JP2009214462A - Manufacturing process of thermoplastic resin elastomer composition/rubber laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing process of a thermoplastic resin elastomer composition/rubber laminate in which weatherability and adhesiveness are compatible with each other. <P>SOLUTION: At least two layers, a layer consisting of the thermoplastic resin elastomer composition obtained by blending a thermoplastic resin with an elastomer and a rubber layer containing an antioxidant, are laminated and heat treating is carried out to manufacture the laminate. In the manufacturing process of the laminate, content of the antioxidant in the rubber layer is 0.1 to 10 parts weight per 100 parts weight of rubber and heat treating is carried out while giving temperature difference where temperature at the rubber layer side is lower than temperature at the thermoplastic resin elastomer composition layer side. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing a thermoplastic resin elastomer composition / rubber laminate, and more particularly, to a method for producing a thermoplastic resin elastomer composition / rubber laminate that achieves both weather resistance and adhesiveness.

  A thermoplastic resin elastomer composition obtained by blending a thermoplastic resin and an elastomer has excellent air permeation resistance and flexibility, and has recently been used as an inner liner for pneumatic tires. It has become. However, when the thermoplastic resin elastomer composition is placed in a state in which a pneumatic tire is exposed to the outdoors or exposed to high temperatures generated during traveling in a state filled with air, the thermoplastic resin elastomer composition is exposed to ultraviolet rays, heat, oxygen, There was a problem that cracks occurred due to aging due to the influence of ozone and the like. Therefore, in order to improve the aging resistance of the thermoplastic resin elastomer composition, when an anti-aging agent is blended in the composition in advance, the rubber is burned during the kneading of the thermoplastic resin and the elastomer, so that desired physical properties are obtained. There was a problem that I could not.

As a countermeasure against this, Patent Document 1 discloses that when a layer made of a thermoplastic resin elastomer composition is laminated with a rubber layer, a large amount of an anti-aging agent is blended in advance in the rubber layer and heat-treated. By transferring the anti-aging agent in the layer to the thermoplastic resin elastomer composition layer, it is possible to solve the problem of rubber burning during the kneading as described above and to maintain the physical properties of the thermoplastic resin elastomer composition. ing. However, in the method of Patent Document 1, when a large amount of an anti-aging agent is blended in the rubber layer, it is effective for improving the weather resistance of the thermoplastic resin elastomer composition, but the anti-aging agent blooms at the interface of the laminate. By doing so, there was a problem that the adhesiveness between the thermoplastic resin elastomer composition layer and the rubber layer was lowered.
International Publication No. 2005/063482 Pamphlet

  An object of the present invention is to provide a method for producing a thermoplastic resin elastomer composition / rubber laminate in which both weather resistance and adhesiveness are compatible.

  The method for producing a thermoplastic resin elastomer composition / rubber laminate of the present invention that achieves the above object comprises a layer comprising a thermoplastic resin elastomer composition obtained by blending a thermoplastic resin and an elastomer, and a rubber layer containing an antioxidant. In the method for producing a laminate in which at least two layers are laminated and subjected to heat treatment, the rubber layer has an anti-aging content of 0.1 to 10 parts by weight per 100 parts by weight of rubber, and the rubber layer side The heat treatment is carried out with a temperature difference that makes the temperature of the thermoplastic resin elastomer composition lower than the temperature on the thermoplastic resin elastomer composition layer side.

  The temperature difference between the temperature on the thermoplastic resin elastomer composition layer side and the temperature on the rubber layer side is preferably 20 to 150 ° C.

  The temperature on the rubber layer side is preferably higher than the melting point of the anti-aging agent, and this heat treatment is preferably performed after previously vulcanizing the laminate of the thermoplastic resin elastomer composition layer and the rubber layer. The anti-aging agent may be an amine anti-aging agent, and the amine anti-aging agent may be N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine, N-phenyl- N′-isopropyl-p-phenylenediamine, N-phenylnaphthylamine, N, N′-di-2-naphthyl-p-phenylenediamine, 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline, It may be selected from alkylated diphenylamine.

