WO2013065768A1

WO2013065768A1 - Rubber anti-aging agent

Info

Publication number: WO2013065768A1
Application number: PCT/JP2012/078281
Authority: WO
Inventors: 進森; 志津香岩田; 井山　浩暢
Original assignee: 住友化学株式会社
Priority date: 2011-11-01
Filing date: 2012-11-01
Publication date: 2013-05-10
Also published as: JP5705089B2; TW201326275A; JP2013095856A

Abstract

The present invention provides a rubber anti-aging agent obtained by loading a zeolite with a rubber anti-aging substance.

Description

Anti-aging agent for rubber

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

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

JP 2007-238803 A

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

As a result of intensive studies under these circumstances, the present inventors have reached the present invention described below.
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). 4. The rubber anti-aging agent according to any one of 1 to 3 above, 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);
5. 5. The anti-aging agent for rubber according to any one of the preceding items 1 to 4, which comprises 1 to 100 parts by weight of zeolite per 10 parts by weight of the anti-aging material for rubber.

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 solid-state NMR measurement of the zeolite before carrying | supporting anti-aging agent (1) for rubber | gum of this invention, and an anti-aging substance for rubber | gum. 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), compound represented by formula (II), etc. Can be mentioned.
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) and a compound represented by the formula (II).

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

(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 also generally called zeolite and has a composition formula M _n O _m · xAl ₂ O ₃ · ySiO ₂ · zH ₂ O (M in the above composition formula is not limited to metals, Represents an element belonging to Group 13. n, m, x, y, and z represent integers), and is a hydrous aluminosilicate having CAS Registry 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. The minimum number of member rings of oxygen atoms means the minimum number of member rings of oxygen atoms constituting a channel. 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, GON, 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.
The content of the zeolite in the rubber anti-aging agent of the present invention is, for example, 1 to 100 parts by weight of zeolite with respect to 10 parts by weight of the rubber anti-aging substance. More preferably, for example, it may contain 1 part by weight to 50 parts by weight with respect to 10 parts by weight of the rubber anti-aging agent. Particularly preferably, for example, 2 to 30 parts by weight may be contained per 10 parts by weight 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. The mixture is then dried (and ground).

In the methods (1) and (2), the amount of zeolite added may be, for example, 1 to 100 parts by weight with respect to 10 parts by weight of the rubber anti-aging substance. Preferable examples include 1 part by weight to 50 parts by weight with respect to 10 parts by weight of the rubber anti-aging substance. More preferably, for example, 2 to 30 parts by weight can be mentioned with respect to 10 parts by weight 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 antiaging agent for rubber of the present invention may be a 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 to 990 parts by weight with respect to 100 parts by weight of the rubber component. Can do.
When the rubber composition containing the rubber anti-aging agent of the present invention is a rubber composition further containing a filler, zinc oxide, stearic acid, a crosslinking agent, a vulcanization accelerator component, etc., the rubber anti-aging agent of the present invention is used. Examples of the content of the anti-aging agent for rubber of the present invention in the rubber composition include 0.1 to 50 parts by weight with respect to 100 parts by weight of the rubber component. Preferably, for example, 1 to 30 parts by weight can be mentioned. More preferred examples include 2 to 20 parts by weight.
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 The content of the anti-aging agent can be 11 to 990 parts by weight, preferably 31 to 990 parts by weight, for example, with respect to 100 parts by weight 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 thereof 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 deproteinized natural rubber having a total nitrogen content of 0.3% by weight 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 the 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 “Rubber Industry Handbook <Fourth Edition>” edited by the Japan Rubber Association. Can be mentioned. As a rubber composition for a 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 “Nipol (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 used as a tread rubber composition.

