JP6701620B2 - Tire laminate, tire inner liner material and pneumatic tire - Google Patents

Description

  The present invention relates to a laminate in which a film of a thermoplastic resin composition or a thermoplastic elastomer composition and a layer of a rubber composition are integrated by vulcanization, an innerliner material for a tire formed from the laminate, and the inner. The present invention relates to a pneumatic tire including a liner material.

  As a technique for adhering a layer of a thermoplastic resin composition and a layer of a rubber composition without using an adhesive layer when manufacturing a laminate or a pneumatic tire constituting a pneumatic tire, a thermoplastic resin or a thermosetting resin is used. A technique (Patent Document 1) in which a film of a plastic elastomer composition and a layer of a rubber composition containing a condensate of a phenolic compound and formaldehyde and a methylene donor are laminated is known.

Japanese Patent No. 4858654

  The present inventor has conducted intensive studies for the purpose of further improving the adhesive strength between the thermoplastic resin film and the layer of the rubber composition, and as a result, the rubber composition has a specific amount of phenol-formaldehyde condensate and methylene. It has been found that the above object can be achieved by containing a donor and further containing two or more rubbers containing at least a rubber having a specific amount of a dicarboxylic acid group and/or a dicarboxylic acid anhydride group in a side chain. Completed the invention. When the rubber composition contains a rubber having a dicarboxylic acid group and/or a dicarboxylic acid anhydride group in a side chain, a phenol-formaldehyde condensate and a methylene donor, the dicarboxylic acid anhydride is a phenol in the rubber composition. -Reaction with formaldehyde condensate and methylene donor is expected to result in reduced processability and inhibition of the reaction of the film with the phenol-formaldehyde condensate and methylene donor. When the composition contains a rubber having a specific amount of a dicarboxylic acid group and/or a dicarboxylic acid anhydride group in a side chain, and a specific amount of a phenol-formaldehyde condensate and a methylene donor, the rubber composition has a dicarboxylic acid group and/or Or containing a rubber having a dicarboxylic acid anhydride group in a side chain but not containing a phenol-formaldehyde condensate and a methylene donor, and a rubber composition containing a phenol-formaldehyde condensate and a methylene donor, a dicarboxylic acid group and/or Further, they have found an unexpected effect that the adhesive strength is improved as compared with the case where a rubber having a dicarboxylic acid anhydride group in the side chain is not included.

According to the present invention, a laminate for a tire is obtained by integrating a laminate including a film of a thermoplastic resin composition or a thermoplastic elastomer composition and a layer of a rubber composition laminated on the film by vulcanization. There, the rubber composition,
(A) A rubber component containing two or more rubbers,
(B) The following formula (1):

(In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are independently selected from hydrogen, a hydroxyl group, an alkyl group having 1 to 8 carbon atoms and an ether group having 1 to 8 carbon atoms. )
A condensation product of a compound represented by
(C) methylene donor, and (d) vulcanizing agent,
The rubber component (A) contains a rubber having a dicarboxylic acid group and/or a dicarboxylic acid anhydride group in the side chain in an amount of 5 to 40% by mass based on the total amount of the rubber component (A), and condensation The substance (B) is present in an amount of 0.5 to 20 parts by mass with respect to 100 parts by mass of the rubber component (A), and the methylene donor (C) is 0.25 to 100 parts by mass with respect to 100 parts by mass of the rubber component (A). A tire laminate is provided, which is present in an amount of 200 parts by mass and has a mass ratio of the methylene donor (C) and the condensate (B) of 0.5:1 to 10:1.
According to the present invention, there is further provided an inner liner material for a pneumatic tire, which comprises the above-mentioned laminate.
According to the present invention, there is further provided a pneumatic tire including the inner liner material for a pneumatic tire, which comprises the above-mentioned laminate.

The present invention specifically includes the following aspects [1] to [8].
[1] A laminate for a tire, which is obtained by integrating a laminate including a film of a thermoplastic resin composition or a thermoplastic elastomer composition and a layer of a rubber composition laminated on the film by vulcanization. The rubber composition
(A) A rubber component containing two or more rubbers,
(B) The following formula (1):

