WO2013094719A1 - Agent anti-vieillissement pour caoutchoucs - Google Patents

Agent anti-vieillissement pour caoutchoucs Download PDF

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Publication number
WO2013094719A1
WO2013094719A1 PCT/JP2012/083188 JP2012083188W WO2013094719A1 WO 2013094719 A1 WO2013094719 A1 WO 2013094719A1 JP 2012083188 W JP2012083188 W JP 2012083188W WO 2013094719 A1 WO2013094719 A1 WO 2013094719A1
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rubber
weight
parts
aging
rubber composition
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PCT/JP2012/083188
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English (en)
Japanese (ja)
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志津香 岩田
進 森
井山　浩暢
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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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • 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

Definitions

  • the present invention relates to an anti-aging agent for rubber.
  • Patent Document 1 describes a vulcanized rubber composition containing N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine, which is an anti-aging material for rubber, and silica. .
  • the conventional vulcanized rubber composition contains the rubber anti-aging substance itself as it is, and its anti-aging effect may not always be sufficiently satisfactory in terms of sustainability.
  • the present invention includes the following inventions.
  • 3 pore volume of the mesopores is equal to or less than 0.84 cm 3 / g or more 5.0 cm 3 / g. Or 2.
  • the peak chemical shift based on 13 C contained in the rubber anti-aging substance supported on the mesoporous silica is based on 13 C contained in the rubber anti-aging substance not supported on the mesoporous silica. 1. It is different from the chemical shift of the peak. ⁇ 3.
  • the mesoporous silica has a mesopore diameter of 6 nm or more and 50 nm or less. ⁇ 4.
  • the rubber anti-aging substance is a compound represented by the formula (I): ⁇ 4. The anti-aging agent for rubber
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 13 carbon atoms.
  • the mesoporous silica is contained in an amount of 0.1 to 100 parts by weight with respect to 10 parts by weight of the rubber anti-aging material. ⁇ 6.
  • gum as described in any one of these.
  • the durability of the antiaging effect of the antiaging substance for rubber contained therein is improved.
  • FIG. 2 is a diagram showing the results of solid state NMR measurement of the rubber anti-aging agent (1) of the present invention obtained in Example 1.
  • FIG. It is a figure explaining the method for measuring the transfer amount of the antiaging substance for rubber
  • 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.
  • mesoporous silica with a mesopore volume exceeding 0.81 cm 3 / g>
  • the composition formula of mesoporous silica is SiO 2 ⁇ nH 2 O, and the CAS registration number of silica is 7631-86-9.
  • mesoporous silica means silica having mesopores, and mesopores mean pores having a diameter of 2 nm or more and 50 nm or less in the catalyst field in IUPAC.
  • the mesoporous silica those having relatively large mesopores on the surface are preferable.
  • the mesopore diameter of the mesoporous silica is preferably 6 nm or more and 50 nm or less.
  • the diameter of the mesopore is an average value of the diameters of the pores measured by the nitrogen adsorption method (BJH method) under the conditions described in the examples described later.
  • the mesoporous silica used in the present invention has a mesopore volume exceeding 0.81 cm 3 / g.
  • the pore volume of the mesopores is preferably not more than 0.84 cm 3 / g or more 5.0 cm 3 / g, more preferably not more than 1.0 cm 3 / g or more 5.0 cm 3 / g, particularly preferably Is 1.3 cm 3 / g or more and 5.0 cm 3 / g or less.
  • the pore volume of the mesopores can be measured by a nitrogen adsorption method (BJH method) under the conditions described in Examples described later.
  • the BET specific surface area of mesoporous silica is preferably 10 m 2 / g or more and 550 m 2 / g or less, more preferably 20 m 2 / g or more and 500 m 2 / g or less, and further preferably 25 m 2 / g or more and 400 m 2 / g or less.
  • This BET specific surface area can be measured by the method described in Examples described later.
  • Examples of commercially available mesoporous silica having a mesopore volume exceeding 0.81 cm 3 / g include Fuji Silysia Silicia 310P, 420, and 530, Fuji Silysia Silophobic 100, 507, and 702.
  • a rubber anti-aging substance is supported on mesoporous silica.
  • the rubber anti-aging substance is preferably supported in the mesopores of mesoporous silica.
  • the content of mesoporous silica in the rubber anti-aging agent of the present invention is, for example, 0.1 to 100 parts by weight, preferably 0.1 to 50 parts by weight, more preferably 0 to 10 parts by weight of the rubber anti-aging substance. 1 to 30 parts by weight.
  • 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 mesoporous silica, and examples thereof include the following method (1) and the following method (2). be able to.
  • a rubber anti-aging substance is dissolved in a solvent to obtain a solution, and the solution and mesoporous silica are mixed to obtain a mixture.