  The weight ratio (A / B) of the thermoplastic resin (A) and the elastomer (B) in the thermoplastic resin elastomer composition may be 10/90 to 90/10. The thermoplastic resin is at least one selected from the group consisting of polyamide resins, polyester resins, polynitrile resins, polymethacrylate resins, polyvinyl resins, cellulose resins, fluorine resins, and imide resins. The elastomer may be at least one selected from the group consisting of a diene rubber and a hydrogenated product thereof, an olefin rubber, an acrylic rubber, a halogen-containing rubber, a silicon rubber, and a thermoplastic elastomer.

  The rubber constituting the rubber layer is at least one rubber selected from the group consisting of natural rubber, styrene-butadiene copolymer rubber, polybutadiene rubber, chloroprene rubber, butyl rubber, and ethylene-propylene-diene terpolymer rubber. It is good to.

  The thermoplastic resin elastomer composition / rubber laminate obtained by the above-described production method is preferably used as an inner liner of a pneumatic tire.

  According to the method for producing a thermoplastic resin elastomer composition / rubber laminate of the present invention, the content of the anti-aging agent in the rubber layer is limited to 0.1 to 10 parts by weight per 100 parts by weight of the rubber. Aging by performing a heat treatment on both sides of the laminate of the rubber layer and the thermoplastic resin elastomer composition layer so that the temperature difference on the rubber layer side is lower than the temperature on the thermoplastic resin elastomer composition layer side. The transition of the inhibitor to the thermoplastic resin elastomer composition layer side is promoted. For this reason, the anti-aging agent can be transferred to the thermoplastic resin elastomer composition layer so as not to lower the adhesion between the thermoplastic resin elastomer composition layer and the rubber layer, and both weather resistance and adhesiveness are achieved. To do.

  The production method of the present invention forms a thermoplastic resin elastomer composition / rubber laminate in which a rubber layer containing an anti-aging agent and a thermoplastic resin elastomer composition layer containing no anti-aging agent are laminated. A part of the antioxidant is removed from the rubber layer by performing a heat treatment with a temperature difference that causes the temperature of the rubber layer side to be lower than the temperature of the thermoplastic resin elastomer composition layer on both sides of the laminate. Promote the transition to the composition layer.

  The rubber layer in the thermoplastic resin elastomer composition / rubber laminate is not particularly limited, but is composed of any diene rubber used for tires. Examples of the diene rubber include natural rubber (NR), isoprene rubber (IR), various styrene-butadiene copolymer rubbers (SBR), various butadiene rubbers (BR), chloroprene rubber (CR), butyl rubber (IIR), Examples thereof include acrylonitrile-butadiene copolymer rubber (NBR). These can be used alone or as any blend. Further, ethylene-propylene-diene terpolymer rubber (EPDM) or the like may be used as a minor component. The rubber constituting the rubber layer is preferably at least selected from the group consisting of natural rubber, styrene-butadiene copolymer rubber, butadiene rubber, chloroprene rubber, butyl rubber, and ethylene-propylene-diene terpolymer rubber. One kind of rubber should be used.

  The anti-aging agent blended in the rubber layer may be at least one selected from amine-based anti-aging agents, phenol-based anti-aging agents, sulfur-based anti-aging agents, phosphorus-based anti-aging agents and the like. Of these, amine-based antioxidants are preferable in order to improve weather resistance. Examples of the amine anti-aging agent include N-naphthylamines such as N-phenyl-2-naphthylamine and N-phenyl-1-naphthylamine, 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, p- (P-toluene-sulfonylamide) -diphenylamine, diphenylamines such as alkylated diphenylamine, N, N'-diphenyl-p-phenylenediamine, N, N'-di-2-naphthyl-p-phenylenediamine, N-phenyl P-phenylenediamines such as -N'-isopropyl-p-phenylenediamine, N-phenyl-N '-(1,3-dimethylbutyl) -p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine 2,2,4-trimethyl-1,2-dihydroquinoline polymer, 6-ethoxy Examples include amines and ketones such as a reaction product of -1,2-dihydro-2,2,4-trimethylquinoline, diphenylamine and acetone. Among them, N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine, N-phenyl-N′-isopropyl-p-phenylenediamine, and N-phenylnaphthylamine are used as amine-based antioxidants. N, N'-di-2-naphthyl-p-phenylenediamine, 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline, and alkylated diphenylamine are preferred.

