WO2013089215A1 - Agent antivieillissement pour caoutchouc - Google Patents

Agent antivieillissement pour caoutchouc Download PDF

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Publication number
WO2013089215A1
WO2013089215A1 PCT/JP2012/082451 JP2012082451W WO2013089215A1 WO 2013089215 A1 WO2013089215 A1 WO 2013089215A1 JP 2012082451 W JP2012082451 W JP 2012082451W WO 2013089215 A1 WO2013089215 A1 WO 2013089215A1
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Prior art keywords
rubber
weight
parts
rubber composition
aging
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PCT/JP2012/082451
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English (en)
Japanese (ja)
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佳余子 阿部
志津香 岩田
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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
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose

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 a rubber anti-aging substance.
  • the anti-aging effect of the rubber anti-aging substance may not always be satisfactory in terms of sustainability.
  • a rubber anti-aging agent comprising an anti-aging agent for rubber supported on roasted starch (hereinafter sometimes referred to as “anti-aging agent for rubber of the present invention”). 2. 1. It is obtained by supporting an antiaging substance for rubber on roasted starch. Antiaging agent for rubber of description. 3. 1. The rubber anti-aging substance is a compound represented by the formula (I): Or 2. Antiaging agent for rubber of description.
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 13 carbon atoms.
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 13 carbon atoms.
  • the durability of the antiaging effect of the antiaging substance for rubber contained therein is improved.
  • 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.
  • the anti-aging material 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.
  • the anti-aging agent for rubber is more likely to migrate in the vulcanized rubber composition as the molecular weight is lower, but the present invention can suppress the migration even with such a low molecular weight anti-aging agent for rubber. . 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 400) can be used.
  • an amine-based anti-aging substance is preferable.
  • the amine-based anti-aging substance include a compound represented by the formula (I), a compound represented by the formula (II), or a polymer thereof.
  • 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 number of carbon atoms is preferably 1 to 10, more preferably 2 to 8, and further preferably 3 to 8.
  • the alkoxy group having 1 to 13 carbon atoms may be linear or branched.
  • the number of carbon atoms is preferably 1 to 10, more preferably 1 to 8, and further preferably 1 to 5.
  • R 1 is preferably an alkyl group having 1 to 13 carbon atoms, more preferably a branched alkyl group having 3 to 8 carbon atoms, still more preferably isopropyl or 1,3-dimethylbutyl, and particularly preferably Is 1,3-dimethylbutyl.
  • R 2 is preferably a hydrogen atom.
  • R 3 is preferably a hydrogen atom or an alkoxy group having 1 to 5 carbon atoms, 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. be able to.
  • 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.
  • the roasted starch in the present invention is a modified starch obtained by heating (ie, decomposing) the raw material starch.
  • the roasted starch may be a modified starch obtained by heating the raw starch with the acid added and denatured (decomposition etc.) (acid roasting method). The raw starch is heated with the alkali added. Modified starch obtained by denaturation (decomposition etc.) (alkali roasting method) may be used.
  • raw material starch examples include potato starch, corn starch, sweet potato starch, tapioca starch, sago palm starch, wheat starch, and rice starch.
  • roasted starch examples include white dextrin, yellow dextrin and British gum.
  • White dextrin and yellow dextrin are obtained by the acid roasting method of the above-mentioned raw material starch.
  • the yellow dextrin is obtained by further modifying (re-polymerizing) white dextrin by an acid roasting method.
  • British gum can be obtained by heating raw material starch in an additive-free state or by alkali roasting of raw material starch.
  • the water content in the baked starch is preferably 20% by weight or less, more preferably 18% by weight or less, and still more preferably 15% by weight or less. This water content can be calculated by the change in weight after drying at 100 ° C. overnight.
  • the viscosity of a 50% by weight aqueous solution of roasted starch is preferably 100 to 100,000 cps, more preferably 150 to 90,000 cps, and even more preferably 200 to 80,000 cps.
  • This viscosity can be measured as follows.
  • a 50% by weight aqueous solution of roasted starch is prepared. The concentration of the aqueous solution is based on the weight of the anhydride of roasted starch.
  • the obtained aqueous solution is heated in an oil bath at 100 ° C. while stirring. When the temperature of the aqueous solution reaches 85 ° C. or higher, the stirring is stopped and left at 85 ° C. or higher for 10 minutes.
  • viscosity (30 ° C., 6 rpm) the viscosity measured under the former condition
  • viscosity (30 ° C., 30 rpm) the viscosity measured under the latter condition
  • the BET specific surface area of the roasted starch is preferably 0.1 to 0.5 m 2 / g, more preferably 0.15 to 0.4 m 2 / g. This BET specific surface area can be measured by the method described in Examples described later.
  • a rubber anti-aging substance is supported on the roasted starch.
  • the loading in the present invention means that an extraction rate of an anti-aging material for rubber from an anti-aging agent for rubber calculated by the following method (hereinafter sometimes referred to as “extraction rate of an anti-aging agent for rubber”) is used for rubber.