(In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are independently selected from hydrogen, a hydroxyl group, an alkyl group having 1 to 8 carbon atoms and an ether group having 1 to 8 carbon atoms. )
A condensation product of a compound represented by
(C) methylene donor, and (d) vulcanizing agent,
The rubber component (A) contains a rubber having a dicarboxylic acid group and/or a dicarboxylic acid anhydride group in the side chain in an amount of 5 to 40% by mass based on the total amount of the rubber component (A), and condensation The substance (B) is present in an amount of 0.5 to 20 parts by mass with respect to 100 parts by mass of the rubber component (A), and the methylene donor (C) is 0.25 to 100 parts by mass with respect to 100 parts by mass of the rubber component (A). A tire laminate, which is present in an amount of 200 parts by mass and has a mass ratio of the methylene donor (C) and the condensate (B) of 0.5:1 to 10:1.
[2] The rubber having a dicarboxylic acid group and/or a dicarboxylic acid anhydride group in the side chain is selected from the group consisting of a maleic anhydride modified ethylene-α-olefin copolymer and a maleic anhydride modified ethylene-ethyl acrylate copolymer. The laminated body for tire according to the above aspect [1], characterized in that it is at least one selected from the following.
[3] The tire laminate according to the above aspect [1], wherein the rubber component (A) contains a rubber having a dicarboxylic acid group and/or a dicarboxylic acid anhydride group in a side chain and a diene rubber.
[4] The thermoplastic resin composition is polyvinyl alcohol, ethylene-vinyl alcohol copolymer, nylon 6, nylon 66, nylon 11, nylon 12, nylon 610, nylon 612, nylon 6/66, nylon MXD6, and nylon 6T. The tire laminate according to any one of the above aspects [1] to [3], which comprises at least one thermoplastic resin selected from the group consisting of:
[5] The thermoplastic elastomer composition contains a thermoplastic resin component and an elastomer component dispersed in the thermoplastic resin component, and the thermoplastic resin component is polyvinyl alcohol, ethylene-vinyl alcohol copolymer, nylon 6, It contains at least one thermoplastic resin selected from the group consisting of nylon 66, nylon 11, nylon 12, nylon 610, nylon 612, nylon 6/66, nylon MXD6 and nylon 6T, and the elastomer component is brominated isobutylene-p. -Methylstyrene copolymer, maleic anhydride modified ethylene-α-olefin copolymer, ethylene-glycidyl methacrylate copolymer and at least one selected from the group consisting of maleic anhydride modified ethylene-ethyl acrylate copolymer The tire laminate according to any one of the above aspects [1] to [4], which comprises an elastomer.
[6] The above aspect, wherein the methylene donor is at least one selected from the group consisting of modified etherified methylolmelamine, paraformaldehyde, hexamethylenetetramine, pentamethylenetetramine, and hexamethoxymethylmelamine. 1] to the laminated body for tire according to any one of [5].
[7] An inner liner material for a pneumatic tire, which comprises the tire laminate according to any one of the above aspects [1] to [6].
[8] A pneumatic tire including an inner liner material for a pneumatic tire, which comprises the tire laminate according to any one of the above aspects [1] to [6].

  The tire laminate of the present invention exhibits improved adhesive strength between the film of the thermoplastic resin composition or the thermoplastic elastomer composition and the layer of the rubber composition. The tire laminate of the present invention, without using an adhesive layer, achieves excellent adhesive strength between the film of the thermoplastic resin composition or the thermoplastic elastomer composition and the layer of the rubber composition, The manufacturing process of the laminate and the tire can be simplified. Furthermore, the tire laminate of the present invention has a layer of the rubber composition which is different from that of the rubber composition when the laminate containing the film of the thermoplastic resin composition or the thermoplastic elastomer composition and the layer of the rubber composition is vulcanized. When laminated or adjacent to a vulcanizable rubber member, a vulcanization reaction also occurs between the layer of the rubber composition constituting the tire laminate of the present invention and another vulcanizable rubber member, so that a rubber is obtained. A strong bond is also achieved between the layer of composition and the other rubber component. Therefore, according to the present invention, the above rubber containing a rubber having a specific amount of a dicarboxylic acid group and/or a dicarboxylic acid anhydride group in a side chain, a specific amount of a phenol-formaldehyde condensate, and a specific amount of a methylene donor. It is possible to firmly bond the film of the thermoplastic resin composition or the thermoplastic elastomer composition and the other rubber member constituting the tire through the layer of the composition.

  Regarding the film of the thermoplastic resin composition or the thermoplastic elastomer composition in the laminate of the present invention, examples of the thermoplastic resin capable of constituting the thermoplastic resin composition or the thermoplastic elastomer composition include polyamide resins, Examples thereof include polyester resins, polynitrile resins, polymethacrylate resins, polyvinyl resins, cellulose resins, fluorine resins, imide resins, polystyrene resins, polyolefin resins and the like. The thermoplastic resin composition or the thermoplastic elastomer composition can include at least one thermoplastic resin.