  The blending amount of the antioxidant is 0.1 to 10 parts by weight, preferably 3 to 8 parts by weight, with respect to 100 parts by weight of the rubber constituting the rubber layer. When the blending amount of the anti-aging agent is less than 0.1 parts by weight, the amount of the anti-aging agent transferred from the rubber layer to the thermoplastic resin elastomer composition layer is insufficient, and the weather resistance of the thermoplastic resin elastomer composition layer is improved. Can not do it. Moreover, when the compounding quantity of an anti-aging agent exceeds 10 weight part, an anti-aging agent will bloom on the interface of a laminated body, and adhesiveness will fall.

  The rubber layer containing the anti-aging agent described above is laminated on the thermoplastic resin elastomer composition layer not containing the anti-aging agent to form a thermoplastic resin elastomer composition / rubber laminate. The temperature of the rubber layer side is lowered with respect to both sides of this laminate, and a heat treatment is performed to give a temperature difference that raises the temperature of the thermoplastic resin elastomer composition layer. The transition to the resin elastomer composition layer is promoted.

  The temperature difference between the temperature on the thermoplastic resin elastomer composition layer side and the temperature on the rubber layer side is not particularly limited, but is preferably 20 to 150 ° C, more preferably 50 to 150 ° C, and still more preferably 100. It is good to set it to -150 degreeC. If the temperature difference between the two layers is less than 20 ° C., the migration of the antioxidant is insufficient and the weather resistance of the thermoplastic resin elastomer composition layer cannot be improved. If the temperature difference between the two layers is greater than 150 ° C, the thermoplastic resin elastomer composition on the high temperature side may be thermally deteriorated.

  Moreover, the temperature on the rubber layer side is preferably higher than the melting point of the anti-aging agent, and part of the anti-aging agent is promoted to migrate from the rubber layer to the thermoplastic resin elastomer composition layer. As the temperature on the rubber layer side becomes higher than the melting point of the anti-aging agent, it becomes easier to shift. When the temperature on the rubber layer side is lower than the temperature 5 ° C. higher than the melting point of the anti-aging agent, the migration of the anti-aging agent becomes insufficient. However, if the temperature on the rubber layer side is higher than the temperature 150 ° C. higher than the melting point of the anti-aging agent, the temperature on the thermoplastic resin elastomer composition layer side becomes too high, and the material may be thermally deteriorated. Undesirable phenomena such as vaporization and evaporation occur.

  The time for performing such heat treatment is not particularly limited, but is preferably 10 to 60 minutes, more preferably 10 to 40 minutes, and further preferably 15 to 30 minutes. When the heat treatment time is shorter than 10 minutes, the migration amount of the antioxidant from the rubber layer to the thermoplastic resin elastomer composition layer is insufficient. Even if the heat treatment time is longer than 60 minutes, the migration amount of the anti-aging agent reaches its peak and the productivity is lowered.

  This heat treatment may be performed at any stage before, during or after the vulcanization process of the laminate of the rubber layer and the thermoplastic resin elastomer composition layer, but preferably the rubber It is preferable to heat-treat the laminate of the layer and the thermoplastic resin elastomer composition layer after vulcanization in advance. By performing vulcanization before the anti-aging agent moves to the surface of the rubber layer and blooms, the adhesion between the rubber layer and the thermoplastic resin elastomer composition layer can be further improved.

  As a method of heat-treating the rubber layer and the thermoplastic resin elastomer composition layer, known means can be used, for example, a method of heating using heat exchange using a heater or steam, a cooling device or a blow of liquid nitrogen. Examples thereof include a method of lowering the temperature on the rubber layer side by using means such as attaching, or by bringing it into contact with a coolant or a cooling drum.

  The thermoplastic resin elastomer composition used in the present invention is formed by blending a thermoplastic resin and an elastomer, and does not contain an antioxidant when melt-kneaded. By melt-kneading in the absence of an anti-aging agent, the elastomer does not cause problems such as burning. In addition, although it is preferable that the thermoplastic resin and elastomer used as a raw material do not contain an anti-aging agent, the anti-aging agent required at the time of a shaping | molding process may be included.

