WO2013151115A1 - Caoutchouc agent anti-vieillissement - Google Patents

Caoutchouc agent anti-vieillissement Download PDF

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Publication number
WO2013151115A1
WO2013151115A1 PCT/JP2013/060269 JP2013060269W WO2013151115A1 WO 2013151115 A1 WO2013151115 A1 WO 2013151115A1 JP 2013060269 W JP2013060269 W JP 2013060269W WO 2013151115 A1 WO2013151115 A1 WO 2013151115A1
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Prior art keywords
rubber
weight
rubber composition
parts
aging
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PCT/JP2013/060269
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English (en)
Japanese (ja)
Inventor
佳余子 阿部
志津香 岩田
進 森
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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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C08L91/02—Vulcanised oils, e.g. factice

Definitions

  • the solid factice is at least one selected from the group consisting of (a) a sulfur factice having an acetone extract of 10 to 50% and (b) a sulfur chloride factice having an acetone extract of 1 to 10%.
  • the migration of the antiaging substance for rubber can be suppressed, and the antiaging effect is sufficiently sustained.
  • Anti-aging agent for rubber is not particularly limited.
  • amine-based anti-aging material amine-ketone-based anti-aging material, phenol-based anti-aging material, imidazole-based anti-aging material, sulfur-based anti-aging material, phosphorus-based anti-aging material.
  • Prevention substances and the like Specifically, those described in pages 436 to 443 of the “Rubber Industry Handbook ⁇ Fourth Edition>” edited by the Japan Rubber Association, reaction products of aniline and acetone (TMDQ), synthetic wax (paraffin) Wax, etc.), vegetable wax and the like.
  • the anti-aging material for rubber is more likely to migrate in the crosslinked rubber composition as the molecular weight is lower, but the present invention can suppress such migration even with such an anti-aging material for rubber having a low molecular weight. Therefore, in the present invention, an antiaging material for rubber having a relatively low molecular weight (for example, a molecular weight of about 150 to 600, particularly a molecular weight of about 150 to 400) can be used.
  • a relatively low molecular weight for example, a molecular weight of about 150 to 600, particularly a molecular weight of about 150 to 400
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 13 carbon atoms.
  • Solid factice Only one type of solid factice may be used, or two or more types may be used in combination.
  • the solid fact refers to a rubbery substance obtained by reacting a fat and oil with a cross-linking agent, and means a solid at 0 to 60 ° C.
  • factice is also called a sub-rubber-substitute as will be described later.
  • the fats and oils include vegetable oils, fish oils, mineral oils (eg, naphthenic mineral oils), synthetic esters, modified alkyd resins, and the like. Among these, vegetable oils are preferred.
  • the solid factis is more preferably (a) a sulfur factice having an acetone extract of 10 to 50% and (b) a chloride having an acetone extract of 1 to 10%. It is at least one selected from the group consisting of sulfur factices.
  • acetone extract (%) is a value calculated as follows: About 0.5 g of the solid factis sample is wrapped in filter paper or placed in a cylindrical filter paper and placed in the siphon cup of the Kunefrel extractor. Moreover, 50 mL of acetone is put into the extraction flask. Extraction is performed while heating. After 15 minutes of preheating, the heating is adjusted so that the acetone in the siphon cup falls about every 3 minutes.
  • the solid factis is more preferably a sulfur factice having an acetone extract of 10 to 50%, and still more preferably a sulfur factice having an acetone extract of 20 to 40%.
  • a solution of a rubber anti-aging substance may be mixed with a solid factice swollen with a dispersion of a solid factis or a solvent.
  • a large amount of a solvent (dispersion medium) is used to prepare a solid factice dispersion.
  • the solid factice swells. These methods differ in that they are only used to the extent.
  • the method (2) (iii) is different from the method (2) (ii) in that a melted antiaging material for rubber is used.
  • the method (2) (iii) is different from the method (1) in that a solvent is used to swell the solid factice.
  • solvent (dispersion medium) of (2) above As the solvent (dispersion medium) of (2) above, (A) the solid factice can be dispersed or swollen; (B) A rubber anti-aging substance can be dissolved, and (c) a substance capable of being distilled off can be used.
  • a solvent (dispersion medium) examples include hydrocarbon solvents such as toluene, xylene, hexane, and heptane, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and alcohol solvents such as methanol, ethanol, and isopropanol. be able to. Any of these solvents (dispersion media) may be used alone or in combination of two or more.
