JP5417802B2 - Pneumatic tire manufacturing method - Google Patents

Description

  The present invention relates to a cylindrical laminate for a pneumatic tire, more specifically, a cylindrical laminate for a pneumatic tire comprising a thermoplastic elastomer inner liner layer and a thermoplastic resin layer as a protective film for protecting the inner liner layer. The present invention relates to a body and a pneumatic tire with a protective film.

It is known to use a thermoplastic elastomer as an inner liner for a pneumatic tire in the innermost layer (Patent Document 1).
JP 2007-030691 A

  Since the thermoplastic elastomer is thermoplastic, there is a problem that local irregularities are formed on the film due to foreign matters attached to the surface during vulcanization, dust adhering to the bladder, and the like, and the film is easily broken during running. In addition, when selling tires, tires are sometimes placed in stores, and in that case, the inner liner is exposed to sunlight, so that there has been a problem of ultraviolet deterioration when left for a long time.

The present invention is a laminate for a pneumatic tire comprising a thermoplastic elastomer inner liner layer and a thermoplastic resin layer having a melting point of 190 ° C. to 300 ° C., wherein the laminate has the thermoplastic resin layer on the inside. A cylindrical laminate that is co-extruded into a cylindrical shape by cylindrical molding, and has an adhesive force of 0.001 to 20 N / mm ² by a peel test between the thermoplastic elastomer inner liner layer and the thermoplastic resin layer. To do.

The thermoplastic resin constituting the thermoplastic resin layer is preferably selected from the group consisting of nylon 6, nylon 66, nylon 46, nylon 610, nylon 612, and nylon 6/66 copolymer.
The thermoplastic resin constituting the thermoplastic resin layer is preferably selected from the group consisting of methylpentene copolymer, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate.

The thermoplastic resin layer preferably has a UVB transmittance of 10% or less.
The thermoplastic resin layer preferably contains 0.1 to 10% by mass of carbon black.
The thermoplastic resin layer preferably contains 0.1 to 10% by mass of an ultraviolet absorber.
The thermoplastic resin layer preferably contains 0.1 to 10% by mass of titanium oxide.

  The present invention is also a pneumatic tire with a protective film, including the laminate, wherein the thermoplastic resin layer of the laminate is provided as the protective film on the innermost surface side of the pneumatic tire with the protective film. It is characterized by being.

By providing the laminate for a pneumatic tire of the present invention on the inner surface side of the pneumatic tire, the thermoplastic resin layer functions as a protective film for the inner liner layer. To prevent adhesion.
Moreover, the pneumatic tire with a protective film of the present invention can prevent the inner liner layer from being damaged during handling, and the inner liner layer will not be deteriorated by ultraviolet rays even if it is left outdoors for a long time at the time of sale.
In addition, the pneumatic tire with a protective film of the present invention provides a tire in which the thermoplastic resin layer as a protective film can be easily peeled off with an adhesive tape or the like immediately before use, and the inner liner layer has no defects or deterioration. can do.

  The laminate for a pneumatic tire of the present invention comprises a thermoplastic elastomer inner liner layer and a thermoplastic resin layer having a melting point of 190 ° C to 300 ° C.

  The thermoplastic elastomer constituting the thermoplastic elastomer inner liner layer is not particularly limited as long as it can be used as an inner liner. For example, styrene thermoplastic elastomer, polyolefin thermoplastic elastomer, polyvinyl chloride Thermoplastic elastomers, polyurethane-based thermoplastic elastomers, polyester-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, 1,2-polybutadiene-based thermoplastic elastomers, trans-polyisoprene-based thermoplastic elastomers, fluororubber-based thermoplastic elastomers, chlorinated polyethylene -Based thermoplastic elastomers and dynamic cross-linked thermoplastic elastomers. A thermoplastic elastomer composed of a thermoplastic resin and an elastomer component is preferable.