  • mesoporous silica may be mixed with a solvent to obtain a slurry, and the slurry may be mixed with a solution of an antiaging substance for rubber 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 material is melted to obtain a melt, the melt and mesoporous silica 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 mesoporous silica added is, for example, 0.1 to 100 parts by weight, preferably 0.1 to 100 parts by weight with respect to 10 parts by weight of the rubber anti-aging substance. 50 parts by weight, more preferably 0.1 to 30 parts by weight.
  • the anti-aging material for rubber is supported on mesoporous silica (particularly in the mesopores).
  • mesoporous silica particularly in the mesopores.
  • the presence or absence of a change in the chemical shift of the peak based on 13 C contained in the rubber anti-aging substance may be observed before and after the rubber anti-aging substance is supported on mesoporous silica.
  • a change occurs in the three-dimensional structure, and as a result, a change in the chemical shift of the peak based on 13 C contained in the anti-aging substance for rubber occurs. And what is necessary is just to confirm that this change exists by solid state NMR measurement.
  • the rubber anti-aging substance is not supported on the mesoporous silica, the interaction between the functional group of the rubber anti-aging substance and the functional group of the mesoporous silica does not occur, and as a result, it is included in the rubber anti-aging substance. No change in peak chemical shift based on 13 C occurs. And what is necessary is just to confirm by solid-state NMR measurement that this change does not exist.
  • ⁇ 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 antioxidant for rubber of the present invention in the rubber composition is, for example, 0.1 to 50 parts by weight, preferably 0.5 to 30 parts by weight, more preferably 1 to 1 part by weight with respect to 100 parts by weight of the rubber component. 20 parts by weight.
  • the content of the anti-aging agent for rubber of the present invention in the rubber composition is, for example, 1 to 990 parts by weight, preferably 1 to 900 parts by weight with respect to 100 parts by weight of the rubber component. More preferably, it is 1 to 700 parts by weight, particularly preferably 1 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.
  • Example 1 (Production Example of Anti-aging Agent for Rubber of the Present Invention) A 500 mL beaker is charged with 20 g of mesoporous silica (B1), and 200 mL of methanol is added thereto to form a slurry liquid. On the other hand, 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.
  • the resulting mixture was stirred at 25 ° C. under air for 1 day. After the stirring was completed, the resulting mixture was dried by an evaporator to obtain an antiaging agent for rubber of the present invention (1) as a gray solid.
  • Example 2 (Production Example of Anti-aging Agent for Rubber of the Present Invention) An anti-aging agent (2) for rubber of the present invention was obtained in the same manner as in Example 1 except that the mesoporous silica (B1) was changed to the mesoporous silica (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 mesoporous silica (B1) was changed to the mesoporous silica (B3).
  • Measuring device BELSORP-mini (manufactured by Nippon BEL Co., Ltd.)
  • Pretreatment device BELPREP-vacII (manufactured by Nippon BEL Co., Ltd.)
  • Test method Nitrogen adsorption method
  • Pretreatment method Vacuum degassing at 120 ° C.
  • 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.
  • Reference Example 3 (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 2 (Production Example of Vulcanized Rubber Composition not Containing Antiaging Agent for Rubber of the Present Invention) 163.5 parts by weight of the basic rubber composition obtained in Reference Example 3, 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 resulting rubber composition was heat-press molded 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 agent for rubber nor mesoporous silica 2 mm sheet shape
  • a vulcanized rubber composition width 15.5 cm, length 16.0 cm, thickness containing neither an antiaging agent for rubber nor mesoporous silica 2 mm sheet shape
  • Reference Example 4 Method for measuring the migration amount of anti-aging substances for rubber
  • the amount of migration of the rubber anti-aging substance was measured.
  • Three blank sheets manufactured from a vulcanized rubber composition that does not contain both an antioxidant for rubber and mesoporous silica, and a vulcanized rubber composition that contains an antioxidant for rubber and does not contain mesoporous silica The initial weight of each sheet was measured for three measurement sheets to be measured.
  • FIG. 3 is a diagram for explaining a method for measuring the amount of migration of the rubber anti-aging substance in the 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 3, 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.
  • the amount of migration of the rubber anti-aging substance was measured in the same manner as in Reference Example 4. did.
  • 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 3, 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.
  • the amount of migration of the rubber anti-aging substance was measured in the same manner as in Reference Example 4. did.
  • 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 3, 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.
  • a vulcanization accelerator N-tert-butyl-2-benzothiazolesulfenamide (TBBS)
