JP5705089B2 - Anti-aging agent for rubber - Google Patents

Description

  The present invention relates to an anti-aging agent for rubber.

  Patent Document 1 describes N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine as an anti-aging material for rubber.

JP 2007-238803 A

  In a vulcanized rubber composition containing the conventional rubber anti-aging substance itself as it is, the anti-aging effect may not always be sufficiently satisfactory in terms of sustainability.

（式（Ｉ）中、Ｒ^１は、水素原子又は炭素数１〜１３のアルキル基を表す。）；
４．ゴム用老化防止物質１０質量部に対して、ゼオライト１質量部〜１００質量部を含有することを特徴とする前項１〜３のいずれかの前項記載のゴム用老化防止剤；
等を提供するものである。 As a result of intensive studies under these circumstances, the present inventors have reached the present invention.
1. An anti-aging agent for rubber obtained by supporting an anti-aging agent for rubber on zeolite (hereinafter sometimes referred to as "anti-aging agent for rubber of the present invention");
2. In solid state NMR measurement, the peak chemical shift based on ²⁹ Si contained in the zeolite carrying the rubber anti-aging substance is compared with the peak chemical shift based on ²⁹ Si contained in the zeolite not carrying the rubber anti-aging substance. The rubber anti-aging agent according to the item 1, characterized in that
3. 3. The rubber anti-aging agent according to item 1 or 2, wherein the zeolite is a zeolite containing pores having a minimum number of oxygen atom member rings of 8 or more;
4). The rubber anti-aging agent according to any one of the preceding items 1 to 3, wherein the rubber anti-aging substance is a compound represented by the formula (I)

(In formula (I), R ¹ represents a hydrogen atom or an alkyl group having 1 to 13 carbon atoms);
4). The antiaging agent for rubber according to any one of the preceding items 1 to 3, which comprises 1 to 100 parts by mass of zeolite with respect to 10 parts by mass of the antiaging substance for rubber;
Etc. are provided.

  In the vulcanized rubber composition containing the antiaging agent for rubber of the present invention, the durability of the antiaging effect is improved.

It is a figure which shows the result of the solid-state NMR measurement of anti-aging agent (1) for rubber | gum of this invention. It is a figure explaining the method for measuring the transfer amount of the antiaging substance for rubber | gum in a vulcanized rubber composition.

<Rubber aging prevention substances>
The “anti-aging agent 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. The “anti-aging agent for rubber” in the present invention is not particularly limited, and examples thereof include those described in pages 436 to 443 of “Rubber Industry Handbook <Fourth Edition>” edited by the Japan Rubber Association. be able to. Specifically, for example, N-phenyl-N′-1,3-dimethylbutyl-p-phenylenediamine (6PPD), reaction product of aniline and acetone (TMDQ), poly (2,2,4-trimethyl-1) , 2-) Dihydroquinoline) (“Antioxidant FR” manufactured by Matsubara Sangyo Co., Ltd.), synthetic wax (paraffin wax, etc.), vegetable wax, compound represented by formula (I), or compound represented by formula (II) Etc.
Preferable examples include substances having a relatively low molecular weight (specifically, for example, a molecular weight of about 150 to 400).
More preferable examples include a compound represented by the formula (I) or a compound represented by the formula (II).

（式（Ｉ）中、Ｒ^１は、水素原子又は炭素数１〜１３のアルキル基を表す。）

(In formula (I), R ¹ represents a hydrogen atom or an alkyl group having 1 to 13 carbon atoms.)

（式（ＩＩ）中、Ｒ^２は、水素原子又は、炭素数１〜１３のアルキル基を表す。Ｒ^３は、水素原子又は、炭素数１〜１３のアルコキシ基を表す）

(In formula (II), 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)

  More specifically, for example, N-isopropyl-N′-phenyl-p-phenylenediamine (IPPD), N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine (6PPD), ETMDQ ( 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline) and 2,2,4-trimethyl-1,2-dihydroquinoline.

<Zeolite>
The “zeolite” in the present invention is generally called zeolite, and the composition formula M _n O _m · xAl ₂ O ₃ · ySiO ₂ · zH ₂ O (M in the composition formula is not limited to metals, It represents an element belonging to Group 13. n, m, x, y, and z represent integers.), Which is a hydrous aluminosilicate having CAS registration number 1318-02-1.
The “zeolite” in the present invention is not particularly limited, but for example, those having relatively large voids in the crystal structure are preferable.
Preferable “zeolite” includes, for example, zeolite containing pores having a minimum number of member rings of oxygen atoms of 8 or more. Preferable examples include zeolite containing pores having a minimum number of member rings of oxygen atoms of 12 or more. More preferably, for example, a zeolite containing only pores having a minimum number of member rings of oxygen atoms of 12 or more can be used.
Here, the “pore” means a cylindrical part into which another substance (molecule) can enter from the outside of the zeolite. Specific examples include zeolite pores described in Yoshio Ono and Isao Suzuki, “Adsorption Science and Application”, page 121.
In addition, the “minimum number of oxygen atom ring” means the number of oxygen atoms when the number of oxygen atoms is counted on the circumference forming the pores of the zeolite so as to be the minimum. .

Specific examples of the “zeolite” in the present invention include Ch. Baerlocher, Lynn B. et al. McCusker, D.C. H. DON, SFH, SFN, CFI, AFI, MTW, VFI, GFI, MFI, RFI, MTL, LTL, based on the Framework Type Code compiled by Olson “Atlas of Zeolite Framework Types” (ELSEVIER) , Zeolites classified into SSY, FAU, BEA, EMT, ISV, BEC, UTL, and the like. Preferably, zeolite classified into FAU, UTL, BEA etc. is mentioned, for example.
Examples of zeolite classified as FAU include Faujasite, USY-type zeolite, Y-type zeolite, and X-type zeolite. Examples of zeolite classified as UTL include IM-12 type zeolite and ITQ-15 type zeolite.

The rubber anti-aging agent of the present invention is obtained by supporting an anti-aging agent for rubber on zeolite.
As content of the zeolite in this rubber | gum anti-aging agent, it is good to contain 1 mass part-100 mass parts of zeolite with respect to 10 mass parts of anti-aging substances for rubber | gum, for example. More preferably, it is good to contain 1 mass part-50 mass parts with respect to 10 mass parts of antiaging substances for rubber | gum, for example. Particularly preferably, for example, 2 to 30 parts by mass may be contained with respect to 10 parts by mass of the rubber anti-aging substance.

  The method for producing the anti-aging agent for rubber of the present invention is not particularly limited as long as it can support the anti-aging material for rubber on zeolite. For example, the following method (1), the following method (2), etc. Can be mentioned.

<Method for producing anti-aging agent for rubber of the present invention>
(1): After the rubber anti-aging substance is dissolved in a solvent, zeolite is added to the resulting solution to obtain a mixture. The solvent is then removed from the mixture and the solid is dried (and crushed). Here, the “solvent” is not particularly limited as long as it can dissolve the anti-aging substance for rubber and can be removed by distillation. For example, hydrocarbon solvents such as toluene, xylene, hexane, heptane, etc. And ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and alcohol solvents such as methanol, ethanol and isopropanol.