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. Further, for example, tin-modified BR such as “Nipol (registered trademark) BR 1250H” manufactured by Nippon Zeon Co., Ltd., 4,4′-bis- (dialkylamino) benzophenone, tin halide compound, lactam compound, amide compound, urea A single compound, an N, N-dialkylacrylamide compound, an isocyanate compound, an imide compound, an alkoxy group-containing silane compound (trialkoxysilane compound, etc.), an aminosilane compound, or a tin compound and an alkoxy group. Using two or more different compounds such as a silane compound having an alkyl acrylamide compound and an alkoxy group, and by modifying the molecular ends, either nitrogen, tin, or silicon Or solution polymerization with multiple elements R and the like and more preferably a.
These BRs can be preferably cited for use in rubber compositions for treads and rubber compositions for sidewalls. In addition, BR is normally used by the blend of SBR and / or natural rubber. As the blend ratio, in the case of a rubber composition for a tread, 60% to 100% by weight of SBR and / or natural rubber, 0% to 40% by weight of BR, etc. with respect to the total rubber weight Can do. In the case of the rubber composition for a sidewall, SBR and / or natural rubber may be 10% by weight to 70% by weight, BR may be 90% by weight to 30% by weight, etc. with respect to the total rubber weight. . Preferably, a blend of natural rubber 40 wt% to 60 wt% and BR 60 wt% to 40 wt% with respect to the total rubber weight. 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 a tire tread rubber composition, a CTAB (Cetyl Tri-methyl Ammonium Bromide) specific surface area of 40 m ² / g to 250 m ² / g, a nitrogen adsorption specific surface area of 20 m ² / g to 200 m ² / g, and 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. Specifically, for example, in the ASTM standard, 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 is also preferable. 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 rubber composition for carcass and the rubber composition for sidewall, 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. 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.

The amount of the filler used is not particularly limited, and examples thereof include 5 to 100 parts by weight with respect to 100 parts by weight of the rubber component. In the case where only carbon black is used as the filler, for example, 30 to 80 parts by weight is preferably mentioned with respect to 100 parts by weight of the rubber component. When carbon black and silica are used together as fillers in tread member applications, for example, 5 to 60 parts by weight of carbon black is preferably included with respect to 100 parts by weight of the rubber component.

Examples of the silica used as the filler 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. 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. In addition, for example, silica having a pH of 6 to 8, silica containing 0.2 wt% to 1.5 wt% 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, and silica having two or more different nitrogen adsorption specific surface areas.

The amount of the filler used is not particularly limited, and examples thereof include 10 to 120 parts by weight with respect to 100 parts by weight of the rubber component.
When silica is blended, for example, 5 to 50 parts by weight of carbon black is preferably blended with 100 parts by weight of the rubber component. Examples of the silica / carbon black compounding ratio include a range of 0.7 / 1 to 1 / 0.1.
When silica is used as a filler, 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-octa “NXT silane” manufactured by General Electronic Silicons Co., Ltd.), octanethioic acid S- [3-{(2-methyl-1,3-propanedialkoxy) ethoxysilyl} propyl] ester, also referred to as “noylthiopropyltriethoxysilane” Octanethioic acid S- [3-{(2-methyl-1,3 Propanedialkoxy) methylsilyl} propyl] ester phenyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, isobutyltrimethoxysilane, isobutyl Triethoxysilane, 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-glycidoxy Propyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxy One or more silane coupling agents selected from the group consisting of silane, 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane, elements such as silicon that can be bonded to silica, or alkoxysilanes It is preferable to add a compound having a functional group of 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.
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. Examples of the compounding amount include 2% by weight to 10% by weight with respect to the weight of silica. Preferably, for example, 7 to 9% by weight can be mentioned.
Examples of the compounding temperature when compounding the above compound into rubber include 80 ° C. to 200 ° C. Preferably, for example, 110 ° C. to 180 ° C. may be mentioned.
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 polyols and other dihydric alcohols, N-alkylamines, amino acids, liquid polybutadienes whose molecular ends are carboxyl-modified or amine-modified, Etc. may be blended.

Examples of the amount of zinc oxide used include 1 to 15 parts by weight with respect to 100 parts by weight of the rubber component. Preferably, for example, 1 to 8 parts by weight can be mentioned.

Examples of the amount of stearic acid used include 0.5 to 10 parts by weight with respect to 100 parts by weight of the rubber component. Preferably, for example, 1 to 5 parts by weight is used.