  • extraction rate of an anti-aging agent for rubber A value smaller than the extraction rate of rubber anti-aging substances (hereinafter sometimes referred to as “extraction rate of simple mixture”) from a mixture of anti-aging material and roasted starch (hereinafter also referred to as “simple mixture”). The state shown.
  • the above-mentioned simple mixture is obtained by mixing a rubber anti-aging substance and a roasted starch in a powder state at room temperature.
  • a predetermined amount (for example, 20 mL) of a solution is obtained by adding a solvent (for example, methanol) that can dissolve the anti-aging substance for rubber to the concentrate obtained in (1). 6). 5. above.
  • the solution obtained in step 1 is subjected to liquid chromatography (LC).
  • LC liquid chromatography
  • the mobile phase of LC for example, methanol / water, methanol or the like can be used. 7).
  • the extraction rate of the anti-aging agent for rubber in the anti-aging agent for rubber is calculated by the absolute calibration method.
  • the extraction rate of the anti-aging agent for rubber is caused by the interaction between the anti-aging agent for rubber and the roasted starch. Indicates a value smaller than the extraction rate of the simple mixture. If the anti-aging agent for rubber is not supported on the roasted starch in the anti-aging agent for rubber, there is no interaction between the anti-aging agent for rubber and the roasted starch, so the extraction rate of the anti-aging agent for rubber is It shows a value equivalent to the extraction rate of a simple mixture.
  • the loading in the present invention includes not only the state where the rubber anti-aging substance is attached to the surface of the roasted starch but also the state where the rubber anti-aging substance is incorporated in the roasted starch. .
  • the content of the roasted starch in the rubber anti-aging agent of the present invention is, for example, 1 to 100 parts by weight, preferably 1 to 50 parts by weight, more preferably 2 to 30 parts by weight with respect to 10 parts by weight of the rubber anti-aging substance. Part.
  • a rubber anti-aging substance is dissolved in a solvent to obtain a solution, and the solution and roasted starch are mixed to obtain a mixture.
  • the roasted starch may be mixed with a solvent to obtain a slurry liquid, and the slurry liquid and a rubber anti-aging substance solution may be mixed to prepare a mixture.
  • the solvent is removed from the mixture to obtain the rubber anti-aging agent of the present invention. You may grind
  • the solvent is not particularly limited as long as it can dissolve the anti-aging substance for rubber and can be distilled off.
  • hydrocarbon solvents such as toluene, xylene, hexane, heptane, acetone, methyl ethyl ketone, etc.
  • ketone solvents such as methyl isobutyl ketone
  • alcohol solvents such as methanol, ethanol and isopropanol.
  • a rubber anti-aging substance is melted to obtain a melt, the melt and roasted starch are mixed to obtain a mixture, and the mixture is cooled to obtain the rubber anti-aging agent of the present invention.
  • the method for cooling the mixture and for example, forced air cooling by blowing or cooling can be employed. You may grind
  • the amount of the roasted starch added is, for example, 1 to 100 parts by weight, preferably 1 to 50 parts by weight, with respect to 10 parts by weight of the antiaging substance for rubber. More preferably, it is 2 to 30 parts by weight.
  • ⁇ Use of anti-aging agent for rubber of the present invention a rubber composition containing the antiaging agent for rubber of the present invention and a rubber component will be described. Only one type of anti-aging agent for rubber of the present invention may be used, or two or more types may be used in combination. Similarly, only 1 type may be used for a rubber component and it may use 2 or more types together.
  • the rubber composition is preferably obtained by kneading the rubber anti-aging agent of the present invention and a rubber component. Kneading can be performed by a known method.
  • the rubber composition may be produced by kneading the rubber anti-aging agent of the present invention and the total amount of rubber component to be used, or the rubber anti-aging agent of the present invention and a part of the rubber component to be used. May be produced by first kneading the master batch and the remaining rubber component.
  • the rubber composition may be a master batch.
  • the rubber composition may further contain a filler, zinc oxide, stearic acid, a crosslinking agent, a vulcanization accelerator and the like.
  • the content of the anti-aging agent for rubber 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 by weight with respect to 100 parts by weight of the rubber component. Part.
  • the content of the anti-aging agent for rubber 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. More preferably, it is 51 to 600 parts by weight, particularly preferably 60 to 500 parts by weight.
  • Natural rubber and modified natural rubber eg, epoxidized natural rubber, deproteinized natural rubber, etc.
  • SBR styrene / butadiene copolymer rubber
  • BR polybutadiene rubber
  • NBR acrylonitrile / butadiene copolymer rubber
  • IIR isoprene / isobutylene copolymer rubber
  • ethylene / propylene-diene copolymer ethylene / propylene-diene copolymer
  • synthetic rubbers such as rubber (EPDM) and halogenated butyl rubber (HR); Can be mentioned.
  • 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 mol% to 60 mol% (specifically, 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.