(2): After the rubber anti-aging material is melted, zeolite is added to the resulting melt to obtain a mixture. Next, a method of drying (and crushing) the mixture.

  In the method (1) and the method (2), examples of the addition amount of zeolite include 1 part by mass to 100 parts by mass with respect to 10 parts by mass of the antiaging substance for rubber. Preferably, 1 mass part-50 mass parts are mentioned with respect to 10 mass parts of antiaging substances for rubber | gum, for example. More preferably, for example, 2 to 30 parts by mass can be mentioned with respect to 10 parts by mass of the anti-aging agent for rubber.

Incidentally, it can be easily confirmed, for example, by solid state NMR measurement that the rubber anti-aging substance is supported on the zeolite. Specifically, for example, the presence or absence of a change in the chemical shift of the peak based on ²⁹ Si contained in the zeolite may be observed before and after the rubber anti-aging substance is supported on the zeolite.
By supporting the rubber anti-aging substance on the zeolite, an interaction between the functional group of the rubber anti-aging substance and the functional group of the zeolite surface occurs, and as a result, the chemical shift of the peak based on ²⁹ Si contained in the zeolite Changes occur. And what is necessary is just to confirm by the solid state NMR measurement that the said change exists. On the other hand, if the rubber anti-aging substance is not supported on the zeolite, the interaction between the functional group of the rubber anti-aging substance and the functional group of the zeolite surface does not occur, and as a result, the peak based on ²⁹ Si contained in the zeolite No change in chemical shift occurs. And what is necessary is just to confirm by the solid state NMR measurement that the said change does not exist.

<Use of anti-aging agent for rubber of the present invention>
The rubber composition containing the antiaging agent for rubber of the present invention contains an antiaging material for rubber, zeolite and a rubber component. The rubber composition containing the antiaging agent for rubber of the present invention is preferably obtained by kneading the antiaging agent for rubber of the present invention and a rubber component. Kneading can be performed by a known method. The rubber composition containing the rubber anti-aging agent of the present invention is, for example, a master batch (usually a vulcanized rubber composition) used to produce a more uniform vulcanized rubber composition having a more constant quality. And a rubber composition containing a high-concentration anti-aging material for rubber, which is a granular material in which a rubber component and a large amount of the anti-aging agent for rubber of the present invention are pre-kneaded before production of .). The rubber composition containing the rubber anti-aging agent of the present invention may be a kneaded rubber composition further containing a filler, zinc oxide, stearic acid, a crosslinking agent, a vulcanization accelerator component, and the like.

Examples of the content of the anti-aging agent for rubber of the present invention in the rubber composition containing the anti-aging agent for rubber of the present invention include 0.1 parts by mass to 990 parts by mass with respect to 100 parts by mass of the rubber component. Can do.
When the rubber composition containing the rubber anti-aging agent of the present invention is a kneaded rubber composition further containing a filler, zinc oxide, stearic acid, a crosslinking agent, a vulcanization accelerator component, and the like, Examples of the content of the anti-aging agent for rubber of the present invention in the rubber composition containing an agent include 0.1 to 50 parts by mass, preferably 100 parts by mass of the rubber component, For example, 1 mass part-30 mass parts can be mentioned. More preferably, for example, 2 to 20 parts by mass can be used.
When the rubber composition containing the antiaging agent for rubber of the present invention is a masterbatch used for producing a vulcanized rubber composition, the rubber of the present invention in the rubber composition containing the antiaging agent for rubber of the present invention Examples of the content of the anti-aging agent include 11 parts by mass to 990 parts by mass, preferably 31 parts by mass to 990 parts by mass with respect to 100 parts by mass of the rubber component. More preferably, for example, 51 parts by weight to 600 parts by weight can be mentioned, and particularly preferably, for example, 60 parts by weight to 500 parts by weight can be mentioned.

  Examples of rubber components include natural rubber, epoxidized natural rubber, deproteinized natural rubber and other modified natural rubber, polyisoprene rubber (IR), styrene / butadiene copolymer rubber (SBR), polybutadiene rubber (BR), acrylonitrile. Examples include various synthetic rubbers such as butadiene copolymer rubber (NBR), isoprene / isobutylene copolymer rubber (IIR), ethylene / propylene-diene copolymer rubber (EPDM), and halogenated butyl rubber (HR). Preferable examples include natural rubber, highly unsaturated rubber such as styrene / butadiene copolymer rubber and polybutadiene rubber. More preferably, natural rubber etc. can be mentioned. It is also effective to combine several rubber components such as a combination of natural rubber and styrene / butadiene copolymer rubber, a combination of natural rubber and polybutadiene 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 a deproteinized natural rubber having a total nitrogen content of 0.3% by mass or less.
As the modified natural rubber, for example, 4-vinylpyridine, N, N-dialkylaminoethyl acrylate (specifically, N, N-diethylaminoethyl acrylate, etc.), 2-hydroxy acrylate, etc. are reacted in advance with natural rubber. And modified natural rubber containing a polar group.

Examples of the styrene-butadiene copolymer rubber (SBR) include emulsion polymerization SBR and solution polymerization SBR described in pages 210 to 211 of the “Rubber Industry Handbook <Fourth Edition>” edited by the Japan Rubber Association. Can be mentioned. As the rubber composition for tread, for example, solution polymerization SBR can be preferably mentioned. Further, for example, solution polymerization SBR in which molecular ends are modified using 4,4′-bis- (dialkylamino) benzophenone such as “Nippol (registered trademark) NS116” manufactured by Nippon Zeon Co., Ltd., “SL574” manufactured by JSR, etc. Solution-polymerized SBR having a molecular end modified with a tin halide compound of No. 1, commercially available products of silane-modified solution-polymerized SBR such as “E10” and “E15” manufactured by Asahi Kasei Corporation, lactam compounds, amide compounds, urea compounds, N, An N-dialkylacrylamide compound, an isocyanate compound, an imide compound, a silane compound having an alkoxy group (trialkoxysilane compound, etc.) and an aminosilane compound alone, or a silane compound having a tin compound and an alkoxy group, Alkylacrylamide compounds and silane compounds having alkoxy groups A solution polymerization SBR having a plurality of different compounds such as nitrogen, tin, silicon, or a plurality of elements at the molecular ends obtained by modifying the molecular ends, respectively. More preferred can be mentioned.
An oil-extended SBR obtained by adding an oil such as process oil or aroma oil after polymerization into emulsion polymerization SBR and solution polymerization SBR can also be preferably mentioned as a rubber composition for tread.