  Examples of the thermoplastic resin constituting the thermoplastic elastomer composed of a thermoplastic resin and an elastomer component include polyamide resins (for example, nylon 6, nylon 66, nylon 46, nylon 11, nylon 12, nylon 610, nylon 612, nylon 6/66). Copolymer, nylon 6/66/610 copolymer, nylon MXD6, nylon 6T, nylon 6 / 6T copolymer, nylon 66 / PP copolymer, nylon 66 / PPS copolymer), 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 diimi Aromatic polyester such as acid / polybutyrate terephthalate copolymer), polynitrile resin (for example, polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile / styrene copolymer (AS), methacrylonitrile / styrene copolymer) , Methacrylonitrile / styrene / butadiene copolymer), polymethacrylate resins (for example, polymethyl methacrylate (PMMA), polyethyl methacrylate), polyvinyl resins (for example, vinyl acetate (EVA), polyvinyl alcohol (PVA), Vinyl alcohol / ethylene copolymer (EVOH), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinyl chloride / vinylidene chloride copolymer, vinylidene chloride / methyl acrylate copolymer), cellulosic tree (For example, cellulose acetate, cellulose acetate butyrate), fluorine-based resin (for example, polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polychlorofluoroethylene (PCTFE), tetrafluoroethylene / ethylene copolymer (ETFE)), Examples thereof include imide resins (for example, aromatic polyimide (PI)), and nylon 6 and nylon 6/66 copolymers are preferable.

  Examples of the elastomer component constituting the thermoplastic elastomer comprising the thermoplastic resin and the elastomer component include diene rubbers and hydrogenated products thereof (for example, NR, IR, epoxidized natural rubber, SBR, BR (high cis BR and low cis BR)). , NBR, hydrogenated NBR, hydrogenated SBR), olefin rubber (for example, ethylene propylene rubber (EPDM, EPM), maleic acid modified ethylene propylene rubber (M-EPM), IIR, isobutylene and aromatic vinyl or diene monomer) Polymer, acrylic rubber (ACM), ionomer), halogen-containing rubber (eg brominated butyl rubber (Br-IIR), chlorinated butyl rubber (Cl-IIR), brominated product of isobutylene paramethylstyrene copolymer (Br-IPMS)) , Chloroprene rubber (CR), hydrin 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 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 silicon rubber, fluorine-containing phosphazene rubber), thermoplasticity Elastomers (for example, styrene elastomers, polyolefin elastomers, polyester elastomers, polyurethane elastomers, polyamide elastomers). A brominated butylene paramethylstyrene copolymer.

  Particularly preferred thermoplastic elastomers include polyamide resin such as nylon 6 and nylon 6/66 copolymer as a continuous phase (matrix), and an elastomer component such as bromide of isobutylene paramethylstyrene copolymer. Is a thermoplastic elastomer that is at least partially dynamically vulcanized to form a dispersed phase.

  The thermoplastic resin constituting the thermoplastic resin layer is not particularly limited as long as the melting point is 190 ° C. to 300 ° C., but is not limited to polyamide resin, polyester resin, polynitrile resin (for example, polyacrylonitrile (PAN), polymethacrylate). Ronitrile, acrylonitrile / styrene copolymer (AS), methacrylonitrile / styrene copolymer, methacrylonitrile / styrene / butadiene copolymer), polymethacrylate resin (for example, polymethyl methacrylate (PMMA), polymethacryl Acid acid), polyvinyl resin, cellulose resin, fluorine resin, imide resin, and the like. Nylon 6, nylon 66, nylon 46, nylon 610, nylon 612, nylon 6/66 copolymer, methyl pentene copolymer, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, more preferably Nylon 6, nylon 66, nylon 46, nylon 610, nylon 612, nylon 6/66 copolymer.

  The thermoplastic resin constituting the thermoplastic resin layer has a melting point of 190 to 300 ° C, preferably 190 to 270 ° C, more preferably 190 to 250 ° C. If the melting point is too low, there is a problem of dissolution in the tire vulcanization process, and if the melting point is too high, coextrusion with the thermoplastic elastomer for the inner liner becomes difficult. The melting point can be measured by thermal analysis (DTA or DSC).

