WO2013133397A1 - Agent antivieillissement destiné à des caoutchoucs - Google Patents

Agent antivieillissement destiné à des caoutchoucs Download PDF

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WO2013133397A1
WO2013133397A1 PCT/JP2013/056386 JP2013056386W WO2013133397A1 WO 2013133397 A1 WO2013133397 A1 WO 2013133397A1 JP 2013056386 W JP2013056386 W JP 2013056386W WO 2013133397 A1 WO2013133397 A1 WO 2013133397A1
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rubber
weight
rubber composition
parts
aging
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PCT/JP2013/056386
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English (en)
Japanese (ja)
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進 森
佳余子 阿部
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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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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

Definitions

  • the present invention relates to an anti-aging agent for rubber.
  • Patent Document 1 describes N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine as an anti-aging agent for rubber.
  • the rubber anti-aging substance migrates in the crosslinked rubber composition (finally, the rubber anti-aging substance bleeds out to the surface). In some cases, the anti-aging effect is not sufficiently sustained.
  • the present invention has been made paying attention to such circumstances, and an object of the present invention is to provide an anti-aging agent for rubber that has a sufficient anti-aging effect.
  • a metal oxide selected from the group consisting of zinc oxide, copper oxide (II), iron oxide (II), iron oxide (III) and iron oxide (III) iron (II);
  • a rubber anti-aging agent comprising the rubber anti-aging substance supported on the metal oxide.
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 13 carbon atoms.
  • the migration of the antiaging substance for rubber can be suppressed, and the antiaging effect is sufficiently sustained.
  • the rubber anti-aging agent of the present invention contains a specific metal oxide and an anti-aging agent for rubber supported on the metal oxide.
  • the anti-aging material for rubber and the metal oxide will be described in this order.
  • the anti-aging substance for rubber in the present invention is an organic substance blended for the purpose of preventing the aging of the rubber product and extending its life. Only one type of rubber anti-aging substance may be used, or two or more types may be used in combination.
  • 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.
  • a rubber anti-aging substance 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 is used. Can do.
  • an amine-based anti-aging substance is preferable.
  • an amine type anti-aging substance for example, formula (I):
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 13 carbon atoms.
  • R 2 represents a hydrogen atom or an alkyl group having 1 to 13 carbon atoms.
  • R 3 represents a hydrogen atom or an alkoxy group having 1 to 13 carbon atoms.
  • the alkyl group having 1 to 13 carbon atoms may be linear or branched, and is preferably branched.
  • the carbon number is preferably 1 to 6, more preferably 3 to 6.
  • the alkoxy group having 1 to 13 carbon atoms may be linear or branched.
  • the number of carbon atoms is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 2.
  • R 1 is preferably an alkyl group having 1 to 13 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably a branched alkyl group having 3 to 6 carbon atoms, particularly preferably isopropyl. Or 1,3-dimethylbutyl, most preferably 1,3-dimethylbutyl.
  • R 2 is preferably a hydrogen atom.
  • R 3 is preferably a hydrogen atom or an alkoxy group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkoxy group having 1 to 3 carbon atoms, still more preferably a hydrogen atom or ethoxy.
  • Examples of the compound represented by the formula (I) include N-isopropyl-N′-phenyl-p-phenylenediamine (IPPD) and N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine. (6PPD).
  • Examples of the compound represented by the formula (II) include 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline (ETMDQ), 2,2,4-trimethyl-1,2-dihydroquinoline and the like. Can be mentioned.
  • polymer of the compound represented by the formula (II) examples include poly (2,2,4-trimethyl-1,2-dihydroquinoline) (“Antioxidant FR” manufactured by Matsubara Sangyo Co., Ltd.). Of these, compounds represented by the formula (I) are preferred, and N-isopropyl-N′-phenyl-p-phenylenediamine and N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine are preferred. N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine is more preferable.
  • Zinc oxide zinc oxide (ZnO), copper (II) oxide (CuO), iron oxide (II) (FeO), iron oxide (III) (Fe 2 O 3 , Selected from the group consisting of ferric oxide (sometimes referred to as ferric trioxide or ferric oxide) and iron (III) oxide (II) (also referred to as Fe 3 O 4 , triiron tetroxide or tetrairon tetroxide)
  • ferric oxide sometimes referred to as ferric trioxide or ferric oxide
  • iron (III) oxide iron (III) oxide (II) (also referred to as Fe 3 O 4 , triiron tetroxide or tetrairon tetroxide)
  • the said metal oxide may use only 1 type and may use 2 or more types together.
