JPH09314752A - Rubber-thermoplastic elastomer laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To hold air in a tire well by making a rubber-thermoplastic elastomer laminate by strongly bonding a thermoplastic elastomer composition in which a continuous phase is a thermoplastic resin as a gas-barrier layer and a dispersed phase in an elastomer composition and a rubber composition together. SOLUTION: A laminate contains (A) at least 10wt.% per total component weight of a thermoplastic resin component which has an air transmission coefficient of not exceeding 25×10-<12> cc.cm/cm<2> .sec.cmHg and Young's modulus of more than 500MPa and (B) at least 10wt.% per total polymer component weight of an elastomer component which has an air transmission coefficient of more than 25×10-<12> cc.cm/cm<2> .sec.cmHg and Young's modulus of not exceeding 500MPa, and the sum of the component (A) and the component (B) is at least 30wt.% per total thermoplastic elastomer component weight. A composition which contains (C) 3-50wt.% of epoxy-modified block copolymer of a vinyl aromatic compound and a conjugated diene compound and/or its partially hydrogenated product contained in the thermoplastic resin and has an air transmission coefficient of not exceeding 25×10-<12> cc.cm/cm<2> .sec.cmHg and Young's modulus of 1-500MPa is made a barrier layer, on which a rubber composition layer is laminated.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber which can reduce the weight of a tire and the thickness of a hose by thinning an inner liner layer of a pneumatic tire and a gas (air) permeation preventive layer such as a hose. TECHNICAL FIELD The present invention relates to a thermoplastic elastomer laminate, and in particular, a thermoplastic resin constituting the thermoplastic elastomer in the rubber / thermoplastic elastomer laminate structure, particularly a rubber having an improved adhesive force at the interface between a polyamide resin composition and a rubber composition. -It relates to a thermoplastic elastomer laminate.

[0002]

2. Description of the Related Art Reducing the fuel consumption rate is one of the major technical problems in automobiles, and as part of this measure, there is an increasing demand for weight reduction of pneumatic tires.

By the way, an inner liner layer made of rubber having low gas permeability such as butyl rubber is provided on the inner surface of the pneumatic tire in order to keep the tire air pressure constant. However, halogenated butyl rubber has a large hysteresis loss, so after vulcanization of the tire,
When the inner rubber of the carcass layer and the inner liner layer are corrugated in the gap between the carcass cords, the inner liner rubber layer is deformed together with the deformation of the carcass layer, so that the rolling resistance increases. Therefore, in general, the inner liner layer (halogenated butyl rubber) and the inner surface rubber of the carcass layer are joined to each other via a rubber sheet called a tie rubber having a small hysteresis loss. Therefore, in addition to the thickness of the inner liner layer of the halogenated butyl rubber, the thickness of the tie rubber is added, resulting in a thickness exceeding 1 mm (1000 μm) as a whole, which results in an increase in the weight of the product tire. Had become one.

Techniques have been proposed for using various materials for the inner liner layer of a pneumatic tire in place of low gas permeability rubber such as butyl rubber. For example,
No. 7,317,761 discloses that an inner surface of a vulcanized tire has an air permeability coefficient [cm ³ (standard state) / cm · sec · mmHg] of 30 ° C.
A solution or dispersion of a synthetic resin such as polyvinylidene chloride, a saturated polyester resin, or a polyamide resin having a size of 10 × 10 ^-13 or less and 50 × 10 ^-13 or less at 70 ° C. is 0.1 mm.
It is disclosed to apply below.

However, the technique disclosed in this publication is
A synthetic resin coating layer having a specific air permeability coefficient may be provided on the inner circumferential surface of the carcass of the vulcanized tire or on the inner circumferential surface of the inner liner so that the synthetic resin coating layer has a thickness of 0.1 mm or less. However, the pneumatic tire described in this publication has a problem in adhesiveness between the rubber and the synthetic resin film, and the inner liner layer is inferior in heat resistance and moisture resistance (or water resistance). Have.

JP-A-5-330307 discloses that the inner surface of a tire is subjected to a halogenation treatment (using a conventionally known chlorination treatment liquid, a bromine solution, an iodine solution), and then methoxymethylated nylon, A technique for enhancing the adhesiveness to rubber by forming a polymer film (film thickness: 10 to 200 μm) of a copolymerized nylon, a blend of polyurethane and polyvinylidene chloride, or a blend of polyurethane and polyvinylidene fluoride is disclosed.

Furthermore, Japanese Patent Application Laid-Open No. Hei 5-318618 discloses a pneumatic tire using a methoxymethylated nylon thin film as an inner liner. According to this technique, a methoxymethylated nylon is coated on the inner surface of a green tire. A pneumatic tire is manufactured by spraying or applying a solution or emulsion and then vulcanizing the tire, or spraying or applying a solution or emulsion of methoxymethylated nylon on the inner surface of the tire after vulcanization. However, the techniques disclosed in these publications also have a drawback that it is difficult to maintain the uniformity of the film thickness, in addition to the defect that the thin film has poor water resistance.

Further, JP-A-6-40207 discloses that
A multilayer film having a low air permeable layer made of a polyvinylidene chloride film or an ethylene vinyl alcohol copolymer film and an adhesive layer made of a polyolefin film, an aliphatic polyamide film, or a polyurethane film is used as an air permeation preventing layer of a tire. There is an example used. However, in this system, the low air permeable layer lacks flexibility, and the film cannot follow the expansion and contraction of the material during running of the tire, and cracks may occur.