  The thermoplastic resin layer preferably has a UVB transmittance of 10% or less, more preferably 7% or less, and even more preferably 5% or less. UVB refers to ultraviolet light having a wavelength of 315 to 280 nm. When the UVB transmittance is high, when the thermoplastic resin layer of the laminate of the present invention is used as a protective film, deterioration of the thermoplastic elastomer inner liner layer due to ultraviolet rays cannot be sufficiently prevented.

The UVB transmittance is measured as follows. A UVB measuring probe (manufactured by Delta Ohm) is attached to a UV measuring instrument (manufactured by Delta Ohm), the energy E1 (W / m ² ) is measured by directing the UVB measuring probe toward the sun, and then the UVB measuring probe is thermoplastic. The resin layer is placed, the energy E2 (W / m ² ) is measured, and the UVB transmittance is calculated by the following formula.
UVB transmittance (%) = E2 / E1 × 100

  The method for setting the UVB transmittance of the thermoplastic resin layer to 10% or less is not particularly limited. For example, there is a method of blending carbon black, an ultraviolet absorber, a colorant, or the like into the thermoplastic resin layer. The ultraviolet absorber is not particularly limited as long as it absorbs UVB, but titanium oxide can be preferably used. The compounding quantity of carbon black becomes like this. Preferably it is 0.1-10 mass%, More preferably, it is 1-10 mass%. The compounding quantity of a ultraviolet absorber becomes like this. Preferably it is 0.1-10 mass%, More preferably, it is 0.1-5 mass%. The compounding quantity of a titanium oxide becomes like this. Preferably it is 0.1-10 mass%, More preferably, it is 1-10 mass%. If the blending amount is too small, the ultraviolet transmittance cannot be lowered. On the contrary, when there are too many compounding quantities, there exists a possibility of having a bad influence on the other physical property of a thermoplastic resin layer.

  The laminate of the present invention is produced by coextrusion into a cylindrical shape by cylindrical molding. Cylindrical molding, also known as inflation molding, is a method in which a tube is extruded upward, downward, or forward from a circular extrusion die by an extruder, which is expanded by fluid pressure, then cooled, flattened and wound up as it is. It is. Co-extrusion refers to a method of forming a laminate simultaneously with extrusion by simultaneously extruding two or more materials. The molding method includes a sheet shape in addition to a cylindrical shape, but the sheet shape has a problem of sandwiching the thermoplastic resin layer at the joint, and the thermoplastic resin layer and the thermoplastic elastomer for the inner liner at the end of the sheet Since the layer is easily peeled off, it needs to be cylindrical. Further, by using this molding method, the inner liner layer and the thermoplastic resin layer protecting the inner liner layer can be molded simultaneously, and can be supplied as a laminate for a tire.

  The thickness of the thermoplastic elastomer inner liner layer is usually 10 to 300 μm, preferably 20 to 250 μm, more preferably 30 to 200 μm. If the thickness of the thermoplastic elastomer inner liner layer is too thick, there is a problem in the adhesive force with the carcass layer. If the thickness of the thermoplastic elastomer inner liner layer is too thin, there is a problem that air leakage becomes large.

  The thickness of the thermoplastic resin layer is usually 5 to 100 μm, preferably 5 to 50 μm, and more preferably 5 to 30 μm. When the thickness of the thermoplastic resin layer is too thick, it becomes easy to peel off from the inner liner layer during tire molding. If the thickness of the thermoplastic resin layer is too thin, ultraviolet light transmission cannot be prevented.