  • the particle diameter of the metal oxide is preferably 0.1 to 80 ⁇ m, more preferably 0.1 to 50 ⁇ m. This particle diameter is a value of D 50 obtained from a chart obtained by analyzing the particle size distribution of the metal oxide by a laser diffraction method.
  • metal oxides zinc oxide, iron (II) oxide and iron (III) are preferable, iron (II) oxide and iron (III) are more preferable, and iron (II) oxide is most preferable.
  • the content of the metal oxide in the rubber anti-aging agent of the present invention is preferably 1 to 100 parts by weight, more preferably 1 to 50 parts by weight, and still more preferably 10 parts by weight of the rubber anti-aging agent. 2 to 30 parts by weight.
  • the said content points out the total amount of a metal oxide.
  • the method for producing the anti-aging agent for rubber of the present invention is not particularly limited as long as the anti-aging agent for rubber can be supported on the metal oxide.
  • “supporting” means that a substance to be supported is attached to the surface of the carrier.
  • the carrier is a porous body
  • the fact that the supported substance is attached to the inside of the porous body is also included in “supporting”. Examples of the production method include the following method (1) and the following method (2).
  • the “solvent” is not particularly limited as long as it can dissolve the rubber anti-aging substance and can be removed (for example, distilled off), but for example, toluene, xylene, hexane, heptane, etc.
  • examples thereof include hydrocarbon solvents, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and alcohol solvents such as methanol, ethanol, and isopropanol.
  • the mixing method of the rubber anti-aging substance solution and the metal oxide there is no particular limitation on the mixing method of the rubber anti-aging substance solution and the metal oxide.
  • the metal oxide may be added to the solution, and the solution is sprayed onto the metal oxide. Also good.
  • the method for cooling the mixture is not particularly limited, and for example, forced air cooling by blowing or cooling can be employed. In the said method, you may grind
  • 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 metal oxide and the anti-aging substance for rubber carried on the metal oxide move together in the rubber component. Therefore, in the obtained rubber composition, the anti-aging agent for rubber is an anti-aging substance. Is presumed to exist in a state of being supported on a metal oxide.
  • the rubber composition may be a master batch.
  • 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, filler, zinc oxide, stearic acid, crosslinking agent, vulcanization accelerator, etc.). Each compounding agent may be used alone or in combination of two or more.
  • the crosslinking agent and the rubber anti-aging agent of the present invention may be kneaded together with the rubber component, or the rubber anti-aging agent of the present invention and the rubber component are kneaded together. Later, the obtained kneaded product and the crosslinking agent (or sulfur and vulcanization accelerator) may be further kneaded.
  • a crosslinking agent is sulfur, it is preferable to knead
  • 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 component examples include natural rubber and modified natural rubber (for example, epoxidized natural rubber, deproteinized natural rubber, etc.); polyisoprene rubber (IR), styrene-butadiene copolymer rubber (SBR), polybutadiene rubber (BR).
  • IR polyisoprene rubber
  • SBR styrene-butadiene copolymer rubber
  • BR polybutadiene rubber
  • Various synthetic rubbers such as acrylonitrile / butadiene copolymer rubber (NBR), isoprene / isobutylene copolymer rubber (IIR), ethylene / propylene-diene copolymer rubber (EPDM), and halogenated butyl rubber (HR). it can.
  • the rubber component is preferably highly unsaturated, and natural rubber, modified natural rubber, styrene / butadiene copolymer rubber, and polybutadiene rubber are more preferable, and natural rubber is more preferable. Moreover, you may use together the above-mentioned various rubber
  • 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 treads and sidewalls 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.
  • BR polybutadiene rubber
  • solution polymerization BR such as high cis BR having 90% or more of cis 1,4 bond, low cis BR having cis bond of around 35%, and low cis BR having a high vinyl content. It is done. Among these, low cis BR having a high vinyl content is preferable.
  • 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.
  • Solution polymerization BR having an element of nitrogen, tin or silicon at the molecular end, obtained by modifying the molecular end with either a trialkoxysilane compound or the like and an aminosilane compound.
  • 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.
  • the content of natural rubber in the rubber component is preferably 40 to 60% by weight, and the content of BR is preferably 60 to 40% by weight.
  • a blend of modified SBR and non-modified SBR or a blend of modified BR and non-modified BR can also be preferably used.