  • (2) (i) and (2) (ii) are preferable and (2) (i) are more preferable from the viewpoint of having no heat of dissolution and maintaining the operating temperature.
  • the methods (1) and (2) (iii) are preferred in that the solvent (dispersion medium) is not used or the amount used is small and the production cost can be suppressed. Is more preferable.
  • This rubber composition is obtained by kneading the rubber anti-aging agent of the present invention and a rubber component.
  • the rubber composition may be produced by kneading the rubber anti-aging agent of the present invention and the total amount of the rubber component scheduled to be used, or a part of the rubber anti-aging agent of the present invention and the expected use amount.
  • a master batch may be first produced by pre-kneading the rubber component, and the master batch and the remaining rubber component may be kneaded.
  • the rubber composition may be a master batch.
  • the content of the rubber anti-aging agent of the present invention in the rubber composition is, for example, 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight, more preferably 2 to 20 parts per 100 parts by weight of the rubber component. Parts by weight.
  • the content of the rubber anti-aging agent of the present invention in the rubber composition is, for example, 11 to 990 parts by weight, preferably 31 to 990 parts by weight with respect to 100 parts by weight of the rubber component. Parts, more preferably 51 to 600 parts by weight, particularly preferably 60 to 500 parts by weight.
  • the rubber anti-aging agent of the present invention may be used alone or in combination of two or more. Similarly, only 1 type may be used for a rubber component and it may use 2 or more types together.
  • the kneading is not particularly limited and can be performed by a known method.
  • the rubber composition may further contain other compounding agents (for example, a filler, zinc oxide, stearic acid, a crosslinking agent, a vulcanization accelerator, etc.). Each compounding agent may be used alone or in combination of two or more.
  • Examples of the natural rubber include grades of natural rubber such as RSS # 1, RSS # 3, TSR20, and SIR20.
  • Examples of the epoxidized natural rubber include those having a degree of epoxidation of 10 to 60 mol% (for example, ENR25, ENR50, etc. manufactured by Kumpoulan Guthrie).
  • Examples of the deproteinized natural rubber include deproteinized natural rubber having a total nitrogen content of 0.3% by weight or less.
  • Other modified natural rubbers are obtained, for example, by reacting natural rubber with 4-vinylpyridine, N, N-dialkylaminoethyl acrylate (for example, N, N-diethylaminoethyl acrylate, etc.), 2-hydroxy acrylate, etc. And modified natural rubber containing a polar group.
  • SBR styrene / butadiene copolymer rubber
  • examples of the styrene / butadiene copolymer rubber (SBR) include emulsion polymerization SBR and solution polymerization SBR described in pages 210 to 211 of the “Rubber Industry Handbook ⁇ Fourth Edition>” edited by the Japan Rubber Association. Can be mentioned.
  • Examples of preferable rubber components of the rubber composition for tread and the rubber composition for sidewall include the following.
  • Examples of the modified solution polymerization SBR include the following.
  • Silane-modified solution polymerization SBR such as “E10” and “E15” manufactured by Asahi Kasei Corporation.
  • More preferable polybutadiene rubber includes, for example, the following.
  • Tin-modified BR such as “Nipol (registered trademark) BR 1250H” manufactured by Nippon Zeon Co., Ltd.
  • Polybutadiene rubber is preferable as the rubber component of the rubber composition for treads and the rubber composition for sidewalls.
  • BR may be blended with SBR and / or natural rubber.
  • the content of SBR and / or natural rubber in the rubber component is, for example, 60 to 100% by weight, and the content of BR is, for example, 40 to 0% by weight.
  • the content of SBR and / or natural rubber in the rubber component is, for example, 10 to 70% by weight, and the content of BR is, for example, 90 to 30% by weight.
  • Examples of carbon black include those described on page 494 of the “Rubber Industry Handbook ⁇ Fourth Edition>” edited by the Japan Rubber Association.
  • HAF High-Abrasion-Furnace
  • SAF Super-Abrasion-Furnace
  • ISAF Intermediate-Surf
  • FEF Fluorescence-Furnace
  • MAF Medium-Abrasion-Furnace
  • GPF General-Purpose-Furnace
  • SRF Carbon black such as Reinforcing (Furnace).