Adhesion between the thermoplastic elastomer inner liner layer and the thermoplastic resin layer of the laminate of the present invention is 0.001~20N / mm ^2, preferably 0.01~5N / mm ^2, more preferably 0.01 to 1 N / mm ² . Adhesion is measured by a peel test. When the adhesive strength is too weak, it is difficult for the thermoplastic resin layer to be peeled off from the thermoplastic elastomer inner liner layer.For example, during the process of manufacturing a pneumatic tire using the laminate of the present invention, There is a risk of peeling during storage. When using the pneumatic tire including the laminate of the present invention, it is necessary to peel off the thermoplastic resin layer, which is a protective film, from the thermoplastic elastomer inner liner layer before being mounted on a vehicle, that is, before being assembled on a rim. On the contrary, if the adhesive strength is too strong, the thermoplastic resin layer as the protective film is difficult to peel off from the thermoplastic elastomer inner liner layer.

The adhesive force between the thermoplastic elastomer inner liner layer and the thermoplastic resin layer is measured by a peel test. The peel test is performed as follows. The thermoplastic elastomer inner liner layer side of the laminate was laminated with rubber having the following composition, pressed at 180 ° C. for 10 minutes at 23 kg / cm ² , cut into a size of 20 mm in width and 150 mm in length, and 50 mm in length. Remove the space between the thermoplastic resin layer and the thermoplastic elastomer inner liner layer / rubber layer in advance by using release paper, etc., and then remove the thermoplastic resin layer and the thermoplastic elastomer inner liner layer / rubber of the peeled portion. The peel force is measured by attaching the layer to the chuck of a tensile tester and pulling it up and down at a tensile speed of 50 mm / min. The test is performed at room temperature.
(Rubber composition)
Natural rubber (TSR20) 50 parts by mass SBR (Nippon Zeon Co., Ltd., Nipol 1502) 50 parts by mass GPF carbon (Nisshin Carbon Co., Ltd., HTC # G) 50 parts by mass Aroma oil (Sankyo Oil Chemical Co., Ltd., A- OMIX) 10 parts by mass Terpene resin (Yasuhara Chemical Co., Ltd., YS Resin D105)) 10 parts by mass Zinc Hana (Shodou Chemical Co., Ltd., Zinc Hana 3) 3 parts by mass Stearic acid (Nichio Corporation, Beads stearic acid) 1.5 parts by mass 2,2,4-trimethyl-1,2-dihydroquinoline polymer (anti-aging agent, Nocrack 224, manufactured by Ouchi Shinsei Chemical Industry) 1 part by mass N- (1,3-dimethylbutyl) -N '-Phenyl-p-phenylenediamine (Antioxidant manufactured by FLEXSYS, SANTOFLEX 6PPD) 1 part by mass N-te t- butyl-2-benzothiazolyl sulfenamide (Ouchi Shinko Chemical Industrial Ltd. vulcanization accelerator, Nocceler NS-P) 1.5 parts by weight

  The adhesive strength between the thermoplastic elastomer inner liner layer and the thermoplastic resin layer is almost determined by the combination of the thermoplastic elastomer inner liner layer and the thermoplastic resin layer, so that the appropriate combination can be selected to obtain the desired adhesive strength. That's fine.

  In order to manufacture a pneumatic tire with a protective film using the laminate of the present invention, for example, the following method is used. The laminate of the present invention is cut in advance to a predetermined width, and the laminate is placed on the tire molding drum such that the thermoplastic resin layer surface of the laminate is on the tire molding drum side. On top of that, members used for normal tire production such as a carcass layer, a belt layer, a tread layer and the like made of unvulcanized rubber are sequentially laminated, and the drum is removed to obtain a green tire. Next, a pneumatic tire with a protective film can be produced by heat vulcanizing the green tire according to a conventional method.

