WO2012002521A1 - Procédé de production de composition de caoutchouc vulcanisé - Google Patents

Procédé de production de composition de caoutchouc vulcanisé Download PDF

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WO2012002521A1
WO2012002521A1 PCT/JP2011/065136 JP2011065136W WO2012002521A1 WO 2012002521 A1 WO2012002521 A1 WO 2012002521A1 JP 2011065136 W JP2011065136 W JP 2011065136W WO 2012002521 A1 WO2012002521 A1 WO 2012002521A1
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kneading
rubber
temperature
weight
kneading step
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PCT/JP2011/065136
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English (en)
Japanese (ja)
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泰生 上北
竹内　謙一
太田　義輝
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住友化学株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives

Definitions

  • the present invention relates to a method for producing a vulcanized rubber composition.
  • Rubber compositions are used in various fields, and in particular as raw materials for automobile tires.
  • a tire raw material a rubber composition containing various components in addition to rubber components such as natural rubber and synthetic rubber is used.
  • the component other than the rubber component include a filler such as carbon black, a sulfur component necessary for vulcanization, and a vulcanization accelerator for promoting vulcanization.
  • various substances are blended to impart predetermined characteristics to the rubber component.
  • Japanese Patent Publication No. 5-15173 discloses the use of 6-aminohexylthiosulfuric acid S-ester as a substance that promotes adhesion between rubber and metal.
  • the present invention ⁇ 1> A method for producing a vulcanized rubber composition
  • a rubber component a filler, a metal salt of S- (3-aminopropyl) thiosulfuric acid, a sulfur component and a vulcanization accelerator
  • the rubber component, filler, and S- (3-aminopropyl) thio are used under the temperature rising conditions in which the temperature at the start is 40 ° C. or higher and 100 ° C. or lower and the temperature at the end is 110 ° C. or higher and 155 ° C. or lower.
  • kneading is performed under a temperature rising condition in which the temperature at the start is 80 ° C. or more and 100 ° C.
  • the weight of the metal salt of S- (3-aminopropyl) thiosulfuric acid relative to 100 parts by weight of the rubber component is 0.05 part by weight or more and 2.5 parts by weight or less, according to ⁇ 1> or ⁇ 2>. The manufacturing method of this is provided.
  • the present invention is a method for producing a vulcanized rubber composition
  • a rubber component a filler, a metal salt of S- (3-aminopropyl) thiosulfuric acid, a sulfur component and a vulcanization accelerator
  • the rubber component, filler, and S- (3-aminopropyl) thio are used under the temperature rising conditions in which the temperature at the start is 40 ° C. or higher and 100 ° C. or lower and the temperature at the end is 110 ° C. or higher and 155 ° C. or lower.
  • Rubber components include natural rubber, epoxidized natural rubber, deproteinized natural rubber and other modified natural rubber, as well as styrene / butadiene copolymer rubber (SBR), polybutadiene rubber (BR), polyisoprene rubber (IR), acrylonitrile.
  • SBR styrene / butadiene copolymer rubber
  • BR polybutadiene rubber
  • IR polyisoprene rubber
  • IR acrylonitrile
  • NBR butadiene copolymer rubber
  • IIR isoprene / isobutylene copolymer rubber
  • EPDM ethylene / propylene-diene copolymer rubber
  • HR halogenated butyl rubber
  • highly unsaturated rubbers such as natural rubber, styrene / butadiene copolymer rubber and polybutadiene rubber are preferably used, and natural rubber is more preferable. It is also effective to use a combination of several rubber components such as a combination of natural rubber and styrene / butadiene copolymer rubber, or a combination of natural rubber and polybutadiene rubber.
  • natural rubber include natural rubber of grades such as RSS # 1, RSS # 3, TSR20, SIR20, and SMR20.
  • the epoxidized natural rubber those having an epoxidation degree of 10 to 60 mol% are preferable, and examples thereof include ENR25 and ENR50 manufactured by Kumphuran Guthrie.
  • the deproteinized natural rubber a deproteinized natural rubber having a total nitrogen content of 0.3% by weight or less is preferable.
  • a modified natural rubber a modified rubber containing 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 preferred.
  • Specific 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.
  • solution-polymerized SBR is preferably used as the rubber component of the tread rubber composition.
  • Solution polymerized SBR modified with 4,4′-bis- (dialkylamino) benzophenone such as “Nippol (registered trademark) NS116” manufactured by Nippon Zeon Co., Ltd., tin halide compound such as “SL574” manufactured by JSR Solution-polymerized SBR with modified molecular terminals using Asahi Kasei, commercially available silane-modified solution-polymerized SBR such as “E10” and “E15”, lactam compounds, amide compounds, urea compounds, N, N-dialkylacrylamides A compound, an isocyanate compound, an imide compound, a silane compound having an alkoxy group (trialkoxysilane compound, etc.) and an aminosilane compound, or a silane compound having a tin compound and an alkoxy group, an alkylacrylamide compound And silane compounds having alkoxy groups
  • Specific 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%. preferable.