  • Examples of the filler include carbon black, silica, talc, clay, titanium oxide and the like that are usually used in the rubber field. Among these, carbon black and silica are preferable, and carbon black is more preferable.
  • 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 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 is preferable.
  • 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.
  • N110, N220, N234, N299, N326, N330, N330T, N339, N343, N351 and the like can be mentioned.
  • 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 filler include silica having a CTAB specific surface area of 50 to 180 m 2 / g, silica having a nitrogen adsorption specific surface area of 50 to 300 m 2 / g, and the like.
  • Examples of commercially available silica products include “AQ” and “AQ-N” manufactured by Tosoh Silica Co., Ltd., “Ultra Gil (registered trademark) VN3”, “Ultra Gil (registered trademark) 360”, and “Ultra Gil” manufactured by Degussa.
  • silica having a pH of 6 to 8 (ii) silica containing sodium in an amount of 0.2 to 1.5% by weight, (iii) having a roundness of 1 to 1.3 Spherical silica, (iv) Silicone oil such as dimethylsilicone oil; Organosilicon compound containing ethoxysilyl group; Silica surface-treated with alcohol such as ethanol and polyethylene glycol, (v) Different nitrogen adsorption specific surface area You may mix
  • 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.
  • silica When silica is blended as a filler, for example, carbon black is preferably blended in an amount of 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.
  • silica when silica is used as the filler, it is preferable to add a compound capable of binding to silica such as a silane coupling agent.
  • the silane coupling agent include bis (3-triethoxysilylpropyl) tetrasulfide (eg, “Si-69” manufactured by Degussa), bis (3-triethoxysilylpropyl) disulfide (eg, manufactured by Degussa) Si-75 "), bis (3-diethoxymethylsilylpropyl) tetrasulfide, bis (3-diethoxymethylsilylpropyl) disulfide, octanethioic acid S- [3- (triethoxysilyl) propyl] ester (" 3- Also referred to as “octanoylthiopropyltriethoxysilane”, for example: “NXT silane” manufactured by General Electronic Silicons), octanethioic acid S- [
  • the addition timing of the compound capable of binding to silica is not particularly limited, but it is preferably blended with rubber 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.
  • stearic acid When stearic acid is used, its content in the rubber composition is, for example, 0.5 to 10 parts by weight, preferably 1 to 5 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.
  • insoluble sulfur is preferable.
  • sulfur is added to the rubber composition, its content in the rubber composition is, for example, 0.3 to 5 parts by weight, preferably 0.5 to 3 parts by weight with respect to 100 parts by weight of the rubber component.
  • 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.
  • vulcanization accelerator examples include N-cyclohexyl-2-benzothiazolylsulfenamide (CBS), N-tert-butyl-2-benzothiazolylsulfenamide (BBS), and N, N-dicyclohexene.
  • CBS N-cyclohexyl-2-benzothiazolylsulfenamide
  • BSS N-tert-butyl-2-benzothiazolylsulfenamide
  • N, N-dicyclohexene examples include xyl-2-benzothiazolylsulfenamide (DCBS), 2-mercaptobenzothiazole (MBT), dibenzothiazyl disulfide (MBTS), and diphenylguanidine (DPG).
  • DCBS xyl-2-benzothiazolylsulfenamide
  • MTT 2-mercaptobenzothiazole
  • MBTS dibenzothiazyl disulfide
  • DPG diphenyl
  • N-cyclohexyl-2-benzothiazolylsulfenamide CBS
  • N-tert-butyl-2-benzothiazolylsulfenamide CBS
  • BBS N-cyclohexyl-2-benzothiazolylsulfenamide
  • DCBS N-dicyclohexyl-2-benzothiazolylsulfenamide
  • MBTS dibenzothiazyl disulfide
  • DPG diphenylguanidine
  • N-cyclohexyl-2-benzothiazolylsulfenamide CBS
  • N-tert-butyl-2-benzo Any one of thiazolylsulfenamide (BBS), N, N-dicyclohexyl-2-benzothiazolylsulfenamide (DCBS), dibenzothiazyl disulfide (MBTS) and diphenylguanidine (DPG) may be used in combination preferable.
  • the weight ratio of sulfur and vulcanization accelerator is not particularly limited, but is, for example, 2/1 to 1/2.
  • 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. 95 ° C.) coumarone / indene resin; terpene resins such as terpene resin, terpene / phenol resin, aromatic modified terpene resin; “Nikanol (registered trademark) HP-100” (softening point 105 to 125) manufactured by Mitsubishi Gas Chemical Co., Ltd.