  In the thermoplastic resin elastomer composition, the weight ratio (A / B) between the thermoplastic resin (A) and the elastomer (B) is not particularly limited, but is preferably 10/90 to 90/10. Preferably it is good to set it as 20 / 80-85 / 15. When the weight ratio (A / B) is smaller than 10/90, it is impossible to take a structure in which the matrix is a thermoplastic resin. On the other hand, when the weight ratio (A / B) is larger than 90/10, flexibility is impaired.

  Examples of the thermoplastic resin include polyamide-based resins [for example, nylon 6 (N6), nylon 66 (N66), nylon 46 (N46), nylon 11 (N11), nylon 12 (N12), nylon 610 (N610), Nylon 612 (N612), nylon 6/66 copolymer (N6 / 66), nylon 6/66/610 copolymer (N6 / 66/610), nylon MXD6 (MXD6), nylon 6T, nylon 6 / 6T Polymer, nylon 66 / PP copolymer, nylon 66 / PPS copolymer) and their N-alkoxyalkylated products, for example, methoxymethylated product of nylon 6, methoxymethylated product of nylon 6/610 copolymer, nylon 612 methoxymethylated product, polyester resin [for example, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), PET / PEI copolymer, polyarylate (PAR), polybutylene naphthalate (PBN), liquid crystal polyester, polyoxyalkylene diimide diacid / poly Aromatic polyesters such as butylene terephthalate copolymer], polynitrile resins (for example, polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile / styrene copolymer (AS), (meth) acrylonitrile / styrene copolymer, ( (Meth) acrylonitrile / styrene / butadiene copolymer], polymethacrylate resin [for example, polymethyl methacrylate (PMMA), polyethyl methacrylate], polyvinyl resin [for example, vinyl acetate, polyvinyl Lucol (PVA), vinyl alcohol / ethylene copolymer (EVOH), polyvinylidene chloride (PDVC), polyvinyl chloride (PVC), vinyl chloride / vinylidene chloride copolymer, vinylidene chloride / methyl acrylate copolymer, vinylidene chloride / Acrylonitrile copolymer (ETFE)], cellulose resin [eg, cellulose acetate, cellulose acetate butyrate], fluorine resin [eg, polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polychlorofluoroethylene (PCTFE) ), Tetrafluoroethylene / ethylene copolymer], imide resin [for example, aromatic polyimide (PI)] and the like can be preferably used. In particular, the thermoplastic resin is at least one selected from the group consisting of polyamide resins, polyester resins, polynitrile resins, polymethacrylate resins, polyvinyl resins, cellulose resins, fluorine resins, and imide resins. Good.

  Examples of the elastomer constituting the thermoplastic resin elastomer composition used in the present invention include diene rubbers and hydrogenated products thereof (for example, natural rubber (NR), isoprene rubber (IR), epoxidized natural rubber, styrene butadiene). Rubber (SBR), butadiene rubber (BR, high cis BR and low cis BR), nitrile rubber (NBR), hydrogenated NBR, hydrogenated SBR], olefin rubber [eg, ethylene propylene rubber (EPDM, EPM), malee Acid-modified ethylene propylene rubber (M-EPM), butyl rubber (IIR), isobutylene and aromatic vinyl or diene monomer copolymer, acrylic rubber (ACM), ionomer], halogen-containing rubber [for example, Br-IIR, CI- IIR, bromide of isobutylene paramethylstyrene copolymer (B -IPMS), chloroprene rubber (CR), hydrin rubber (CHR), chlorosulfonated polyethylene rubber (CSM), chlorinated polyethylene rubber (CM), maleic acid modified chlorinated polyethylene rubber (M-CM)], silicone rubber [for example , Methyl vinyl silicone rubber, dimethyl silicone rubber, methyl phenyl vinyl silicone rubber), sulfur-containing rubber (for example, polysulfide rubber), fluorine rubber (for example, vinylidene fluoride rubber, fluorine-containing vinyl ether rubber, tetrafluoroethylene-propylene rubber) , Fluorine-containing silicone rubber, fluorine-containing phosphazene rubber), thermoplastic elastomers (for example, styrene elastomer, olefin elastomer, ester elastomer, urethane elastomer, polyamide elastomer) It can be preferably used mer] and the like. In particular, the elastomer may be at least one selected from the group consisting of diene rubbers and hydrogenated products thereof, olefin rubbers, acrylic rubbers, halogen-containing rubbers, silicon rubbers, and thermoplastic elastomers.

