145 ° C. Such vulcanized rubber is suitable for undertread.

Reference Example 10
<First step>
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 , 1 part by weight of S- (3-aminopropyl) thiosulfuric acid, 10 parts by weight of hydrous silica (“Nipsil (registered trademark) AQ” manufactured by Tosoh Silica Co., Ltd.), anti-aging agent FR (“antioxidant manufactured by Matsubara Sangyo Co., Ltd. FR "), 2 parts by weight, 2 parts by weight of resorcin, and 2 parts by weight of cobalt naphthenate are kneaded and mixed to obtain a rubber composition. In this step, the components are kneaded for 5 minutes at a rotation speed of a mixer of 50 rpm. The rubber temperature at that time is 160 to 175 ° C.
<Second step>
The rubber composition obtained in the first step, 5 parts by weight of zinc oxide, and vulcanization accelerator N, N-dicyclohexyl-2-benzothiazolylsulfene at a temperature of 60 to 80 ° C. in an open roll machine A rubber composition is obtained by kneading and mixing 1 part by weight of amide (DCBS), 6 parts by weight of sulfur and 3 parts by weight of a methoxylated methylol melamine resin (“SUMIKANOL 507AP” manufactured by Sumitomo Chemical Co., Ltd.).

Reference Example 11
A vulcanized rubber is obtained by heat-treating the rubber composition obtained in the second step of Reference Example 10 at 145 ° C. Such vulcanized rubber is suitable for a belt.

Reference Example 12
<First step>
Using a Banbury mixer (600 ml Lab Plast Mill manufactured by Toyo Seiki Co., Ltd.), 100 parts by weight of halogenated butyl rubber (“Br-IIR2255” manufactured by ExxonMobil), 60 parts by weight of GPF, 3 parts by weight of zinc oxide, S- (3-amino) 1 part by weight of propyl) thiosulfuric acid and 10 parts by weight of paraffin oil (“Diana Process Oil” manufactured by Idemitsu Kosan Co., Ltd.) are kneaded and mixed to obtain a rubber composition. This step is carried out by kneading for 5 minutes at a rotational speed of a mixer of 50 rpm for 5 minutes after charging each component, and the rubber temperature at that time is 160 to 175 ° C.
<Second step>
The rubber composition obtained by the first step, 1 part by weight of stearic acid, 1 part by weight of an anti-aging agent (condensation product of aniline and acetone (TMDQ)) at a temperature of 60 to 80 ° C. in an open roll machine, A rubber composition is obtained by kneading and mixing 1 part by weight of a sulfur accelerator dibenzothiazyl disulfide (MBTS) and 2 parts by weight of sulfur.

Reference Example 13
A vulcanized rubber is obtained by heat-treating the rubber composition obtained in the second step of Reference Example 12 at 145 ° C. Such vulcanized rubber is suitable for an inner liner.

Reference Example 14
<First step>
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, 1 part by weight of S- (3-aminopropyl) thiosulfuric acid, 10 parts by weight of aromatic oil (“NC-140” manufactured by Cosmo Oil Co., Ltd.) and wax (“Sannok (registered trademark)” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.) 2 parts by weight of wax ") are kneaded and mixed to obtain a rubber composition. This step is carried out by kneading for 5 minutes at a rotational speed of a mixer of 50 rpm for 5 minutes after charging each component, and the rubber temperature at that time is 160 to 175 ° C.
<Second step>
The rubber composition obtained by the first step, 3 parts by weight of zinc oxide, an anti-aging agent (N-phenyl-N′-1,3-dimethylbutyl-p at a temperature of 60 to 80 ° C. in an open roll machine -Phenylenediamine (6PPD): 2 parts by weight of trade name “Antigen (registered trademark) 6C” manufactured by Sumitomo Chemical Co., Ltd., vulcanization accelerator N-tert-butyl-2-benzothiazolylsulfenamide (BBS) 0. 75 parts by weight and 1.5 parts by weight of sulfur are kneaded and mixed to obtain a rubber composition.

Reference Example 15
A vulcanized rubber is obtained by heat-treating the rubber composition obtained in the second step of Reference Example 14 at 145 ° C. Such vulcanized rubber is suitable for side walls.

