JPH1110779A - Rubber/thermoplastic resin laminate, and pneumatic tire using resin laminate, and manufacture of resin laminate and pneumatic tire - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a rubber/thermoplastic resin laminate which allows a solvent-free and extremely tacky pressure-sensitive adhesive to be applied extremely thinly and uniformly and therefore, is free from the possibility of peeling and is highly durable. SOLUTION: A solvent-free pressure-sensitive adhesive composition is applied to the surface of a film or a sheet of thermoplastic resin in the thickness of 100 μm or less using a coating device having a gear pump mechanism with two gears engaged with each other. In addition, a rubber composition is laminated on the pressure-sensitive adhesive composition and these compositions are bonded together through vulcanization to manufacture the rubber/thermoplastic resin laminate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber / thermoplastic resin laminate having a very thin and uniform high tack adhesive layer and a pneumatic tire using the same as an inner liner.

[0002]

2. Description of the Related Art Reduction of the fuel consumption rate is one of the great technologies in automobiles, and as a measure against this, the demand for reducing the weight of pneumatic tires is increasing. By the way, on the inner surface of the pneumatic tire, an air permeation preventing layer such as an inner liner layer made of rubber having low gas permeability such as halogenated butyl rubber is provided to keep the tire air pressure constant.

In recent years, a technique has been proposed in which various materials are used as an air permeation preventing layer such as an inner liner layer of a pneumatic tire in place of a low gas permeable rubber such as butyl rubber to reduce the weight of the tire. For example, JP-A-6-4
No. 0207 discloses a thin film formed by laminating a low-ventilation layer made of a polyvinylidene chloride-based film or an ethylene vinyl alcohol copolymer film and an adhesive layer made of a polyolefin-based film, an aliphatic polyamide-based film or a polyurethane-based film. Then, after laminating this thin film on the inner surface of a green tire made of unvulcanized rubber such that the adhesive layer is in contact with the carcass layer, by vulcanizing the green tire, an air permeation preventing layer is provided inside the tire. It has been proposed.

Further, Japanese Patent Application Laid-Open No. Hei 8-259741 discloses
Means that (A) the air permeability coefficient is 25 × 10 ^-12cc ・ cm / cm^Two
・ Sec ・ cmHg or less and Young's modulus is over 500MPa
Also, one kind of thermoplastic resin is added at 10
% By weight or more and (B) the air permeability coefficient is 25 × 10
^-12cc ・ cm / cm^Two・ Sec ・ Young's modulus is 500MP over cmHg
a At least one elastomer component below
-At least 10% by weight of the components (A) and
The total amount (A) + (B) of component (B) is the total polymer component weight.
Included in an amount of 30% by weight or more per amount and air permeation
Coefficient is 25 × 10^{-1 Two}cc ・ cm / cm^Two・ Sec ・ cmHg or less
A polymer composition for tires having a Young's modulus of 1 to 500 MPa
A pneumatic tire used for an air permeation prevention layer has been proposed.
You. Use of such a film for the air permeation prevention layer
The thickness of the air permeation prevention layer can be made thinner than before
Tire weight without sacrificing air pressure retention performance
Can be reduced.

[0005] As a method of bonding these thermoplastic films to a tire, a green tire is manufactured and then a belt-like film is adhered to the inner surface, or the belt-like film and the carcass are combined and wound around a forming drum to inflation. However, in such a method, if the adhesion of the splice portion (joining portion) of the film is poor, there is a problem that the splice portion is opened (splice open) at the time of tire molding.

To adhere the thermoplastic film and the green tire in close contact, an adhesive having sufficient tackiness;
For example, it is necessary to apply a tacky adhesive mainly composed of a rubber and a tackifier such as natural rubber on the film, or to apply a cement in which this is dissolved in a solvent to the thermoplastic film, This adhesive cannot be extruded when applied on a film with a T-type die due to its high viscosity, or even if it can be applied, the applied thickness becomes very thick. However, there is a problem that the adhesive is broken from the inside of the adhesive, and it is also disadvantageous for weight reduction. In addition, if the viscosity of the adhesive is reduced so that it can be applied thinly with a T-die, the adhesive easily flows during vulcanization of the tire. There is a problem that a portion where no adhesive is present is generated and the adhesive is peeled off during running. Further, when a cement in which an adhesive is dissolved in an organic solvent is used, application is easy, but the working environment is significantly deteriorated.