Examples of polyamide resins include nylon 6 (N6), nylon 66 (N66), nylon 46 (N46), nylon 11 (N11), nylon 12 (N12), nylon 610 (N610), nylon 612 (N612), Nylon 6/66 (N6/66), Nylon 6/66/12 (N6/66/12), Nylon 6/66/610 (N6/66/610), Nylon MXD6 (MXD6), Nylon 6T, Nylon 6/ 6T, nylon 9T, nylon 66/PP copolymer, nylon 66/PPS copolymer and the like.
Examples of the polyester resin include polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), PET/PEI copolymer, polyarylate (PAR), polybutylene naphthalate (PBN), liquid crystal. Examples thereof include polyesters and aromatic polyesters such as polyoxyalkylene diimidic acid/polybutyrate terephthalate copolymers. Examples of the polynitrile resin include polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile/styrene copolymer (AS), methacrylonitrile/styrene copolymer, methacrylonitrile/styrene/butadiene copolymer, and the like. Can be mentioned. Examples of polymethacrylate resins include polymethylmethacrylate (PMMA) and polyethylmethacrylate. Examples of polyvinyl resins include polyvinyl acetate (PVAc), polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (EVOH), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinyl chloride/chloride. Examples thereof include vinylidene copolymers and vinylidene chloride/methyl acrylate copolymers. Examples of cellulosic resins include cellulose acetate, cellulose acetate butyrate, and the like. Examples of the fluorine-based resin include polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polychlorofluoroethylene (PCTFE), and tetrafluoroethylene/ethylene copolymer (ETFE). Examples of the imide resin include aromatic polyimide (PI). Examples of polystyrene-based resins include polystyrene (PS). Examples of the polyolefin-based resin include polyethylene (PE) and polypropylene (PP). Among them, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, nylon 6, nylon 66, nylon 11, nylon 12, nylon 610, nylon 612, nylon 6/66, nylon MXD6 and nylon 6T have fatigue resistance and air barrier properties. It is preferable in terms of compatibility of properties.

  The thermoplastic elastomer composition includes one or more elastomers dispersed in one or more thermoplastic resins, and one or more thermoplastic resins constitutes a matrix phase (or continuous phase). However, the elastomer constitutes the dispersed phase (or discontinuous phase).

  Examples of elastomers that can constitute the thermoplastic elastomer composition include diene rubbers and hydrogenated products thereof, olefin rubbers, halogen-containing rubbers, silicone rubbers, sulfur-containing rubbers, and fluororubbers. Examples of diene rubbers and hydrogenated products thereof include natural rubber (NR), isoprene rubber (IR), epoxidized natural rubber, styrene butadiene rubber (SBR), butadiene rubber (BR) (high cis BR and low cis BR. ), acrylonitrile-butadiene rubber (NBR), hydrogenated NBR, hydrogenated SBR and the like. Examples of the olefin rubber include ethylene propylene rubber (EPM), ethylene propylene diene rubber (EPDM), maleic acid modified ethylene propylene rubber (M-EPM), maleic anhydride modified ethylene-α-olefin copolymer, ethylene- Glycidyl methacrylate copolymer, maleic anhydride modified ethylene-ethyl acrylate copolymer (modified EEA), butyl rubber (IIR), isobutylene and aromatic vinyl or diene monomer copolymer, acrylic rubber (ACM), ionomer and the like. Be done. Examples of the halogen-containing rubber include halogenated butyl rubber such as brominated butyl rubber (Br-IIR) and chlorinated butyl rubber (Cl-IIR), brominated isobutylene-p-methylstyrene copolymer (BIMS), halogenated isobutylene- Examples thereof include isoprene copolymer rubber, chloroprene rubber (CR), hydrin rubber (CHR), chlorosulfonated polyethylene (CSM), chlorinated polyethylene (CM), and maleic acid-modified chlorinated polyethylene (M-CM). Examples of the silicone rubber include methyl vinyl silicone rubber, dimethyl silicone rubber, methylphenyl vinyl silicone rubber and the like. Examples of the sulfur-containing rubber include polysulfide rubber and the like. Examples of fluororubber include vinylidene fluoride rubber, fluorovinyl ether rubber, tetrafluoroethylene-propylene rubber, fluorosilicone rubber, fluorophosphazene rubber, and the like. Among them, brominated isobutylene-p-methylstyrene copolymer, maleic anhydride-modified ethylene-α-olefin copolymer, ethylene-glycidyl methacrylate copolymer and maleic anhydride-modified ethylene-ethyl acrylate copolymer are It is preferable from the viewpoint of blocking property.