Examples of the polybutadiene rubber (BR) include 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%. Preferably, for example, low cis BR having a high vinyl content can be used. Furthermore, for example, “Nipol (registered trademark) BR 1250H” manufactured by Nippon Zeon, tin-modified BR, 4,4′-bis- (dialkylamino) benzophenone, tin halide compound, lactam compound, amide compound, urea compound, etc. , N, N-dialkylacrylamide compound, isocyanate compound, imide compound, silane compound having alkoxy group (trialkoxysilane compound, etc.), aminosilane compound alone, or silane having tin compound and alkoxy group A compound, a plurality of different compounds such as an alkylacrylamide compound and an alkoxy group-containing silane compound, or the like, and each of the molecular ends obtained by modifying the molecular ends is nitrogen, tin, or silicon, or , Solution polymerization BR having a plurality of these elements It can be cited more preferably.
These BR can be preferably mentioned as a rubber composition for a tread or a rubber composition for a sidewall. Usually, it is used in a blend of SBR and / or natural rubber. As a blend ratio, in the case of a rubber composition for treads, SBR and / or natural rubber is 60% by mass to 100% by mass, BR is 0% by mass to 40% by mass, etc. with respect to the total rubber mass. Can do. Moreover, in the case of the rubber composition for sidewalls, SBR and / or natural rubber may be 10% by mass to 70% by mass, BR may be 90% by mass to 30% by mass, etc. with respect to the total rubber mass. . Preferably, a blend of natural rubber 40% by mass to 60% by mass and BR 60% by mass to 40% by mass with respect to the total rubber mass. In this case, a blend of modified SBR and non-modified SBR and a blend of modified BR and non-modified BR are also preferable.

Examples of the filler include carbon black, silica, talc, clay, titanium oxide and the like that are usually used in the rubber field. Preferably, carbon black, silica, etc. are mentioned, for example. More preferably, carbon black etc. can be mentioned, for example.
Examples of the carbon black include those described on page 494 of “Rubber Industry Handbook <Fourth Edition>” edited by the Japan Rubber Association. Preferably, for example, HAF (High Abrasion Furnace), SAF (Super Abrasion Furnace), ISAF (Intermediate SAF), FEF (Fast Extrusion Furnace), MAF, GPF (General Purpose Furnace), SRF (Semi-Reinforcing Furnace), etc. Carbon black is mentioned.
In the case of tire tread rubber composition, CTAB (Cetyl Tri-methyl Ammonium Bromide) surface area 40m ² / g~250m ² / g, nitrogen adsorption specific surface area 20m ² / g~200m ² / g, particle size 10nm~50nm Preferably, carbon black can be mentioned. More preferably, for example, carbon black and the like is CTAB surface 70m ² / g~180m ² / g. Specifically, for example, in the ASTM standard, N110, N220, N234, N299, N326, N330, N330T, N339, N343, N351 and the like can be mentioned. Moreover, the surface treatment carbon black which made 0.1 mass%-50 mass% adhere the silica to the surface of carbon black can also be mentioned preferably. More preferably, for example, a combination of several 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 or both carbon black and silica can be preferably mentioned.
In the case of the carcass rubber composition, the rubber composition for a side wall is, CTAB surface area of 20m ² / g~60m ² / g, it can be preferably exemplified a carbon black particle size 40 nm to 100 nm. Specifically, for example, in the ASTM standard, N330, N339, N343, N351, N550, N568, N582, N630, N642, N660, N662, N754, N762 and the like can be mentioned.

  Although the usage-amount of this filler is not specifically limited, For example, 5 mass parts-100 mass parts can be mentioned with respect to 100 mass parts of rubber components. In the case of using only carbon black as a filler, for example, 30 to 80 parts by mass is preferably cited with respect to 100 parts by mass of the rubber component. Moreover, when using together carbon black and a silica as a filler in a tread member use, 5-60 mass parts of carbon black is mentioned preferably with respect to 100 mass parts of rubber components, for example.

The silica used as a filler, for example, a CTAB specific surface area 50m ² / g~180m ² / g of silica, silica nitrogen adsorption specific surface area 50m ² / g~300m ² / g or the like. Specifically, for example, “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. 7000 ”,“ Zeosil (registered trademark) 115GR ”,“ Zeosil (registered trademark) 1115MP ”,“ Zeosil (registered trademark) 1205MP ”,“ Zeosil (registered trademark) Z85MP ”manufactured by Rhodia, (Registered trademark) AQ "and the like. Further, for example, silica having a pH of 6 to 8, silica containing 0.2% by mass to 1.5% by mass of sodium, true spherical silica having a roundness of 1 to 1.3, silicone oil such as dimethyl silicone oil It is also preferable to blend an organosilicon compound containing an ethoxysilyl group, silica surface-treated with an alcohol such as ethanol or polyethylene glycol, silica having two or more different nitrogen adsorption specific surface areas, and the like.

Although the usage-amount of this filler is not specifically limited, For example, 10 mass parts-120 mass parts can be mentioned with respect to 100 mass parts of rubber components.
Moreover, when mix | blending a silica, it is good to mix | blend 5-50 mass parts of carbon black with respect to 100 mass parts of rubber components, for example. As a compounding ratio of silica / carbon black, the range of 0.7 / 1-1 / 0.1 can be mentioned, for example.
When silica is used as the filler, bis (3-triethoxysilylpropyl) tetrasulfide (“Si-69” manufactured by Degussa), bis (3-triethoxysilylpropyl) disulfide (“Si-Si” manufactured by Degussa) -75 "), bis (3-diethoxymethylsilylpropyl) tetrasulfide, bis (3-diethoxymethylsilylpropyl) disulfide, octanethioic acid S- [3- (triethoxysilyl) propyl] ester (General Electronic Silicones) "NXT silane"), octanethioic acid S- [3-{(2-methyl-1,3-propanedialkoxy) ethoxysilyl} propyl] ester and octanethioic acid S- [3-{(2-methyl-1) , 3-propanedialkoxy) methylsilyl} propyl] ester Rutriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, n-octyltrimethoxysilane , N-octyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (methoxyethoxy) silane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, 3-methacryloxypropyltrimethoxysilane, 3 -Methacryloxypropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) ) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxy Silane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyl It is preferable to add a compound having a functional group such as an element such as silicon or alkoxysilane that can be bonded to silica, such as one or more silane coupling agents selected from the group consisting of triethoxysilane. Specifically, for example, bis (3-triethoxysilylpropyl) tetrasulfide (“Si-69” manufactured by Degussa), bis (3-triethoxysilylpropyl) disulfide (“Si-75” manufactured by Degussa), 3 -Octanoylthiopropyltriethoxysilane ("NXT silane" manufactured by General Electronic Silicones) and the like can be mentioned.
Although the addition time of these compounds is not particularly limited, it is preferable to add to the rubber at the same time as the silica. As a compounding quantity, 2 mass%-10 mass% can be mentioned with respect to the mass of a silica, for example. Preferably, 7 mass%-9 mass% are mentioned, for example.
As compounding temperature at the time of compounding the above-mentioned compound with rubber, 80 ° C-200 ° C can be mentioned, for example. Preferably, 110 degreeC-180 degreeC is mentioned, for example.
When silica is used as the filler, for example, monohydric alcohols such as ethanol, butanol, octanol, etc., in addition to compounds having functional groups such as silica, elements such as silicon that can be bonded to silica, or alkoxysilane. , Ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, pentaerythritol, polyether polyol and other dihydric alcohols, N-alkylamines, amino acids, liquid polybutadienes whose molecular ends are carboxyl-modified or amine-modified, Etc. may be blended.

  As usage-amount of a zinc oxide, 1 mass part-15 mass parts can be mentioned with respect to 100 mass parts of rubber components, for example. Preferably, 1 mass part-8 mass parts are mentioned, for example.

  As a usage-amount of a stearic acid, 0.5 mass part-10 mass parts can be mentioned with respect to 100 mass parts of rubber components, for example. Preferably, 1 mass part-5 mass parts are mentioned, for example.