  • carbon black preferably having a CTAB (Cetyl Tri-methyl Ammonium Bromide) specific surface area of 40 to 250 m 2 / g, a nitrogen adsorption specific surface area of 20 to 200 m 2 / g, and a particle diameter of 10 to 50 nm.
  • CTAB Cosmetic Acid Tri-methyl Ammonium Bromide
  • More preferable examples include carbon black having a CTAB specific surface area of 70 to 180 m 2 / g.
  • a combination of carbon black and silica for example, surface-treated carbon black in which 0.1 to 50% by weight of silica is attached to the surface of carbon black can be given as a preferable one.
  • carbon black having a CTAB specific surface area of 20 to 60 m 2 / g and a particle size of 40 to 100 nm is preferred as the filler.
  • N330, N339, N343, N351, N550, N568, N582, N630, N642, N660, N662, N754, N762 and the like can be mentioned.
  • the filler When the filler is used, its content in the rubber composition is not particularly limited, but is, for example, 5 to 100 parts by weight with respect to 100 parts by weight of the rubber component. When only carbon black is used as the filler, its content is preferably 30 to 80 parts by weight with respect to 100 parts by weight of the rubber component. When a combination of carbon black and silica is used as a filler in the tread rubber composition, the carbon black content is preferably 5 to 60 parts by weight with respect to 100 parts by weight of the rubber component. Examples of the blending ratio (weight ratio) of silica / carbon black include a range of 0.7 / 1 to 1 / 0.1.
  • the addition time of the compound capable of binding to silica such as a silane coupling agent is not particularly limited, it is preferably blended with the rubber component simultaneously with silica.
  • the compounding amount (the total amount when two or more are used in combination) is, for example, 2 to 10 parts by weight, preferably 7 to 10 parts by weight with respect to 100 parts by weight of silica. 9 parts by weight.
  • the compounding temperature when compounding the compound capable of binding to silica with the rubber component is, for example, 80 to 200 ° C., preferably 110 to 180 ° C.
  • the polyvalent alcohols such as monohydric alcohols such as ethanol, butanol and octanol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, pentaerythritol and polyether polyol are further used.
  • Alcohol, N-alkylamine, amino acid, liquid polybutadiene having a molecular terminal carboxyl-modified or amine-modified may be blended.
  • its content in the rubber composition is, for example, 1 to 15 parts by weight, preferably 1 to 8 parts by weight with respect to 100 parts by weight of the rubber component.
  • crosslinking agent examples include sulfur, a sulfur-containing compound (for example, morpholine disulfide), a peroxide crosslinking agent (for example, dicumyl peroxide), a metal crosslinking agent (for example, zinc oxide), and an amine crosslinking agent (for example, hexagonal). Methylenediamine), oxime crosslinking agents (for example, p-quinonedioxime, 4,4′-dibenzoylquinonedioxime) and the like. Among them, sulfur is preferable. Examples of sulfur include powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur. Of these, powdered sulfur is preferred.
  • a vulcanization accelerator When performing crosslinking (ie, vulcanization) using sulfur, it is preferable to use a vulcanization accelerator.
  • the vulcanization accelerator include thiazole vulcanization accelerators and sulfenamide vulcanization accelerators described in pages 412 to 413 of “Rubber Industry Handbook ⁇ Fourth Edition>” edited by the Japan Rubber Association. And guanidine vulcanization accelerators.
  • N-cyclohexyl-2-benzothiazole sulfenamide CBS
  • N-tert-butyl-2-benzothiazole sulfenamide BVS
  • N, N-dicyclohexyl-2-benzothiazolesulfenamide (DCBS) or dibenzothiazyl disulfide (MBTS) is preferably used in combination with diphenylguanidine (DPG).
  • various compounding agents usually used in the rubber field may be further blended.
  • Such compounding agents include, for example, oils; fatty acids other than stearic acid; Coumarone resin G-90 (softening point 80 to 100 ° C.) manufactured by Nikko Chemical, and process resin AC8 (softening point) manufactured by Kobe Oil Chemical Co., Ltd.
  • coumarone / indene resin examples include terpene resins such as terpene resin, terpene / phenol resin, and aromatic modified terpene resin; ° C) xylene / formaldehyde resin; rosin derivatives such as “Ester gum” series and “neotol” series manufactured by Arakawa Chemical; hydrogenated rosin derivatives; novolac alkylphenol resins; resole alkylphenol resins; C5 petroleum resins; Liquid polybutadiene; naphthenic acid metal salts such as cobalt naphthenate; resor Down; and the like can be given.