  • Examples of other modified natural rubbers include, for example, 4-vinylpyridine, N, N-dialkylaminoethyl acrylate (specifically, for example, N, N-diethylaminoethyl acrylate), 2-hydroxy acrylate, etc. Examples thereof include a modified natural rubber containing a polar group obtained by reaction.
  • 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 “Rubber Industry Handbook ⁇ Fourth Edition>” edited by the Japan Rubber Association. Can be mentioned.
  • solution polymerization SBR can be preferably mentioned.
  • solution polymerization SBR in which molecular ends are modified using 4,4′-bis- (dialkylamino) benzophenone such as “Nipol (registered trademark) NS116” manufactured by Nippon Zeon Co., Ltd., “SL574” manufactured by JSR, etc.
  • silane-modified solution polymerized SBR such as “E10” and “E15” manufactured by Asahi Kasei Co., Ltd., lactam compounds, amide compounds, urea compounds, N, N -A dialkylacrylamide compound, an isocyanate compound, an imide compound, a silane compound having an alkoxy group (for example, trialkoxysilane) and an aminosilane compound alone, or a tin compound, an alkylacrylamide compound, and a silane compound having an alkoxy group
  • two or more different compounds such as More preferred examples include solution polymerization SBR having nitrogen, tin, silicon, or a plurality of these elements at the molecular terminals obtained by modifying the molecular terminals.
  • oil-added SBR in which oil such as process oil and aroma oil is added after emulsion polymerization SBR and solution polymerization SBR can be preferably exemplified as a rubber for tread.
  • BR polybutadiene rubber
  • solution polymerization BR such as a high cis BR having 90% or more of cis 1,4 bond and a low cis BR having a cis bond of around 35%.
  • low cis BR having a high vinyl content can be used.
  • tin-modified BR such as “Nipol (registered trademark) BR 1250H” manufactured by Nippon Zeon, 4,4′-bis- (dialkylamino) benzophenone, tin halide compound, lactam compound, amide compound, urea compound, An N, N-dialkylacrylamide compound, an isocyanate compound, an imide compound, a silane compound having an alkoxy group (trialkoxysilane compound, etc.), an aminosilane compound alone, or a tin compound, an alkylacrylamide compound, an alkoxy group
  • a solution polymerization BR or the like having any one of nitrogen, tin, silicon, or a plurality of these elements at the molecular ends obtained by modifying the molecular ends using two or more different compounds such as silane compounds having Can be mentioned.
  • BRs can be preferably cited as tread rubber or sidewall rubber.
  • BR is normally used by the blend with SBR and / or natural rubber.
  • SBR and / or natural rubber is 60 to 100% by weight and BR is 40 to 0% by weight with respect to the total rubber weight.
  • sidewall rubber for example, SBR and / or natural rubber is 10 to 70% by weight, BR is 90 to 30% by weight, preferably natural rubber is 40 to 60% by weight based on the total rubber weight.
  • % BR is 60 to 40% by weight.
  • a blend of modified SBR and non-modified SBR, and blend of modified BR and non-modified BR are also preferred.
  • the filler examples include carbon black, silica, talc, clay, titanium oxide and the like that are usually used in the rubber field.
  • carbon black, silica, etc. are mentioned, for example. More preferably, carbon black etc. can be mentioned, for example.
  • 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).
  • a CTAB Cosmetic Acid Bromide
  • a nitrogen adsorption specific surface area of 20 m 2 / g to 200 m 2 / g
  • a particle diameter of 10 nm to A preferred example is 50 nm carbon black.
  • More preferable examples include carbon black having a CTAB specific surface area of 70 m 2 / g to 180 m 2 / g.
  • N110, N220, N234, N299, N326, N330, N330T, N339, N343, N351 and the like can be mentioned.
  • a surface-treated carbon black in which 0.1 to 50% by weight of silica is attached to the surface of the carbon black can also be preferably exemplified. More preferably, for example, a combination of several kinds of fillers such as a combination of carbon black and silica is used. In the case of the tire tread rubber composition, for example, carbon black alone and both carbon black and silica can be preferably exemplified.
  • carbon black having a CTAB specific surface area of 20 m 2 / g to 60 m 2 / g and a particle diameter of 40 nm to 100 nm can be preferably exemplified.
  • N330, N339, N343, N351, N550, N568, N582, N630, N642, N660, N662, N754, N762 and the like can be mentioned.
  • silica used as the filler examples include silica having a CTAB specific surface area of 50 m 2 / g to 180 m 2 / g, silica having a nitrogen adsorption specific surface area of 50 m 2 / g to 300 m 2 / g, and the like.
  • AQ and “AQ-N” manufactured by Tosoh Silica Co., Ltd. “Ultra Gil (registered trademark) VN3”, “Ultra Gil (registered trademark) 360”, and “Ultra Gil (registered trademark)” manufactured by Degussa.
  • silica having a pH of 6 to 8 silica containing 0.2 to 1.5% by weight of sodium, true spherical silica having a roundness of 1 to 1.3, silicone oil such as dimethyl silicone oil, ethoxy It is also preferable to blend an organosilicon compound containing a silyl group, silica surface-treated with an alcohol such as ethanol or polyethylene glycol; a mixture of two or more types of silica having different nitrogen adsorption specific surface areas; and the like.
