JP4867175B2 - Laminated body and pneumatic tire using the same - Google Patents

Description

  The present invention relates to a laminate and a pneumatic tire using the laminate, and more specifically, a laminate of a thermoplastic resin film and an unvulcanized rubber composition that can be bonded thereto, and a tire without using an adhesive layer. The present invention relates to a pneumatic tire used as an inner liner and a carcass layer and / or a tie rubber layer.

  A technique using a film of a thermoplastic resin and a thermoplastic elastomer for an inner liner (air permeation prevention layer) of a pneumatic tire is known (see, for example, Patent Document 1). This film does not have sufficient adhesion to the carcass layer and the tie rubber layer (the cushioning material between the carcass layer and the inner liner). Therefore, the adhesion can be improved by applying an adhesive or coextruding with the film. It has been proposed to ensure (see, for example, Patent Documents 2 and 3).

Japanese Patent Laid-Open No. 10-25375 Japanese Patent No. 3320420 Japanese Patent Laid-Open No. 11-240108

  Therefore, the present invention can be used, for example, as a laminate in which a thermoplastic resin layer is bonded to a rubber layer by vulcanization without using an adhesive layer, and as an inner liner and a carcass layer and / or a tie rubber layer of a pneumatic tire. It aims at providing the laminated body which can be manufactured.

According to the present invention, (A) a thermoplastic resin film comprising a thermoplastic elastomer composition in which rubber at least partially vulcanized in a thermoplastic resin matrix is dispersed; and (B) per 100 parts by weight of (i ) (50 / 100-80 / 95) × 100 parts by weight of a diene rubber and (ii) (15 / 95-50 / 100) × 100 parts by weight of a polymer containing an epoxy group And a pneumatic tire using the same.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to ensure adhesiveness with a thermoplastic resin film with the rubber composition which can be mixed with rubber kneaders, such as a normal Banbury mixer, and it has a carcass layer which has adhesiveness with a film And / or the laminated body of a tie rubber layer and a thermoplastic resin film, and a pneumatic tire using the same can be obtained. Specifically, by using a rubber compound containing an epoxy-based polymer that can be kneaded with a rubber-type closed mixer (such as a Banbury mixer) for the carcass layer or tie rubber layer, there is no need to use an adhesive layer. Moreover, the manufacturing process of a laminated body and a tire can be simplified.

The laminate according to the present invention comprises a thermoplastic elastomer composition film (A) in which a vulcanized rubber is dispersed in a thermoplastic resin matrix and an unvulcanized rubber composition (B) containing a diene rubber and a polymer containing an epoxy group. The film (A) preferably has an air permeability coefficient of 25 × 10 ⁻¹² cc · cm / cm ² · sec · cmHg or less and a Young's modulus of 1 It is preferable to have ~ 500 MPa. The film (A) is, for example, a matrix of at least one thermoplastic resin such as polyamide resin, polyester resin, polynitrile resin, polymethacrylate resin, polyvinyl resin, cellulose resin, fluorine resin, and imide resin. In the (continuous phase), at least one kind of at least partially vulcanized rubber such as diene rubber and hydrogenated product thereof, olefin rubber, halogen-containing rubber, silicon rubber, sulfur-containing rubber, fluororubber and thermoplastic elastomer The dispersed thermoplastic elastomer can be obtained by molding by extrusion molding or the like. Specifically, it can be obtained by previously melt-kneading a thermoplastic resin and unvulcanized rubber with a twin-screw kneading extruder or the like and dispersing the elastomer component in the thermoplastic resin forming a continuous phase. When the elastomer component is vulcanized, a vulcanizing agent is added under kneading to dynamically vulcanize the elastomer component. Further, various compounding agents (excluding the vulcanizing agent) to the thermoplastic resin and / or the elastomer component may be added during the kneading, but it is preferable to premix them before kneading. The kneading machine used for kneading the thermoplastic resin and the elastomer component is not particularly limited, and examples thereof include a screw extruder, a kneader, a Banbury mixer, and a biaxial kneading extruder. Among them, a biaxial kneading extruder is used. Is preferred. In addition, about the manufacturing method of a thermoplastic resin film (A), and others, it describes in more detail in literature, such as Unexamined-Japanese-Patent No. 8-258506, It can be based on the method described in these literature also in this invention. .