  As a crosslinking agent, sulfur etc. can be mentioned, for example. Examples of sulfur include powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur. Preferably, powder sulfur etc. are mentioned. Moreover, when using for tire members with many amounts of sulfur, such as a member for belts, insoluble sulfur etc. can be mentioned preferably, for example. Note that the sulfur does not contain a vulcanization accelerator. As usage-amount of sulfur, 0.3 mass part-5 mass parts can be mentioned with respect to 100 mass parts of rubber components, for example. Preferably, 0.5 mass part-3 mass parts are mentioned, for example.

  Examples of the vulcanization accelerator include thiazole-based vulcanization accelerators and sulfenamide-based vulcanization accelerators described in pages 412 to 413 of “Rubber Industry Handbook <Fourth Edition>” edited by the Japan Rubber Association. And guanidine vulcanization accelerators.

Specifically, for example, N-cyclohexyl-2-benzothiazolylsulfenamide (CBS), N-tert-butyl-2-benzothiazolylsulfenamide (BBS), N, N-dicyclohexyl-2- Examples include benzothiazolylsulfenamide (DCBS), 2-mercaptobenzothiazole (MBT), dibenzothiazyl disulfide (MBTS), and diphenylguanidine (DPG). Also, morpholine disulfide, which is a known vulcanizing agent, can be used.
When carbon black is used as the filler, for example, N-cyclohexyl-2-benzothiazolylsulfenamide (CBS), N-tert-butyl-2-benzothiazolylsulfenamide (BBS), N, N It is preferable to use either dicyclohexyl-2-benzothiazolylsulfenamide (DCBS) or dibenzothiazyl disulfide (MBTS) and diphenylguanidine (DPG).
When 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) and diphenylguanidine (DPG) are preferably used in combination.

Although it does not restrict | limit especially as a ratio of sulfur and a vulcanization accelerator, For example, sulfur / vulcanization accelerator = 2 / 1-1 / 2 can be mentioned by mass ratio.
EV vulcanization in which the mass ratio of sulfur / vulcanization accelerator, which is a method for improving heat resistance in a rubber member mainly composed of natural rubber, is 1 or less is preferably used in applications requiring improvement in heat resistance.

  In addition, you may mix | blend various compounding agents normally used in the rubber | gum field | area. Examples of such compounding agents include 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 (softened) manufactured by Kobe Oil Chemical Co., Ltd. Coumarone-indene resin such as terpene resin, terpene / phenol resin, aromatic modified terpene resin, etc .; “Nikanol (registered trademark) HP-100” (softening point 105-105) manufactured by Mitsubishi Gas Chemical Company 125 ° C.) xylene / formaldehyde resin; rosin derivatives such as “Ester gum” series and “neotol” series manufactured by Arakawa Chemical Co .; hydrogenated rosin derivatives; novolac alkylphenol resins; resol alkylphenol resins; Resin; liquid polybutadiene;

  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.

<Vulcanized rubber composition containing anti-aging agent for rubber of the present invention>
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. As temperature conditions in heat processing, 120 degreeC-180 degreeC can be mentioned, for example. 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. Examples of 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, that is, 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 It is also suitably used as a tire inner liner, a tire cap tread, or a tire under tread.

  The vulcanized rubber composition containing the rubber anti-aging agent 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 engine mounts, strut mounts, bushes, and exhaust hangers.

EXAMPLES Hereinafter, although an Example, a reference example, a comparative example, etc. are given and this invention is demonstrated concretely, this invention is not limited to these.
<Rubber aging prevention substances>
A1: Antigen 6C (N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine) manufactured by Sumitomo Chemical Co., Ltd.
<Zeolite>
B1: Union Showa Co., Ltd. HiSiv-6000 (FAU-USY type)
B2: Union Showa Co., Ltd. molecular sieve 13X (FAU-X type)
B3: H-Mordenite (MOR type) manufactured by NE CHEMCAT
B4: Union Showa's HiSiv-3000 (MFI type)

Example 1 (Production Example of Anti-aging Agent for Rubber of the Present Invention)
A 200 ml beaker was charged with 3 parts by mass of an anti-aging material for rubber (A1), and 80 ml of acetone was added thereto to obtain an acetone solution of the anti-aging material for rubber (A1). By adding the obtained acetone solution into a 200 ml beaker containing 9 parts by mass of zeolite (B1), and further adding a washing solution produced by washing the 200 ml beaker containing the acetone solution with 20 ml of acetone. A mixture was obtained. The resulting mixture was stirred at 25 ° C. under air for 5 days. After completion of the stirring, the obtained mixture was dried for 25 days to obtain an antiaging agent for rubber of the present invention (1) as a blue-violet solid.

Example 2 (Production Example of Anti-aging Agent for Rubber of the Present Invention)
In the same manner as in Example 1 except that the amount of the rubber anti-aging substance (A1) was changed to 3 parts by mass and the amount of the zeolite (B1) was changed to 3 parts by mass, the rubber anti-aging agent (2) of the present invention was used. Obtained.

Example 3 (Production example of the anti-aging agent for rubber of the present invention)
An anti-aging agent (3) for rubber of the present invention was obtained in the same manner as in Example 1 except that the zeolite (B1) was changed to the zeolite (B2).

Reference Example 11 (Preparation of rubber for anti-aging agent)
Except that zeolite (B1) was changed to Zeolite (B3) in the same manner as in Example 1 to obtain rubber for anti-aging agent (4).

Reference Example 12 (Preparation of rubber for anti-aging agent)
Except that zeolite (B1) was changed to Zeolite (B4) in the same manner as in Example 1 to obtain rubber for anti-aging agent (5).

In addition, the content rate of the anti-aging substance for rubber | gum in this invention anti-aging agent for rubber | gum was confirmed with the following method.
<Method of extracting anti-aging substances for rubber>
1. A 1M KCl aqueous solution: acetone = 1: 1 (mass ratio) solution was prepared.
2. 0.5 g of the antiaging agent for rubber of the present invention was weighed in a beaker.
3. 2. The above 1. 100 mL of the solution obtained in the above was added, and the resulting mixture was subjected to ultrasonic irradiation (irradiation time was 30 minutes, 60 minutes, and 90 minutes).
4). 3. above. The mixture obtained in was filtered with suction. The filter cake was washed until the color of the rubber anti-aging substance (red) disappeared. Such an operation was performed to collect the filtrate.
5. 4. above. From the filtrate collected in step 1, the solvent was distilled off under reduced pressure using an evaporator to obtain a concentrate.
6). 5. above. By adding dimethylformamide to the concentrate obtained in step 50, a 50 mL solution was obtained.
7). Above 6. The solution obtained in the above was subjected to liquid chromatography (LC) (mobile phase: phosphate buffer / acetonitrile / water system).
8). The content of the anti-aging agent for rubber in the anti-aging agent for rubber of the present invention was calculated by the following formula.
<Calculation formula>
Content of anti-aging agent for rubber in anti-aging agent for rubber of the present invention (actual value) (%)
= ((UV detection peak area of anti-aging agent for rubber on LC) -5385.7) / 1324900

About the anti-aging agent for rubber of the present invention obtained in the Examples, the content of the anti-aging agent for rubber confirmed by the above extraction method was compared with the theoretical value. The theoretical value is a value calculated by the following method.
<Calculation formula>
Content of rubber anti-aging substances (theoretical value) (%)
= 100 x (Rubber anti-aging substance charge) / (Rubber anti-aging substance charge + Zeolite charge)
For example, Table 1 shows values obtained for the anti-aging agent for rubber of the present invention (2) obtained in Example 2.