  The combination of the elastomer and the thermoplastic resin that can form the thermoplastic resin composition in the laminate of the present invention is not limited, but halogenated butyl rubber and polyamide resin, brominated isobutylene-p-methylstyrene. Copolymer rubber and polyamide resin, butadiene rubber and polystyrene resin, isoprene rubber and polystyrene resin, hydrogenated butadiene rubber and polystyrene resin, ethylene propylene rubber and polyolefin resin, ethylene propylene diene rubber and polyolefin resin, amorphous Butadiene rubber and syndiotactic poly(1,2-polybutadiene), non-crystalline isoprene rubber and trans poly(1,4-isoprene), fluororubber and fluororesin, etc. may be mentioned, but butyl rubber and polyamide having excellent air barrier properties. A combination of a series resin is preferable, and among them, a combination of a modified butyl rubber such as brominated isobutylene-p-methylstyrene copolymer rubber and nylon 6/66 or nylon 6 or a blend resin of nylon 6/66 and nylon 6 is resistant to It is particularly preferable in terms of achieving both fatigue properties and air barrier properties.

  The thermoplastic elastomer composition is obtained by melting and kneading at least one thermoplastic resin and at least one elastomer with, for example, a twin-screw kneading extruder or the like to disperse the elastomer component in the thermoplastic resin forming the matrix phase. It can be produced by dispersing as a phase. The mass ratio of the thermoplastic resin to the elastomer is not limited, but is preferably 10/90 to 90/10, more preferably 15/85 to 90/10.

  The thermoplastic resin composition, within the range of not impairing the effects of the present invention, for improving processability, dispersibility, heat resistance, antioxidant properties, for example, fillers, reinforcing agents, processing aids, stabilizers, Ingredients commonly incorporated in resin compositions, such as antioxidants, may be included. The elastomer of the thermoplastic elastomer composition can be used in rubber compositions such as other reinforcing agents (fillers) such as carbon black and silica, softening agents, antioxidants, processing aids, etc. within a range that does not impair the effects of the present invention. The compounding agent generally compounded may be included.

In the present invention, the rubber composition constituting the layer of the rubber composition,
(A) a rubber component containing two or more rubbers,
(B) The following formula (1):

(In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are independently selected from hydrogen, a hydroxyl group, an alkyl group having 1 to 8 carbon atoms and an ether group having 1 to 8 carbon atoms. )
A condensation product of a compound represented by
(C) methylene donor, and (d) vulcanizing agent,
The rubber component (A) contains a rubber having a dicarboxylic acid group and/or a dicarboxylic acid anhydride group in the side chain in an amount of 5 to 40% by mass based on the total amount of the rubber component (A), and condensation The substance (B) is present in an amount of 0.5 to 20 parts by mass with respect to 100 parts by mass of the rubber component (A), and the methylene donor (C) is 0.25 to 100 parts by mass with respect to 100 parts by mass of the rubber component (A). It is present in an amount of 200 parts by mass, and the mass ratio of the methylene donor (C) and the condensate (B) is 0.5:1 to 10:1.

  In the present invention, examples of the rubber having a dicarboxylic acid group and/or a dicarboxylic acid anhydride group in its side chain include maleic anhydride-modified liquid polyisoprene rubber, maleic anhydride-modified ethylene-propylene copolymer rubber, and maleic anhydride. Examples thereof include modified ethylene-butene copolymer rubber and maleic anhydride-modified liquid polybutadiene rubber. A rubber having a dicarboxylic acid group and/or a dicarboxylic acid anhydride group in a side chain can be produced by grafting a dicarboxylic acid and/or a dicarboxylic acid anhydride to the rubber. A rubber having a dicarboxylic acid group and/or a dicarboxylic acid anhydride group in its side chain is commercially available. For example, an acid anhydride maleic anhydride-modified liquid polyisoprene rubber is available from Kuraray Co., Ltd. in Kuraprene LIR-403. The maleic anhydride-modified ethylene-propylene copolymer rubber is available from Mitsui Chemicals, Inc. under the trade name of Toughmer MP0620, and the maleic anhydride-modified ethylene-butene copolymer rubber is available from Mitsui. It is available from Kagaku Co., Ltd. under the trade name of Toughmer MH7020. In the present invention, the amount of rubber having a dicarboxylic acid group and/or a dicarboxylic acid anhydride group in its side chain is 5 to 40% by mass based on the total amount of the rubber component (A). When the amount of the rubber having a dicarboxylic acid group and/or a dicarboxylic acid anhydride group in the side chain is less than the lower limit of the above range, the adhesive strength between the layer of the thermoplastic resin composition and the layer of the rubber composition is increased. If the amount of the rubber that cannot be sufficiently improved and has a dicarboxylic acid group and/or a dicarboxylic acid anhydride group in the side chain exceeds the upper limit of the above range, the rubber composition is burnt during processing (also called scorch). Occurs and the workability deteriorates.