  • the amount used is not particularly limited, but is 5 to 120 parts by weight, preferably 5 to 100 parts by weight, and more preferably 10 to 100 parts by weight with respect to 100 parts by weight of the rubber component. 100 parts by weight.
  • the amount of carbon black used is preferably 30 to 80 parts by weight with respect to 100 parts by weight of the rubber component.
  • the amount of carbon black used is, for example, 5 to 60 parts by weight, preferably 5 to 50 parts by weight with respect to 100 parts by weight of the rubber component. Examples of the weight ratio of silica / carbon black include a range of 0.7 / 1 to 1 / 0.1.
  • silica bis (3-triethoxysilylpropyl) tetrasulfide (Degussa “Si-69”), bis (3-triethoxysilylpropyl) disulfide (Degussa “Si-75”) )), Bis (3-diethoxymethylsilylpropyl) tetrasulfide, bis (3-diethoxymethylsilylpropyl) disulfide, octanethioic acid S- [3- (triethoxysilyl) propyl] ester (“3-octanoylthio” “NXT silane” manufactured by General Electronic Silicons Co., Ltd.), octanethioic acid S- [3- (2- ⁇ 3- [2- (3-mercaptopropyl) -4,4,6-trimethyl] [1,3,2] Dioxacillinan-2-yloxy] -1,1-dimethyl Toxi ⁇ -4
  • the addition timing of the compound capable of binding to silica is not particularly limited, but it is preferable to add to the rubber at the same time as silica.
  • the blending amount is, for example, 2 to 10 parts by weight, preferably 7 to 9 parts by weight with respect to 100 parts by weight of silica.
  • Examples of the compounding temperature when compounding a compound capable of binding to silica with rubber include 80 ° C. to 200 ° C., for example. Preferably, for example, 110 ° C. to 180 ° C. may be mentioned.
  • silica when silica is used as the filler, for example, in addition to silica and a compound capable of binding to silica, monohydric alcohols such as ethanol, butanol and octanol; ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene Polyhydric alcohols such as glycol, pentaerythritol, and polyether polyols; N-alkylamines; amino acids; liquid polybutadienes whose molecular ends are carboxyl-modified or amine-modified;
  • monohydric alcohols such as ethanol, butanol and octanol
  • ethylene glycol diethylene glycol, triethylene glycol
  • polyethylene glycol polypropylene
  • Polyhydric alcohols such as glycol, pentaerythritol, and polyether polyols
  • N-alkylamines amino acids
  • liquid polybutadienes whose molecular ends are carboxyl
  • the amount used 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.
  • the amount used 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.
  • the crosslinking agent examples include sulfur.
  • sulfur examples include powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur. Of these, powdered sulfur is preferred.
  • insoluble sulfur is preferable.
  • the sulfur does not contain a vulcanization accelerator.
  • the amount of sulfur used 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.
  • vulcanization accelerator examples 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-benzothiazolylsulfenamide CBS
  • N-tert-butyl-2-benzothiazolylsulfenamide BSS
  • DCBS benzothiazolylsulfenamide
  • MBT 2-mercaptobenzothiazole
  • MBTS dibenzothiazyl disulfide
  • DPG diphenylguanidine
  • morpholine disulfide which is a known vulcanizing agent, can be used.
  • CBS N-cyclohexyl-2-benzothiazolylsulfenamide
  • BSS N-tert-butyl-2-benzothiazolylsulfenamide
  • DPG diphenylguanidine
  • silica and carbon black are used in combination as fillers, for example, N-cyclohexyl-2-benzothiazolylsulfenamide (CBS), N-tert-butyl-2-benzothiazolylsulfenamide (BBS) N, N-dicyclohexyl-2-benzothiazolylsulfenamide (DCBS) or dibenzothiazyl disulfide (MBTS) is preferably used in combination with diphenylguanidine (DPG).
  • CBS N-cyclohexyl-2-benzothiazolylsulfenamide
  • BSS N-tert-butyl-2-benzothiazolylsulfenamide
  • DCBS N-dicyclohexyl-2-benzothiazolylsulfenamide
  • MBTS dibenzothiazyl disulfide
  • DPG diphenylguanidine
  • Compounding agents include, for example, oils; fatty acids such as stearic acid; Coumarone resin G-90 (softening point 80 ° C. to 100 ° C.) manufactured by Nikkaku Chemical, and process resin AC8 (softening point 95 ° C.) manufactured by Kobe Oil Chemical Co., Ltd. ), Etc .; Terpene resins such as terpene resin, terpene / phenol resin, aromatic modified terpene resin; “Nikanol (registered trademark) HP-100” manufactured by Mitsubishi Gas Chemical Co., Ltd.