[0007]

SUMMARY OF THE INVENTION In the present invention, in view of the above circumstances, as a result of studying to solve these problems,
The rubber / thermoplastic resin laminate and the solvent-free, high tack adhesive used for joining the tire member and the thermoplastic elastomer film can be applied extremely thinly and uniformly, so that when forming these laminates, It is an object of the present invention to provide a rubber / thermoplastic resin laminate and a pneumatic tire that have no problem of peeling, have excellent bonding strength, improve durability, and can be reduced in weight.

[0008]

According to the present invention, a solvent-free adhesive composition is coated with a thermoplastic resin film or sheet using a coating device having a gear pump mechanism in which two gears mesh with each other. A rubber / thermoplastic resin laminate is provided, which is coated on the top with a thickness of 100 μm or less, laminated with a rubber composition, and vulcanized and bonded.

According to the present invention, the Young's modulus is 500
MPa or less, air permeability 25 × 10 ^-12cc ・ cm / cm^Two・
The above-mentioned thermoplastic film having a height of not more than cmHg
Pneumatic tire having the laminated structure used as a tire
Is provided.

According to the present invention, the adhesive composition containing no solvent is coated on the thermoplastic resin film or sheet by using a coating apparatus having a gear pump mechanism in which two gears mesh with each other. 100 μm or less
A method for producing a rubber / thermoplastic resin laminate, which is laminated with a rubber composition and vulcanized and bonded, is provided.

Further, according to the present invention, the adhesive composition containing no solvent is coated on the thermoplastic resin film with a thickness of 100 μm by using a coating apparatus having a gear pump mechanism in which two gears mesh with each other. A method for producing a pneumatic tire is provided below, which is applied, laminated with a tire member, and vulcanized and bonded.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The configuration, operation and effect of the present invention will be described below.

The thermoplastic resin used in the present invention is, 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 (N61)
2), nylon 6/66 copolymer (N6 / 66), nylon 6/66/610 copolymer (N / 6/66/61)
0), nylon MXD6 (MXD6), nylon 6T,
Nylon 6 / 6T copolymer, Nylon 66 / PP copolymer, Nylon 66 / PPS copolymer) and their N
-Alkoxyalkylated compounds, for example, methoxymethylated 6-nylon, methoxymethylated 6-610-nylon, methoxymethylated 612-nylon, polyester resins (for example, polybutylene terephthalate (PBT), polyethylene terephthalate (PE
T), polyethylene isophthalate (PE10), PE
T / PEI copolymer, polyarylate (PAR), polybutylene naphthalate (PBN), liquid crystal polyester,
Aromatic polyesters such as polyoxyalkylenediimidic acid / polybutylate terephthalate copolymer), polynitrile resins (eg, polyacrylonitrile (PA
N), polymethacrylonitrile, 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 (P
DVC), polyvinyl chloride (PVC), vinyl chloride / vinylidene chloride copolymer, vinylidene chloride / methyl acrylate copolymer, vinylidene chloride / acrylonitrile copolymer), cellulose resin (eg, cellulose acetate, cellulose acetate butyrate) , Fluorinated resins (eg, polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polychlorofluoroethylene (PCTF)
E), tetrafluoroethylene / ethylene copolymer), imide-based resin (for example, aromatic polyimide (PI)) and the like, and two or more kinds may be used.

Further, as the thermoplastic resin film used in the present invention, a film obtained by blending an elastomer with the above-mentioned thermoplastic resin may be used. As the elastomer component that can be blended with the thermoplastic resin, the composition and the blended state with the thermoplastic resin component, as a result, if it has the above air permeability coefficient and Young's modulus, the type and amount thereof are There is no particular limitation.