  Examples of the matrix resin of the thermoplastic resin film (A) made of the thermoplastic elastomer composition in which at least partially vulcanized rubber of the thermoplastic matrix in the present invention is dispersed include, for example, a polyamide resin (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 copolymer, nylon 66 / PP copolymer, nylon 66 / PPS copolymer) and Methoxymethylation of their N-alkoxyalkylates such as 6-nylon , 6-610-nylon methoxymethylated product, 612-nylon methoxymethylated product, polyester resin (eg polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PE10), PET / PEI copolymer) , Polyarylate (PAR), polybutylene naphthalate (PBN), liquid crystalline polyester, aromatic polyester such as polyoxyalkylene diimidic acid / polybutyrate terephthalate copolymer), polynitrile resin (for example, polyacrylonitrile (PAN), polymer) Acrylonitrile, acrylonitrile / styrene copolymer (AS), methacrylonitrile / styrene copolymer, methacrylonitrile / styrene / butadiene copolymer), polymethacrylate resin For example, polymethyl methacrylate (PMMA), polyethyl methacrylate), polyvinyl resins (for example, vinyl acetate, polyvinyl alcohol (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), cellulosic resins (eg, cellulose acetate, cellulose acetate butyrate), fluorine resins (eg, polyfluoride) Examples thereof include vinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polychlorofluoroethylene (PCTFE), tetrafluoroethylene / ethylene copolymer), and imide resins (for example, aromatic polyimide (PI)). , These can be used alone or as any blend.

  On the other hand, examples of the at least partially vulcanized rubber of the thermoplastic resin film (A) of the present invention include diene rubbers and hydrogenated products thereof (for example, NR, IR, epoxidized natural rubber, SBR, BR (high cis). BR and low cis BR) and its maleic acid adduct, NBR, hydrogenated NBR, hydrogenated SBR), olefinic rubber (eg ethylene propylene rubber (EPDM, EPM), maleic acid modified ethylene propylene rubber (M-EPM)), IIR, isobutylene and aromatic vinyl or diene monomer copolymer, acrylic rubber (ACM), ionomer), halogen-containing rubber (eg brominated butyl rubber (Br-IIR), chlorinated butyl rubber (Cl-IIR), isobutylene paramethyl Brominated product of styrene copolymer (Br-IPMS), chloroprene rubber (CR), Drin rubber (CHR, CHC), chlorosulfonated polyethylene (CSM), chlorinated polyethylene (CM), maleic acid modified chlorinated polyethylene (M-CM)), silicone rubber (eg methyl vinyl silicone rubber, dimethyl silicone rubber, methyl phenyl) Vinyl silicon 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 silicon rubber, fluorine-containing phosphazene rubber), Thermoplastic elastomers (for example, styrene-based elastomers, polyolefin-based elastomers, polyester-based elastomers, polyurethane-based elastomers, polyamide-based elastomers). Or as any blend.

  The unvulcanized rubber composition (B) constituting the laminate according to the present invention contains a diene rubber and a polymer containing an epoxy group, and the composition (B) is formed into a sheet form, for example, in the film (A). And the diene rubber is vulcanized (for example, 140 to 190 ° C. × 5 to 60 minutes) so that the film (A) and the composition (B) are integrated without using an adhesive layer. It can be a body. This laminate can be used as it is in a conventional tire manufacturing process as a carcass layer or a tie rubber layer of a pneumatic tire.

  As the diene rubber compounded in the composition (B) of the present invention, for example, any diene rubber that can be used for tires can be used. Specifically, various natural rubbers (NR) and various polybutadienes can be used. Rubber (BR), various polyisoprene rubber (IR), various styrene-butadiene copolymer rubber (SBR), acrylonitrile-butadiene copolymer rubber (NBR), styrene-isoprene copolymer rubber, styrene-isoprene-butadiene copolymer Examples thereof include diene rubber such as polymer rubber, butyl rubber, halogenated butyl rubber, ethylene-propylene-diene copolymer rubber, and the like, and these can be used alone or as any blend.