<Confirmation of loading of rubber anti-aging agent on zeolite by solid state NMR measurement>
0.5 g of the antiaging agent for rubber of the present invention (1) obtained in Example 1 was weighed in a beaker. 100 g of heptane was added to the beaker, and the resulting mixture was subjected to ultrasonic irradiation for 30 minutes. The resulting mixture was filtered with suction. The obtained filtrate was washed once with 5 mL of heptane and then collected. Next, after the collected filtrate was dried, solid NMR measurement was performed on the obtained filtrate under the following conditions. The result is shown in FIG.
When comparing before and after loading of rubber anti-aging substances on zeolite, we observed changes in the peak chemical shift based on ²⁹ Si contained in zeolite, confirming the loading of rubber anti-aging substances on zeolite. .

[Solid state NMR measurement conditions]
Device: ECA400 [manufactured by JEOL Ltd.]
MAS: 6kHz
Measurement: ²⁹ Si CPMAS
contact time: 8ms
Integration: 10,000 times

Reference Example 1 (Production example of basic rubber composition)
Into a 10 L kneader, 50 parts by mass of both natural rubber (product name: SMR-CV60) and butadiene rubber (product name: JSR BR01, manufactured by JSR Corporation) were added and kneaded for 2 minutes. After adding the materials shown in Table 2 to the obtained kneaded product, the mixture was further kneaded for 10 minutes to obtain a rubber composition as 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 mass of the basic rubber composition obtained in Reference Example 1, 2 parts by mass of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS)) 0.8 A rubber composition was obtained by kneading parts by mass and 1.5 parts by mass of sulfur with an open roll machine having a roll set temperature of 60 ° C. The obtained rubber composition was hot press molded at 145 ° C. Thus, a vulcanized rubber composition not containing the antiaging agent for rubber of the present invention in the form of a sheet having a width of 15.5 cm, a length of 16.0 cm and a thickness of 2 mm (however, both an antiaging agent for rubber and zeolite) was obtained the exclusive). Incidentally, between 90% vulcanization of the measured rubber composition in conformity with JIS K 6300-2 to _(t c (90)) than the extended 5 minutes time and vulcanization time .
Next, 163.5 parts by mass of the basic rubber composition obtained in Reference Example 1, 2 parts by mass of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS)) A rubber composition was obtained by kneading 0.8 parts by mass, 1.5 parts by mass of sulfur, and 3 parts by mass of an anti-aging agent for rubber (A1) with an open roll machine having a roll set temperature of 60 ° C. . The obtained rubber composition is heated and press-molded at 145 ° C. to obtain a vulcanized rubber having a width of 15.5 cm, a length of 16.0 cm, and a thickness of 2 mm, which does not contain the antiaging agent for rubber of the present invention. A composition (however, containing a rubber anti-aging substance and no zeolite) was obtained. Incidentally, between 90% vulcanization of the measured rubber composition in conformity with JIS K 6300-2 to _(t c ₍₉₀₎₎ than the extended 5 minutes time and the vulcanization time.

Reference Example 2 (Method for measuring the migration amount of anti-aging substances for rubber)
Vulcanized rubber composition containing no anti-aging agent for rubber of the present invention (however, it does not contain both an anti-aging substance for rubber and zeolite) and a vulcanized rubber composition containing no anti-aging agent for rubber of the present invention (however, The amount of migration of the rubber anti-aging substance was measured using a rubber anti-aging substance and no zeolite.
4 sheets manufactured from a vulcanized rubber composition containing no anti-aging agent for rubber of the present invention (but not including both an anti-aging material for rubber and zeolite) and an anti-aging agent for rubber of the present invention The initial weight of each sheet was measured for four sheets produced from a non-vulcanized rubber composition (but containing rubber anti-aging material and no zeolite).
FIG. 2 is a diagram for explaining a method for measuring the migration amount of the rubber anti-aging substance in the vulcanized rubber composition. 8 sheets after weight measurement (sheets 1 to 4 produced from a vulcanized rubber composition containing an antioxidant for rubber of the present invention, manufactured from a vulcanized rubber composition not containing an antioxidant for rubber of the present invention) After the sheets 5 to 8) were laminated, the entire laminate was wrapped with an aluminum foil 9 and further wrapped with an aluminum laminate 10. About 3 kg of weight 11 was placed on the aluminum foil and the aluminum laminate 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 antiaging substance for rubber was defined as a change in weight from the initial weight of the sheet produced from the vulcanized rubber composition not containing the antiaging agent for rubber of the present invention. Separately, as a result of extracting and quantifying the anti-aging agent for rubber from the vulcanized rubber composition of each sheet, it was confirmed that the weight change was caused by the migration of the anti-aging agent for rubber.

Example 6 (Production Example of Vulcanized Rubber Composition Containing Antiaging Agent for Rubber of the Present Invention)
163.5 parts by mass of the basic rubber composition obtained in Reference Example 1, 2 parts by mass of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS)) 0.8 By kneading 12 parts by mass of an anti-aging agent for rubber of the present invention (1) obtained in Example 1 with a mass part, 1.5 parts by mass of sulfur, and an open roll machine with a roll set temperature of 60 ° C, A rubber composition was obtained. The obtained rubber composition is heated and press-molded at 145 ° C. to form a vulcanized rubber composition containing the antioxidant for rubber of the present invention in the form of a sheet having a width of 15.5 cm, a length of 16.0 cm, and a thickness of 2 mm. I got a thing. Incidentally, between 90% vulcanization of the measured rubber composition in conformity with JIS K 6300-2 to _(t c ₍₉₀₎₎ than the extended 5 minutes time and the vulcanization time.

(Production Example of Vulcanized Rubber Composition not Containing Anti-aging Agent for Rubber of the Present Invention)
On the other hand, 163.5 parts by mass of the basic rubber composition obtained in Reference Example 1, 2 parts by mass of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS)] 0 The rubber composition was obtained by kneading 8 parts by mass, 1.5 parts by mass of sulfur, and 9 parts by mass of zeolite (B1) with an open roll machine having a roll set temperature of 60 ° C. By heat-pressing the composition at 145 ° C., a vulcanized rubber composition containing a sheet-shaped sheet having a width of 15.5 cm, a length of 16.0 cm, and a thickness of 2 mm, which does not contain the antioxidant for rubber of the present invention (however, From the 90% vulcanization time (t _c (90)) of the rubber composition measured according to JIS K 6300-2, 5 was obtained. The time extended for a minute was taken as the vulcanization time.
Using a vulcanized rubber composition containing the antiaging agent for rubber of the present invention and a vulcanized rubber composition not containing the antiaging agent for rubber of the present invention (however, containing no antiaging substance for rubber and containing zeolite), In the same manner as in Reference Example 2, the amount of migration of the rubber anti-aging substance was measured.