  • Xylene / formaldehyde resins such as “Ester gum” series and “Neotor” series manufactured by Arakawa Chemical Co., Ltd .; Hydrogenated rosin derivatives; Novolac alkylphenol resins; Resole alkylphenol resins; C5 petroleum resins; Liquid polybutadienes; Can be mentioned.
  • Examples of the oil include process oil and vegetable oil.
  • Examples of the process oil include paraffinic process oil, naphthenic process oil, and aromatic process oil.
  • the vulcanized rubber composition containing the antiaging agent for rubber of the present invention is usually obtained by heat-treating a rubber composition obtained by kneading the antiaging agent for rubber of the present invention, a rubber component and a crosslinking agent.
  • temperature conditions in the heat treatment include 120 ° C. to 180 ° C.
  • the heat treatment may be usually performed at normal pressure or under pressure.
  • the vulcanized rubber composition containing the rubber anti-aging agent of the present invention is suitably used for tires.
  • the tire include a pneumatic tire and a solid tire.
  • the vulcanized rubber composition containing the rubber anti-aging agent of the present invention is a tire comprising a steel cord coated with each member constituting the tire (for example, a vulcanized rubber composition containing the rubber anti-aging agent of the present invention).
  • Sidewall for tires comprising a belt for tires, a carcass for tires containing a carcass fiber cord coated with a vulcanized rubber composition containing an antioxidant for rubber of the present invention, and a vulcanized rubber composition containing an antioxidant for rubber of the present invention , Tire inner liner, tire cap tread or tire under tread).
  • the vulcanized rubber composition containing the antiaging agent for rubber of the present invention can extend the life of rubber materials such as tires. Further, the vulcanized rubber composition can be used not only for the above-mentioned tire use but also as an anti-vibration rubber for automobiles such as an engine mount, a strut mount, a bush, and an exhaust hanger.
  • B2 Dextrin ND-S (yellow dextrin, water content: 10% by weight, viscosity of 50% by weight aqueous solution (30 ° C., 30 rpm): 200 to 550 cps)
  • B3 Dextrin 4-C manufactured by Nissho Chemical Co., Ltd. (white dextrin, water content: 12% by weight, viscosity of 50% by weight aqueous solution (30 ° C., 30 rpm): 400 to 800 cps)
  • the BET specific surface area was calculated by subjecting the measurement results obtained under the above conditions to a specific surface area analysis by the BET method. Moreover, said equilibrium waiting time is a waiting time after reaching an adsorption equilibrium state.
  • Example 1 (Production Example of Anti-aging Agent for Rubber of the Present Invention)
  • 20 g of roasted starch (B1) is charged, and 200 mL of methanol is added thereto to form a slurry liquid.
  • 20 g of rubber anti-aging substance (A1) was charged into a 100 mL Erlenmeyer flask, and 50 mL of methanol was added thereto to obtain a methanol solution.
  • Add a methanol solution of the rubber anti-aging substance (A1) to the beaker of the roasted starch slurry prepared previously, and then wash the 100 mL Erlenmeyer flask containing the methanol solution with 20 mL of methanol.
  • the resulting washing solution was also added to obtain a mixture.
  • the resulting mixture was stirred at 25 ° C. under air for 1 day. After completion of the stirring, the obtained mixture was dried by an evaporator to obtain an antiaging agent for rubber of the present invention (1) as a black solid.
  • Example 2 (Production Example of Anti-aging Agent for Rubber of the Present Invention)
  • the rubber anti-aging agent (2) of the present invention was obtained in the same manner as in Example 1 except that the roasted starch (B1) was changed to the roasted starch (B2).
  • Example 3 (Production example of the anti-aging agent for rubber of the present invention)
  • the rubber anti-aging agent (3) of the present invention was obtained in the same manner as in Example 1 except that the roasted starch (B1) was changed to the roasted starch (B3).
  • Example 1 ⁇ Confirmation of rubber anti-aging agent loading on roasted starch> 0.1 g of the antiaging agent for rubber of the present invention (1) obtained in Example 1 was weighed in a beaker. 30 g of heptane was added to the beaker, and the resulting mixture was subjected to ultrasonic irradiation for 30 minutes. This mixture was subjected to suction filtration, and the solvent was distilled off from the filtrate using an evaporator to obtain a concentrate. By adding methanol to the resulting concentrate, a 20 mL solution was obtained.
  • the obtained solution was subjected to liquid chromatography (LC) (mobile phase: methanol / water, ratio of methanol in the mobile phase [(1) measurement start: 50% by volume, (2) 20% from start to start of measurement] Up to minutes: Increase the methanol ratio by applying a gradient so that the methanol ratio becomes 75% by volume 20 minutes after the start. (3) 20-30 minutes after start: 100% by volume ⁇ 10 minutes with methanol Wash column>]).
  • LC liquid chromatography
  • the extraction rate of the rubber anti-aging agent (1) of the present invention was calculated by an absolute calibration method.
  • the extraction rate of the simple mixture was calculated in the same manner except that 0.1 g of a simple mixture of rubber anti-aging agent 0.05 g and roasted starch 0.05 g was used.