  • Tin modified BR such as “Nipol (registered trademark) BR1250H” manufactured by Nippon Zeon, 4,4′-bis- (dialkylamino) benzophenone, tin halide compound, lactam compound, amide compound, urea compound, N, N— Dialkylacrylamide compound, isocyanate compound, imide compound, silane compound having alkoxy group (trialkoxysilane compound etc.) and aminosilane compound, or silane compound having tin compound and alkoxy group, alkyl
  • Two or more of the above-mentioned different compounds such as an acrylamide compound and an alkoxy group-containing silane compound are used to modify the molecular ends, respectively, and at any one of nitrogen, tin and silicon at the molecular ends, or Have these multiple elements Particularly preferred is solution polymerized BR.
  • BRs are preferable as a rubber component of a rubber composition for treads and a rubber composition for sidewalls, and are usually blended with SBR and / or natural rubber.
  • 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.
  • the SBR and / or natural rubber is preferably 10 to 70% by weight and the BR is 90 to 30% by weight with respect to the total rubber weight, and the natural rubber is 40 to 60% by weight and BR 60 to 40% by weight with respect to the total rubber weight.
  • % Blend is more preferred.
  • the filler is used in the pre-kneading step A.
  • the filler include fillers such as carbon black, silica, talc, clay, aluminum hydroxide, and titanium oxide that are usually used in the rubber field. Carbon black and silica are preferable, and carbon black is more preferable. Specific examples of carbon black include those described on page 494 of the “Guide to Rubber Industry ⁇ Fourth Edition>” edited by the Japan Rubber Association.
  • HAF High Abrasion Furnace
  • SAF Super Abrasion Furnace
  • ISAF Intermediate SAF
  • FEF Fluor Extraction Furnace
  • MAF MAF
  • GPF General FurSurFurS
  • a CTAB Cosmetic Tri-methyl Ammonium Bromide
  • a nitrogen adsorption specific surface area is 20 to 200 m 2 / g
  • particles Carbon black having a diameter of 10 to 50 nm is preferably used, the CTAB surface area is 70 to 180 m 2 / g, the nitrogen adsorption specific surface area is 20 to 200 m 2 / g, and the particle diameter is 10 to 50 nm. Carbon black is more preferred.
  • 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. It is also effective to use a combination of several kinds of fillers such as a combination of carbon black and silica.
  • carbon black alone or both carbon black and silica In the rubber composition for carcass or 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. Specific examples thereof are as per ASTM standards.
  • the amount of the filler used is preferably in the range of 5 to 100 parts by weight per 100 parts by weight of the rubber component.
  • the amount used is more preferably in the range of 30 to 80 parts by weight, and when used in combination with silica in a tread member application, the amount used is 5 to 50.
  • a range of parts by weight is more preferred.
  • the silica include silica having a CTAB surface area of 50 to 180 m 2 / g or a nitrogen adsorption specific surface area of 50 to 300 m 2 / g.
  • 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 blend a silicon-containing organic silicon compound, silica surface-treated with an alcohol such as ethanol or polyethylene glycol, silica having two or more different nitrogen adsorption specific surface areas, and the like.
  • Silica is preferably used in the rubber composition for treads for passenger cars, and the amount used is preferably in the range of 10 to 120 parts by weight per 100 parts by weight of the rubber component.
  • silica When silica is blended, it is preferable to further blend 5 to 50 parts by weight of carbon black, and the blending ratio of silica / carbon black is particularly preferably 0.7 / 1 to 1 / 0.1.
  • silica When silica is used as the filler, bis (3-triethoxysilylpropyl) tetrasulfide (“Si-69” manufactured by Degussa), bis (3-triethoxysilylpropyl) disulfide (“Si-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,
  • These compounds are preferably blended with the rubber component at the same time as the silica, and the blending amount is preferably 2 to 10% by weight, more preferably 7 to 9% by weight, based on silica.
  • the blending temperature when blending these compounds is preferably 80 to 200 ° C, more preferably 110 to 180 ° C.
  • silica 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, ethylene glycol, Diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, pentaerythritol, polyether polyols and other dihydric or higher alcohols, N-alkylamines, amino acids, liquid polybutadienes whose molecular ends are carboxyl-modified or amine-modified, etc. Is also preferable.
  • monohydric alcohol such as ethanol, butanol, octanol
  • ethylene glycol Diethylene glycol, triethylene glycol
  • polyethylene glycol polypropylene glycol
  • pentaerythritol polyether polyols and other dihydric or higher alcohols
  • Examples of 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.