Example 7 (Production Example of Vulcanized Rubber Composition Containing Antiaging Agent for Rubber of the Present Invention)
163.5 parts by mass of the basic rubber composition obtained in Reference Example 1, 2 parts by mass of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS)) 0.8 By kneading a mass part, 1.5 parts by mass of sulfur, and 6 parts by mass 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. The obtained rubber composition is heated and press-molded at 145 ° C. to form a vulcanized rubber composition containing the antioxidant for rubber of the present invention in the form of a sheet having a width of 15.5 cm, a length of 16.0 cm, and a thickness of 2 mm. I got a thing. Incidentally, between 90% vulcanization of the measured rubber composition in conformity with JIS K 6300-2 to _(t c ₍₉₀₎₎ than the extended 5 minutes time and the vulcanization time.

(Production Example of Vulcanized Rubber Composition not Containing Anti-aging Agent for Rubber of the Present Invention)
On the other hand, 163.5 parts by mass of the basic rubber composition obtained in Reference Example 1, 2 parts by mass of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS)] 0 A rubber composition was obtained by kneading 0.8 parts by mass, 1.5 parts by mass of sulfur, and 3 parts by mass of zeolite (B1) with an open roll machine having a roll set temperature of 60 ° C. By heat-pressing the composition at 145 ° C., a vulcanized rubber composition containing a sheet-shaped sheet having a width of 15.5 cm, a length of 16.0 cm, and a thickness of 2 mm, which does not contain the antioxidant for rubber of the present invention (however, From the 90% vulcanization time (t _c (90)) of the rubber composition measured according to JIS K 6300-2, 5 was obtained. The time extended for a minute was taken as the vulcanization time.
Using a vulcanized rubber composition containing the antiaging agent for rubber of the present invention and a vulcanized rubber composition not containing the antiaging agent for rubber of the present invention (however, containing no antiaging substance for rubber and containing zeolite), In the same manner as in Reference Example 2, the amount of migration of the rubber anti-aging substance was measured.

Example 8 (Production Example of Vulcanized Rubber Composition Containing Antiaging Agent for Rubber of the Present Invention)
163.5 parts by mass of the basic rubber composition obtained in Reference Example 1, 2 parts by mass of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS)) 0.8 By kneading 12 parts by mass of an 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. The obtained rubber composition is heated and press-molded at 145 ° C. to form a vulcanized rubber composition containing the antioxidant for rubber of the present invention in the form of a sheet having a width of 15.5 cm, a length of 16.0 cm, and a thickness of 2 mm. I got a thing. Incidentally, between 90% vulcanization of the measured rubber composition in conformity with JIS K 6300-2 to _(t c ₍₉₀₎₎ than the extended 5 minutes time and the vulcanization time.

(Production Example of Vulcanized Rubber Composition not Containing Anti-aging Agent for Rubber of the Present Invention)
On the other hand, 163.5 parts by mass of the basic rubber composition obtained in Reference Example 1, 2 parts by mass of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS)] 0 A rubber composition was obtained by kneading 0.8 parts by mass, 1.5 parts by mass of sulfur, and 9 parts by mass of zeolite (B2) with an open roll machine having a roll set temperature of 60 ° C. By heat-pressing the composition at 145 ° C., a vulcanized rubber composition containing a sheet-shaped sheet having a width of 15.5 cm, a length of 16.0 cm, and a thickness of 2 mm, which does not contain the antioxidant for rubber of the present invention (however, From the 90% vulcanization time (t _c (90)) of the rubber composition measured according to JIS K 6300-2, 5 was obtained. The time extended for a minute was taken as the vulcanization time.
Using a vulcanized rubber composition containing the antiaging agent for rubber of the present invention and a vulcanized rubber composition not containing the antiaging agent for rubber of the present invention (however, containing no antiaging substance for rubber and containing zeolite), In the same manner as in Reference Example 2, the amount of migration of the rubber anti-aging substance was measured.

Reference Example 13 (Production Example of Vulcanized Rubber Composition Containing Rubber Antiaging Agent)
163.5 parts by mass of the basic rubber composition obtained in Reference Example 1, 2 parts by mass of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS)) 0.8 and parts by weight, and the sulfur 1.5 parts by mass, and reference example 11 obtained in rubber for anti-aging agent (4) 12 parts by mass, by kneading at a roll set temperature 60 ° C. in an open roll mill, rubber A composition was obtained. Obtained in rubber compositions 145 ° C., by hot pressing, width 15.5cm, length 16.0 cm, the sheet shape having a thickness of 2 mm, a vulcanized rubber composition containing an antioxidant for rubber Got. Incidentally, between 90% vulcanization of the measured rubber composition in conformity with JIS K 6300-2 to _(t c ₍₉₀₎₎ than the extended 5 minutes time and the vulcanization time.

(Preparation of vulcanized rubber composition which does not contain an antioxidant for rubber)
On the other hand, 163.5 parts by mass of the basic rubber composition obtained in Reference Example 1, 2 parts by mass of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS)] 0 A rubber composition was obtained by kneading 0.8 parts by mass, 1.5 parts by mass of sulfur, and 9 parts by mass of zeolite (B3) with an open roll machine having a roll set temperature of 60 ° C. the composition at 145 ° C., by hot pressing, width 15.5cm, length 16.0 cm, the sheet shape having a thickness of 2 mm, a vulcanized rubber composition which does not contain an antioxidant for rubber (provided that 5 minutes from the 90% vulcanization time (t _c (90)) of the rubber composition measured according to JIS K 6300-2. The extended time was taken as the vulcanization time.
Gore vulcanized rubber composition comprising a beam for antioxidant及beauty rubber for anti-aging agent contains no vulcanized rubber composition (excluding the rubber anti-aging agent, containing zeolite) using a reference In the same manner as in Example 2, the amount of migration of the rubber anti-aging substance was measured.

Reference Example 14 (Production of the vulcanized rubber composition containing an antioxidant for rubber)
163.5 parts by mass of the basic rubber composition obtained in Reference Example 1, 2 parts by mass of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS)) 0.8 and parts by weight, and the sulfur 1.5 parts by mass, and reference example 12 obtained in rubber for anti-aging agent (5) 12 parts by mass, by kneading at a roll set temperature 60 ° C. in an open roll mill, rubber A composition was obtained. Obtained in rubber compositions 145 ° C., by hot pressing, width 15.5cm, length 16.0 cm, the sheet shape having a thickness of 2 mm, a vulcanized rubber composition containing an antioxidant for rubber Got. Incidentally, between 90% vulcanization of the measured rubber composition in conformity with JIS K 6300-2 to _(t c ₍₉₀₎₎ than the extended 5 minutes time and the vulcanization time.