Examples of the crosslinking agent include sulfur. Examples of sulfur include powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur. Preferably, powder sulfur etc. are mentioned. In addition, when the vulcanized rubber composition is used for a tire member having a large amount of sulfur such as a belt member, for example, insoluble sulfur can be preferably exemplified. Note that the sulfur does not contain a vulcanization accelerator. Examples of the amount of sulfur used include 0.3 to 5 parts by weight with respect to 100 parts by weight of the rubber component. Preferably, for example, 0.5 to 3 parts by weight are used.

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

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) is preferably used in combination with diphenylguanidine (DPG).

The ratio of sulfur to the vulcanization accelerator is not particularly limited, and examples thereof include sulfur / vulcanization accelerator = 2/1 to 1/2 by weight ratio.
EV vulcanization in which the weight ratio of sulfur / vulcanization accelerator is 1 or less, which is a method for improving heat resistance in a rubber member mainly composed of natural rubber, is preferably used in applications where heat resistance needs to be improved.

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 (softening manufactured by Kobe Oil Chemical Industries) Coumarone-indene resin such as terpene resin, terpene / phenol resin, aromatic modified terpene resin, etc .; “Nikanol (registered trademark) HP-100” (softening point 105- 125 ° C) xylene / formaldehyde resin; rosin derivatives such as “Ester Gum” series and “Neotor” series manufactured by Arakawa Chemical Co., Ltd .; 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. Examples of 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. 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 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 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 zeolite)
B2: Union Showa Co., Ltd. molecular sieve 13X (FAU-X type zeolite)
B3: H-Mordenite (MOR type zeolite) manufactured by NE CHEMCAT
B4: Union Showa HiSiv-3000 (MFI type zeolite)
Table 4 below shows the minimum number of member rings of oxygen atoms in the pores contained in the zeolite used.

Example 1 (Production Example of Anti-aging Agent for Rubber of the Present Invention)
A 200 mL beaker was charged with 3 parts by weight 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). The obtained acetone solution was added into a 200 mL beaker containing 9 parts by weight of zeolite (B1), and a 200 mL beaker containing the acetone solution was further washed with 20 mL of acetone to add a cleaning solution. 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)
The rubber anti-aging agent (2) of the present invention was obtained in the same manner as in Example 1 except that the amount of zeolite (B1) was changed to 3 parts by weight.

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).

Example 4 (Production Example of Rubber Anti-aging Agent of the Present Invention)
An anti-aging agent (4) 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 (B3).

Example 5 (Production Example of Rubber Anti-aging Agent of the Present Invention)
An anti-aging agent (5) 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 (B4).

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 (weight 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. Further, the filter cake was washed until the color of the rubber anti-aging substance 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 rubber anti-aging agent on LC) −5385.7) / 1324900

About the anti-aging agent for rubber of the present invention obtained in Examples, the measured value of the content of anti-aging agent for rubber confirmed by the above extraction method was compared with the theoretical value. The theoretical value is a value calculated from the following equation.
<Calculation formula>
Content of rubber anti-aging substances (theoretical value) (%)
= 100 x (Amount of anti-aging substance for rubber) / (Amount of anti-aging substance for rubber + Amount of zeolite)
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, the collected filtrate was dried. Solid-state NMR measurement was performed on the zeolite before supporting the antiaging substance for rubber and the obtained filtrate (that is, zeolite supporting the antiaging substance for rubber) under the following conditions. The result is shown in FIG.
Comparing before and after loading of rubber anti-aging substance on zeolite, a change in the chemical shift of the peak based on ²⁹ Si contained in zeolite was observed, confirming the loading of rubber anti-aging substance 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)
A 10-liter kneader was charged with 50 parts by weight of both commercially available natural rubber (product name: SMR-CV60) and butadiene rubber (product name: JSR BR01, manufactured by JSR) and kneaded for 2 minutes. After adding materials other than natural rubber and butadiene rubber shown in Table 2 to the obtained kneaded material, the mixture was further kneaded for 10 minutes to obtain a basic rubber composition. The discharge temperature of the rubber composition from the kneader was 95 ° C.