Reference Example 16
<First step>
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, 7 parts by weight of process oil (“Diana Process PS32” manufactured by Idemitsu Kosan Co., Ltd.), 5 parts by weight of zinc oxide and 1 part by weight of S- (3-aminopropyl) thiosulfuric acid are kneaded and mixed to obtain a rubber composition. . This step is carried out by kneading for 5 minutes at a rotational speed of a mixer of 50 rpm for 5 minutes after charging each component, and the rubber temperature at that time is 160 to 175 ° C.
<Second step>
The rubber composition obtained by the first step, 2 parts by weight of stearic acid, vulcanization accelerator N-tert-butyl-2-benzothiazolylsulfenamide (at 60 to 80 ° C. in an open roll machine) BBS) 1 part by weight, sulfur 3 parts by weight, anti-aging agent (N-phenyl-N′-1,3-dimethylbutyl-p-phenylenediamine (6PPD): trade name “Antigen (registered trademark) 6C” Sumitomo Chemical Co., Ltd. A rubber composition is obtained by kneading and mixing 1 part by weight of a company) and 1 part by weight of an antioxidant (condensation product of aniline and acetone (TMDQ)).

Reference Example 17
A vulcanized rubber is obtained by heat treating the rubber composition obtained in the second step of Reference Example 16 at 145 ° C. Such vulcanized rubber is suitable for carcass.

Reference Example 18
<First step>
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 Co., Ltd.), 2 parts by weight of stearic acid and S- (3-aminopropyl) thio 3 parts by weight of sulfuric acid is kneaded and mixed to obtain a rubber composition. This step is operated in a temperature range of 70 ° C. to 120 ° C., and is carried out by kneading at a rotational speed of a mixer of 80 rpm for 5 minutes after charging each component, and subsequently kneading at a rotational speed of a mixer of 100 rpm for 5 minutes. .
<Second step>
The rubber composition obtained by the second step and the 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, vulcanization accelerator N-cyclohexyl-2-benzothiazolylsulfenamide (CBS) 1 Parts by weight, 1 part by weight of a vulcanization accelerator 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. The rubber composition is obtained by kneading and blending.

Reference Example 19
A vulcanized rubber is obtained by heat-treating the rubber composition obtained in the second step of Reference Example 18 at 160 ° C. Such vulcanized rubber is suitable for cap treads.

Reference Example 20
In Reference Example 18, the same procedure as in Example 17 was used except that solution-polymerized SBR (“ASAPREN (registered trademark)” manufactured by Asahi Kasei Chemicals Corporation) was used instead of styrene-butadiene copolymer rubber SBR # 1500 (manufactured by JSR). A rubber composition is obtained.

Reference Example 21
A vulcanized rubber is obtained by heat-treating the rubber composition obtained in the second step of Reference Example 18 at 160 ° C. Such vulcanized rubber is suitable for cap treads.

  According to the method for producing a vulcanized rubber of the present invention, the viscoelastic properties of the obtained vulcanized rubber can be improved.

Claims (6)

A first step of kneading one component of the group consisting of stearic acid and zinc oxide, a rubber component and a filler;
A second step of kneading the other component of the group consisting of stearic acid and zinc oxide, a kneaded product obtained in the first step, a sulfur component and a vulcanization accelerator;
A third step of heat treating the kneaded product obtained in the second step;
Including
A method for producing a vulcanized rubber, wherein the first step is a step of kneading one component of a group consisting of stearic acid and zinc oxide, a rubber component, a filler, and a compound represented by the formula (I).

(In formula (I), M ^{n +} represents H ⁺ or an n-valent metal ion.
n represents an integer of 1 or 2.
R ¹ and R ² each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, or R ¹ and R ² are bonded to each other, and a ring together with the nitrogen atom to which they are bonded Form.
m represents an integer of 2 to 9. ) Second step, the kneaded product obtained in the first step, according to claim 1 other component of said group consisting of stearic acid and zinc oxide is added at the same time the sulfur component and the vulcanization accelerator is a step of kneading The manufacturing method of vulcanized rubber of description. Claim 1 process for producing a vulcanized rubber in the second one by the method described, and the resulting vulcanized rubber des steel step of coating the cord manufacturing method of a belt for a tire comprising a. Method of manufacturing a carcass for a tire comprising the steps of coating the mosquitoes carcass fiber cord in claim 1 process for producing a vulcanized rubber method according to any one of 2 and the resulting vulcanized rubber. A step of producing a vulcanized rubber by the method according to any one of claims 1 to 2 , and a tire sidewall including the obtained vulcanized rubber, a tire inner liner, a tire cap tread, or a tire undertread . A method for manufacturing a sidewall for a tire, an inner liner for a tire, a cap tread for a tire, or an under tread for a tire, comprising a manufacturing step . A manufacturing method of a tire provided with the process of manufacturing a vulcanized rubber by the method according to any one of claims 1 and 2 , and the process of manufacturing the tire containing the obtained vulcanized rubber.