(Preparation of vulcanized rubber composition which does not contain an antioxidant for rubber)
On the other hand, 163.5 parts by mass of the basic rubber composition obtained in Reference Example 1, 2 parts by mass of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS)] 0 The rubber composition was obtained by kneading 0.8 parts by mass, 1.5 parts by mass of sulfur, and 9 parts by mass of zeolite (B4) with an open roll machine having a roll set temperature of 60 ° C. the composition at 145 ° C., by hot pressing, width 15.5cm, length 16.0 cm, the sheet shape having a thickness of 2 mm, a vulcanized rubber composition which does not contain an antioxidant for rubber (provided that 5 minutes from the 90% vulcanization time (t _c (90)) of the rubber composition measured according to JIS K 6300-2. The extended time was taken as the vulcanization time.
Gore vulcanized rubber composition comprising a beam for antioxidant及beauty rubber for anti-aging agent contains no vulcanized rubber composition (excluding the rubber anti-aging agent, containing zeolite) using a reference In the same manner as in Example 2, the amount of migration of the rubber anti-aging substance was measured.

Comparative Example 2 (Production Example of Vulcanized Rubber Composition not Containing Antiaging Agent for Rubber of the Present Invention)
163.5 parts by mass of the basic rubber composition obtained in Reference Example 1, 2 parts by mass of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS)) 0.8 Kneading part by mass, 1.5 parts by mass of sulfur, 3 parts by mass of the antioxidant for rubber of the present invention (A1), and 3 parts by mass of zeolite (B1) with an open roll machine having a roll set temperature of 60 ° C. Thus, a rubber composition was obtained. The obtained rubber composition is heated and press-molded at 145 ° C. to obtain a vulcanized rubber having a width of 15.5 cm, a length of 16.0 cm, and a thickness of 2 mm, which does not contain the antiaging agent for rubber of the present invention. A composition (however, containing both an antiaging material for rubber and zeolite) was obtained. Incidentally, between 90% vulcanization of the measured rubber composition in conformity with JIS K 6300-2 to _(t c ₍₉₀₎₎ than the extended 5 minutes time and the vulcanization time.

(Production Example of Vulcanized Rubber Composition not Containing Anti-aging Agent for Rubber of the Present Invention)
On the other hand, 163.5 parts by mass of the basic rubber composition obtained in Reference Example 1, 2 parts by mass of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS)] 0 A rubber composition was obtained by kneading 0.8 parts by mass, 1.5 parts by mass of sulfur, and 3 parts by mass of zeolite (B1) with an open roll machine having a roll set temperature of 60 ° C. By heat-pressing the composition at 145 ° C., a vulcanized rubber composition containing a sheet-shaped sheet having a width of 15.5 cm, a length of 16.0 cm, and a thickness of 2 mm, which does not contain the antioxidant for rubber of the present invention (however, From the 90% vulcanization time (t _c (90)) of the rubber composition measured according to JIS K 6300-2, 5 was obtained. The time extended for a minute was taken as the vulcanization time.
Vulcanized rubber composition containing no anti-aging agent for rubber of the present invention (including both an anti-aging substance for rubber and zeolite) and a vulcanized rubber composition containing no anti-aging agent for rubber of the present invention (provided that The amount of migration of the rubber anti-aging substance was measured in the same manner as in Reference Example 2 except that the rubber anti-aging substance was contained and the zeolite was contained.

The results obtained are summarized in Table 4.
The "migration rate of rubber anti-aging substances" described in Table 4 is a vulcanized rubber composition containing no anti-aging agent for rubber of the present invention obtained in Comparative Example 1 (however, anti-aging substances for rubber) Is the relative migration amount of the anti-aging material for rubber in Examples 6 to 10 and Comparative Example 2 when the migration amount of the anti-aging material for rubber 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. Further, as is clear from the comparison between Comparative Example 2 and Example 7, when the zeolite and the rubber anti-aging substance were added separately, the rubber anti-aging substance was supported on the zeolite (that is, It was also confirmed that the migration rate of the rubber anti-aging substance does not decrease compared to the case of adding as the rubber anti-aging agent of the present invention.

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 (600ml Lab Plast Mill manufactured by Toyo Seiki Co., Ltd.), 100 parts by mass of styrene / butadiene copolymer rubber SBR # 1502 (manufactured by Sumitomo Chemical Co., Ltd.), ISAF-HM (manufactured by Asahi Carbon Co., Ltd., trade name "Asahi # 80") ) 35 parts by mass, 2 parts by mass of stearic acid, 3 parts by mass of zinc oxide, 1 part by mass of sodium salt of S- (3-aminopropyl) thiosulfuric acid, anti-aging agent for rubber of the present invention obtained in Example 1 (1 ) 8 parts by mass and 2 parts by mass of wax (“OZOACE-0355” manufactured by Nippon Seiwa) were kneaded in the range of 160 ° C. to 175 ° C. for 5 minutes at a rotation speed of a mixer of 50 rpm, thereby producing rubber. A composition is obtained.
(Procedure 2)
The rubber composition obtained in step 1 and 2 parts by mass of N-cyclohexyl-2-benzothiazolesulfenamide (CBS) as a vulcanization accelerator within the range of 60 ° C. to 80 ° C. in an open roll machine. By kneading 0.5 parts by mass of diphenylguanidine (DPG) as a vulcanization accelerator, 0.8 parts by mass of dibenzothiazyl disulfide (MBTS) as a vulcanization accelerator and 1 part by mass of sulfur, rubber was obtained. A kneaded product is obtained.
<Second step>
The rubber kneaded material obtained in the first step (procedure 2) is heat-treated at 145 ° C. to obtain a vulcanized rubber composition.

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 Co., Ltd.), 100 parts by mass of commercially available natural rubber (RSS # 1), 45 parts by mass of HAF (Asahi Carbon Co., Ltd., trade name “Asahi # 70”), stearic acid 3 1 part by mass, 5 parts by mass of zinc oxide, 1 part by mass of sodium salt of S- (3-aminopropyl) thiosulfuric acid, 10 parts by mass of hydrous silica (“Nipsil (registered trademark) AQ” manufactured by Tosoh Silica Co., Ltd.) The obtained anti-aging agent for rubber of the present invention (1) 16 parts by mass, resorcin 2 parts by mass and cobalt naphthenate 2 parts by mass within the range of 160 ° C. to 175 ° C. for 5 minutes at a rotation speed of a mixer of 50 rpm. A rubber composition is obtained by kneading.
(Procedure 2)
The rubber composition obtained in Procedure 1 and N, N-dicyclohexyl-2-benzothiazolesulfenamide (DCBS) 1 as a vulcanization accelerator within the range of 60 ° C. to 80 ° C. in an open roll machine. A rubber kneaded material is obtained by kneading 3 parts by mass of 6 parts by mass of sulfur, 6 parts by mass of sulfur, and 3 parts by mass of a methoxylated methylol melamine resin (“SUMIKANOL 507AP” manufactured by Sumitomo Chemical Co., Ltd.).
<Second step>
The rubber kneaded material obtained in the first step (procedure 2) is heat-treated at 145 ° C. to obtain a vulcanized rubber composition.