  • the oil examples include process oil and vegetable oil.
  • the process oil include paraffinic process oil, naphthenic process oil, aromatic process oil, and T-DAE oil.
  • the crosslinked rubber composition can be suitably used for tires, for example.
  • the tire include a pneumatic tire and a solid tire.
  • a crosslinked rubber composition can be used in order to manufacture each member which comprises a tire.
  • examples of such members include a tire belt including a steel cord coated with a crosslinked rubber composition, a tire carcass including a carcass fiber cord coated with a crosslinked rubber composition, and a tire including a crosslinked rubber composition.
  • Production Example 7 (Production of rubber anti-aging agent of the present invention) A 300 mL round bottom flask was charged with 2 parts by weight of an anti-aging agent for rubber, and 1.33 parts by weight of Neo N was added. The resulting mixture was stirred at 80 ° C. for 1 hour under nitrogen. This mixture was allowed to cool to obtain a rubber anti-aging agent (7) of the present invention.
  • Production Example 8 (Production of rubber anti-aging agent of the present invention) An anti-aging agent for rubber (8) of the present invention was obtained in the same manner as in Production Example 7 except that 1.33 parts by weight of Neo N was changed to 0.86 parts by weight of Golden T.
  • Test Example 1 Measurement of migration amount of anti-aging agent for rubber
  • the amount of migration of the anti-aging agent for rubber of the crosslinked rubber composition (C2) obtained in Production Example 11 was measured as follows.
  • FIG. 1 is a diagram for explaining a method for measuring the amount of migration of an anti-aging substance for rubber in a crosslinked rubber composition.
  • Production Example 12 (Production of a crosslinked rubber composition containing the rubber anti-aging agent of the present invention) 163.5 parts by weight of the basic rubber composition obtained in Production Example 9, 3 parts by weight of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (BBS)) 0.8 By kneading parts by weight, 1.5 parts by weight of sulfur, and 6 parts by weight of the antiaging agent for rubber (1) of the present invention obtained in Production Example 1 with an open roll machine having a roll set temperature of 60 ° C. A rubber composition was obtained. The obtained rubber composition is heat-press molded at 145 ° C.
  • BSS N-tert-butyl-2-benzothiazolesulfenamide
  • a crosslinked rubber composition containing the antiaging agent for rubber of the present invention in the form of a sheet having a width of 15.5 cm, a length of 16.0 cm and a thickness of 2 mm.
  • a product (1) was obtained. Incidentally, between 90% vulcanization of the measured rubber composition in conformity with JIS K 6300-2 to (t c (90)) than the extended 5 minutes time and the vulcanization time.
  • Test Example 2 Measurement of migration amount of anti-aging agent for rubber
  • the crosslinked rubber composition (C2) was changed to the crosslinked rubber composition (1) obtained in Production Example 12
  • the anti-aging agent for rubber of the crosslinked rubber composition (1) was used.
  • the amount transferred was measured. The results are shown in Table 2 below.
  • Production Example 13 (Production of a crosslinked rubber composition containing the rubber anti-aging agent of the present invention) 163.5 parts by weight of the basic rubber composition obtained in Production Example 9, 3 parts by weight of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (BBS)) 0.8
  • a vulcanization accelerator N-tert-butyl-2-benzothiazolesulfenamide (BBS)
  • BSS N-tert-butyl-2-benzothiazolesulfenamide
  • a crosslinked rubber composition containing the antiaging agent for rubber of the present invention in the form of a sheet having a width of 15.5 cm, a length of 16.0 cm and a thickness of 2 mm.
  • a product (2) was obtained. Incidentally, between 90% vulcanization of the measured rubber composition in conformity with JIS K 6300-2 to (t c (90)) than the extended 5 minutes time and the vulcanization time.
  • Test Example 3 Measurement of migration amount of anti-aging agent for rubber
  • the crosslinked rubber composition (C2) was changed to the crosslinked rubber composition (2) obtained in Production Example 13
  • the anti-aging agent for rubber of the crosslinked rubber composition (2) was used.
  • the amount transferred was measured. The results are shown in Table 2 below.