  Examples of rubbers other than the rubber having a dicarboxylic acid group and/or dicarboxylic acid anhydride group constituting the rubber component (A) in its side chain include diene rubbers and hydrogenated products thereof, olefin rubbers, halogen-containing rubbers, Examples thereof include silicone rubber, sulfur-containing rubber, and fluororubber. Examples of diene rubbers and hydrogenated products thereof include natural rubber (NR), isoprene rubber (IR), styrene butadiene rubber (SBR), butadiene rubber (BR) (high cis BR and low cis BR), acrylonitrile butadiene. Examples thereof include rubber (NBR), hydrogenated NBR, hydrogenated SBR and the like. Examples of the olefin rubber include ethylene propylene rubber (EPM), ethylene propylene diene rubber (EPDM), maleic acid modified ethylene propylene rubber (M-EPM), maleic anhydride modified ethylene-α-olefin copolymer, maleic anhydride. Examples thereof include acid-modified ethylene-ethyl acrylate copolymer (modified EEA), butyl rubber (IIR), isobutylene and aromatic vinyl or diene monomer copolymer, acrylic rubber (ACM), and ionomer. Examples of the halogen-containing rubber include halogenated butyl rubber such as brominated butyl rubber (Br-IIR) and chlorinated butyl rubber (Cl-IIR), brominated isobutylene-p-methylstyrene copolymer (BIMS), halogenated isobutylene- Examples thereof include isoprene copolymer rubber, chloroprene rubber (CR), hydrin rubber (CHR), chlorosulfonated polyethylene (CSM), chlorinated polyethylene (CM), and maleic acid-modified chlorinated polyethylene (M-CM). Examples of the silicone rubber include methyl vinyl silicone rubber, dimethyl silicone rubber, methylphenyl vinyl silicone rubber and the like. Examples of the sulfur-containing rubber include polysulfide rubber and the like. Examples of fluororubber include vinylidene fluoride rubber, fluorovinyl ether rubber, tetrafluoroethylene-propylene rubber, fluorosilicone rubber, fluorophosphazene rubber, and the like. Among them, from the viewpoint of co-crosslinkability with the adjacent rubber material, as the rubber other than the rubber having a dicarboxylic acid group and/or a dicarboxylic acid anhydride group in the side chain, a diene rubber, an olefin rubber, and a halogen-containing rubber may be mentioned. Natural rubber, styrene-butadiene rubber, butadiene rubber, brominated butyl rubber, and ethylene-propylene-diene rubber are preferable and more preferable. The proportion of the diene rubber in the rubber component constituting the rubber composition is preferably 50% by mass or more, more preferably 70% by mass or more, and the dicarboxylic acid group and/or the dicarboxylic acid anhydride group has a side chain. It is further preferred that all of the rubbers other than the rubbers contained in 1 are diene rubbers.

One preferable example of the compound represented by the above formula (1) is that at least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ is an alkyl group having 1 to 8 carbon atoms, and the rest are It is hydrogen. One of the preferred specific examples of the compound represented by the formula (1) is cresol. Another preferable example of the compound represented by the formula (1) is that at least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ is a hydroxyl group, and the rest is hydrogen or 1 to 10 carbon atoms. 8 is an alkyl group. Another preferred specific example of the compound represented by formula (1) is resorcin.

  Examples of the condensate of the compound represented by the formula (1) and formaldehyde include a cresol-formaldehyde condensate and a resorcin-formaldehyde condensate. Further, these condensates may be modified as long as the effects of the present invention are not impaired. For example, a modified resorcinol-formaldehyde condensate modified with an epoxy compound can also be used in the present invention. These condensates are commercially available, and commercially available products can be used in the present invention.

  The condensate of the compound represented by the formula (1) and formaldehyde is preferably the compound represented by the formula (2) or the formula (3).

In the formula, n is an integer of 1 to 20, preferably an integer of 1 to 10, and more preferably an integer of 1 to 5.