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 Co., Ltd.), 100 parts by mass of halogenated butyl rubber (“Br-IIR2255” manufactured by ExxonMobil), 60 parts by mass of GPF, 1 part by mass of stearic acid, 3 parts by mass of zinc oxide, 1 part by mass of sodium salt of S- (3-aminopropyl) thiosulfuric acid and 10 parts by mass of paraffin oil (“Diana Process Oil” manufactured by Idemitsu Kosan Co., Ltd.) within the range of 160 ° C. to 175 ° C. for 5 minutes at 50 rpm A rubber composition is obtained by kneading at the rotational speed of the mixer.
(Procedure 2)
The rubber composition obtained in Procedure 1 and the anti-aging agent for rubber of the present invention obtained in Example 1 (1) 2 parts by mass within a range of 60 ° C. to 80 ° C. in an open roll machine, vulcanization accelerator A rubber kneaded product is obtained by kneading 1 part by mass of dibenzothiazyl disulfide (MBTS) and 2 parts by mass of sulfur.
<Second step>
A vulcanized rubber composition is obtained by heat-treating the kneaded product obtained in the first step (procedure 2) at 145 ° 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 Labo Plast Mill manufactured by Toyo Seiki Co., Ltd.), 40 parts by mass of commercially available natural rubber (RSS # 3), 60 parts by mass of polybutadiene rubber (“BR150B” manufactured by Ube Industries), 50 parts by mass of FEF, and stearic acid 2 0.5 part by mass, 3 parts by mass of zinc oxide, 1 part by mass of sodium salt of S- (3-aminopropyl) thiosulfuric acid, anti-aging agent for rubber of the present invention obtained in Example 1 (1) 16 parts by mass, aroma 10 parts by weight of tic oil (“NC-140” manufactured by Cosmo Oil Co., Ltd.) and 2 parts by weight of wax (“Sannok (registered trademark) wax” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.) within a range of 160 ° C. to 175 ° C. A rubber composition is obtained by kneading for 5 minutes at a rotation speed of a mixer of 50 rpm.
(Procedure 2)
The rubber composition obtained in Procedure 1 and N-tert-butyl-2-benzothiazolylsulfenamide (BBS) 0. A rubber kneaded material is obtained by kneading 75 parts by mass and 1.5 parts by mass of sulfur.
<Second step>
The rubber kneaded material obtained in the first step (procedure 2) is heat-treated at 145 ° C. to obtain a vulcanized rubber composition.

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 Labo Plast Mill manufactured by Toyo Seiki Co., Ltd.), 70 parts by mass of commercially available natural rubber (TSR20), 30 parts by mass of styrene / butadiene copolymer rubber SBR # 1502 (manufactured by Sumitomo Chemical), N339 (Mitsubishi Chemical Corporation) 60 parts by mass, 2 parts by mass of stearic acid, 5 parts by mass of zinc oxide, 7 parts by mass of process oil (“Diana Process PS32” manufactured by Idemitsu Kosan Co., Ltd.) and 1 mass of sodium salt of S- (3-aminopropyl) thiosulfuric acid The rubber composition is obtained by kneading the part within a range of 160 ° C. to 175 ° C. for 5 minutes at a rotation speed of a mixer of 50 rpm.
(Procedure 2)
The rubber composition obtained in Procedure 1 and N-tert-butyl-2-benzothiazolylsulfenamide (BBS) 1 mass as a vulcanization accelerator within the range of 60 ° C. to 80 ° C. in an open roll machine. A rubber kneaded product is obtained by kneading 8 parts by mass of 3 parts by mass of sulfur, 3 parts by mass of sulfur and the anti-aging 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 Laboplast Mill manufactured by Toyo Seiki Co., Ltd.), 100 parts by mass of styrene / butadiene copolymer rubber SBR # 1500 (manufactured by JSR), silica (trade name: “Ultrasil (registered trademark) VN3-G” Degussa 78.4 parts by mass, carbon black (trade name “N-339” manufactured by Mitsubishi Chemical Corporation), 6.4 parts by mass, silane coupling agent (bis (3-triethoxysilylpropyl) tetrasulfide: trade name “ 6.4 parts by mass of Si-69 “manufactured by Degussa), 47.6 parts by mass of process oil (trade name“ NC-140 ”manufactured by Cosmo Oil Co., Ltd.), anti-aging agent for rubber of the present invention obtained in Example 1 ( 1) 12 parts by mass, 2 parts by mass of zinc oxide, 2 parts by mass of stearic acid, and 3 parts by mass of sodium salt of S- (3-aminopropyl) thiosulfuric acid at 70 ° C. to 120 ° C. In 囲内, 5 minutes, and kneaded at a rotational speed of the mixer of 80 rpm, with subsequently the range of 70 ° C. to 120 ° C., for 5 minutes, by kneading at a rotation speed of 100rpm of mixer to obtain a rubber composition.
(Procedure 2)
The rubber composition obtained in step 1 and 1 part by mass of N-cyclohexyl-2-benzothiazolesulfenamide (CBS) as a vulcanization accelerator within the range of 30 ° C. to 80 ° C. in an open roll machine 1 part by weight of diphenylguanidine (DPG) as a vulcanization accelerator, 1.5 parts by weight of wax (trade name “Sannok (registered trademark) N” manufactured by Ouchi Shinsei Chemical Co., Ltd.) and 1.4 parts by weight of sulfur By kneading, a rubber kneaded product is obtained.
<Second step>
The rubber kneaded material obtained in the first step (procedure 2) is heat-treated at 160 ° C. to obtain a vulcanized rubber composition.

Reference Example 9 (Production Example of Vulcanized Rubber Composition)
In Reference Example 8, the same procedure as in Reference Example 8 was used, except that solution-polymerized SBR (“ASAPrene (registered trademark)” manufactured by Asahi Kasei Chemicals) was used instead of styrene-butadiene copolymer rubber SBR # 1500 (manufactured by JSR). Thus, a vulcanized rubber composition is obtained. The obtained vulcanized rubber composition is suitable as a cap tread.

Reference Example 10 (Production Example of Vulcanized Rubber Composition)
In Reference Example 8, in place of styrene / butadiene copolymer rubber SBR # 1500 (manufactured by JSR), SBR # 1712 (manufactured by JSR) was used, the amount of process oil used was changed to 21 parts by mass, 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 obtained vulcanized rubber composition is suitable as a cap tread.

  In the vulcanized rubber composition containing the antiaging agent for rubber of the present invention, the durability of the antiaging effect is improved.

1, 2, 3, 4 Sheets manufactured from a vulcanized rubber composition containing an antioxidant for rubber of the present invention 5, 6, 7, 8 Manufactured from a vulcanized rubber composition not containing an antioxidant for rubber of the present invention Sheet 9 Aluminum foil 10 Aluminum laminate 11 Weight

Claims (4)

Obtained by supporting rubber anti-aging agent on zeolite ,
An antiaging agent for rubber, wherein the zeolite includes pores having a minimum number of oxygen atom member rings of 12 or more . In solid state NMR measurement, the peak chemical shift based on ²⁹ Si contained in the zeolite carrying the rubber anti-aging substance is compared with the peak chemical shift based on ²⁹ Si contained in the zeolite not carrying the rubber anti-aging substance. The anti-aging agent for rubber according to claim 1, which is different from each other. The rubber anti-aging agent according to claim 1 or 2, wherein the rubber anti-aging substance is a compound represented by the formula (I).

(In formula (I), R ¹ represents a hydrogen atom or an alkyl group having 1 to 13 carbon atoms.) The rubber anti-aging agent according to any one of claims 1 to 3 , comprising 1 to 100 parts by mass of zeolite with respect to 10 parts by mass of the anti-aging substance for rubber.

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