  • xylene / formaldehyde resins examples include rosin derivatives such as “Ester gum” series and “neotol” series manufactured by Arakawa Chemical Co .; hydrogenated rosin derivatives; novolac alkylphenol resins; resole alkylphenol resins; C5 petroleum resins; Liquid polybutadiene; and the like.
  • oil examples include process oil and vegetable oil.
  • process oil examples include paraffinic process oil, naphthenic process oil, and aromatic process oil.
  • the crosslinked rubber composition is obtained by crosslinking the above rubber composition.
  • Crosslinking is usually performed using a crosslinking agent (eg, sulfur or peroxide crosslinking agent).
  • a crosslinking agent eg, sulfur or peroxide crosslinking agent.
  • crosslinking ie, vulcanization
  • crosslinking is normally performed by heat-processing or light-irradiating the said rubber composition.
  • the crosslinking is preferably vulcanized, and the crosslinked rubber composition is preferably a vulcanized rubber composition.
  • the heat treatment temperature is, for example, 120 to 180 ° C.
  • the heat treatment may be usually performed at normal pressure or under pressure.
  • the anti-aging agent for rubber exists in a state where the anti-aging substance is supported on the metal oxide. If the crosslinked rubber composition containing the anti-aging agent for rubber of the present invention is used, the effect of the anti-aging agent for rubber is sustained, so that the life of the rubber product obtained therefrom can be extended.
  • 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.
  • the crosslinked rubber composition can be used not only for the tire applications described above but also as an anti-vibration rubber for automobiles such as engine mounts, strut mounts, bushes, and exhaust hangers.
  • the rubber anti-aging substances and metal oxides used in the production examples are as follows.
  • Production Example 1 (Production of rubber anti-aging agent of the present invention) A 200 mL beaker was charged with 3 parts by weight of an anti-aging material for rubber, and 80 mL of acetone was added thereto to obtain an acetone solution of the anti-aging material for rubber. The obtained acetone solution was added into a 200 mL beaker containing 2 parts by weight of zinc oxide, and a 200 mL beaker containing the acetone solution was further washed with 20 mL of acetone to obtain a mixture. It was. The resulting mixture was stirred at 25 ° C. under air for 1 day. After completion of the stirring, the obtained mixture was dried under reduced pressure for 1 day to obtain a rubber anti-aging agent (1) of the present invention as a purple solid.
  • Production Example 2 (Production of rubber anti-aging agent of the present invention)
  • the rubber anti-aging agent (2) of the present invention was obtained in the same manner as in Production Example 1 except that 2 parts by weight of zinc oxide was changed to 1.95 parts by weight of copper (II) oxide.
  • Production Example 3 (Production of rubber anti-aging agent of the present invention)
  • the rubber anti-aging agent (3) of the present invention was obtained in the same manner as in Production Example 1 except that 2 parts by weight of zinc oxide was changed to 1.77 parts by weight of iron (II) oxide.
  • Production Example 4 (Production of rubber anti-aging agent of the present invention) An anti-aging agent for rubber (4) of the present invention was obtained in the same manner as in Production Example 1 except that 2 parts by weight of zinc oxide was changed to 1.97 parts by weight of iron (III) oxide.
  • Production Example 5 (Production of rubber anti-aging agent of the present invention)
  • the rubber anti-aging agent (5) of the present invention was obtained in the same manner as in Production Example 1, except that 2 parts by weight of zinc oxide was changed to 1.89 parts by weight of iron (III) iron (II).
  • Production Example 6 (Production of basic rubber composition) 50 parts by weight of each of natural rubber (standard Malaysian natural rubber: SMR-CV60) and butadiene rubber (product name: JSR BR01, manufactured by JSR) were charged into a 600 mL Banbury mixer and kneaded for 3 minutes. After adding the raw materials shown in Table 1 to the obtained kneaded material, the mixture was further kneaded for 8 minutes to obtain a basic rubber composition (B1). The discharge temperature of the rubber composition from the kneader was 160 ° C.
  • Production Example 7 (Production of a crosslinked rubber composition not containing the rubber anti-aging agent of the present invention) 163.5 parts by weight of the basic rubber composition (B1) obtained in Production Example 6, 2 parts by weight of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS))
  • TBBS vulcanization accelerator
  • a rubber composition was obtained by kneading 0.8 parts by weight and 1.5 parts by weight of sulfur with an open roll machine having a roll set temperature of 60 ° C.