In the formula, m is an integer of 1 to 20, preferably an integer of 1 to 10, and more preferably an integer of 1 to 3.

  The compounding amount of the condensate of the compound represented by the formula (1) and formaldehyde (hereinafter, also simply referred to as “condensate”) is 0.5 to 20 parts by mass with respect to 100 parts by mass of the rubber component (A). And preferably 1 to 10 parts by mass. If the amount of the condensate is too small, the vulcanization efficiency deteriorates because the amount of heat required to obtain good adhesion and the time increases, and if it is too large, the vulcanization elongation of the resulting rubber composition is impaired. And easily break.

  In the present specification, the “methylene donor” refers to a basic compound that generates formaldehyde by heating or the like, and examples thereof include hexamethylenetetramine, pentamethylenetetramine, hexamethylenediamine, methylolmelamine, etherified methylolmelamine, and modified etherified methylol. Melamine, esterified methylol melamine, hexamethoxymethyl melamine, hexamethylol melamine, hexakis(ethoxymethyl)melamine, hexakis(methoxymethyl)melamine, N,N',N"-trimethyl-N,N',N"- Trimethylolmelamine, N,N',N"-trimethylolmelamine, N-methylolmelamine, N,N'-bis(methoxymethyl)melamine, N,N',N"-tributyl-N,N', Examples thereof include N″-trimethylolmelamine and paraformaldehyde. Among them, modified etherified methylol melamine is preferable from the viewpoint of formaldehyde emission temperature.

  The amount of the methylene donor (C) is 0.25 to 200 parts by mass, preferably 0.5 to 80 parts by mass, and more preferably 1 to 40 parts by mass with respect to 100 parts by mass of the rubber component. When the amount of the methylene donor is too small, the donor is consumed in the resin reaction in the rubber composition system, the reaction in the interfacial reaction does not proceed, and the adhesion deteriorates. On the other hand, if the amount is too large, the reaction in the rubber composition system is promoted too much, or the crosslinking reaction in the resin system to be adhered is induced to deteriorate the adhesion.

  The mass ratio of the methylene donor (C) to the condensate (B) is 0.5:1 to 10:1, preferably 1:1 to 4:1 and more preferably 1:1 to 3:1. If the ratio of the methylene donor to the condensate is too small, the donor is consumed in the resin reaction in the rubber composition system, the reaction in the interfacial reaction does not proceed, and the adhesion deteriorates. On the other hand, if it is too large, the reaction in the rubber composition system is promoted too much, or the crosslinking reaction in the resin system to be adhered is induced to deteriorate the adhesion.

  Examples of the vulcanizing agent include an inorganic vulcanizing agent and an organic vulcanizing agent. Examples of inorganic vulcanizing agents include sulfur, sulfur monochloride, selenium, tellurium, zinc oxide, magnesium oxide, lead monoxide, and the like, and examples of organic vulcanizing agents include sulfur-containing organic compounds, dithiocarbamine. Examples thereof include acid salts, oximes, tetrachloro-p-benzoquinone, dinitroso compounds, modified phenolic resins, polyamines and organic peroxides. Among them, sulfur, organic peroxides such as 1,3-bis-(t-butylperoxyisopropyl)-benzene, modified phenol resins such as brominated alkylphenol-formaldehyde condensate, zinc oxide, sulfur-containing organic compounds Is preferred.

  Examples of the vulcanization accelerator include aldehyde-ammonia system, aldehyde-amine system, thiourea system, guanidine system, thiazole system, sulfenamide system, thiuram system, dithiocarbamate system system, and xanthate system system, and preferably thiazole system. System, sulfenamide system, thiuram system. The thiazole vulcanization accelerator is a compound having a thiazole structure, and examples thereof include di-2-benzothiazolyl disulfide, mercaptobenzothiazole, benzothiazyl disulfide, zinc salt of mercaptobenzothiazole, and (dinitrophenyl)mercaptobenzo. Examples thereof include thiazole and (N,N-diethylthiocarbamoylthio)benzothiazole. Of these, di-2-benzothiazolyl disulfide is preferable. The sulfenamide vulcanization accelerator is a compound having a sulfenamide structure, and examples thereof include N-cyclohexylbenzothiazolesulfenamide, Nt-butylbenzothiazolesulfenamide, and N-oxydiethylenebenzothiazolesulfene. Examples thereof include amide, N,N-dicyclohexylbenzothiazolesulfenamide, and (morpholinodithio)benzothiazole. Among them, Nt-butyl-2-benzothiazolesulfenamide is preferable. The thiuram vulcanization accelerator is a compound having a thiuram structure, and examples thereof include tetrakis(2-ethylhexyl)thiuram disulfide, tetramethylthiuram disulfide, tetramethylthiuram monosulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, dipentamethylene. Examples thereof include thiuram hexasulfide, and among them, tetrakis(2-ethylhexyl)thiuram disulfide is preferable.