The pneumatic tire with a protective film of the present invention includes the laminate, and the thermoplastic resin layer of the laminate is provided as the protective film on the innermost surface side of the pneumatic tire with the protective film. This thermoplastic resin layer in the pneumatic tire with a protective film of the present invention functions as a protective film for protecting the thermoplastic elastomer inner liner layer. That is, since the thermoplastic elastomer is thermoplastic, if the surface of the thermoplastic elastomer inner liner layer is locally uneven due to foreign matters attached to the surface during vulcanization, dust attached to the bladder, etc., it becomes fragile during running. . Therefore, if a pneumatic tire is manufactured in a state where the thermoplastic resin layer is provided on the thermoplastic elastomer inner liner layer, it is possible to prevent foreign matters, dust, and the like from adhering to the surface of the thermoplastic elastomer inner liner layer. it can. Further, it is possible to prevent the thermoplastic elastomer inner liner layer from being damaged during handling such as transportation of the tire. In some cases, tires may be placed in stores at the time of tire sales. At that time, the thermoplastic elastomer inner liner layer is exposed to sunlight, so that it is deteriorated by ultraviolet rays if left for a long time. Therefore, if a thermoplastic resin layer is provided on the thermoplastic elastomer inner liner layer, the thermoplastic resin layer can block ultraviolet rays and prevent the ultraviolet degradation of the thermoplastic elastomer inner liner layer. When the pneumatic tire of the present invention is actually used as a tire, that is, when mounted on an automobile or the like, the thermoplastic resin layer, which is a protective film, is peeled off from the pneumatic tire before being attached to the rim. In that case, since the adhesive force between the thermoplastic elastomer inner liner layer and the thermoplastic resin layer is 0.001 to 20 N / mm ² in the pneumatic tire of the present invention, the thermoplastic resin layer is formed with an adhesive tape or the like. It is possible to provide a tire that can be easily peeled off and has no defects or deterioration in the inner liner portion. Furthermore, in tire vulcanization, an anti-adhesive agent may be applied to prevent the inner liner and bladder from sticking to each other, but by attaching a thermoplastic resin layer, the tire can be vulcanized without using an anti-adhesive agent. .

The following composition was used as the thermoplastic elastomer for the thermoplastic elastomer inner liner layer.
Exxpro ^™ MDX89-4 (ExxonMobile Chemical Company) 100 parts by weight Zinc Hana (Shodo Chemical Industry Co., Ltd., Zinc Hana 3) 0.15 parts by mass Stearic acid (NOF Corporation, beads stearic acid) ) 0.6 parts by mass Zinc stearate (Sakai Chemical Industry Co., Ltd.) 0.3 parts by mass Nylon 6/66 (Ube Industries, UBE Nylon 5033B) 45 parts by mass Nylon 6 (Ube Industries, UBE Nylon 1030B) 18 parts by mass Butylbenzenesulfonamide (Daihachi Chemical Industry Co., Ltd., BM-4) 27 parts by mass Maleic acid-modified ethylene ethyl acrylate (Mitsui DuPont Polychemical Co., Ltd., HPR AR201) 10 parts by mass

Durability was measured as follows.
A rubber having the same composition as that of the rubber used in the peel test for measuring the adhesive force was used, and the thermoplastic elastomer inner liner layer side of the sample laminate was laminated with the rubber at 180 ° C. for 10 minutes, 23 kg / cm. After pressing at ² , after irradiating with ultraviolet rays for 168 hours with a sunshine weather meter (manufactured by Suga Test Instruments) from the thermoplastic resin layer side, and peeling off the thermoplastic resin layer, a fatigue test is performed with a constant strain tester, and the number of breaks is determined. It was measured. The test conditions were an in-layer temperature of −30 ° C., a 40% elongation strain, and a frequency of 6.7 Hz. The test was terminated after 1 million times.

Example 1
A nylon 612 “Vestamid D26” manufactured by Daicel Degussa Co., Ltd. is used as the thermoplastic resin for the thermoplastic resin layer in the extruder connected to the layer 1 using a two-layer cylindrical die, and the above thermoplastic elastomer is used in the extruder connected to the layer 2. The cylindrical laminate was extruded so that the layer 1 was inside. The temperature was set to 250 ° C. for layer 1 and 230 ° C. for layer 2. The formed cylinder was folded with a pinch roll and wound with a winder. As a result of measuring the thickness of each layer after molding, the layer 1 was 40 μm and the layer 2 was 0.1 mm. The obtained laminate was measured for UVB transmittance of the thermoplastic resin layer, adhesive strength by a peel test between the thermoplastic elastomer inner liner layer and the thermoplastic resin layer, and durability. The UVB transmittance was 20%. The adhesive strength was 1 N / mm ² and the durability was 100,000 times.