  • the obtained rubber composition was subjected to hot press molding at 145 ° C. to obtain a sheet-shaped crosslinked rubber composition (C1) having a width of 15.5 cm, a length of 16.0 cm, and a thickness of 2 mm.
  • the obtained crosslinked rubber composition (C1) does not contain the rubber anti-aging agent of the present invention.
  • Production Example 8 (Production of a crosslinked rubber composition not containing the rubber anti-aging agent of the present invention) 163.5 parts by weight of the basic rubber composition (B1) obtained in Production Example 6, 2 parts by weight of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS))
  • TBBS vulcanization accelerator
  • a rubber composition was obtained by kneading 0.8 parts by weight, 1.5 parts by weight of sulfur, and 3 parts by weight of an anti-aging material for rubber with an open roll machine having a roll set temperature of 60 ° C.
  • the obtained rubber composition was subjected to hot press molding at 145 ° C.
  • a sheet-shaped crosslinked rubber composition (C2) having a width of 15.5 cm, a length of 16.0 cm, and a thickness of 2 mm. 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.
  • the obtained crosslinked rubber composition (C2) does not contain the rubber anti-aging agent of the present invention (that is, the rubber anti-aging substance supported on the metal oxide), but contains the rubber anti-aging substance.
  • 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 8 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.
  • the package on which the weight was placed was left in a thermostatic chamber at 25 ° C. for 6 days, then the aluminum foil and the aluminum laminate package were opened, each sheet was taken out, and the weight of each sheet was measured.
  • the amount of migration of the rubber anti-aging substance was calculated from the weight change from the initial weight of the blank sheet. Specifically, the concentration of the anti-aging substance increased in the blank sheet was calculated from the weight change of the three blank sheets, and the increased concentration was calculated as the amount of migration.
  • Table 4 The results are shown in Table 4 below.
  • Table 4 As a result of separately extracting and quantifying the rubber anti-aging substance from each sheet, it was confirmed that the weight change was caused by the migration of the rubber anti-aging substance.
  • Production Example 9 (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 (B1) obtained in Production Example 6, 2 parts by weight of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS)) 0.8 parts by weight, 1.5 parts by weight of sulfur, and 5 parts by weight of the antiaging agent for rubber of the present invention (1) obtained in Production Example 1 are kneaded with an open roll machine at a roll set temperature of 60 ° C. By doing so, a rubber composition was obtained. The obtained rubber composition is heat-press molded at 145 ° C.
  • a vulcanization accelerator N-tert-butyl-2-benzothiazolesulfenamide (TBBS)
  • 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.
  • Production Example 10 (Production of a crosslinked rubber composition not containing the rubber anti-aging agent of the present invention) 163.5 parts by weight of the basic rubber composition (B1) obtained in Production Example 6, 4 parts by weight of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS))
  • TBBS N-tert-butyl-2-benzothiazolesulfenamide
  • a rubber composition was obtained by kneading 0.8 parts by weight and 1.5 parts by weight of sulfur with an open roll machine having a roll set temperature of 60 ° C.
  • the obtained rubber composition was subjected to hot press molding at 145 ° C. to obtain 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.
  • the obtained crosslinked rubber composition (C3) was obtained by producing the crosslinked rubber obtained in Production Example 7 by the amount of zinc oxide (2 parts by weight) contained in the anti-aging agent for rubber (1) used in Production Example 9. It is the same as the crosslinked rubber composition (C1) except that the amount of zinc oxide in the composition (C1) is increased (that is, the amount of zinc oxide is changed from 2 parts by weight to 4 parts by weight).
  • 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 9, and the crosslinked rubber composition (C1) was changed to the crosslinked rubber composition (C3) obtained in Production Example 10. Except that, the amount of migration of the anti-aging agent for rubber in the crosslinked rubber composition (1) was measured in the same manner as in Test Example 1. The results are shown in Table 4 below.
  • Production Example 11 (Production of basic rubber composition) 50 parts by weight of each of natural rubber (standard Malaysian natural rubber: SMR-CV60) and butadiene rubber (product name: JSR BR01, manufactured by JSR) were charged into a 600 mL Banbury mixer and kneaded for 3 minutes. After adding the raw materials shown in Table 2 to the obtained kneaded material, the mixture was further kneaded for 8 minutes to obtain a basic rubber composition (B2). The discharge temperature of the rubber composition from the kneader was 160 ° C.
  • the obtained basic rubber composition (B2) is the same as the basic rubber composition (B1) obtained in Production Example 6 except that it contains 5 parts by weight of the antiaging agent for rubber (1) of the present invention.