Comparative Example 1 (Production Example of Vulcanized Rubber Composition not Containing Anti-aging Agent for Rubber of the Present Invention)
163.5 parts by weight of the basic rubber composition obtained in Reference Example 1, 2 parts by weight of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS)) 0.8 A rubber composition was obtained by kneading parts by weight and 1.5 parts by weight of sulfur with an open roll machine having a roll set temperature of 60 ° C. The obtained rubber composition 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 (but not including both an anti-aging 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.
Next, 163.5 parts by weight of the basic rubber composition obtained in Reference Example 1, 2 parts by weight of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS)) A rubber composition was obtained by kneading 0.8 parts by weight, 1.5 parts by weight of sulfur, and 3 parts by weight of an anti-aging 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 whole 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 weight of the basic rubber composition obtained in Reference Example 1, 2 parts by weight of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS)) 0.8 By kneading 12 parts by weight of an 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. 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 weight of the basic rubber composition obtained in Reference Example 1, 2 parts by weight of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS)) 0 A rubber composition was obtained by kneading 0.8 parts by weight, 1.5 parts by weight of sulfur, and 9 parts by weight of zeolite (B1) 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 no anti-aging material for rubber and containing 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.
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 weight of the basic rubber composition obtained in Reference Example 1, 2 parts by weight of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS)) 0.8 By kneading, by weight, 1.5 parts by weight of sulfur, and 6 parts by weight of the anti-aging agent for rubber of the present invention (2) obtained in Example 2 with an open roll machine having a roll set temperature of 60 ° C. A rubber composition was obtained. 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 weight of the basic rubber composition obtained in Reference Example 1, 2 parts by weight of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS)) 0 A rubber composition was obtained by kneading 0.8 parts by weight, 1.5 parts by weight of sulfur, and 3 parts by weight of zeolite (B1) 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 no anti-aging material for rubber and containing 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.
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 weight of the basic rubber composition obtained in Reference Example 1, 2 parts by weight of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS)) 0.8 By kneading 12 parts by weight 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 weight of the basic rubber composition obtained in Reference Example 1, 2 parts by weight of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS)) 0 A rubber composition was obtained by kneading 0.8 parts by weight, 1.5 parts by weight of sulfur, and 9 parts by weight of zeolite (B2) 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 no anti-aging material for rubber and containing 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.
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 9 (Production Example of Vulcanized Rubber Composition Containing Antiaging Agent for Rubber of the Present Invention)
163.5 parts by weight of the basic rubber composition obtained in Reference Example 1, 2 parts by weight of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS)) 0.8 By kneading 12 parts by weight, 1.5 parts by weight of sulfur, and 12 parts by weight of the anti-aging agent for rubber of the present invention (4) obtained in Example 4, 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 weight of the basic rubber composition obtained in Reference Example 1, 2 parts by weight of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS)) 0 A rubber composition was obtained by kneading 0.8 parts by weight, 1.5 parts by weight of sulfur, and 9 parts by weight of zeolite (B3) 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 no anti-aging material for rubber and containing 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.
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 10 (Production Example of Vulcanized Rubber Composition Containing Antiaging Agent for Rubber of the Present Invention)
163.5 parts by weight of the basic rubber composition obtained in Reference Example 1, 2 parts by weight of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS)) 0.8 By kneading 12 parts by weight, 1.5 parts by weight of sulfur, and 12 parts by weight of the anti-aging agent for rubber of the present invention (5) obtained in Example 5, with an open roll machine having a roll set temperature of 60 ° C, A rubber composition was obtained. The obtained rubber composition is 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 weight of the basic rubber composition obtained in Reference Example 1, 2 parts by weight of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS)) 0 A rubber composition was obtained by kneading 0.8 parts by weight, 1.5 parts by weight of sulfur, and 9 parts by weight of zeolite (B4) 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 no anti-aging material for rubber and containing 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.
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.