  In addition to the essential polymer component, the thermoplastic resin elastomer composition can be mixed with another polymer such as a compatibilizer as a third component. The purpose of mixing other polymers is to improve the compatibility between the thermoplastic resin and the elastomer, to improve the molding processability of the material, to improve the heat resistance, to reduce the cost, etc. Examples of materials that can be used include polyethylene (PE), polypropylene (PP), polystyrene (PS), acrylonitrile butadiene styrene (ABS), styrene butadiene styrene block copolymer (SBS), and polycarbonate (PC). it can.

The thermoplastic resin elastomer composition is produced by a method in which a thermoplastic resin and an elastomer (unvulcanized in the case of rubber) are melt-kneaded in advance with a twin-screw kneading extruder or the like to form a continuous phase (matrix). By dispersing the elastomer as a dispersed phase (domain) in the resin. When the elastomer is vulcanized, a vulcanizing agent may be added under kneading to dynamically vulcanize the elastomer. Further, various compounding agents (excluding the vulcanizing agent) for the thermoplastic resin or elastomer may be added during the kneading, but it is preferable to mix them in advance before kneading. The kneading machine used for kneading the thermoplastic resin and the elastomer is not particularly limited, and a screw extruder, a kneader, a Banbury mixer, a biaxial kneading extruder, or the like can be used. Among them, it is preferable to use a twin-screw kneading extruder for kneading the thermoplastic resin and the elastomer and for dynamic vulcanization of the elastomer. Further, two or more types of kneaders may be used and kneaded sequentially. As conditions for melt kneading, the temperature may be higher than the temperature at which the thermoplastic resin melts. The shear rate during kneading is preferably 2500 to 7500 sec- ¹ . The total kneading time is from 30 seconds to 10 minutes, and when a vulcanizing agent is added, the mixing time after addition is preferably from 15 seconds to 5 minutes.

  The thermoplastic resin elastomer composition thus obtained has a structure in which an elastomer is dispersed as a discontinuous phase in a thermoplastic resin matrix. By adopting a dispersion structure in such a state, it is possible to set the Young's modulus in a range of 1 to 500 MPa and to impart appropriate rigidity as a tire constituent member.

  In addition to the essential components described above, any additive that can be conventionally blended in a thermoplastic elastomer composition or rubber composition is used for the rubber constituting the thermoplastic resin elastomer composition or rubber layer according to the present invention. For example, other reinforcing fillers such as carbon black and silica, vulcanization or cross-linking agents, vulcanization or cross-linking accelerators, various oils, tires such as plasticizers, and other general rubbers. Various additives can be blended, and such additives can be kneaded and vulcanized by a general method to obtain a composition, which can be used for vulcanization or crosslinking. The blending amounts of these additives may be conventional conventional blending amounts as long as the object of the present invention is not adversely affected.

  Lamination of the thermoplastic resin elastomer composition layer and the rubber layer can be performed by a general method as in the prior art. For example, methods such as coating, laminating, and coextrusion can be used. Moreover, the adhesion method of a thermoplastic resin elastomer composition layer and a rubber layer is not specifically limited, For example, arbitrary methods, such as an adhesive agent, cement, and direct adhesion | attachment, can be used. The layer containing the thermoplastic resin elastomer composition and the rubber layer do not necessarily have to be in direct contact. If the anti-aging agent can be transferred from the rubber layer to the thermoplastic resin elastomer composition by heat treatment, the other layers may be used. The layers may be laminated with an adhesive layer interposed therebetween.

  The thermoplastic resin elastomer composition / rubber laminate obtained by the above-described production method is preferably used as an inner liner of a pneumatic tire. The thermoplastic elastomer composition of the laminate functions as an air permeation preventive layer, and the rubber layer of the laminate covers the inner surface of the tie rubber or air permeation preventive layer between the air permeation preventive layer and the carcass layer. Functions as a protective rubber layer.

  Hereinafter, the present invention will be described with reference to examples, but the scope of the present invention is not limited thereby.