  • Metal salt of S- (3-aminopropyl) thiosulfuric acid is represented by the following formula (1) (H 2 N— (CH 2 ) 3 —SSO 3 ⁇ ) n ⁇ M n + (1) (In the formula, M n + represents a metal ion, and n represents its valence.) It is a compound shown by these.
  • the metal ion represented by M n + is preferably a lithium ion, sodium ion, potassium ion, cesium ion, cobalt ion, copper ion or zinc ion, and more preferably a lithium ion, sodium ion or potassium ion.
  • n represents a valence of a metal ion, and is not limited as long as the valence can be possessed by the metal ion.
  • n is 1 in the case of alkali metal ions such as lithium ion, sodium ion, potassium ion, and cesium ion
  • n is 2 or 3 in the case of cobalt ion
  • n is 1 in the case of copper ion.
  • the weight of the metal salt of S- (3-aminopropyl) thiosulfuric acid used is preferably 0.05 parts by weight or more and 2.5 parts by weight or less with respect to 100 parts by weight of the rubber component.
  • the use weight of the metal salt of S- (3-aminopropyl) thiosulfuric acid is more preferably 0.5 parts by weight or more and 1.0 part by weight or less with respect to 100 parts by weight of the rubber component.
  • the temperature of the rubber component at the start of blending is 40 ° C. or more and 100 ° C. or less, and the temperature of the rubber component at the end of blending is 110 ° C. It is 155 degreeC or more.
  • the median diameter of the metal salt of S- (3-aminopropyl) thiosulfuric acid is preferably 0.05 to 100 ⁇ m, more preferably 1 to 100 ⁇ m. Such median diameter can be measured by a laser diffraction method.
  • a metal salt of S- (3-aminopropyl) thiosulfuric acid is a method of reacting 3-halopropylamine and sodium thiosulfate; a compound obtained by reacting potassium phthalimide with 1,3-dihalopropane Can be produced by any known method such as a method of reacting sodium thiosulfate and then hydrolyzing the obtained compound.
  • the metal salt of S- (3-aminopropyl) thiosulfuric acid thus produced can be isolated by operations such as concentration and crystallization, and the isolated S- (3-aminopropyl) thiosulfuric acid is isolated.
  • the metal salt usually contains about 0.1% to 5% of water.
  • the metal salt of S- (3-aminopropyl) thiosulfuric acid can be previously blended with a support agent.
  • a carrier include the above-mentioned fillers and “inorganic fillers and reinforcing agents” described on pages 510 to 513 of “Rubber Industry Handbook ⁇ Fourth Edition>” edited by the Japan Rubber Association. Of these, carbon black, silica, calcined clay and aluminum hydroxide are preferred.
  • the amount of the carrier used is preferably in the range of 10 to 1000 parts by weight per 100 parts by weight of the metal salt of S- (3-aminopropyl) thiosulfuric acid.
  • the amount of zinc oxide used is preferably in the range of 1 to 15 parts by weight, more preferably in the range of 3 to 8 parts by weight per 100 parts by weight of the rubber component. .
  • An agent (viscoelasticity improving agent) for improving the viscoelastic properties conventionally used in the rubber field can be blended and kneaded in the pre-kneading step A. What is necessary is just to add a viscoelasticity improving agent as needed.
  • the viscoelasticity improver can be blended and kneaded in the post-kneading step B.
  • the viscoelasticity improver can be blended and kneaded in both the pre-kneading step A and the post-kneading step B.
  • examples of the viscoelasticity improver 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)” manufactured by Taoka Chemical Co., Ltd.
  • alkylphenol / sulfur chloride condensates described in JP 2009-138148 A such as“ Waltac 2, 3, 4, 5, 7, 710 ”manufactured by Penwald, etc., bis (3-tri Ethoxysilylpropyl) tetrasulfide (“De-Gussa“ Si-69 ”), bis (3-triethoxysilylpropyl) disulfide (Degussa“ Si-75 "), bis (3-diethoxymethylsilylpropyl) tetrasulfide, bis (3-diethoxymethylsilylpropyl) disulfide, octanethioic acid S- [3- (triethoxysilyl) propyl] ester, octanethioic acid S -[3- ⁇ (2-methyl-1,3-propanedialkoxy) ethoxysilyl ⁇ propyl] ester and octanethioic acid S-
  • 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-biscitraconimidomethylbenzene ( Such as “Parka Link 900” manufactured by Flexis Co., Ltd., “Tacchiroll (registered trademark) AP, V-200” manufactured by Taoka Chemical, etc.
  • the use weight of the viscoelasticity improver is preferably in the range of 0.1 to 10 parts by weight per 100 parts by weight of the rubber component. By being in said range, the effect which improves a viscoelastic property can be acquired efficiently. Subsequently, each component used in the post-kneading step B will be described.