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 1, 2 parts by weight of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS)) 0.8 Kneading part by weight, 1.5 parts by weight of sulfur, 3 parts by weight of the antioxidant for rubber of the present invention (A1) and 3 parts by weight of zeolite (B1) in an open roll machine at 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 weight of the basic rubber composition obtained in Reference Example 1, 2 parts by weight of zinc oxide, and a vulcanization accelerator (N-tert-butyl-2-benzothiazolesulfenamide (TBBS)) 0 A rubber composition was obtained by kneading 0.8 parts by weight, 1.5 parts by weight of sulfur, and 3 parts by weight of zeolite (B1) 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 no anti-aging material for rubber and containing 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.
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 rubber anti-aging substance in Examples 6 to 10 and Comparative Example 2 when the migration amount of the rubber anti-aging substance 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 (600 mL lab plast mill manufactured by Toyo Seiki Co., Ltd.), 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., trade name “Asahi # 80”) ] 35 parts by weight, stearic acid 2 parts by weight, zinc oxide 3 parts by weight, sodium salt of S- (3-aminopropyl) thiosulfuric acid 1 part by weight, anti-aging agent for rubber of the present invention obtained in Example 1 ( 1) By kneading 8 parts by weight and 2 parts by weight of wax (“OZOACE-0355” manufactured by Nippon Seiwa Co., Ltd.) within a 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.
(Procedure 2)
Within a range of 60 ° C. to 80 ° C. with an open roll machine, the rubber composition obtained in Procedure 1 and 2 parts by weight of N-cyclohexyl-2-benzothiazole sulfenamide (CBS) as a vulcanization accelerator, Rubber kneading is carried out by kneading 0.5 parts by weight of diphenylguanidine (DPG) as a vulcanization accelerator, 0.8 parts by weight of dibenzothiazyl disulfide (MBTS) as a vulcanization accelerator and 1 part by weight of sulfur. Get things.
<Second step>
The rubber kneaded product 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 weight of commercially available natural rubber (RSS # 1), 45 parts by weight of HAF (trade name “Asahi # 70” manufactured by Asahi Carbon Co., Ltd.), stearic acid 3 parts by weight, 5 parts by weight of zinc oxide, 1 part by weight of sodium salt of S- (3-aminopropyl) thiosulfuric acid, 10 parts by weight of hydrous silica (“Nipsil® AQ” manufactured by Tosoh Silica), Example 1 16 parts by weight of the anti-aging agent for rubber of the present invention (1), 2 parts by weight of resorcin, and 2 parts by weight of cobalt naphthenate obtained in the above are within the range of 160 ° C. to 175 ° C. for 5 minutes, and the rotational speed of the mixer at 50 rpm. A rubber composition is obtained by kneading with the above.
(Procedure 2)
In a range of 60 ° C. to 80 ° C. with an open roll machine, the rubber composition obtained in the

procedure

1 and 1 weight of N, N-dicyclohexyl-2-benzothiazolesulfenamide (DCBS) as a vulcanization accelerator Parts by weight, 6 parts by weight of sulfur and 3 parts by weight of methoxylated methylol melamine resin (“SUMIKANOL 507AP” manufactured by Sumitomo Chemical Co., Ltd.) to obtain a rubber kneaded product.
<Second step>
The rubber kneaded product 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 Laboplast Mill, manufactured by Toyo Seiki Co., Ltd.), 100 parts by weight of halogenated butyl rubber (“Br-IIR2255” manufactured by ExxonMobil), 60 parts by weight of GPF, 1 part by weight of stearic acid, 3 parts by weight of zinc oxide , 1 part by weight of sodium salt of S- (3-aminopropyl) thiosulfuric acid and 10 parts by weight of paraffin oil (“Diana Process Oil” manufactured by Idemitsu Kosan Co., Ltd.) in the range of 160 ° C. to 175 ° C. for 5 minutes at 50 rpm A rubber composition is obtained by kneading at a rotational speed of the mixer.
(Procedure 2)
In the range of 60 ° C. to 80 ° C. with an open roll machine, the rubber composition obtained in Procedure 1, the anti-aging agent for rubber of the present invention (1) obtained in Example 1, 2 parts by weight, and a vulcanization accelerator A rubber kneaded product is obtained by kneading 1 part by weight of a certain dibenzothiazyl disulfide (MBTS) and 2 parts by weight of sulfur.
<Second step>
The rubber kneaded product obtained in the first step (procedure 2) is heat-treated at 145 ° C. to obtain a vulcanized rubber composition.