  • Production Example 12 (Production of a crosslinked rubber composition containing the rubber anti-aging agent of the present invention) 168.5 parts by weight of the basic rubber composition (B2) obtained in Production Example 11, 1 part by weight of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS))
  • a rubber composition was obtained by kneading 0.8 parts by weight and 1.5 parts by weight of sulfur with an open roll machine having a roll set temperature of 60 ° C.
  • the obtained rubber composition is heat-press molded at 145 ° C.
  • 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.
  • the obtained crosslinked rubber composition (2) was obtained by kneading the rubber kneaded product and the rubber anti-aging agent (1) of the present invention before blending and kneading the vulcanization accelerator and sulfur. This is the same as the crosslinked rubber composition (1) obtained in Production Example 9, except that the amount of zinc oxide to be blended in the basic rubber composition is changed from 2 parts by weight to 1 part by weight.
  • Production Example 13 (Production of basic rubber composition) 50 parts by weight of each of natural rubber (standard Malaysian natural rubber: SMR-CV60) and butadiene rubber (product name: JSR BR01, manufactured by JSR) were charged into a 600 mL Banbury mixer and kneaded for 3 minutes. After adding the raw materials shown in Table 3 to the obtained kneaded material, the mixture was further kneaded for 8 minutes to obtain a basic rubber composition (B3). The discharge temperature of the rubber composition from the kneader was 160 ° C. The obtained basic rubber composition (B3) is the same as the basic rubber composition (B1) obtained in Production Example 6 except that it contains 2 parts by weight of zinc oxide.
  • Production Example 14 (Production of a crosslinked rubber composition not containing the rubber anti-aging agent of the present invention) 165.5 parts by weight of the basic rubber composition (B3) obtained in Production Example 13, 1 part by weight of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS))
  • TBBS N-tert-butyl-2-benzothiazolesulfenamide
  • a rubber composition was obtained by kneading 0.8 parts by weight, 1.5 parts by weight of sulfur, and 3 parts by weight of an anti-aging material for rubber with an open roll machine having a roll set temperature of 60 ° C.
  • the obtained rubber composition was subjected to hot press molding at 145 ° C.
  • 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.
  • the obtained crosslinked rubber composition (C4) is the same as the crosslinked rubber composition (C1) obtained in Production Example 7, except that the total amount of zinc oxide was changed from 2 parts by weight to 3 parts by weight.
  • 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 12, and the crosslinked rubber composition (C1) was changed to the crosslinked rubber composition (C4) obtained in Production Example 14. Except for this, the amount of migration of the anti-aging material for rubber in the crosslinked rubber composition (2) was measured in the same manner as in Test Example 1. The results are shown in Table 4 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 (B1) obtained in Production Example 6, 2 parts by weight of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS)) 0.8 parts by weight, 1.5 parts by weight of sulfur, and 4.95 parts by weight of the anti-aging agent for rubber (2) of the present invention obtained in Production Example 2 are used in an open roll machine having a roll set temperature of 60 ° C. By kneading with a rubber composition, a rubber composition was obtained. The obtained rubber composition is heat-press molded at 145 ° C.
  • TBBS 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 (3) 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 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 15
  • the anti-aging material for rubber of the crosslinked rubber composition (3) was used.
  • the amount transferred was measured. The results are shown in Table 4 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 (B1) obtained in Production Example 6, 2 parts by weight of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS)) 0.8 parts by weight, 1.5 parts by weight of sulfur, and 4.77 parts by weight of the anti-aging agent for rubber (3) of the present invention obtained in Production Example 3 are used in an open roll machine having a roll set temperature of 60 ° C. By kneading with a rubber composition, a rubber composition was obtained. The obtained rubber composition is heat-press molded at 145 ° C.
  • TBBS 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 (4) 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 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 16
  • the anti-aging material for rubber of the crosslinked rubber composition (4) was used.
  • the amount transferred was measured. The results are shown in Table 4 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 (B1) obtained in Production Example 6, 2 parts by weight of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS)) 0.8 parts by weight, 1.5 parts by weight of sulfur, and 4.97 parts by weight of the anti-aging agent for rubber (4) of the present invention obtained in Production Example 4 are used in an open roll machine having a roll set temperature of 60 ° C. By kneading with a rubber composition, a rubber composition was obtained. The obtained rubber composition is heat-press molded at 145 ° C.