  • Sulfur component The sulfur component is used in the post-kneading step B.
  • Sulfur components include powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur and highly dispersible sulfur. 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 sulfur component does not include a metal salt of S- (3-aminopropyl) thiosulfuric acid and a vulcanization accelerator.
  • the use amount of the sulfur component is preferably in the range of 0.3 to 10 parts by weight, and in the range of 0.5 to 5 parts by weight per 100 parts by weight of the rubber component. It is more preferable. By being in the above range, vulcanization can be performed efficiently.
  • Vulcanization accelerator examples include thiazole-based vulcanization accelerators and sulfenes described on pages 412 to 413 of the Rubber Industry Handbook ⁇ Fourth Edition> (issued by the Japan Rubber Association on January 20, 1994).
  • Examples thereof include amide type vulcanization accelerators and guanidine type vulcanization accelerators.
  • CBS N-cyclohexyl-2-benzothiazolylsulfenamide
  • BSS N-tert-butyl-2-benzothiazolylsulfenamide
  • DPG diphenylguanidine
  • morpholine disulfide which is a known vulcanizing agent, can be used.
  • N-cyclohexyl-2-benzothiazolylsulfenamide CBS
  • N-tert-butyl-2-benzothiazolylsulfenamide BSS
  • N, N-dicyclohexyl -2-Benzothiazolylsulfenamide DCBS
  • MBTS dibenzothiazyl disulfide
  • DPG diphenylguanidine
  • the vulcanization accelerator does not include S- (3-aminopropyl) thiosulfuric acid and its metal salt.
  • the used weight of the vulcanization accelerator is usually 0.1 parts by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the rubber component, and 0.3 parts by weight or more with respect to 100 parts by weight of the rubber component.
  • the amount is preferably 3 parts by weight or less.
  • [Other ingredients] in the pre-kneading step A and / or the post-kneading step B, various compounding agents that can be blended in addition to the components described above are shown below.
  • Such compounding agents include anti-aging agents; oils; fatty acids such as stearic acid; Coumarone resin NG4 (softening point 81 to 100 ° C.) of Nippon Steel Chemical Co., Ltd., process resin AC5 (Kobe Oil Chemical Co., Ltd.) Coumarone-indene resin such as terpene resin, terpene / phenol resin, aromatic modified terpene resin, etc .; Mitsubishi Gas Chemical Co., Ltd.
  • Nekanol (registered trademark) A70 softening point 70 ⁇ Rosin derivatives such as 90 ° C.
  • hydrogenated rosin derivatives novolac alkylphenol resins; resole alkylphenol resins; C5 petroleum resins; and liquid polybutadiene.
  • the oil include process oil and vegetable oil.
  • the process oil include paraffinic process oil, naphthenic process oil, and aromatic process oil.
  • the anti-aging agent include those described in pages 436 to 443 of “Rubber Industry Handbook ⁇ Fourth Edition>” edited by the Japan Rubber Association.
  • N-phenyl-N′-1,3-dimethylbutyl-p-phenylenediamine (6PPD), reaction product of aniline and acetone (TMDQ), poly (2,2,4-trimethyl-1,2) -) Dihydroquinoline (“Antioxidant FR” manufactured by Matsubara Sangyo Co., Ltd.), synthetic wax (paraffin wax, etc.) and vegetable wax are preferred.
  • a peptizer and a retarder may be blended and kneaded, and various general rubber chemicals and softeners may be blended and kneaded as necessary.
  • Retarders include phthalic anhydride, benzoic acid, salicylic acid, N-nitrosodiphenylamine, N- (cyclohexylthio) -phthalimide (CTP), sulfonamide derivatives, diphenylurea and bis (tridecyl) pentaerythritol-diphosphite.
  • CTP Cyclohexylthio) -phthalimide
  • the retarder may be blended and kneaded in the pre-kneading step A, but is preferably blended and kneaded in the post-kneading step B.
  • the amount of the retarder used is preferably in the range of 0.01 to 1 part by weight, more preferably in the range of 0.05 to 0.5 part by weight, per 100 parts by weight of the rubber component.
  • [Combination of each component] According to the production method of the present invention, by blending and kneading predetermined components in the pre-kneading step A and the post-kneading step B, respectively, and by heat-treating the kneaded product B obtained in the post-kneading step B in the heat treatment step C, Vulcanized rubber compositions that can be used for various applications can be obtained.
  • the rubber component is natural rubber alone or a blend with SBR and / or BR containing natural rubber as a main component. Is preferred.
  • the filler carbon black alone or a blend with carbon black containing silica as a main component is preferably used.