Preparation of thermoplastic elastomer composition layer Partially brominated polyisobutylene-p-methylstyrene copolymer (BIMS: Exxpro 89-4 manufactured by ExxonMobil Chemical): 100 parts by weight, zinc oxide: 0.3 parts by weight Zinc stearate: 1.2 parts by weight and stearic acid: 0.6 parts by weight were mixed in an enclosed Banbury mixer at an initial temperature of 40 ° C. for 5 minutes to prepare a rubber master batch. The rubber master batch was then pelletized with a rubber pelletizer. In a biaxial kneader, 50 parts by weight of the obtained rubber pellets, 13 parts by weight of nylon 6,66 copolymer (Amilan CM6041 manufactured by Toray Industries, Inc.) and 25 parts by weight of nylon 11 (Rilsan BMNO manufactured by Atofina) were mixed. Dynamic vulcanization was performed at a temperature of 220 ° C. for 5 minutes and pelletized to obtain a thermoplastic resin elastomer composition.
The thermoplastic resin elastomer composition and the adhesive layer were molded by coextrusion to produce a thermoplastic resin elastomer composition layer having a thermoplastic resin elastomer composition thickness of 170 μm and an adhesive layer thickness of 30 μm. The composition of the adhesive layer was 50 parts by weight of an epoxy-modified styrene butadiene styrene block copolymer (Epofriend AT501 manufactured by Daicel Chemical Industries), 50 parts by weight of a styrene butadiene styrene block copolymer (D1102JS manufactured by Kraton Polymer Co., Ltd.), and a terpene resin. (YShara Chemical YS Resin D105) was 50 parts by weight.

Preparation of Rubber Layer Six types of rubber compositions (compounds 1 to 6) having the composition shown in Table 1 were kneaded for 5 minutes with a 1 liter closed mixer except for sulfur and a vulcanization accelerator, and 165 ± When the temperature reached 5 ° C, it was discharged to obtain a master batch. A vulcanization accelerator and sulfur were added to this master batch and mixed with an open roll to obtain a sheet-like rubber layer.

Production of Thermoplastic Resin Elastomer Composition / Rubber Laminate As shown in Table 2, the thermoplastic resin elastomer composition layer obtained above is composed of six rubber compositions (formulations 1 to 6). Ten types of laminated bodies (Examples 1 to 6, Comparative Examples 1 to 4) were press vulcanized at 180 ° C. for 10 minutes. The thickness of the obtained laminate was 2 mm.
10 types of vulcanized laminates (Examples 1 to 6 and Comparative Examples 1 to 4) are subjected to the presence or absence of heat treatment, the temperature on the rubber layer side when performing heat treatment, and the temperature on the thermoplastic resin elastomer composition layer side. Processed differently as shown in FIG. The heat treatment was performed at a predetermined temperature by bringing the thermoplastic resin elastomer composition layer side of the laminate into contact with a heater, and at a predetermined temperature by bringing the rubber layer side into contact with a coolant. However, in Comparative Example 4, the rubber layer side was also brought into contact with the heater to a predetermined temperature.

  The following 10 methods evaluated the weather resistance and adhesiveness of 10 types of obtained laminated bodies (Examples 1-6, Comparative Examples 1-4).

Weather resistance First, the obtained laminate was subjected to a weather resistance deterioration test in accordance with the SA method of JIS K6266. In the weather resistance deterioration test, the laminate is mounted so that the thermoplastic elastomer composition layer side of the laminate faces the light source (carbon arc lamp), the test temperature is 63 ° C., the light irradiation is continuous, and the water spray cycle to the laminate Sprayed water every 102 minutes for 18 minutes. After the weather resistance deterioration test was performed for 168 hours, a JIS No. 2 dumbbell was cut out from the laminate after the deterioration test, and a constant strain fatigue test was performed. The constant strain fatigue test was performed under the conditions of 40% cyclic elongation strain at a cycle of 6.7 Hz, a temperature of −30 ° C., and 500,000 cycles of repeated fatigue. As a result, the number [of cracks] generated on the surface of the thermoplastic resin elastomer per dumbbell was visually evaluated, and the number is shown in Table 2. The smaller the number of cracks, the better the weather resistance.