  • Test Example 4 Measurement of migration amount of anti-aging agent for rubber
  • the crosslinked rubber composition (C2) was changed to the crosslinked rubber composition (3) obtained in Production Example 14
  • the anti-aging agent for rubber of the crosslinked rubber composition (3) was used.
  • the amount transferred was measured. The results are shown in Table 2 below.
  • Production Example 15 (Production of a crosslinked rubber composition containing the rubber anti-aging agent of the present invention) 163.5 parts by weight of the basic rubber composition obtained in Production Example 9, 3 parts by weight of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (BBS)) 0.8
  • a vulcanization accelerator N-tert-butyl-2-benzothiazolesulfenamide (BBS)
  • BSS N-tert-butyl-2-benzothiazolesulfenamide
  • Test Example 5 Measurement of migration amount of anti-aging agent for rubber
  • the crosslinked rubber composition (C2) was changed to the crosslinked rubber composition (4) obtained in Production Example 15
  • the anti-aging agent for rubber of the crosslinked rubber composition (4) was used.
  • the amount transferred was measured.
  • Table 2 The results are shown in Table 2 below.
  • Production Example 16 (Production of a crosslinked rubber composition containing the rubber anti-aging agent of the present invention) 163.5 parts by weight of the basic rubber composition obtained in Production Example 9, 3 parts by weight of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (BBS)) 0.8 By kneading parts by weight, 1.5 parts by weight of sulfur, and 6 parts by weight of the anti-aging agent for rubber (5) of the present invention obtained in Production Example 5 with an open roll machine having a roll set temperature of 60 ° C. A rubber composition was obtained. The obtained rubber composition is heat-press molded at 145 ° C.
  • BSS N-tert-butyl-2-benzothiazolesulfenamide
  • Test Example 6 Measurement of migration amount of anti-aging agent for rubber
  • the crosslinked rubber composition (C2) was changed to the crosslinked rubber composition (5) obtained in Production Example 16
  • the anti-aging agent for rubber of the crosslinked rubber composition (5) was used.
  • the amount transferred was measured.
  • Table 2 The results are shown in Table 2 below.
  • Production Example 17 (Production of a crosslinked rubber composition containing the rubber anti-aging agent of the present invention) 163.5 parts by weight of the basic rubber composition obtained in Production Example 9, 3 parts by weight of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (BBS)) 0.8
  • a vulcanization accelerator N-tert-butyl-2-benzothiazolesulfenamide (BBS)
  • BSS N-tert-butyl-2-benzothiazolesulfenamide
  • Test Example 7 Measurement of migration amount of anti-aging agent for rubber
  • the crosslinked rubber composition (C2) was changed to the crosslinked rubber composition (6) obtained in Production Example 17, the anti-aging agent for rubber of the crosslinked rubber composition (6) was used. The amount transferred was measured. The results are shown in Table 2 below.
  • Production Example 18 (Production of a crosslinked rubber composition containing the rubber anti-aging agent of the present invention) 163.5 parts by weight of the basic rubber composition obtained in Production Example 9, 3 parts by weight of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (BBS)) 0.8 By kneading parts by weight, 1.5 parts by weight of sulfur, and 5 parts by weight of the anti-aging agent for rubber (7) of the present invention obtained in Production Example 7 with an open roll machine having a roll set temperature of 60 ° C. A rubber composition was obtained. The obtained rubber composition is heat-press molded at 145 ° C.
  • BSS N-tert-butyl-2-benzothiazolesulfenamide
  • Test Example 9 Measurement of migration amount of anti-aging agent for rubber
  • the crosslinked rubber composition (C2) was changed to the crosslinked rubber composition (8) obtained in Production Example 19, the anti-aging agent for rubber of the crosslinked rubber composition (8) was used.
  • the amount transferred was measured.
  • Table 2 The results are shown in Table 2 below.
  • a crosslinked rubber composition (C3) having a sheet shape having a width of 15.5 cm, a length of 16.0 cm, and a thickness of 2 mm.
  • a crosslinked rubber composition (C3) having a sheet shape having a width of 15.5 cm, a length of 16.0 cm, and a thickness of 2 mm.
  • Test Example 10 Measurement of migration amount of rubber anti-aging substance Except for changing the crosslinked rubber composition (C2) to the crosslinked rubber composition (C3) obtained in Production Example 20, in the same manner as in Test Example 1, the anti-aging agent for rubber of the crosslinked rubber composition (C3) was obtained. The amount transferred was measured. The results are shown in Table 2 below.