Examples of the elastomer to be blended with the thermoplastic resin include diene rubbers and hydrogenated products thereof (eg, NR, IR, epoxidized natural rubber, SBR,
BR (high cis and low cis BR), NBR, hydrogenated N
BR, hydrogenated SBR), olefin rubber (eg, ethylene propylene rubber (EPDM, EPM), maleic acid-modified ethylene propylene rubber (M-EPM), II
R, isobutylene and aromatic vinyl or diene monomer copolymer), acrylic rubber (ACM), ionomer,
Halogen-containing rubber (for example, Br-IIR, CI-II
R, bromide of isobutylene paramethylstyrene copolymer (Br-IPMS), 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 (eg, 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 elastomer (for example, styrene-based elastomer, olefin-based rubber) Elastomer, ester-based elastomer, urethane-based elastomer, polyamide-based elastomer) and the like, and may be two or more kinds.

When the compatibility between the specific thermoplastic resin and the elastomer component is different, it is preferable to add an appropriate compatibilizer as the third component. By mixing the compatibilizing agent into the system, the interfacial tension between the thermoplastic resin and the elastomer component is reduced, and as a result, the rubber particles forming the dispersion layer become finer, so that the properties of both components are more improved. It will be effectively expressed. As such a compatibilizer, generally a copolymer having a structure of both or one of a thermoplastic resin and an elastomer component, or an epoxy group, a carbonyl group, a halogen group, capable of reacting with the thermoplastic resin or the elastomer component, The copolymer may have a copolymer structure having an amino group, an oxazoline group, a hydroxyl group, and the like. These may be selected depending on the types of the thermoplastic resin and the elastomer component to be mixed, and those usually used include styrene / ethylene / butylene block copolymer (SEBS) and its maleic acid-modified product, EPDM: E
PDM / styrene or EPDM / acrylonitrile graft copolymer and its maleic acid modified product, styrene / maleic acid copolymer, reactive phenoxine and the like can be mentioned. The amount of the compatibilizer is not particularly limited, but is preferably 0.5 to 10 parts by weight per 100 parts by weight of the polymer component (total of the thermoplastic resin and the elastomer component).
Good by weight.

When the thermoplastic resin and the elastomer are blended, the composition ratio of the specific thermoplastic resin (A) and the elastomer component (B) is not particularly limited, and the thickness of the film, air permeability, flexibility, It may be appropriately determined by the balance of the properties, but a preferable range is 10/9 by weight ratio (A) / (B).
0-90 / 10, more preferably 15 / 85-90 / 1
0.

The polymer composition (resin film 30) according to the present invention may further comprise, in addition to the above essential polymer components, other compatibilizer polymers such as the above-mentioned compatibilizer polymer as long as the necessary properties of the tire polymer composition of the present invention are not impaired. Can be mixed. The purpose of mixing the other polymer is to improve the compatibility between the thermoplastic resin and the elastomer component, to improve the film forming processability of the material, to improve the heat resistance, to reduce the cost, and the like. As a material to be used, for example, polyethylene (PE),
Polypropylene (PP), polystyrene (PS), AB
S, SBS, polycarbonate (PC) and the like. Further, olefin copolymers such as polyethylene and polypropylene, maleic acid-modified products thereof, and glycidyl group-introduced products thereof can also be mentioned. The polymer composition according to the present invention may further contain a filler, carbon black, quartz powder, calcium carbonate, alumina, titanium oxide, etc., which are generally blended in the polymer blend, with the above air permeability coefficient (and Young's modulus). It can be arbitrarily compounded as long as the requirements are not impaired.

The elastomer component can be dynamically vulcanized when mixed with a thermoplastic resin. The vulcanizing agent, vulcanization aid, vulcanization conditions (temperature, time) and the like for dynamically vulcanizing may be appropriately determined according to the composition of the elastomer component to be added, and are not particularly limited. . As the vulcanizing agent, a general rubber vulcanizing agent (crosslinking agent) can be used. Specifically, examples of the ionic vulcanizing agent include powdered sulfur, precipitated sulfur, highly dispersible sulfur, surface-treated sulfur, insoluble sulfur, dimorpholine disulfide, and alkylphenol disulfide, and for example, 0.5 to 4 phr. [Parts by weight per 100 parts by weight of rubber component (polymer)] can be used.