Adhesiveness A JIS No. 2 dumbbell was cut out from the obtained laminate, and only a cut was made in advance in the thermoplastic resin elastomer composition layer of the elongated portion, and a constant strain fatigue test was conducted. The constant strain fatigue test was performed under the conditions of 40% cyclic elongation strain at a cycle of 6.7 Hz, a temperature of 70 ° C., and 300,000 cycles of repeated fatigue. Each laminate was subjected to a constant strain fatigue test for 10 dumbbells, the ratio of the dumbbells from which the thermoplastic resin elastomer composition layer was peeled (defective rate [%]) was defined as adhesiveness, and the results obtained are shown in Table 2. . The smaller the defect rate, the better the adhesiveness.

In addition, the kind of raw material used in Table 1 is shown below.
NR: natural rubber, RSS # 3
SBR: styrene-butadiene rubber, Nipol 1502 manufactured by Nippon Zeon
Carbon black: HTC # G manufactured by Nippon Nihon Carbon
Stearic acid: Nippon Oil & Fats Co., Ltd. Beads stearate aroma-based oil: Showa Shell Sekiyu Co., Ltd. Extract Zinc Hana: Zodo Chemical Industry Co., Ltd. Zinc Oxide 3 Sulfur: Oil-treated sulfur, Tsurumi Chemical Co., Ltd. 150 mesh
Vulcanization accelerator: Noxeller CZ-G manufactured by Ouchi Shinsei Chemical Co., Ltd.
Anti-aging agent: N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine, Nocrack 6C (melting point: 44 ° C.) manufactured by Ouchi Shinsei Chemical Co., Ltd.

Claims (10)

  In the method for producing a laminate in which at least two layers of a thermoplastic resin elastomer composition obtained by blending a thermoplastic resin and an elastomer and a rubber layer containing an anti-aging agent are laminated and subjected to heat treatment, The content of the antioxidant is 0.1 to 10 parts by weight per 100 parts by weight of rubber, and the temperature difference on the rubber layer side is made lower than the temperature on the thermoplastic resin elastomer composition layer side. A method for producing a thermoplastic resin elastomer composition / rubber laminate in which heat treatment is performed.   The method for producing a thermoplastic resin elastomer composition / rubber laminate according to claim 1, wherein a temperature difference between the temperature on the thermoplastic resin elastomer composition layer side and the temperature on the rubber layer side is set to 20 to 150 ° C.   The method for producing a thermoplastic resin elastomer composition / rubber laminate according to claim 1 or 2, wherein the temperature on the rubber layer side is higher than the melting point of the anti-aging agent.   The method for producing a thermoplastic resin elastomer composition / rubber laminate according to claim 1, 2 or 3, wherein the heat treatment is performed after the laminate of the thermoplastic resin elastomer composition layer and the rubber layer is vulcanized in advance.   The method for producing a thermoplastic resin elastomer composition / rubber laminate according to any one of claims 1 to 4, wherein the anti-aging agent is an amine-based anti-aging agent.   The amine-based antioxidant is N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine, N-phenyl-N′-isopropyl-p-phenylenediamine, N-phenylnaphthylamine, N, 6. Thermoplastic according to claim 5, selected from the group consisting of N'-di-2-naphthyl-p-phenylenediamine, 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline, alkylated diphenylamine. A method for producing a resin elastomer composition / rubber laminate.   The weight ratio (A / B) of the thermoplastic resin (A) and the elastomer (B) in the thermoplastic resin elastomer composition is 10/90 to 90/10. A method for producing a thermoplastic resin elastomer composition / rubber laminate.   The thermoplastic resin is at least one selected from the group consisting of polyamide resins, polyester resins, polynitrile resins, polymethacrylate resins, polyvinyl resins, cellulose resins, fluorine resins, and imide resins. The elastomer is at least one selected from the group consisting of a diene rubber and a hydrogenated product thereof, an olefin rubber, an acrylic rubber, a halogen-containing rubber, a silicon rubber, and a thermoplastic elastomer. A method for producing the thermoplastic resin elastomer composition / rubber laminate as described.   The rubber constituting the rubber layer is at least one rubber selected from the group consisting of natural rubber, styrene-butadiene copolymer rubber, polybutadiene rubber, chloroprene rubber, butyl rubber, and ethylene-propylene-diene terpolymer rubber. A method for producing a thermoplastic resin elastomer composition / rubber laminate according to any one of claims 1 to 8.   A pneumatic tire using the thermoplastic resin elastomer composition / rubber laminate obtained by the production method according to claim 1 as an inner liner.