  • TBBS 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 (5) 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 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 17, the anti-aging agent for rubber of the crosslinked rubber composition (5) was used.
  • the amount transferred was measured.
  • Table 4 The results are shown in Table 4 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 (B1) obtained in Production Example 6, 2 parts by weight of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS)) 0.8 parts by weight, 1.5 parts by weight of sulfur, and 4.89 parts by weight of the anti-aging agent for rubber (5) of the present invention obtained in Production Example 5 are used in an open roll machine having a roll set temperature of 60 ° C. By kneading with a rubber composition, a rubber composition was obtained. The obtained rubber composition is heat-press molded at 145 ° C.
  • TBBS 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 (6) 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 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 18, 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 4 below.
  • Production Example 19 (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 (B1) obtained in Production Example 6, 2 parts by weight of zinc oxide, 2 parts by weight of nickel oxide (NiO), and a vulcanization accelerator (N-tert-butyl-2) -Benzothiazole sulfenamide (TBBS)) 0.8 parts by weight, sulfur 1.5 parts by weight, rubber anti-aging agent (1) of the present invention obtained in Production Example 1 3 parts by weight
  • a rubber composition was obtained by kneading with an open roll machine at a set temperature of 60 ° C. The obtained rubber composition is heat-press molded at 145 ° C.
  • a product (7) 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.
  • the obtained crosslinked rubber composition (7) was produced except that the amount of the rubber anti-aging agent (1) of the present invention was changed from 5 parts by weight to 3 parts by weight and further 2 parts by weight of nickel oxide was added. This is the same as the crosslinked rubber composition (1) obtained in Example 9.
  • Test Example 8 Measurement of migration amount of anti-aging agent for rubber
  • the crosslinked rubber composition (C2) was changed to the crosslinked rubber composition (7) obtained in Production Example 19, the anti-aging agent for rubber of the crosslinked rubber composition (7) was used.
  • the amount transferred was measured. The results are shown in Table 4 below.
  • the crosslinked rubber compositions (1) to (7) containing the rubber anti-aging agent of the present invention were compared with the cross-linked rubber composition (C2) containing no rubber anti-aging agent of the present invention. Therefore, the migration amount of rubber anti-aging substances is small. From this result, it can be seen that the crosslinked rubber composition containing the rubber anti-aging agent of the present invention suppresses the migration of the rubber anti-aging substance and sufficiently maintains its anti-aging effect.
  • Production Example 20 (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 Co., Ltd.), 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, 8 parts by weight of the antioxidant 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
  • Production Example 21 (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 a belt.
  • First step> (Procedure 1) Using a Banbury mixer (600 mL Lab Plast Mill manufactured by Toyo Seiki Seisakusho), 100 parts by weight of commercially available natural rubber (RSS # 1), 45 parts by weight of HAF (Asahi Carbon Co., Ltd.
  • a rubber composition is obtained by kneading 2 parts by weight of resorcin and 2 parts by weight of cobalt naphthenate within a range of 160 to 175 ° C. for 5 minutes at a mixer rotational speed of 50 rpm. (Procedure 2) The total amount of the rubber composition obtained in Procedure 1 within the range of 60 to 80 ° C.
  • a rubber kneaded material is obtained by kneading 3 parts by weight, 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.).
  • SUMIKANOL 507AP methoxylated methylol melamine resin
  • Production Example 22 (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 Lab Plast Mill manufactured by Toyo Seiki Seisakusho), halogenated butyl rubber (“Br-IIR2255” manufactured by ExxonMobil) 100 parts by weight, GPF 60 parts by weight, stearic acid 1 part by weight, zinc oxide 3 parts by weight
  • a rubber composition is obtained by kneading 10 parts by weight of paraffin oil (“Diana Process Oil” manufactured by Idemitsu Kosan Co., Ltd.) within a range of 160 to 175 ° C.
  • paraffin oil (“Diana Process Oil” manufactured by Idemitsu Kosan Co., Ltd.)
  • Production Example 23 (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), 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, stearic acid 2.5 parts by weight, zinc oxide 3 parts by weight, rubber anti-aging agent of the present invention obtained in Production Example 1 (1) 16 parts by weight, process oil (“NC-140” manufactured by Cosmo Oil Co., Ltd.) 10 parts by weight And 2 parts by weight of wax (“Sannok (registered trademark) wax” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.) within a range of 160 to 175 ° C.