The organic peroxide-based vulcanizing agents include:
Benzoyl peroxide, t-butyl hydroperoxide, 2,4-bichlorobenzoyl peroxide,
Examples of thiourea-based vulcanization accelerators such as 2, Te-diethyldithiocarbamate, Cu-dimethyldithiocarbamate, Fe-dimethyldithiocarbamate, and pipecoline pipecolyldithiocarbamate include ethylenethiourea,
Diethylthiourea and the like can be mentioned.

As the vulcanization accelerating auxiliary, a general rubber auxiliary can be used in combination. For example, zinc white (about 5 phr), stearic acid, oleic acid and their Zn salts (2 to 2 phr) can be used. About 4 phr) can be used. The method for producing a thermoplastic elastomer composition is as follows: a thermoplastic resin component and an elastomer component (an unvulcanized product in the case of rubber) are used in advance.
By melt-kneading with a shaft kneading extruder or the like, and dispersing an elastomer component as a dispersed phase (domain) in a thermoplastic resin forming a continuous phase (matrix phase). When vulcanizing the elastomer component, a vulcanizing agent may be added under kneading to dynamically vulcanize the elastomer component. The various additives (excluding the vulcanizing agent) to the thermoplastic resin or the elastomer component may be added during the kneading, but it is preferable to mix them before kneading. The kneader used for kneading the thermoplastic resin and the elastomer component is not particularly limited, and may be a screw extruder, a kneader,
A Banbury mixer, a twin screw extruder or the like can be used. Among them, for kneading the thermoplastic resin and the elastomer component and for dynamic vulcanization of the elastomer component, it is preferable to use a twin-screw kneading extruder. Further, two or more kinds of kneaders may be used and the kneading may be performed sequentially. As the conditions for the melt-kneading, the temperature may be at least the temperature at which the thermoplastic resin melts. Further, the shear rate during kneading is preferably 1000 to 7500 sec ^-1 . The whole kneading time is 30 seconds to 10 minutes,
When a vulcanizing agent is added, the vulcanization time after the addition is 1
It is preferably from 5 seconds to 5 minutes. The polymer composition produced by the above method is then formed into a sheet-like film by extrusion or calendering. The method of forming a film may be a method of forming a normal thermoplastic resin or thermoplastic elastomer into a film.

The thus obtained film has a structure in which the elastomer component (B) is dispersed as a dispersed phase (domain) in a matrix of the thermoplastic resin (A). By taking such a dispersed structure, thermoplastic processing becomes possible, and sufficient rigidity can be imparted to the film as the belt reinforcing layer by the effect of the resin layer as the continuous phase and the sufficient flexibility. At the same time, regardless of the amount of the elastomer component, at the time of molding, it is possible to obtain molding processability equivalent to that of a thermoplastic resin, so that it can be formed into a film by a usual resin molding machine, that is, extrusion molding, or calender molding. It becomes possible.

Next, as the adhesive used for bonding the rubber / thermoplastic resin laminate of the present invention, a rubber-based or acrylate copolymer-based adhesive generally used as an adhesive is used. A cross-linking agent and a vulcanization accelerator may be blended with a pressure-sensitive adhesive composition obtained by blending a tackifier with a polymer, and those reacting with a predetermined heat may be used. Thereby, at the time of molding, there is sufficient tackiness to improve workability, and furthermore, it is possible to obtain a desired laminate by bonding by vulcanization. The tackiness is 3N or more and 30N or more.
It is desirable that: If the tackiness is 3 N or less, it is difficult to form the laminated body.
Correct the excessive tackiness at the time of molding (reapply)
Becomes extremely difficult. It is important that the adhesive used in the present invention does not contain an organic solvent. The use of an organic solvent lowers the viscosity of the adhesive and improves coatability, but worsens the working environment and requires equipment for collecting the solvent.