Example 2
A laminate was produced in the same manner as in Example 1 except that a mixture of nylon 612 “Vestamid D26” manufactured by Daicel Degussa Co., Ltd. and carbon black “MA600” (6 mass%) manufactured by Mitsubishi Chemical Corporation was used as the thermoplastic resin. ,evaluated. Layer 1 had a thickness of 35 μm, and layer 2 had a thickness of 0.1 mm. The UVB transmittance was 1%, the adhesive strength was 0.5 N / mm ² , and the durability was 600,000 times.

Example 3
As thermoplastic resins, nylon 612 “Vestamid D26” manufactured by Daicel Degussa Co., Ltd., carbon black “MA600” (6 mass%) manufactured by Mitsubishi Chemical Corporation, and ultraviolet absorber “Tinuvin 328” (2- (3) manufactured by Ciba Specialty Chemicals Co., Ltd. , 5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole) (5% by mass) was produced and evaluated in the same manner as in Example 1 except that a mixture was used. Layer 1 had a thickness of 30 μm, and layer 2 had a thickness of 0.1 mm. The UVB transmittance was 0.5%, the adhesive strength was 0.5 N / mm ² , and the durability was 900,000 times.

Example 4
As the thermoplastic resin, nylon 612 “Vestamid D26” manufactured by Daicel Degussa Co., Ltd., nylon 6 / titanium oxide mixture (60% by mass / 40% by mass) “PAM (F) 25529 White” (10% by mass) manufactured by Dainichi Seika Kogyo Co., Ltd. A laminate was prepared and evaluated in the same manner as in Example 1, except that a mixture of UV absorber “Tinuvin 328” (5 mass%) manufactured by Ciba Specialty Chemicals was used. Layer 1 had a thickness of 30 μm, and layer 2 had a thickness of 0.1 mm. The UVB transmittance was 0.3%, the adhesive strength was 0.6 N / mm ² , and the durability was 800,000 times.

Example 5
As the thermoplastic resin, nylon 612 “Vestamid D26” manufactured by Daicel Degussa Co., Ltd., carbon black “MA600” (6 mass%) manufactured by Mitsubishi Chemical Co., Ltd., nylon 6 / titanium oxide mixture (60 mass% / 40 mass%) “PAM (F) 25529 White” (10 mass%), UV absorber “Tinvin 328” (5 mass%) manufactured by Ciba Specialty Chemicals, and light stabilizer manufactured by Cytec Industries Inc. (HALS) A laminate was prepared in the same manner as in Example 1 except that a mixture of “Cyasorb ^™ UV2908” (hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate) (1.5% by mass) was used. Manufactured and evaluated. The thickness of layer 1 was 20 μm, and the thickness of layer 2 was 0.1 mm. The UVB transmittance was 0.1%, the adhesive strength was 0.2 N / mm ² , and the durability was not broken even after 1 million cycles.

Example 6
A laminate was produced and evaluated in the same manner as in Example 1 except that nylon 6 “CM1061” manufactured by Toray Industries, Inc. was used as the thermoplastic resin. Layer 1 had a thickness of 40 μm, and layer 2 had a thickness of 0.1 mm. The UVB transmittance was 15%, the adhesive strength was 10 N / mm ² , and the durability was 150,000 times.