  In the present invention, an epoxy group-containing polymer is a known resin. For example, an epoxy group-containing compound (glycidyl methacrylate, glycidyl acrylate, etc.) is used as a monomer or comonomer, or a diene rubber or latex thereof is peracetic acid. And is commercially available as a polymer used for applications such as hot-melt adhesives. Specifically, commercially available products such as Bond First 2C, E, 2B, 7B, 7L, 7M (Sumitomo Chemical) and Epofriend AT501 (Daicel Chemical) can be used in the present invention.

  In the unvulcanized rubber composition constituting the laminate according to the present invention, preferably 1 to 2 parts by weight of sulfur and preferably 1 to 2 parts by weight with respect to 100 parts by weight of the total amount of the diene rubber and the epoxy group-containing polymer. It is preferable to add 3.0 parts by weight, more preferably 1 to 1.5 parts by weight of a thiuram vulcanization accelerator because good adhesion to the film and sufficient crosslinking can be obtained after vulcanization.

  As said sulfur which can be used in this invention, it can be set as arbitrary sulfur which can be mix | blended as a vulcanizing agent with the other rubber composition for tires. On the other hand, as the thiuram vulcanization accelerator, any thiuram vulcanizing agent conventionally blended as a vulcanizing agent in a rubber composition can be used. Specifically, tetrakis (2-ethylhexyl) thiuram disulfide, Examples thereof include tetrabenzyl thiuram disulfide, tetramethyl thiuram disulfide, and monosulfide compounds of these compounds.

  In addition to the sulfur and thiuram vulcanization accelerator, the unvulcanized rubber composition used in the present invention is preferably 0.3 to 2 per 100 parts by weight of the polymer containing the diene rubber and the epoxy group. 0.0 part by weight, more preferably 0.5 to 1.0 part by weight of a peroxide compound can be blended, and this is preferable because good adhesion with the resin film and sufficient crosslinking after vulcanization can be obtained. . The peroxide compound that can be used in the present invention is not particularly limited, and can be any peroxide compound that can be used for crosslinking of resin and rubber. Specific examples of the peroxide compound include 1,3-bis (tert-butylperoxyisopropyl) benzene and dicumyl peroxide.

  In the rubber composition according to the present invention, arbitrary carbon black is blended in an amount of preferably 40 to 80 parts by weight per 100 parts by weight of the diene rubber and the epoxy-containing polymer to adjust the modulus and strength as a vulcanizate. Aging resistance can be improved.

  In the laminate according to the present invention, the thermoplastic resin film (A) and the unvulcanized rubber composition (B) are vulcanized with the unvulcanized rubber composition (B) without using an adhesive layer. A tire or the like can be manufactured by stacking and integrating.

  In addition to the above-described essential components, the rubber composition according to the present invention includes other reinforcing agents (fillers) such as carbon black and silica, vulcanization or crosslinking agents, vulcanization or crosslinking accelerators, various oils, and anti-aging. Various additives that are generally blended for tires such as additives and plasticizers, and other general rubbers can be blended, and such additives are kneaded and vulcanized by a general method to obtain a composition. Can be used to vulcanize or crosslink. As long as the amount of these additives is not contrary to the object of the present invention, a conventional general amount can be used.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, it cannot be overemphasized that the scope of the present invention is not limited to these Examples.

Examples 1-16 and Comparative Examples 1-3
Sample preparation In the formulation shown in Table I or II, components other than sulfur and thiuram vulcanization accelerator or peroxide were charged into a 1.6 liter Banbury mixer, kneaded for 5 minutes, and reached 150 ± 5 ° C. When it was released, a master batch was obtained. A vulcanization accelerator and sulfur or peroxide were kneaded with this master batch with an open roll to obtain a sheet of an unvulcanized rubber composition. The adhesion of the unvulcanized rubber composition sheet was evaluated using the following adhesion evaluation test method. The results are shown in Table I or II.