  • the extraction rate of the simple mixture was 99%, whereas the extraction rate of the rubber anti-aging agent (1) of the present invention was 78%. From this, it was confirmed that the anti-aging agent for rubber is supported on the roasted starch in the anti-aging agent for rubber of the present invention (1).
  • Reference Example 1 (Production example of basic rubber composition) A 10-liter kneader was charged with 50 parts by weight of each of commercially available natural rubber (product name: SMR-CV60) and butadiene rubber (product name: JSR BR01, manufactured by JSR Corporation) and kneaded for 2 minutes. After adding materials other than natural rubber and butadiene rubber shown in Table 2 to the obtained kneaded material, the mixture was further kneaded for 10 minutes to obtain a basic rubber composition. The discharge temperature of the rubber composition from the kneader was 95 ° C.
  • Comparative Example 1 (Production Example of Vulcanized Rubber Composition not Containing Anti-aging Agent for Rubber of the Present Invention) 163.5 parts by weight of the basic rubber composition obtained in Reference Example 1, 2 parts by weight of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS)) 0.8 A rubber composition was obtained by kneading 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 heat-pressed at 145 ° C.
  • TBBS N-tert-butyl-2-benzothiazolesulfenamide
  • a vulcanized rubber composition width 15.5 cm, length 16.0 cm, thickness containing neither an antiaging substance for rubber and roasted starch 2 mm sheet shape
  • a vulcanized rubber composition width 15.5 cm, length 16.0 cm, thickness containing neither an antiaging substance for rubber and roasted starch 2 mm sheet shape
  • Reference Example 2 (Method for measuring the migration amount of anti-aging substances for rubber) Using the two vulcanized rubber compositions obtained in Comparative Example 1, the migration amount of the antiaging substance for rubber was measured. Three blank sheets manufactured from a vulcanized rubber composition that does not contain both an anti-aging substance for rubber and roasted starch, and a vulcanized rubber composition that contains an anti-aging substance for rubber and contains no roasted starch The initial weight of each sheet was measured for three measurement sheets manufactured from FIG. 1 is a diagram for explaining a method for measuring the amount of migration of a rubber anti-aging substance in a vulcanized rubber composition.
  • the entire laminate was made of aluminum. Wrapped with foil 7, and then wrapped with aluminum laminate 8 from above. About 3 kg of weights 9 were placed on the aluminum foil 7 and the aluminum laminate 8 package thus obtained. 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 a change in weight from the initial weight of the blank sheet.
  • Example 4 (Production Example of Vulcanized Rubber Composition Containing Antiaging Agent for Rubber of the Present Invention) 163.5 parts by weight of the basic rubber composition obtained in Reference Example 1, 2 parts by weight of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS)) 0.8 By kneading, by weight, 1.5 parts by weight of sulfur, and 6 parts by weight of the anti-aging agent for rubber of the present invention (1) obtained in Example 1 with an open roll machine having a roll set temperature of 60 ° C. A rubber composition was obtained.
  • TBBS N-tert-butyl-2-benzothiazolesulfenamide
  • the obtained rubber composition is heated and press-molded at 145 ° C., so that a vulcanized rubber composition containing the antiaging agent for rubber of the present invention (a sheet shape having a width of 15.5 cm, a length of 16.0 cm, and a thickness of 2 mm).
  • a vulcanized rubber composition containing the antiaging agent for rubber of the present invention (a sheet shape having a width of 15.5 cm, a length of 16.0 cm, and a thickness of 2 mm).
  • a vulcanized rubber composition containing the antiaging agent for rubber of the present invention a sheet shape having a width of 15.5 cm, a length of 16.0 cm, and a thickness of 2 mm.
  • a vulcanized rubber composition width 15.5 cm, length 16.0 cm, thickness containing neither an antiaging substance for rubber and roasted starch 2 mm sheet shape
  • a vulcanized rubber composition width 15.5 cm, length 16.0 cm, thickness containing neither an antiaging substance for rubber and roasted starch 2 mm sheet shape
  • Example 5 (Production Example of Vulcanized Rubber Composition Containing Antiaging Agent for Rubber of the Present Invention) 163.5 parts by weight of the basic rubber composition obtained in Reference Example 1, 2 parts by weight of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS)) 0.8 By kneading, by weight, 1.5 parts by weight of sulfur, and 6 parts by weight of the anti-aging agent for rubber of the present invention (2) obtained in Example 2 with an open roll machine having a roll set temperature of 60 ° C. A rubber composition was obtained.
  • TBBS N-tert-butyl-2-benzothiazolesulfenamide
  • the obtained rubber composition is heated and press-molded at 145 ° C., so that a vulcanized rubber composition containing the antiaging agent for rubber of the present invention (a sheet shape having a width of 15.5 cm, a length of 16.0 cm, and a thickness of 2 mm).
  • a vulcanized rubber composition containing the antiaging agent for rubber of the present invention (a sheet shape having a width of 15.5 cm, a length of 16.0 cm, and a thickness of 2 mm).