Examples of the rubber adhesive include natural rubber, isoprene rubber, polybutadiene rubber, styrene-
Rubber obtained by compounding a tackifier with rubber such as butadiene copolymer rubber, chloroprene rubber, and ethylene-propylene copolymer rubber can be used. As the tackifier, any one used for general adhesives and adhesives can be used, for example, about 10 to 100 phr. Specifically, for example, (a) rosin-based resin (rosin such as gum rosin, tall oil rosin, wood rosin; basic rosin such as hydrogenated rosin, disproportionated rosin, polymerized rosin, maleated rosin); rosin glycerin ester ( Ester gums), rosin esters such as hydrogenated rosin / glycerin esters; and (b) resins having polar groups such as terpene phenol resins and resins not having polar groups, for example α
Terpene resins such as pinene-based, β-pinene-based, and dipentene (limonene) -based; natural products such as aromatic hydrocarbon-modified terpene resins and derivatives thereof; and, for example, (c) aliphatic, alicyclic, and aromatic Petroleum resins such as;
(D) Coumarone-indene resin; (e) a polymer resin such as a styrene resin such as a styrene resin or a substituted styrene resin;
Examples include (f) a phenolic resin such as an alkylphenol resin and a rosin-modified phenolic resin; and (g) a condensation resin such as a xylene resin.

Examples of the acrylate copolymer include polymers obtained by polymerizing monomers such as butyl acrylate, 2-ethylhexyl acrylate and ethyl acrylate, and copolymers with ethylene and the like. Can be. This acrylate copolymer may be used as it is, or may contain the tackifier described above.

Further, as the cross-linking agent, a general rubber cross-linking agent (vulcanizing agent) can be used. For example, as a sulfur type, powder ion, precipitated sulfur, highly dispersible sulfur,
1 to 4 phr of surface-treated sulfur, insoluble sulfur, dimorpholine disulfide, alkyl phenol disulfide, etc .; peroxides such as benzoyl peroxide, t-butyl hydroperoxide,
2,4-dichlorodibenzoyl peroxide,
2,5-dimethyl-2,5 di (t-butylperoxy)
Hexane, 2,5-dimethyl-hexane-2,5-di (peroxyl benzoate), etc. are about 1 to 15 phr, others are zinc white (about 5 phr), magnesium oxide (about 4 phr), litharge (about 10 to 20 phr). ), P-quinone dioxime, p-dibenzoylquinone dioxime, tetrachloro-p-benzoquinone, poly-p-dinitrosobenzene (about 2 to 10 phr) and the like.

As the vulcanization accelerator, a general rubber vulcanization accelerator, for example, 0.5 to 2 phr can be used. Specifically, aldehyde / ammonia system (for example, hexamethylenetetramine), guanidine system (for example, diphenyl guanidine), thiazole system (for example, 2-mercaptobenzothiazole and its Zn salt,
Cyclohexylamine salts, dibenzothiazyl disulfide), sulfenamides (for example, cyclohexyl benzothiazyl sulfenamide, N-oxydiethylene benzothiazyl-2-sulfenamide, N
-T-butyl-2-benzothiazolesulfenamide, 2- (thymopolinyldithio) benzothiazole), thiurams (for example, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetramethylthiuram monosulfide, dimethyldisulfide) Pentamethylenethiuram tetrasulfide), dithioate salt (for example, Zn-dimethyl dithiocarbamate,
Zn-diethyl dithiocarbamate, Zn-di-n-
Butyl dithiocarbamate, Zn-ethyl phenyl dithiocarbamate, Te-dimethyl dithiocarbamate, pipecoline pipecolyl dithiocarbamate), thioureas (for example, ethylene thiourea,
Diethylthiourea) and the like.

These adhesives may further contain commonly used fillers, softeners, plasticizers, coloring agents, antioxidants and the like.

In order to apply the solvent-free adhesive composition of the present invention thinly and uniformly on a thermoplastic resin film or sheet, the present invention has a gear pump mechanism in which two gears mesh with each other. It is essential to use a coating device. Such a coating device is currently available, for example, as a GPD system (produced by Yuri Roll Machine Co., Ltd.). In the present invention, the adhesive composition is first applied to a predetermined thermoplastic resin film or sheet in a thickness of 100 μm or less, preferably 5 to 80 μm using the coating device, and then the adhesive composition and the rubber composition are applied. The product can be heated and vulcanized while applying pressure using a conventional hot press molding method to obtain a desired rubber / thermoplastic resin laminate.