Reference Example 6 (Production Example of Vulcanized Rubber Composition)
The vulcanized rubber composition obtained by the following first step and second step is suitable for side walls.
<First step>
(Procedure 1)
Using a Banbury mixer (600 mL lab plast mill manufactured by Toyo Seiki Co., Ltd.), 40 parts by weight of commercially available natural rubber (RSS # 3), 60 parts by weight of polybutadiene rubber (“BR150B” manufactured by Ube Industries, Ltd.), 50 parts by weight of FEF, stearic acid 2.5 parts by weight, zinc oxide 3 parts by weight, sodium salt of S- (3-aminopropyl) thiosulfuric acid 1 part by weight, anti-aging agent for rubber of the present invention (1) obtained in Example 1, 16 parts by weight, 10 parts by weight of aromatic 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 the 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)
Within the range of 60 ° C. to 80 ° C. with an open roll machine, the rubber composition obtained in Procedure 1 and N-tert-butyl-2-benzothiazolylsulfenamide (BBS) 0.75 as a vulcanization accelerator A rubber kneaded material is obtained by kneading parts by weight and 1.5 parts by weight of sulfur.
<Second step>
The rubber kneaded product 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 Laboplast Mill, manufactured by Toyo Seiki Co., Ltd.), 70 parts by weight of commercially available natural rubber (TSR20), 30 parts by weight of styrene / butadiene copolymer rubber SBR # 1502 (manufactured by Sumitomo Chemical), N339 (Mitsubishi Chemical) 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 and sodium salt of S- (3-aminopropyl) thiosulfuric acid 1 A rubber composition is obtained by kneading the parts by weight 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

step

1 and 1 part by weight of N-tert-butyl-2-benzothiazolylsulfenamide (BBS) 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 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 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 weight of styrene / butadiene copolymer rubber SBR # 1500 (manufactured by JSR), silica ("Ultrasil (registered trademark) VN3-G" manufactured by Degussa) 78.4 parts by weight, carbon black (“N-339” manufactured by Mitsubishi Chemical Corporation), 6.4 parts by weight, silane coupling agent (bis (3-triethoxysilylpropyl) tetrasulfide, “Si-69” manufactured by Degussa ) 6.4 parts by weight, process oil (“NC-140” manufactured by Cosmo Oil Co., Ltd.) 47.6 parts by weight, anti-aging agent for rubber of the present invention obtained in Example 1 (1) 12 parts by weight, zinc oxide 2 parts by weight, 2 parts by weight of stearic acid, and 3 parts by weight of sodium salt of S- (3-aminopropyl) thiosulfuric acid in the range of 70 ° C. to 120 ° C. for 5 minutes, 80 r Kneaded at a rotational speed of m of the mixer, subsequently in the range of 70 ℃ ~ 120 ℃, 5 minutes, by kneading at a rotation speed of 100rpm of mixer to obtain a rubber composition.
(Procedure 2)
Within the range of 30 ° C. to 80 ° C. in an open roll machine, the rubber composition obtained in

Procedure

1 and 1 part by weight of N-cyclohexyl-2-benzothiazole sulfenamide (CBS) as a vulcanization accelerator, 1 part by weight of diphenylguanidine (DPG) which is 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 product 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 resulting vulcanized rubber composition is suitable as a cap tread.

Reference Example 10 (Production Example of Vulcanized Rubber Composition)
In Reference Example 8, instead 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 weight, and zinc oxide was charged. A vulcanized rubber composition is obtained in the same manner as in Reference Example 8 except that the timing is changed to Procedure 2. The resulting vulcanized rubber composition is suitable as a cap tread.

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

Rubber anti-aging agent obtained by supporting rubber anti-aging substance on zeolite.
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 zeolite is a zeolite containing pores having a minimum number of oxygen atom member rings of 8 or more.
The rubber anti-aging agent according to any one of claims 1 to 3, wherein the rubber anti-aging substance is a compound represented by the formula (I).

(In the 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 4, comprising 1 to 100 parts by weight of zeolite with respect to 10 parts by weight of the anti-aging material for rubber.