  • a vulcanized rubber composition containing the antiaging agent for rubber of the present invention a sheet shape having a width of 15.5 cm, a length of 16.0 cm, and a thickness of 2 mm.
  • a vulcanized rubber composition width 15.5 cm, length 16.0 cm, thickness containing neither an antiaging substance for rubber and roasted starch 2 mm sheet shape
  • a vulcanized rubber composition width 15.5 cm, length 16.0 cm, thickness containing neither an antiaging substance for rubber and roasted starch 2 mm sheet shape
  • Example 6 (Production Example of Vulcanized Rubber Composition Containing Antiaging Agent for Rubber of the Present Invention) 163.5 parts by weight of the basic rubber composition obtained in Reference Example 1, 2 parts by weight of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS)) 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 of the present invention (3) obtained in Example 3 with an open roll machine having a roll set temperature of 60 ° C, A rubber composition was obtained.
  • TBBS N-tert-butyl-2-benzothiazolesulfenamide
  • the obtained rubber composition is heated and press-molded at 145 ° C., so that a vulcanized rubber composition containing the antioxidant for rubber of the present invention (a sheet shape having a width of 15.5 cm, a length of 16.0 cm, and a thickness of 2 mm).
  • a vulcanized rubber composition containing the antioxidant for rubber of the present invention (a sheet shape having a width of 15.5 cm, a length of 16.0 cm, and a thickness of 2 mm).
  • a vulcanized rubber composition containing the antioxidant for rubber of the present invention a sheet shape having a width of 15.5 cm, a length of 16.0 cm, and a thickness of 2 mm.
  • a vulcanized rubber composition width 15.5 cm, length 16.0 cm, thickness containing neither an antiaging substance for rubber and roasted starch 2 mm sheet shape
  • a vulcanized rubber composition width 15.5 cm, length 16.0 cm, thickness containing neither an antiaging substance for rubber and roasted starch 2 mm sheet shape
  • Comparative Example 2 (Production Example of Vulcanized Rubber Composition Containing Both Anti-aging Agent for Rubber and Roasted Starch) 163.5 parts by weight of the basic rubber composition obtained in Reference Example 1, 2 parts by weight of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS)) 0.8 Kneading part by weight, 1.5 parts by weight of sulfur, 3 parts by weight of anti-aging agent for rubber (A1) and 3 parts by weight of roasted starch (B1) with an open roll machine at a roll set temperature of 60 ° C. Thus, a rubber composition was obtained. The obtained rubber composition was heat-pressed at 145 ° C.
  • a vulcanization accelerator N-tert-butyl-2-benzothiazolesulfenamide (TBBS)
  • a vulcanized rubber composition width 15.5 cm, length 16.0 cm, thickness containing both an anti-aging material for rubber and roasted starch 2 mm sheet shape
  • a vulcanized rubber composition width 15.5 cm, length 16.0 cm, thickness containing both an anti-aging material for rubber and roasted starch 2 mm sheet shape
  • a vulcanized rubber composition width 15.5 cm, length 16.0 cm, thickness containing neither an antiaging substance for rubber and roasted starch 2 mm sheet shape
  • a vulcanized rubber composition width 15.5 cm, length 16.0 cm, thickness containing neither an antiaging substance for rubber and roasted starch 2 mm sheet shape
  • a vulcanized rubber composition containing both a rubber anti-aging substance and a roasted starch, and a vulcanized rubber composition not containing both a rubber anti-aging substance and a roasted starch were used in the same manner as in Reference Example 2. The amount of rubber anti-aging substances transferred was measured.
  • compositions of the vulcanized rubber compositions obtained in Examples 4 to 6 and Comparative Examples 1 and 2 and the composition of the rubber anti-aging agent used are shown in Table 3, and the migration rate of the rubber anti-aging substances is shown in Table 4. Show.
  • the unit of numerical values shown in Table 3 is parts by weight.
  • the “migration rate of the rubber anti-aging substance” described in Table 4 is the rubber anti-aging substance in the vulcanized rubber composition of Comparative Example 1 containing the rubber anti-aging substance and not containing the roasted starch. This is the relative transfer amount of the anti-aging material for rubber when the transfer amount of the substance is 100.
  • Example 4 when the roasted starch and the rubber anti-aging substance were added separately, the present invention was such that the rubber anti-aging substance was supported on the roasted starch. It was confirmed that the migration rate of the rubber anti-aging substance does not decrease compared to the case where the rubber anti-aging agent is added.
  • Reference Example 3 (Production Example of Vulcanized Rubber Composition)
  • the vulcanized 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 (manufactured by Asahi Carbon Co., Ltd., product name “Asahi # 80”) ] 35 parts by weight, stearic acid 2 parts by weight, zinc oxide 3 parts by weight, anti-aging agent for rubber of the present invention obtained in Example 1 (1) 4 parts by weight and wax ("OZOACE-0355" manufactured by Nippon Seiwa) 2) 2 parts by weight are kneaded in a range of 160 ° C.