  • 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.
  • the amount of migration of the rubber anti-aging substance was measured in the same manner as in Reference Example 4. did.
  • Comparative Example 3 ((X1) Production Example of Vulcanized Rubber Composition Containing Anti-aging Agent for Supported Rubber) 163.5 parts by weight of the basic rubber composition obtained in Reference Example 3, 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 supported rubber (X1) obtained in Comparative Example 1 with an open roll machine having a roll set temperature of 60 ° C., rubber is obtained. A composition was obtained. The obtained rubber composition was hot-pressed at 145 ° C.
  • TBBS N-tert-butyl-2-benzothiazolesulfenamide
  • a vulcanized rubber composition sheet having a width of 15.5 cm, a length of 16.0 cm, and a thickness of 2 mm
  • (X1) an anti-aging agent for a supported rubber shape
  • X1 an anti-aging agent for a supported rubber.
  • Shape shape
  • 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 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.
  • Reference Example 5 ((X2) Production Example of Vulcanized Rubber Composition Containing Antiaging Agent for Supported Rubber) 163.5 parts by weight of the basic rubber composition obtained in Reference Example 3, 2 parts by weight of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS)) 0.8 By kneading the weight part, 1.5 parts by weight of sulfur, and 6 parts by weight of the anti-aging agent for supported rubber (X2) obtained in Reference Example 1 with an open roll machine having a roll set temperature of 60 ° C., rubber is obtained. A composition was obtained. The obtained rubber composition was heat-press molded at 145 ° C.
  • TBBS N-tert-butyl-2-benzothiazolesulfenamide
  • a vulcanized rubber composition sheet having a width of 15.5 cm, a length of 16.0 cm and a thickness of 2 mm
  • (X2) an anti-aging agent for a supported rubber shape
  • X2 an anti-aging agent for a supported rubber.
  • Shape a vulcanized rubber composition
  • Reference Example 6 ((X3) Production Example of Vulcanized Rubber Composition Containing Anti-aging Agent for Supported Rubber) 163.5 parts by weight of the basic rubber composition obtained in Reference Example 3, 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 supported rubber (X3) obtained in Reference Example 2 with an open roll machine having a roll set temperature of 60 ° C., rubber is obtained. A composition was obtained. The obtained rubber composition was hot-pressed at 145 ° C.
  • TBBS N-tert-butyl-2-benzothiazolesulfenamide
  • a vulcanized rubber composition sheet having a width of 15.5 cm, a length of 16.0 cm and a thickness of 2 mm
  • (X3) an anti-aging agent for a supported rubber shape
  • X3 an anti-aging agent for a supported rubber.
  • Table 3 shows the compositions of the vulcanized rubber compositions obtained in Examples 4 to 6, Comparative Examples 2 and 3, and Reference Examples 5 and 6, and the composition of the rubber anti-aging agent used.
  • Table 4 shows the transition speed.
  • 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 includes the rubber anti-aging substance obtained in Comparative Example 2, and the rubber for the vulcanized rubber composition containing no mesoporous silica. This is the relative transfer amount of the anti-aging material for rubber when the transfer amount of the anti-aging material is 100. The smaller the value, the slower the migration rate of the anti-aging material for rubber, which means that the durability of the anti-aging effect in the vulcanized rubber composition is improved.
  • 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 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) 8 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 8 (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, zinc oxide 5 parts by weight, hydrous silica ("Nipsil (registered trademark) AQ" manufactured by Tosoh Silica Co., Ltd.) 10 parts by weight, anti-aging agent for rubber of the present invention (1) obtained in Example 1 (16) 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 9 (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 10 (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, zinc oxide 3 parts by weight, anti-aging agent for rubber of the present invention obtained in Example 1 (1) 16 parts by weight, process oil (“NC-140” manufactured by Cosmo Oil Co., Ltd.) 10 parts by weight
  • 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 11 (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, 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 8 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 12 (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 Laboplast Mill, manufactured by Toyo Seiki Seisakusho), 100 parts by weight of styrene / butadiene copolymer rubber SBR # 1500 (manufactured by JSR), silica (product name: “Ultrasil® 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., Ltd.
  • Reference Example 13 (Production Example of Vulcanized Rubber Composition)
  • SBR solution-polymerized SBR
  • SBR # 1500 styrene-butadiene copolymer rubber
  • Reference Example 14 (Production Example of Vulcanized Rubber Composition)
  • SBR # 1712 manufactured by JSR
  • SBR # 1500 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 12 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 7-14. Things are obtained.
  • the durability of the antiaging effect of the antiaging substance for rubber contained therein is improved.