  • 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-biscitraconimidomethylbenzene (“Parkalink 900” manufactured by Flexis), Taoka Viscoelasticity of alkylphenol / sulfur chloride condensates such as chemical “Tacchirol (registered trademark) AP, V-
  • the rubber component may be a solution-polymerized SBR having a molecular terminal modified with a silicon compound alone, or a non-modified, mainly composed of the terminal-modified solution-polymerized SBR.
  • a blend with at least one rubber selected from the group consisting of solution polymerization SBR, emulsion polymerization SBR, natural rubber and BR is preferred.
  • the filler a blend with carbon black mainly composed of silica is preferably used.
  • 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 (“KA91884” manufactured by Bayer AG), hexamethylenebisthiosulfate disodium salt dihydrate, 1,3-biscitraconimidomethylbenzene (“PARKALINK 900” manufactured by Flexis), Taoka Chemical Viscoelasticity of alkylphenol / sulfur chloride condensates such as “Tacchiroll (registered trademark) AP
  • the rubber component is a blend of at least one rubber selected from the group consisting of non-modified solution-polymerized SBR, emulsion-polymerized SBR, and natural rubber containing BR as a main component.
  • the filler carbon black alone or a blend with silica containing carbon black as a main component is preferably used.
  • 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-biscitraconimidomethylbenzene (“Parkalink 900” manufactured by Flexis), Taoka Viscoelasticity of alkylphenol / sulfur chloride condensates such as chemical “Tacchirol (registered trademark) AP, V-
  • the rubber component is preferably natural rubber alone or a blend with BR containing natural rubber as a main component.
  • the filler carbon black alone or a blend with silica containing carbon black as a main component is preferably used.
  • 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-biscitraconimidomethylbenzene (“Parkalink 900” manufactured by Flexis), Taoka Viscoelasticity of alkylphenol / sulfur chloride condensates such as chemical “Tacchirol (registered trademark) AP, V-
  • Pre-kneading step A In the pre-kneading step A, the temperature at the start is 40 ° C. or higher and 100 ° C. or lower, and the temperature at the end is 110 ° C. or higher and 155 ° C. or lower. This is a step of kneading a metal salt of 3-aminopropyl) thiosulfuric acid, and kneaded material A is obtained.
  • the order of blending the rubber component, the filler and the metal salt of S- (3-aminopropyl) thiosulfuric acid is not limited, but for ease of blending, the rubber component is blended with the filler and S- (3-aminopropyl) thio.
  • the order of blending with the metal salt of sulfuric acid is preferred.
  • An example of an apparatus for kneading each component is a Banbury mixer. The number of rotations of the mixer during kneading varies depending on the type of rubber component used and the desired molecular weight, but is generally 10 rpm or more and 100 rpm or less.
  • mixes on the said temperature rising conditions is generally 3 minutes or more and 20 minutes or less.
  • Each component such as a rubber component is heated (or maintained at a predetermined temperature) by heat generated by kneading.
  • a rubber component, a filler, and a metal salt of S- (3-aminopropyl) thiosulfuric acid are blended, and kneading is performed under a temperature rising condition in which the temperature is raised from the starting temperature to the ending temperature. Is called.
  • the temperature at the start is 40 ° C. or more and 100 ° C. or less, and the temperature at the end is 110 ° C. or more and 155 ° C. or less.
  • the temperature at the start and the temperature at the end are specifically the temperatures of the rubber components to be kneaded.
  • the temperature at the start is the temperature of the rubber component when heating the rubber component, the filler, and the metal salt of S- (3-aminopropyl) thiosulfuric acid by the heating member.
  • the temperature at the end is the temperature of the kneaded material A when the kneading of the rubber component, the filler, and the metal salt of S- (3-aminopropyl) thiosulfuric acid is finished.
  • the temperature increase from the temperature at the start to the temperature at the end may be performed gradually as the kneading proceeds, or may be performed step by step at a predetermined temperature, for example, 5 ° C.
  • the kneaded material A is obtained by the kneading in the pre-kneading step A.
  • kneading is started under conditions where the starting temperature is 40 ° C. or higher and 100 ° C. or lower.
  • the energy required for kneading can be reduced.
  • the load on a manufacturing apparatus such as a mixer can be reduced. This has the effect of extending the life of the manufacturing apparatus.
  • a metal salt of S- (3-aminopropyl) thiosulfuric acid is used for kneading.
  • the viscoelastic properties of the finally obtained vulcanized rubber composition can be improved even when kneading at a low temperature.
  • the production method of the present invention can be carried out with low energy, can improve the viscoelastic properties of the vulcanized rubber composition, and is very useful.
  • the kneading start temperature is 80 ° C. or higher and 100 ° C. or lower, and the temperature at the end is 135 ° C.
  • the pre-kneading step A may include a step of kneading the rubber component as a pre-stage of kneading. The molecular chain of natural rubber is cut by mastication, which facilitates the processing of natural rubber.