  • a crosslinked rubber composition (C4) having a sheet shape having a width of 15.5 cm, a length of 16.0 cm, and a thickness of 2 mm.
  • a crosslinked rubber composition (C4) having a sheet shape having a width of 15.5 cm, a length of 16.0 cm, and a thickness of 2 mm.
  • Test Example 11 Measurement of migration amount of anti-aging agent for rubber
  • the crosslinked rubber composition (C2) was changed to the crosslinked rubber composition (C4) obtained in Production Example 21
  • the anti-aging agent for rubber of the crosslinked rubber composition (C4) was used. The amount transferred was measured. The results are shown in Table 2 below.
  • Production Example 22 (Production of Comparative Crosslinked Rubber Composition Including Rubber Antiaging Agent and Solid Factis Separately) 163.5 parts by weight of the basic rubber composition obtained in Production Example 9, 3 parts by weight of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (BBS)) 0.8
  • a rubber composition is kneaded with an open roll machine having a roll set temperature of 60 ° C. by mixing 1 part by weight, 1.5 parts by weight of sulfur, 3 parts by weight of an anti-aging material for rubber, and 3 parts by weight of white sub-S. Obtained.
  • the obtained rubber composition was subjected to hot press molding at 145 ° C.
  • a crosslinked rubber composition (C5) having a sheet shape having a width of 15.5 cm, a length of 16.0 cm, and a thickness of 2 mm.
  • a crosslinked rubber composition (C5) having a sheet shape having a width of 15.5 cm, a length of 16.0 cm, and a thickness of 2 mm.
  • Test Example 12 Measurement of migration amount of rubber anti-aging substance
  • the crosslinked rubber composition (C2) was changed to the crosslinked rubber composition (C5) obtained in Production Example 22
  • the anti-aging agent for rubber of the crosslinked rubber composition (C5) was used. The amount transferred was measured. The results are shown in Table 2 below.
  • Production Example 23 (Production of Comparative Crosslinked Rubber Composition Including Rubber Antiaging Agent and Solid Factis Separately) 163.5 parts by weight of the basic rubber composition obtained in Production Example 9, 3 parts by weight of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (BBS)) 0.8
  • a rubber composition is prepared by kneading, by weight, 1.5 parts by weight of sulfur, 3 parts by weight of an anti-aging material for rubber, and 3 parts by weight of white sub-1 with an open roll machine having a roll set temperature of 60 ° C. Obtained.
  • the obtained rubber composition was subjected to hot press molding at 145 ° C.
  • Test Example 13 Measurement of migration amount of anti-aging agent for rubber
  • the crosslinked rubber composition (C2) was changed to the crosslinked rubber composition (C6) obtained in Production Example 23
  • the anti-aging agent for rubber of the crosslinked rubber composition (C6) was used. The amount transferred was measured. The results are shown in Table 2 below.
  • a crosslinked rubber composition (C7) having a sheet shape having a width of 15.5 cm, a length of 16.0 cm, and a thickness of 2 mm.
  • a crosslinked rubber composition (C7) having a sheet shape having a width of 15.5 cm, a length of 16.0 cm, and a thickness of 2 mm.
  • Production Example 25 (Production of Comparative Crosslinked Rubber Composition Including Rubber Antiaging Agent and Solid Factis Separately) 163.5 parts by weight of the basic rubber composition obtained in Production Example 9, 3 parts by weight of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (BBS)) 0.8
  • a rubber composition is prepared by kneading 1.5 parts by weight of sulfur, 3 parts by weight of an anti-aging agent for rubber, and 3 parts by weight of black sub 30 with an open roll machine having a roll set temperature of 60 ° C. Obtained.
  • the obtained rubber composition was subjected to hot press molding at 145 ° C.
  • a crosslinked rubber composition (C8) having a sheet shape having a width of 15.5 cm, a length of 16.0 cm, and a thickness of 2 mm.
  • a crosslinked rubber composition (C8) having a sheet shape having a width of 15.5 cm, a length of 16.0 cm, and a thickness of 2 mm.
  • Test Example 15 Measurement of migration amount of rubber anti-aging substance
  • the crosslinked rubber composition (C2) was changed to the crosslinked rubber composition (C8) obtained in Production Example 25
  • the anti-aging agent for rubber of the crosslinked rubber composition (C8) was used. The amount transferred was measured. The results are shown in Table 2 below.