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

La présente invention concerne un agent anti-vieillissement pour caoutchoucs qui comprend : une silice mésoporeuse, dans laquelle le volume de pore de chacun des mésopores est supérieur à 0,81 cm3/g, et une substance anti-vieillissement pour caoutchoucs qui est appliquée sur la silice mésoporeuse.
PCT/JP2012/083188 2011-12-21 2012-12-21 Agent anti-vieillissement pour caoutchoucs WO2013094719A1 (fr)

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CN114213714A (zh) * 2021-12-02 2022-03-22 赛轮集团股份有限公司 多孔硅负载防老剂-银离子复合物、其制备方法及应用
CN114437408A (zh) * 2020-10-16 2022-05-06 中国石油化工股份有限公司 改性过氧化物硫化剂及其制备方法和应用
CN115536914A (zh) * 2022-10-17 2022-12-30 山西浙大新材料与化工研究院 一种复合防老剂及其制备方法、耐热橡胶材料

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JP2011132472A (ja) * 2009-12-25 2011-07-07 Toyo Tire & Rubber Co Ltd ゴム組成物及びその製造方法、並びに空気入りタイヤ
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CN114437408A (zh) * 2020-10-16 2022-05-06 中国石油化工股份有限公司 改性过氧化物硫化剂及其制备方法和应用
CN114437408B (zh) * 2020-10-16 2023-07-21 中国石油化工股份有限公司 改性过氧化物硫化剂及其制备方法和应用
CN114213714A (zh) * 2021-12-02 2022-03-22 赛轮集团股份有限公司 多孔硅负载防老剂-银离子复合物、其制备方法及应用
CN115536914A (zh) * 2022-10-17 2022-12-30 山西浙大新材料与化工研究院 一种复合防老剂及其制备方法、耐热橡胶材料
CN115536914B (zh) * 2022-10-17 2023-06-09 山西浙大新材料与化工研究院 一种复合防老剂及其制备方法、耐热橡胶材料

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