  • process oil (“NC-140” manufactured by Cosmo Oil Co
  • Production Example 24 (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 Co., Ltd.), N339 (Mitsubishi Chemical) 60 parts by weight, stearic acid 2 parts by weight, zinc oxide 5 parts by weight, process oil (“Diana Process PS32” by Idemitsu Kosan Co., Ltd.) 7 parts by weight within a range of 160 to 175 ° C.
  • a rubber composition is obtained by kneading at a mixer rotation speed of. (Procedure 2) The total amount of the rubber composition obtained in Procedure 1 within the range of 60 to 80 ° C. in an open roll machine, 1 part by weight of N-tert-butyl-2-benzothiazolylsulfenamide (BBS) as a vulcanization accelerator
  • a rubber kneaded product is obtained by kneading 3 parts by weight of sulfur and 8 parts by weight of the anti-aging agent for rubber (1) of the present invention obtained in Production Example 1.
  • ⁇ Second step> A crosslinked rubber composition is obtained by heat-treating the rubber kneaded product obtained in the first step (procedure 2) at 145 ° C.
  • Production Example 25 (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 cap treads.
  • First step> (Procedure 1) Using a Banbury mixer (600 mL Laboplast Mill manufactured by Toyo Seiki Seisakusho), 100 parts by weight of styrene / butadiene copolymer rubber SBR # 1500 (manufactured by JSR), silica ("Ultrasil (registered trademark) VN3-G” manufactured by Degussa) 78.4 parts by weight, carbon black (“N-339” manufactured by Mitsubishi Chemical Corporation), 6.4 parts by weight, silane coupling agent (bis (3-triethoxysilylpropyl) tetrasulfide, “Si-69” manufactured by Degussa ”6.4 parts by weight, process oil (“ NC-140 ”manufactured by Cosmo Oil Co., Ltd.) 47.6
  • Production Example 26 (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 25, except that solution-polymerized SBR (“ASAPREN (registered trademark)” manufactured by Asahi Kasei Chemicals) is used in place of the styrene / butadiene copolymer rubber SBR # 1500 (manufactured by JSR). Things are obtained.
  • SBR solution-polymerized SBR
  • SBR # 1500 manufactured by Asahi Kasei Chemicals
  • Production Example 27 (Production of a crosslinked rubber composition containing the rubber anti-aging agent of the present invention)
  • SBR # 1712 manufactured by JSR
  • SBR # 1500 manufactured by JSR
  • the amount of process oil used was changed to 21 parts by weight
  • zinc oxide was charged.
  • a crosslinked rubber composition is obtained in the same manner as in Production Example 25 except that the 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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  • Organic Chemistry (AREA)
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Abstract

La présente invention concerne un agent antivieillissement destiné à des caoutchoucs, qui comprend : un oxyde métallique sélectionné dans le groupe constitué par l'oxyde de zinc, l'oxyde de cuivre (II), l'oxyde de fer (II), l'oxyde de fer (III), et l'oxyde de fer (III) et de fer (II) ; et une substance antivieillissement destinée à des caoutchoucs, qui est supportée sur l'oxyde métallique.
PCT/JP2013/056386 2012-03-08 2013-03-08 Agent antivieillissement destiné à des caoutchoucs WO2013133397A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111690179A (zh) * 2019-03-15 2020-09-22 横滨橡胶株式会社 钢帘线粘接用橡胶组合物以及传送带

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004359888A (ja) * 2003-06-06 2004-12-24 Sumitomo Rubber Ind Ltd ゴム用複合剤、その製造方法およびゴム用複合剤を含有するゴム組成物
JP2005113013A (ja) * 2003-10-08 2005-04-28 Sumitomo Rubber Ind Ltd タイヤ用ゴム組成物
JP2008500412A (ja) * 2004-05-28 2008-01-10 カール・フロイデンベルク・カーゲー ゴム組成物、エラストマー、その製造方法および複合体粒子の使用

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004359888A (ja) * 2003-06-06 2004-12-24 Sumitomo Rubber Ind Ltd ゴム用複合剤、その製造方法およびゴム用複合剤を含有するゴム組成物
JP2005113013A (ja) * 2003-10-08 2005-04-28 Sumitomo Rubber Ind Ltd タイヤ用ゴム組成物
JP2008500412A (ja) * 2004-05-28 2008-01-10 カール・フロイデンベルク・カーゲー ゴム組成物、エラストマー、その製造方法および複合体粒子の使用

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111690179A (zh) * 2019-03-15 2020-09-22 横滨橡胶株式会社 钢帘线粘接用橡胶组合物以及传送带

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