  • Production Example 26 (Production of a crosslinked rubber composition containing the rubber anti-aging agent of the present invention)
  • the crosslinked rubber composition obtained by the following first step and second step is suitable for undertread.
  • ⁇ First step> (Procedure 1) Using a Banbury mixer (600 mL lab plast mill manufactured by Toyo Seiki Seisakusho), 100 parts by weight of styrene / butadiene copolymer rubber SBR # 1502 (manufactured by Sumitomo Chemical), ISAF-HM (“Asahi # 80” manufactured by Asahi Carbon Co., Ltd.) 35 parts by weight, 2 parts by weight of stearic acid, 3 parts by weight of zinc oxide, 4 parts by weight of anti-aging agent for rubber of the present invention (1) obtained in Production Example 1 and wax (“OZOACE-0355” manufactured by Nippon Seiwa Co., Ltd.) )
  • a rubber composition is obtained by kneading 2 parts by weight within a range of
  • Production Example 28 (Production of a crosslinked rubber composition containing the rubber anti-aging agent of the present invention)
  • the crosslinked rubber composition obtained by the following first step and second step is suitable for an inner liner.
  • ⁇ First step> (Procedure 1) Using a Banbury mixer (600 mL Laboplast Mill, manufactured by Toyo Seiki Seisakusho), 100 parts by weight of halogenated butyl rubber (“Br-IIR2255” manufactured by ExxonMobil), 60 parts by weight of GPF, 1 part by weight of stearic acid, 3 parts by weight of zinc oxide And 10 parts by weight of paraffin oil (“Diana Process Oil” manufactured by Idemitsu Kosan Co., Ltd.) are kneaded in the range of 160 to 175 ° C.
  • Production Example 29 (Production of a crosslinked rubber composition containing the rubber anti-aging agent of the present invention)
  • the crosslinked rubber composition obtained by the following first step and second step is suitable for sidewalls.
  • First step> (Procedure 1) Using a Banbury mixer (600 mL Lab Plast Mill manufactured by Toyo Seiki Seisakusho Co., Ltd.), 40 parts by weight of commercially available natural rubber (RSS # 3), 60 parts by weight of polybutadiene rubber (“BR150B” manufactured by Ube Industries), 50 parts by weight of FEF, stearin 2.5 parts by weight of acid, 3 parts by weight of zinc oxide, 8 parts by weight of anti-aging agent for rubber of the present invention (1) obtained in Production Example 1, 10 parts by weight of process oil (“NC-140” manufactured by Cosmo Oil Co., Ltd.) Rubber composition by kneading 2 parts by weight and wax (“Sannok (registered trademark) wax” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.) within a range of 160 to 175
  • Production Example 30 (Production of a crosslinked rubber composition containing the rubber anti-aging agent of the present invention)
  • the crosslinked rubber composition obtained by the following first step and second step is suitable for carcass.
  • ⁇ First step> (Procedure 1) Using a Banbury mixer (600 mL lab plast mill manufactured by Toyo Seiki Seisakusho), 70 parts by weight of commercially available natural rubber (TSR20), 30 parts by weight of styrene / butadiene copolymer rubber SBR # 1502 (manufactured by Sumitomo Chemical), N339 (Mitsubishi) Chemical Co., Ltd.) 60 parts by weight, stearic acid 2 parts by weight, zinc oxide 5 parts by weight and process oil (“Diana Process PS32” by Idemitsu Kosan Co., Ltd.) 7 parts by weight within the range of 160 to 175 ° C.
  • Production Example 32 (Production of a crosslinked rubber composition containing the rubber anti-aging agent of the present invention) A crosslinked rubber composition in the same manner as in Production Example 31 except that solution-polymerized SBR ("ASAPRENE (registered trademark)" manufactured by Asahi Kasei Chemicals Corporation) is used in place of the styrene-butadiene copolymer rubber SBR # 1500 (manufactured by JSR). Is obtained. The resulting crosslinked rubber composition is suitable for cap treads.