Hereinafter, as an application example of the laminate of the rubber / thermoplastic resin film, a case will be described in which such a technique is actually applied to a pneumatic tire including an inner liner layer. FIG. 1 is a meridional half-sectional view illustrating a typical example of the pneumatic tire of the present invention. In FIG.
A carcass layer 2 is mounted between a pair of left and right beat cores 1, 1, and an inner liner layer 3 is provided on the inner surface of the tire inside the carcass layer 2. This inner liner layer 3 corresponds to the thermoplastic resin film in the present invention. In FIG. 1, reference numeral 4 denotes a sidewall.

When the rubber / thermoplastic resin laminate of the present invention is used for a pneumatic tire, the thermoplastic resin film forming the inner liner layer has a Young's modulus of 5
00MPa or less, preferably at 10-300, and its air permeability ^{25 × 10 -1 2 cc · cm} / cm 2 · cmHg or less, preferably ^{0.05 × 10 -12 ~25 × 10 -12} cc
・ The one having cm / cm ² · cmHg is used. If the Young's modulus exceeds 500 MPa, it is not preferable because the tire cannot follow the deformation of the tire during running.
By using a material having a density of not more than × 10 ⁻¹² cc · cm / cm ² · cmHg, the thickness of the inner liner layer serving as an air permeation preventing layer can be reduced to 以下 or less of the conventional thickness.

Hereinafter, the present invention will be described more specifically with reference to Examples. However, it goes without saying that the present invention is not limited to the following Examples.

Preparation of Thermoplastic Elastomer Film Pellets of a predetermined thermoplastic resin component shown in Table I below are charged from a first input port of a twin-screw kneading extruder, and after melt-kneading, pellets are input from a second input port. Pour and knead the pellets of the elastomer component that was previously kneaded with a Banbury mixer,
After finely dispersing the elastomer component in the thermoplastic resin, a vulcanizing compounding agent shown in Table I is introduced from the third inlet to dynamically crosslink (vulcanize) the elastomer component to form an elastomer phase. The variance was fixed. The obtained thermoplastic elastomer composition was extruded into a strand shape from a discharge port of a twin-screw kneading extruder, and the strand was water-cooled and then pelletized with a resin pelletizer. Next, the pellets were formed to a thickness of 15 using a resin single screw extruder equipped with a T-die head.
It was formed into a 0 μm film.

Preparation of Thermoplastic Resin Film Only a nylon 6-66 copolymer was formed into a film having a thickness of 150 μm using a single-axis machine equipped with a T-die head.

Measurement of Physical Properties of Film The air permeability and Young's modulus of the two films prepared by the above methods were measured according to the following test methods, and the results are shown in Table I below. Air permeability: JIS K 7126 "A method of gas permeability test for plastic films and sheets"Young's modulus: JIS K 6251 "Tensile test method for vulcanized rubber"

[0036]

[Table 1]

(Note) Thermoplastic resin component 1) Nylon 11: Rilsan BMNO (Achem) 2) Nylon 6-66 copolymer: Amilan CM6001
(Toray) elastomer component 3) Br-IPMS: EXXPRO 98-4 (manufactured by Exxon Chemical) 4) HNBR: Zetpol 1020 (manufactured by Nippon Zeon) 5) ENR: 50% epoxidized natural rubber (Malay)
6) Zinc flower: Zinc flower No. 3 (manufactured by Seido Chemical) 7) Zinc stearate: (manufactured by Seido Chemical) 8) Stearic acid: Beads stearic acid NY (manufactured by NOF CORPORATION) 9) TAIC: Parkerlink 301-70DPD (Akzo Chemical) 10) TT: Noxeller TT (Ouchi Shinko Chemical) 11) M: Noxeller M (Ouchi Shinko Chemical) 12) S: Powdered sulfur (Karuizawa Refinery)

Examples 1 to 3 and Comparative Examples 1 to 3 Preparation of Tires An adhesive having the adhesive composition shown in Table II below was kneaded using a kneader, and this was roll-calendered (Comparative Example 1). ), A T-type die (Comparative Examples 2 and 3) and a gear pump type die (Examples 1 to 3) were applied to a thermoplastic elastomer film and a thermoplastic resin film having a thickness of 150 μm to a predetermined thickness. Using this laminate as the inner liner part, a tire was produced by a usual method, and a durability test was performed under the following conditions. The tackiness of the film coated with the adhesive was measured by the following method.