  A laminate before vulcanization comprising a film of a thermoplastic resin composition or a thermoplastic elastomer composition and a layer of a rubber composition laminated on the film has a rubber composition laminated on a film of the thermoplastic resin composition. It can be manufactured. More specifically, but not limited to, it can be produced as follows. First, the thermoplastic resin composition is molded into a film with a molding device such as an inflation molding device or a T-die extruder to prepare a film of the thermoplastic resin composition. Next, the rubber composition is extruded onto the film and laminated at the same time with a T-die extruder or the like to produce a laminate.

A pneumatic tire can be produced by a conventional method using the laminate of the present invention. For example, on a tire molding drum, the laminate of the present invention as an inner liner material is placed so that the film side of the thermoplastic resin composition faces the tire molding drum, and a carcass made of unvulcanized rubber thereon. Layers, belt layers, tread layers and other members used in ordinary tire production are successively laminated, after molding, the drum is removed to give a green tire, and then the green tire is heated and vulcanized according to a conventional method, A pneumatic tire can be manufactured.
Integration by vulcanization of a laminate including a film of a thermoplastic resin composition or a thermoplastic elastomer composition and a layer of a rubber composition laminated on the film can be performed under conventional heat vulcanization conditions.

(1) Production of film A raw material is blended at a blending ratio shown in Table 1 to prepare a thermoplastic resin composition, and the thermoplastic resin composition is molded by an inflation molding device to manufacture a film having a thickness of 0.2 mm. did. The produced film is called film A.

Ingredients for film A:
BIMS: brominated isobutylene-p-methylstyrene copolymer (Exxpro (registered trademark) 3035 manufactured by ExxonMobil Chemical Co.)
Zinc oxide: Zhonghua No. 3 manufactured by Shodo Chemical Industry Co., Ltd. Stearic acid: Industrial stearic acid manufactured by Chiba Fatty Acid Co., Ltd. Zinc stearate: Zinc stearate manufactured by NOF CORPORATION Thermoplastic resin: Nylon 6 /66 (UBE Nylon (registered trademark) 5033B manufactured by Ube Industries, Ltd.)
Modified EEA: Maleic anhydride modified ethylene-ethyl acrylate copolymer (Rilsan BESNOTL manufactured by ALCARE)
Plasticizer: BM-4 manufactured by Daihachi Chemical Industry Co., Ltd.

(2) Preparation of rubber composition The following raw materials were blended with a Banbury mixer at the blending ratios shown in Tables 2 and 3 to obtain the rubber compositions of Comparative Examples 1 to 4 , Examples 1 to 5 and Reference Examples 1 to 10. Prepared.
Raw material of rubber composition:
SBR: Nipol (registered trademark) 1502 manufactured by Nippon Zeon Co., Ltd.
NR: SIR-20
Liquid maleated IR: Maleic anhydride-modified liquid polyisoprene rubber (Kurapren LIR-403 manufactured by Kuraray Co., Ltd.)
Acid-modified EP rubber: Tuffmer MP0620 manufactured by Mitsui Chemicals, Inc.
Acid-modified EB rubber: Tuffmer MH7020 manufactured by Mitsui Chemicals, Inc.
Carbon black: Tokai Carbon Co., Ltd. Seast V
Stearic acid: Industrial stearic acid manufactured by Chiba fatty acid Co., Ltd. Aroma oil: Desolex 3 manufactured by Showa Shell Sekiyu KK Zinc oxide: Zinc flower 3 manufactured by Shodo Chemical Co., Ltd. Modified resorcin/formaldehyde condensate : Sumikanol 620 manufactured by Taoka Chemical Co., Ltd.
Methylene donor: Modified etherified methylol melamine resin (Sumikanol 507AP manufactured by Taoka Chemical Co., Ltd.)
Sulfur: 5% oil-extended sulfur manufactured by Karuizawa Smelting Co., Ltd. Vulcanization accelerator: Di-2-benzothiazolyl disulfide (Nox Cellar DM manufactured by Ouchi Shinko Chemical Industry Co., Ltd.)