  • solution-polymerized SBR (“ASAPRENE (registered trademark)” manufactured by Asahi Kasei Chemicals Corporation)
  • SBR # 1500 manufactured by Asahi Kasei Chemicals Corporation
  • Production Example 33 (Production of a crosslinked rubber composition containing the rubber anti-aging agent of the present invention)
  • styrene / butadiene copolymer rubber SBR # 1500 manufactured by JSR
  • styrene / butadiene copolymer rubber SBR # 1712 manufactured by JSR
  • the amount of process oil used was changed to 21 parts by weight
  • zinc oxide was used.
  • a crosslinked rubber composition is obtained in the same manner as in Production Example 31 except that the charging timing is changed to Procedure 2.
  • the resulting crosslinked rubber composition is suitable for cap treads.
  • the cross-linked rubber composition containing the rubber anti-aging agent of the present invention sufficiently maintains the anti-aging effect of the rubber anti-aging agent and is suitable for various uses (for example, 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)
  • Oil, Petroleum & Natural Gas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention se rapporte à un agent anti-vieillissement caoutchouc qui est obtenu soit en chauffant et en mélangeant un factice solide et une substance anti-vieillissement caoutchouc soit en mélangeant un factice solide, une substance anti-vieillissement caoutchouc et un solvant et en éliminant le solvant par distillation.
PCT/JP2013/060269 2012-04-05 2013-04-04 Caoutchouc agent anti-vieillissement WO2013151115A1 (fr)

Applications Claiming Priority (4)

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JP2012086648 2012-04-05
JP2012-086648 2012-04-05
JP2012198877A JP2013231155A (ja) 2012-04-05 2012-09-10 ゴム用老化防止剤
JP2012-198877 2012-09-10

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105745085A (zh) * 2013-10-24 2016-07-06 阿朗新科德国有限责任公司 橡胶组合物

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Publication number Priority date Publication date Assignee Title
JPH0680826A (ja) * 1992-08-28 1994-03-22 Erasuto Mitsukusu:Kk クロロプレン系ゴム組成物の製造方法
JPH1192570A (ja) * 1997-09-19 1999-04-06 Bridgestone Corp ゴム用薬品マスターバッチ、そのマスターバッチを使用したゴム組成物の混練方法及びその方法により得られたゴム組成物
JP2006213842A (ja) * 2005-02-04 2006-08-17 Bridgestone Corp 老化防止剤含有ウェットマスターバッチ及びその製造方法、並びにこれを用いたゴム組成物及びタイヤ
JP2011074332A (ja) * 2009-10-02 2011-04-14 Yokohama Rubber Co Ltd:The タイヤサイドウォール用ゴム組成物およびそれを用いた空気入りタイヤ
JP2011162626A (ja) * 2010-02-08 2011-08-25 Toyo Tire & Rubber Co Ltd ゴム組成物及び空気入りタイヤ
JP2012021083A (ja) * 2010-07-14 2012-02-02 Sumitomo Rubber Ind Ltd サイドウォール用ゴム組成物の製造方法、サイドウォール用ゴム組成物及び空気入りタイヤ

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0680826A (ja) * 1992-08-28 1994-03-22 Erasuto Mitsukusu:Kk クロロプレン系ゴム組成物の製造方法
JPH1192570A (ja) * 1997-09-19 1999-04-06 Bridgestone Corp ゴム用薬品マスターバッチ、そのマスターバッチを使用したゴム組成物の混練方法及びその方法により得られたゴム組成物
JP2006213842A (ja) * 2005-02-04 2006-08-17 Bridgestone Corp 老化防止剤含有ウェットマスターバッチ及びその製造方法、並びにこれを用いたゴム組成物及びタイヤ
JP2011074332A (ja) * 2009-10-02 2011-04-14 Yokohama Rubber Co Ltd:The タイヤサイドウォール用ゴム組成物およびそれを用いた空気入りタイヤ
JP2011162626A (ja) * 2010-02-08 2011-08-25 Toyo Tire & Rubber Co Ltd ゴム組成物及び空気入りタイヤ
JP2012021083A (ja) * 2010-07-14 2012-02-02 Sumitomo Rubber Ind Ltd サイドウォール用ゴム組成物の製造方法、サイドウォール用ゴム組成物及び空気入りタイヤ

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105745085A (zh) * 2013-10-24 2016-07-06 阿朗新科德国有限责任公司 橡胶组合物
JP2016539213A (ja) * 2013-10-24 2016-12-15 アランセオ・ドイチュランド・ゲーエムベーハー ゴム組成物

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