Adhesion evaluation test method Adhesion: Extruded thermoplastic elastomer film (dynamically crosslinked product of nylon 11 / butyl rubber produced by the method of Example 1 of Japanese Patent No. 2999188) described in each example This was pasted on a 2 mm sheet of unvulcanized rubber and vulcanized at 160 ° C. for 20 minutes, cut into a strip shape having a width of 25 mm and a length of 100 mm, and then cut in the width direction at the center of the thermoplastic elastomer film .5 mm) was prepared. Using a fatigue tester manufactured by Ueshima Seisakusho, continuous tensile strain with a chuck of 60 mm and a stroke of 10 mm was repeatedly applied 500,000 times, and then film peeling from the cut flaws was visually observed and evaluated according to the following judgment. did.
◎: No peeling of the film was observed at all ○: Although a slight peeling was seen from the cut wound, it was a rubber material destruction ×: A large peeling occurred from the cut wound, resulting in interfacial peeling

  Adhesive strength: The peel strength was measured according to JIS K 6256. Since a thermoplastic elastomer cannot use a film, an extruded sheet having a thickness of 2.5 mm was used. Comparative example 1 was set to 1 and indicated as an index. The larger the value, the higher the adhesion.

Table I and Table II footnote * 1: SBR manufactured by Nippon Zeon Co., Ltd. (Nipol 1502)
* 2: RSS ^# 3
* 3: BR (Nipol 1220) manufactured by Nippon Zeon Co., Ltd.
* 4: Epofriend AT501 manufactured by Daicel Chemical Industries, Ltd.
* 5: Bond First 7B manufactured by Sumitomo Chemical Co., Ltd.
* 6: Nippon Steel Chemical Carbon Co., Ltd. HTC # G
* 7: Zinc oxide manufactured by Shodo Chemical Industry Co., Ltd. * 8: Bead stearic acid manufactured by Nippon Oil & Fats Co., Ltd. * 9: Fine powder sulfur (150 mesh) manufactured by Tsurumi Chemical Co., Ltd.
* 10: Nouchira TOT-N manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
* 11: Kadaku Akzo Parka Dox 14/40

  As described above, the present invention is a diene rubber unvulcanized rubber composition (B) containing, for example, a thermoplastic resin film (A) for an inner liner and a polymer containing an epoxy group of a carcass layer or a tie rubber layer, for example. ) Can be laminated and integrated with the film (A) without using an adhesive layer simultaneously with the vulcanization of the unvulcanized rubber composition (B), thereby simplifying the manufacturing process of the pneumatic tire. Can be made.

Claims (6)

(A) a thermoplastic resin film comprising a thermoplastic elastomer composition in which rubber at least partially vulcanized is dispersed in a thermoplastic resin matrix; (B) per 100 parts by weight of (i) (50 / 100- 80/95) × 100 parts by weight of a diene rubber and (ii) (15 / 95-50 / 100) × 100 parts by weight of an unvulcanized rubber composition containing a polymer containing epoxy groups. Pneumatic tire using a laminated body integrated during vulcanization. 1 to 2 parts by weight of sulfur and 1 to 2.5 parts by weight of thiuram vulcanizing agent per 100 parts by weight of the total amount of diene rubber (i) and epoxy group-containing polymer (ii) contained in the composition (B) The pneumatic tire according to claim 1 including a portion. The peroxide compound is contained in an amount of 0.3 to 1 part by weight per 100 parts by weight of the total amount of the diene rubber (i) and the polymer (ii) containing an epoxy group contained in the composition (B). Pneumatic tires . 4. The composition according to claim 1, comprising 40 to 80 parts by weight of carbon black per 100 parts by weight of the total amount of the diene rubber (i) and the epoxy group-containing polymer (ii) contained in the composition (B). The pneumatic tire according to item 1. The matrix of the thermoplastic resin is at least one thermoplastic resin selected from the group of polyamide resin, polyester resin, polynitrile resin, polymethacrylate resin, polyvinyl resin, cellulose resin, fluorine resin and imide resin. The pneumatic tire according to claim 1. The at least partially vulcanized rubber dispersed in the thermoplastic resin matrix is a diene rubber and its hydrogenated product, an olefin rubber, a halogen-containing rubber, a silicon rubber, a sulfur-containing rubber, a fluorine rubber and a group of thermoplastic elastomers. The pneumatic tire according to claim 1, wherein the pneumatic tire is at least one kind selected from.