(3) Preparation of Laminate A laminate was prepared by extrusion-laminating the rubber composition prepared in (2) above onto the film A prepared in (1) above in a thickness of 0.7 mm.

(4) Evaluation of Laminated Body The produced laminated body was evaluated by the following “peel strength test”. The evaluation results are shown in Tables 2 and 3 .
[Peel strength test]
The sample of the laminate was vulcanized and cut into a width of 25 mm, and the strip strength of the strip-shaped test piece was measured according to JIS-K6256. The value of the peel strength (N/25 mm) measured for Comparative Examples 2 to 4 , Examples 1 to 5 and Reference Examples 1 to 10 was expressed as an index based on the value of the peel strength measured for Comparative Example 1. ..

From Tables 2 and 3, Comparative Example 1 in which the rubber composition contains a phenol-formaldehyde condensate and a methylene donor, but does not contain a rubber having a dicarboxylic acid group and/or a dicarboxylic acid anhydride group in the side chain, and a rubber composition. Contains a rubber having a dicarboxylic acid group and/or a dicarboxylic acid anhydride group in a side chain, but Examples 1 to 5 are excellent in comparison with Comparative Examples 2 to 4 which do not contain a phenol-formaldehyde condensate and a methylene donor. It can be seen that excellent peel strength was exhibited, that is, good adhesive strength was exhibited.

  INDUSTRIAL APPLICABILITY The laminate of the present invention is useful as an inner liner material for pneumatic tires and can be suitably used for manufacturing pneumatic tires. The pneumatic tire including the inner liner material for a pneumatic tire formed of the laminate of the present invention can be preferably used as a tire for automobiles.

Claims (6)

A laminate for a tire, comprising a laminate comprising a film of a thermoplastic resin composition or a thermoplastic elastomer composition and a layer of a rubber composition laminated on the film, which is integrated by vulcanization. Thing is,
(A) a rubber component containing two or more rubbers,
(B) The following formula (1):

(In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are independently selected from hydrogen, a hydroxyl group, an alkyl group having 1 to 8 carbon atoms and an ether group having 1 to 8 carbon atoms. )
A condensation product of a compound represented by
(C) methylene donor, and (D) vulcanizing agent,
Hints, rubber component (A), and maleic acid-modified liquid polyisoprene rubber anhydride, and a diene rubber other than the maleic acid-modified liquid polyisoprene rubber anhydride, the rubber component (A) maleic anhydride-modified liquid poly in The amount of isoprene rubber is 5 to 40% by mass based on the total amount of the rubber component (A), and the amount of the condensate (B) is 0.5 to 20 parts by mass based on 100 parts by mass of the rubber component (A). And the methylene donor (C) is present in an amount of 0.25 to 200 parts by mass with respect to 100 parts by mass of the rubber component (A), and the mass ratio of the methylene donor (C) and the condensate (B) is 0. The laminated body for tires which is 0.5:1-10:1.   The thermoplastic resin composition is a group consisting of polyvinyl alcohol, ethylene-vinyl alcohol copolymer, nylon 6, nylon 66, nylon 11, nylon 12, nylon 610, nylon 612, nylon 6/66, nylon MXD6, and nylon 6T. The laminated body for tires according to claim 1, comprising at least one kind of thermoplastic resin selected from the following.   The thermoplastic elastomer composition contains a thermoplastic resin component and an elastomer component dispersed in the thermoplastic resin component, and the thermoplastic resin component is polyvinyl alcohol, ethylene-vinyl alcohol copolymer, nylon 6, nylon 66, The elastomer component contains at least one thermoplastic resin selected from the group consisting of nylon 11, nylon 12, nylon 610, nylon 612, nylon 6/66, nylon MXD6 and nylon 6T, and the elastomer component is brominated isobutylene-p-methylstyrene. Includes at least one elastomer selected from the group consisting of a copolymer, a maleic anhydride-modified ethylene-α-olefin copolymer, an ethylene-glycidyl methacrylate copolymer, and a maleic anhydride-modified ethylene-ethyl acrylate copolymer. The laminated body for tires according to claim 1 or 2 characterized by things.   The methylene donor is at least one selected from the group consisting of modified etherified methylolmelamine, paraformaldehyde, hexamethylenetetramine, pentamethylenetetramine, and hexamethoxymethylmelamine. The tire laminate according to any one of claims.   An inner liner material for a pneumatic tire, which comprises the tire laminate according to any one of claims 1 to 4. A pneumatic tire comprising a tire laminate according as an innerliner material to one of the claims 1-4.