  • Reference Example 4 (Production Example of Vulcanized Rubber Composition)
  • the vulcanized 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., product name “Asahi # 70”), stearic acid 3 parts by weight, 5 parts by weight of zinc oxide, 10 parts by weight of hydrous silica (“Nipsil (registered trademark) AQ” manufactured by Tosoh Silica Co., Ltd.), 8 parts by weight of the antiaging agent for rubber of the present invention (1) obtained in Example 1
  • 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 ° C.
  • Reference Example 5 (Production Example of Vulcanized Rubber Composition)
  • the vulcanized 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 ° C. to 175 ° C.
  • Reference Example 6 (Production Example of Vulcanized Rubber Composition)
  • the vulcanized rubber composition obtained by the following first step and second step is suitable for side walls.
  • 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, 3 parts by weight of zinc oxide, 8 parts by weight of the anti-aging agent for rubber of the present invention (1) obtained in Example 1, 10 parts by weight of process oil (“NC-140” manufactured by Cosmo Oil Co., Ltd.)
  • a rubber composition was prepared by kneading 2 parts by weight of wax (“Sannok (registered trademark) wax” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.) within a range of 160 ° C.
  • Reference Example 7 (Production Example of Vulcanized Rubber Composition)
  • the vulcanized 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 and process oil (“Diana Process PS32” by Idemitsu Kosan Co., Ltd.) 7 parts by weight within a range of 160 ° C.
  • a rubber composition is obtained by kneading at a rotation speed of a mixer of 50 rpm.
  • a rubber kneaded product is obtained by kneading 3 parts by weight of sulfur and 4 parts by weight of the antiaging agent for rubber of the present invention (1) obtained in Example 1.
  • ⁇ Second step> The rubber kneaded product obtained in the first step (procedure 2) is heat-treated at 145 ° C. to obtain a vulcanized rubber.
  • Reference Example 8 (Production Example of Vulcanized Rubber Composition)
  • the vulcanized 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 lab plast mill manufactured by Toyo Seiki Seisakusho), 100 parts by weight of styrene / butadiene copolymer rubber SBR # 1500 (manufactured by JSR), silica (product name: “Ultrasil (registered trademark) VN3-G” 78.4 parts by weight of Degussa), 6.4 parts by weight of carbon black (product name “N-339” manufactured by Mitsubishi Chemical), silane coupling agent (bis (3-triethoxysilylpropyl) tetrasulfide: product name 6.4 parts by weight of “Si-69” manufactured by Degussa Co., Ltd., 47.6 parts by weight of process oil (product name “NC-140” manufactured by Cosmo Oil Co
  • Reference Example 9 (Production Example of Vulcanized Rubber Composition)
  • solution-polymerized SBR (“ASAPrene (registered trademark)” manufactured by Asahi Kasei Chemicals) was used instead of styrene-butadiene copolymer rubber SBR # 1500 (manufactured by JSR).
  • SBR # 1500 styrene-butadiene copolymer rubber SBR # 1500 (manufactured by JSR).
  • Reference Example 10 (Production Example of Vulcanized Rubber Composition)
  • SBR # 1500 styrene-butadiene copolymer rubber
  • SBR # 1712 manufactured by JSR
  • the amount of process oil used was changed to 21 parts by weight, and zinc oxide was charged.
  • a vulcanized rubber composition is obtained in the same manner as in Reference Example 8 except that the timing is changed to Procedure 2.
  • the resulting vulcanized rubber composition is suitable for cap treads.
  • the vulcanized rubber composition is the same as in Reference Examples 3 to 10. Things are obtained.
  • the durability of the antiaging effect of the antiaging substance for rubber contained therein is improved.

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Abstract

L'invention fournit un agent antivieillissement pour caoutchouc qui comprend un amidon torréfié, et une substance antivieillissement pour caoutchouc supportée par l'amidon torréfié.
PCT/JP2012/082451 2011-12-16 2012-12-14 Agent antivieillissement pour caoutchouc WO2013089215A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61111343A (ja) * 1984-11-06 1986-05-29 Bridgestone Corp 改良されたゴム組成物
JPH03227336A (ja) * 1990-01-31 1991-10-08 Kinugawa Rubber Ind Co Ltd ゴム組成物
JP2002211203A (ja) * 2001-01-19 2002-07-31 Sumitomo Rubber Ind Ltd スタッドレスタイヤ
JP2005281383A (ja) * 2004-03-29 2005-10-13 Sumitomo Rubber Ind Ltd タイヤ用ゴム組成物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61111343A (ja) * 1984-11-06 1986-05-29 Bridgestone Corp 改良されたゴム組成物
JPH03227336A (ja) * 1990-01-31 1991-10-08 Kinugawa Rubber Ind Co Ltd ゴム組成物
JP2002211203A (ja) * 2001-01-19 2002-07-31 Sumitomo Rubber Ind Ltd スタッドレスタイヤ
JP2005281383A (ja) * 2004-03-29 2005-10-13 Sumitomo Rubber Ind Ltd タイヤ用ゴム組成物

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