Example 7
As a thermoplastic resin, GF reinforced nylon 6 (GF 20%) “CM1056K48” manufactured by Toray Industries, Inc., nylon 6 / carbon black mixture (90% by mass / 10% by mass) “PAM (F) 23262 Black” manufactured by Dainichi Seika Kogyo Co., Ltd. (5% by mass), Ciba Specialty Chemicals UV absorber “Tinuvin 328” (5% by mass), and Cytec Industries light stabilizer (HALS) “Cyasorb ^™ UV2908” (1.5% by mass) A laminate was produced and evaluated in the same manner as in Example 1 except that was used. Layer 1 had a thickness of 30 μm, and layer 2 had a thickness of 0.1 mm. The UVB transmittance was 0.1%, the adhesive strength was 7 N / mm ² , and the durability was not broken even after 1 million cycles.

Example 8
A laminate was manufactured and evaluated in the same manner as in Example 1 except that polyethylene naphthalate “TN8756” manufactured by Teijin Chemicals Ltd. was used as the thermoplastic resin, and the temperature of the layer 1 was set to 285 ° C. Layer 1 had a thickness of 40 μm, and layer 2 had a thickness of 0.1 mm. The UVB transmittance was 12%, the adhesive strength was 0.1 N / mm ² , and the durability was 150,000 times.

Example 9
A laminate was produced and evaluated in the same manner as in Example 1 except that polybutylene naphthalate “TQB-OT” manufactured by Teijin Chemicals Ltd. was used as the thermoplastic resin, and the temperature of layer 1 was set to 270 ° C. Layer 1 had a thickness of 40 μm, and layer 2 had a thickness of 0.1 mm. The UVB transmittance was 10%, the adhesive strength was 0.1 N / mm ² , and the durability was 200,000 times.

Example 10
As the thermoplastic resin, a mixture of polybutylene naphthalate “TQB-OT” manufactured by Teijin Chemicals Ltd. and carbon black “MA600” (6 mass%) manufactured by Mitsubishi Chemical Corporation was used, and the temperature of layer 1 was set to 270 ° C. Except for the above, a laminate was produced and evaluated in the same manner as in Example 1. Layer 1 had a thickness of 30 μm, and layer 2 had a thickness of 0.1 mm. The UVB transmittance was 1%, the adhesive strength was 0.05 N / mm ² , and the durability was 700,000 times.

Comparative Example 1
A laminate was produced and evaluated in the same manner as in Example 1 except that nothing was charged into the extruder connected to layer 1 and the temperature of layer 1 (blank) and layer 2 was set to 230 ° C. The durability was 10,000 times or less.

Claims (3)

A laminate comprising a thermoplastic elastomer and a thermoplastic resin having a melting point of 190 to 300 ° C., which is co-extruded into a cylindrical shape by cylindrical molding so that the thermoplastic resin is inside, and comprising a thermoplastic elastomer inner liner layer and a thermoplastic resin layer. A step of producing a laminate having an adhesive strength of 0.001 to 20 N / mm ² by a peel test between the thermoplastic elastomer inner liner layer and the thermoplastic resin layer, and using the laminate, A process for producing a pneumatic tire with a protective film in which the thermoplastic resin layer is provided on the innermost surface side as a protective film, and before attaching the pneumatic tire to the rim, the thermoplastic resin layer which is the protective film is attached to the air with the protective film. A method of manufacturing a pneumatic tire including a step of peeling off from a contained tire , wherein the thermoplastic resin layer has a UVB transmittance of 10%. The method is characterized in that the thermoplastic resin layer contains 0.1 to 10% by mass of carbon black, 0.1 to 10% by mass of an ultraviolet absorber, and 0.1 to 10% by mass of titanium oxide. .   2. The thermoplastic resin constituting the thermoplastic resin layer is selected from the group consisting of nylon 6, nylon 66, nylon 46, nylon 610, nylon 612, and nylon 6/66 copolymer. The manufacturing method of the pneumatic tire of description.   2. The thermoplastic resin constituting the thermoplastic resin layer is selected from the group consisting of methylpentene copolymer, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate. A method of manufacturing a pneumatic tire.