[0039]

[Table 2]

Adhesion (Tackiness) Test A film and a carcass with the upper sample of the measuring instrument attached at the attachment position were pressed against the film to which the adhesive was applied, and the force at which the film and the carcass were peeled off was defined as the adhesive force.
The measurement was carried out using a PICMA tack tester of Toyo Seiki Seisakusho under the following conditions. Measurement conditions Reference sample (upper) dimensions: 12.7 mm x 152 mm Compression load: 4.90 N Peeling speed: 120 mm / min Compression time: 0 sec Temperature: 20 ° C Humidity: 65%

Endurance test: tire size: 165SR13, rim: 13 × 4.5J, air pressure: 140 kPa, load: 5.5 kN, drum rotation speed: 80 km / h (on a 1707 mmφ drum) After running 10,000 km, the inner surface of the tire was observed. The inner liner layer is visually inspected, and those which do not cause a failure such as a crack, peeling, or lifting are judged to be acceptable.

The results are shown in Table III.

[Table 3] (Note) 1) A T-type die was attached to a φ40 mm extruder (Pla Giken Co., Ltd.) and extruded to a width of 400 mm. Extruder rotation speed:
10 rpm, discharge rate: 200 g / min. 2) Extruded to a width of 400 mm using a GPD system (manufactured by Yuri Roll Machine Co., Ltd.). Gear rotation speed: 11 rpm, discharge amount:
100 g / min. (Example 1), 40 g / min. (Example 2)

[0043]

According to the roll calender method of Comparative Example 1,
Since the adhesive was stuck to the roll, it could not be uniformly applied on the film. For T-die, high viscosity adhesive with large die well
It cannot be applied to the thickness below
In a tire using a thick adhesive, the adhesive itself cracks during a durability test. If an adhesive with a low viscosity is used, the thickness of the adhesive can be reduced, but the resin content must be increased to reduce the viscosity, resulting in a hardened adhesive and tire durability Will be reduced. In the gear pump type die, the thickness of the high-viscosity adhesive can be applied as thin as possible to ensure the durability of the tire.

As described above, according to the present invention, a solvent-free, high tack adhesive can be applied very thinly and uniformly, so that there is no problem of peeling and the bonding strength is extremely high. It can be seen that the durability was good and the durability was improved.

[Brief description of the drawings]

FIG. 1 is a meridional half-sectional view showing a structure of a pneumatic tire using a rubber / thermoplastic resin laminate film of the present invention for an inner liner layer.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Bead core 2: Carcass layer 3: Inner liner layer 4: Side wall

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI B60C 5/14 B60C 5/14 A

Claims (4)

[Claims] An adhesive composition containing no solvent is applied on a thermoplastic resin film or sheet to a thickness of 100 μm or less using a coating device having a gear pump mechanism in which two gears mesh with each other. Laminated with a rubber composition and vulcanized and bonded. 2. The laminate according to claim 1, wherein the thermoplastic resin film having a Young's modulus of 500 MPa or less and an air permeability of 25 × 10 ⁻¹² cc · cm / cm ² · cmHg or less is used as an inner liner. A pneumatic tire with a structure. 3. The thickness of the solvent-free adhesive composition on the thermoplastic resin film or sheet according to claim 1, using a coating apparatus having a gear pump mechanism in which two gears mesh with each other. A method for producing a rubber / thermoplastic resin laminate, which is applied to a thickness of 100 μm or less, laminated with a rubber composition, and vulcanized and bonded. 4. The thermoplastic resin film according to claim 2, wherein the solvent-free adhesive composition is coated on the thermoplastic resin film according to claim 2 using a coating device having a gear pump mechanism in which two gears mesh with each other. A method for manufacturing a pneumatic tire, which is applied, laminated on a tire member, and vulcanized and bonded.