  • the post-kneading step B is a step of kneading the kneaded product A obtained in the pre-kneading step A, the sulfur component, and the vulcanization accelerator, and the kneaded product B is obtained.
  • the post-kneading step B is preferably performed immediately after the kneading in the pre-kneading step A is completed.
  • An apparatus for kneading each component includes an open mixer and a Banbury mixer.
  • the mixer temperature condition in the post-kneading step B is preferably 60 ° C. or higher and 120 ° C. or lower.
  • the kneading time in the post-kneading step B may be appropriately set according to the type of each component such as a rubber component, but is usually 0.5 minutes or more and 10 minutes or less.
  • the kneaded product B is obtained by further kneading.
  • the production method of the present invention may include a processing step b for processing the kneaded product B obtained in the post-kneading step B into a specific state between the post-kneading step B and the heat treatment step C.
  • a pre-formed body is obtained by the processing step b, and the pre-formed body becomes a formed body by heat treatment in the heat treatment step C described later.
  • “Processing kneaded product B into a specific state” means, for example, in the field of tires, “step of coating kneaded product B on steel cord”, “step of coating kneaded product B on carcass fiber cord” , “A step of processing the kneaded material B into the shape of a tread member” and the like.
  • processing shall include the process of shape
  • Each member such as a belt, a carcass, an inner liner, a sidewall, and a tread (cap tread or under tread) obtained by these steps is usually combined with other members by a method that is usually performed in the field of tires.
  • a step of incorporating the kneaded material B into the tire a state of a green tire including the kneaded material B is obtained.
  • the heat treatment step C is performed after the post-kneading step B or the processing step b.
  • the kneaded product B obtained in the post-kneading step B or the pre-molded product obtained in the processing step b is subjected to the heat treatment in the heat treatment step C.
  • Such heat treatment is usually performed at normal pressure or under pressure.
  • the temperature condition in the heat treatment in the heat treatment step C is preferably 120 ° C. or higher and 180 ° C. or lower. If the temperature is lower than 120 ° C, the vulcanization speed may be slow, and it may be difficult to determine the degree of vulcanization. If the temperature exceeds 180 ° C, the vulcanization speed may be high, and the vulcanization speed may be difficult to control. There is.
  • a suitable heating time (vulcanization time) in the heat treatment varies depending on the specific composition of the rubber composition. By the heat treatment, a vulcanized rubber composition can be obtained from the kneaded product B obtained in the post-kneading step B.
  • a molded body is obtained from the pre-molded body.
  • the apparatus used for the heat treatment in the heat treatment step C include a vulcanizer, a vulcanization press, and a pressure press.
  • a pneumatic tire can be produced by an ordinary method. That is, the rubber composition in the stage before the heat treatment step C is extruded into a tread member, and 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.
  • Physical properties of vulcanized rubber composition The viscoelastic properties of the vulcanized rubber composition are shown below.
  • the viscoelastic properties of the vulcanized rubber composition are determined from the loss coefficient (tan ⁇ ) calculated by changing the temperature and frequency conditions.
  • the loss factor at 60 ° C. which is a measure of rolling resistance
  • the loss factor at 0 ° C. is a measure of grip strength on wet roads Is large
  • the braking performance of the automobile is good (page 124 of Non-Patent Document 1).
  • the present invention will be described more specifically based on examples and comparative examples, but the present invention is not limited to these.
  • the viscoelastic properties of the rubber compositions in Examples and Comparative Examples were evaluated by the following methods.
  • [Viscoelastic properties] Using a viscoelasticity analyzer manufactured by Ueshima Seisakusho Co., Ltd., the viscoelastic properties of the rubber composition were measured under the following measurement conditions. Measurement conditions: temperature -5 ° C to 80 ° C (temperature increase rate: 2 ° C / min), initial strain 10%, dynamic strain 2.5%, frequency 10 Hz
  • Tables 1 and 2 show loss factors (loss tangents) tan ⁇ at 0 ° C., 20 ° C., 40 ° C. and 60 ° C. of the vulcanized rubber compositions obtained in Examples and Comparative Examples.
  • the obtained sodium salt of S- (3-aminopropyl) thiosulfuric acid was pulverized so that the median diameter (50% D) was 14.6 ⁇ m and used in Example 1.
  • ⁇ Measurement operation> A mixed solution of the obtained sodium salt of S- (3-aminopropyl) thiosulfuric acid at room temperature with a dispersion solvent (toluene) and a dispersant (10% by weight sodium di-2-ethylhexyl sulfosuccinate / toluene solution) Dispersed in. While irradiating the obtained dispersion with ultrasonic waves, the dispersion was stirred for 5 minutes to obtain a test solution.
  • test solution was transferred to a batch cell and measured after 1 minute (refractive index: 1.70-0.20i).
  • the pH of an aqueous solution obtained by dissolving 10.0 g of sodium salt of S- (3-aminopropyl) thiosulfuric acid in 30 mL of water was 11-12.
  • kneaded product A The temperature of the heating member at the end of kneading was 120 ° C. The temperature of the kneaded product during kneading was 180 to 200 ° C. Further, the obtained kneaded material A was passed through an open roll having a set temperature of 50 to 60 ° C. and processed into a sheet shape.
  • the kneaded product A obtained by the pre-kneading step A 2 parts by weight of sulfur, and a vulcanization accelerator (N-cyclohexyl-2-benzothiazolesulfene) Amide (CBS) 1 part by weight and anti-aging agent (N-phenyl-N′-1,3-dimethylbutyl-p-phenylenediamine: trade name “Antigen (registered trademark) 6C” manufactured by Sumitomo Chemical Co., Ltd.) 1 A part by weight was blended and kneaded to obtain a kneaded product B. Furthermore, the kneaded material B was processed into a 2.0 mm sheet.
  • a vulcanization accelerator N-cyclohexyl-2-benzothiazolesulfene
  • anti-aging agent N-phenyl-N′-1,3-dimethylbutyl-p-phenylenediamine: trade name “Antigen (registered trademark) 6C” manufactured by Sumi
  • the sheet-like kneaded product B was aged overnight (approximately 12 hours).
  • ⁇ Heat treatment step C> Using a vulcanizing press, the kneaded product B obtained in the post-kneading step B was vulcanized at 1145 minutes at 145 ° C. to obtain a vulcanized rubber composition. The viscoelastic properties of the obtained vulcanized rubber composition were measured. The results are shown in Tables 1 and 2.
  • Example 1 In Example 1, except that the temperature at the start of kneading in the pre-kneading step A was 40 ° C., the temperature at the end was 112 ° C., and the sodium salt of S- (3-aminopropyl) thiosulfuric acid was not blended. Kneading was performed in the same manner as in Example 1 to obtain a vulcanized rubber composition. In the same manner as in Example 1, the viscoelastic properties of the obtained vulcanized rubber composition were measured. The results are shown in Tables 1 and 2.
  • Example 1 except that the temperature at the start of kneading in the pre-kneading step A was 60 ° C., the temperature at the end was 136 ° C., and the vulcanization time of the kneaded product B in the heat treatment step C was 16.0 minutes. Kneading was performed in the same manner as in Example 1 to obtain a vulcanized rubber composition. In the same manner as in Example 1, the viscoelastic properties of the obtained vulcanized rubber composition were measured. The results are shown in Tables 1 and 2.
  • Example 2 In Example 1, the temperature at the start of kneading in the pre-kneading step A is 60 ° C., the temperature at the end is 135 ° C., and the sodium salt of S- (3-aminopropyl) thiosulfuric acid is not blended, and the heat treatment step C A vulcanized rubber composition was obtained by kneading in the same manner as in Example 1 except that the vulcanization time of the kneaded product B was 17.5 minutes. In the same manner as in Example 1, the viscoelastic properties of the obtained vulcanized rubber composition were measured. The results are shown in Tables 1 and 2.
  • Example 1 except that the temperature at the start of kneading in the pre-kneading step A was 80 ° C., the temperature at the end was 142 ° C., and the vulcanization time of the kneaded product B in the heat treatment step C was 15.0 minutes, Kneading was performed in the same manner as in Example 1 to obtain a vulcanized rubber composition. In the same manner as in Example 1, the viscoelastic properties of the obtained vulcanized rubber composition were measured. The results are shown in Tables 1 and 2.
  • Example 3 In Example 1, the temperature at the start of kneading in the pre-kneading step A is 80 ° C., the temperature at the end is 137 ° C., and the sodium salt of S- (3-aminopropyl) thiosulfuric acid is not blended.
  • the vulcanized rubber composition was obtained by kneading in the same manner as in Example 1 except that the vulcanization time of the kneaded product B was 16.0 minutes. In the same manner as in Example 1, the viscoelastic properties of the obtained vulcanized rubber composition were measured. The results are shown in Tables 1 and 2.
  • Example 1 kneading was carried out in the same manner as in Example 1 except that the temperature at the start of kneading in the pre-kneading step A was 100 ° C. and the temperature at the end was 154 ° C. to obtain a vulcanized rubber composition. .
  • the viscoelastic properties of the obtained vulcanized rubber composition were measured. The results are shown in Tables 1 and 2.
  • Example 4 In Example 1, the temperature at the start of kneading in the pre-kneading step A is 100 ° C., the temperature at the end is 153 ° C., and the sodium salt of S- (3-aminopropyl) thiosulfuric acid is not blended, and the heat treatment step C A vulcanized rubber composition was obtained by kneading in the same manner as in Example 1 except that the vulcanization time of the kneaded product B was 17.5 minutes. In the same manner as in Example 1, the viscoelastic properties of the obtained vulcanized rubber composition were measured. The results are shown in Tables 1 and 2.
  • the tan ⁇ of Example 3 is 77.3% of tan ⁇ of Comparative Example 3, and the tan ⁇ of Example 4 is 85.7% of tan ⁇ of Comparative Example 4. That is, according to the production method of the present invention, the metal salt of S- (3-aminopropyl) thiosulfuric acid is used even when the pre-kneading step A is kneaded under conditions where the temperature at the start and end of kneading is low. Tan ⁇ at 60 ° C. of the obtained vulcanized rubber composition can be improved by the effect of blending. On the other hand, in Examples 1 to 4, tan ⁇ at 0 ° C. is larger than tan ⁇ at 20 ° C.
  • tan ⁇ at 0 ° C. of the vulcanized rubber composition of Example 1 is 203.2% of tan ⁇ at 80 ° C.
  • the tan ⁇ at 0 ° C. of the vulcanized rubber composition obtained by the production method of the present invention is also a good value, and when the vulcanized rubber composition is used as an automobile tire raw material, the braking performance of the automobile is improved. Can be improved.
  • the vulcanized rubber composition obtained by the production method of the present invention has improved viscoelastic properties. As shown in Examples 3 and 4, when the temperature at the start of kneading in the pre-kneading step A is 80 ° C.
  • the tan ⁇ at 60 ° C. was 77.3% and 85.7% of tan ⁇ of Comparative Examples 3 and 4, respectively, and it can be seen that tan ⁇ at 60 ° C. was further reduced. That is, the fuel efficiency improvement effect of the automobile can be further increased.
  • the present invention it is possible to provide a vulcanized rubber composition having low energy and improved viscoelastic properties. Therefore, the present invention can be used in the field of using a rubber composition, particularly in the field of tires.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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Abstract

L'invention concerne un procédé de production d'une composition de caoutchouc vulcanisé comprenant un ingrédient caoutchouc, une charge, un sel métallique d'acide S-(3-aminopropyl)thiosulfurique, un ingrédient soufre et un accélérateur de vulcanisation. Le procédé se caractérise en ce qu'il comprend une étape de pré-malaxage (A) dans laquelle un ingrédient caoutchouc, une charge et un sel métallique d'acide S-(3-aminopropyl)thiosulfurique sont malaxés dans des conditions de chauffe présentant une température initiale de 40-100°C et une température finale de 110-155°C; une étape de post-malaxage (B) dans laquelle le mélange (A) obtenu dans l'étape de pré-malaxage (A), un ingrédient soufre et un accélérateur de vulcanisation sont malaxés; et une étape de traitement thermique (C) dans laquelle le mélange (B) obtenu dans l'étape de post-malaxage (B) est traité thermiquement de manière qu'un caoutchouc vulcanisé soit obtenu.
PCT/JP2011/065136 2010-06-30 2011-06-24 Procédé de production de composition de caoutchouc vulcanisé WO2012002521A1 (fr)

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WO2013115403A1 (fr) * 2012-02-03 2013-08-08 住友化学株式会社 Procédé de production de caoutchouc vulcanisé
JP2014005381A (ja) * 2012-06-25 2014-01-16 Bridgestone Corp ゴム組成物の製造方法
JP2014031447A (ja) * 2012-08-03 2014-02-20 Sumitomo Rubber Ind Ltd タイヤ用ゴム組成物及び空気入りタイヤ
US20230019388A1 (en) * 2019-12-12 2023-01-19 The Yokohama Rubber Co., Ltd. Pneumatic tire

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US20130289183A1 (en) * 2012-04-26 2013-10-31 Michael Lester Kerns Triglyceride containing solution polymerization prepared styrene/butadiene elastomer and tire with component
US10435545B2 (en) 2012-04-26 2019-10-08 The Goodyear Tire & Rubber Company Triglyceride containing solution polymerization prepared styrene/butadiene elastomer and tire with component
JP6029940B2 (ja) 2012-11-07 2016-11-24 東洋ゴム工業株式会社 タイヤ部材及びタイヤの製造方法

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WO2013115403A1 (fr) * 2012-02-03 2013-08-08 住友化学株式会社 Procédé de production de caoutchouc vulcanisé
JP2014005381A (ja) * 2012-06-25 2014-01-16 Bridgestone Corp ゴム組成物の製造方法
JP2014031447A (ja) * 2012-08-03 2014-02-20 Sumitomo Rubber Ind Ltd タイヤ用ゴム組成物及び空気入りタイヤ
US20230019388A1 (en) * 2019-12-12 2023-01-19 The Yokohama Rubber Co., Ltd. Pneumatic tire

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