On the other hand, vinyl aromatic compounds in the molecule
It is possible to apply a resin composition containing an epoxy-modified block copolymer in which a double bond of a conjugated diene compound copolymer is epoxidized and / or a partial hydrogenated product thereof to various uses including use as an adhesive, JP-A-5-295197, JP-A-6-256417, and JP-A-6-26
No. 3820, No. 6-279538, No. 6-340859, No. 7-10921, No. 7-26106, and No. 7-339.
It is known from Japanese Patent No. 58.

However, in these publications, the resin composition is a thermoplastic elastomer composition as in the present invention, or in particular, the thermoplastic resin component of the thermoplastic elastomer comprises a polyamide resin as a continuous phase (matrix). None, a rubber component is mixed with a thermoplastic elastomer composition to form a dispersed phase (domain), and the thermoplastic elastomer composition is laminated with a rubber composition layer, or the resin composition is used alone. Nothing is disclosed about the use of such a thermoplastic elastomer composition, in particular, a rubber / thermoplastic elastomer laminate by using an adhesive layer of a polyamide-based thermoplastic resin composition layer and a rubber composition layer in a continuous phase (matrix). Absent.

[0011]

As described above, various materials have been proposed as an alternative to butyl rubber for the inner liner layer of pneumatic tires having a reduced gas (air) permeability, but they are still in practical use. Has not reached. Especially,
A pneumatic tire having an air permeation preventive layer having an excellent balance between air permeation resistance and flexibility required as an inner liner layer of a pneumatic tire and further excellent in adhesiveness to rubber has not yet been developed. Therefore, the object of the present invention, without impairing the air pressure retention of the pneumatic tire,
To provide a rubber / thermoplastic elastomer laminate for a pneumatic tire, which enables weight reduction of a tire, has an excellent balance with air permeability resistance and flexibility, and has excellent adhesiveness with a rubber layer. It is in. Further, it is an object of the present invention to provide a rubber / thermoplastic elastomer laminate for a hose which is excellent in gas permeation resistance and flexibility, and is also excellent in adhesiveness with a rubber layer.

[0012]

According to the present invention, (A)
Air permeability coefficient is 25 × 10 ^-12 cc · cm / cm ² · sec · cm
At least one thermoplastic resin having a Young's modulus of more than 500 MPa and a Hg of 10% by weight or more based on the weight of all polymer components,
In addition, (B) the air permeability coefficient is 25 × 10 ⁻¹² cc · cm /
cm ² · sec · cmHg and Young's modulus of 500 MPa or less at least one elastomer component is 10 wt% or more based on the total weight of the polymer components, the total amount of component (A) and component (B) (A) + (B) Is 30% by weight based on the weight of all polymer components
In the above-mentioned amount, and (C) the thermoplastic resin of the component (A), an epoxidized product of a block copolymer composed of a vinyl aromatic compound and a conjugated diene compound and / or a partially hydrogenated product thereof is used. A thermoplastic elastomer composition having an air permeation coefficient of 25 × 10 ⁻¹² cc · cm / cm ² · sec · cmHg or less and a Young's modulus of 1 to 500 MPa as a gas permeation preventive layer and containing rubber in the layer. A rubber / thermoplastic elastomer laminate formed by laminating composition layers is provided. Here, the gas of the gas permeation preventive layer refers to air or another gas, that is, a low molecular weight hydrocarbon compound such as gasoline, lubricating oil, LPG gas, or a refrigerant transportation medium such as Freon gas.

According to the present invention, a thin film containing, as a main component, an epoxidized product of a block copolymer composed of a vinyl aromatic compound and a conjugated diene compound contained in the component (C) and / or a partial hydrogenated product thereof. There is provided a rubber / thermoplastic elastomer laminate in which the above is laminated between the thermoplastic elastomer composition layer composed of the components (A) and (B) and the rubber composition layer.

The thermoplastic resin blended as the component (A) in the thermoplastic elastomer composition used in the gas permeation preventive layer according to the present invention has an air permeability coefficient of 25 × 10 ^-12.
cc ・ cm / cm ²・ sec ・ cmHg or less, preferably 0.1 × 1
Young's modulus at 0 ^-12 to 10 x 10 ^-12 cc · cm / cm ² · sec · cmHg exceeds 500 MPa, preferably 500 to 3000 MP
Any thermoplastic resin of a can be used, and the compounding amount thereof is 10% by weight or more, preferably 20 to 85% by weight based on the total weight of the polymer components including the thermoplastic resin and rubber.

Examples of such a thermoplastic resin include the following thermoplastic resins, and any of these or any thermoplastic resin mixture containing them.
Further, it may be a thermoplastic resin component containing an antioxidant, a heat resistance preventing agent, a stabilizer, a processing aid, a pigment, a dye, and the like.

Polyamide resin (eg nylon 6 (N
6), nylon 66 (N66), nylon 46 (N4
6), nylon 11 (N11), nylon 12 (N1
2), nylon 610 (N610), nylon 612
(N612), nylon 6/66 copolymer (N6 / 6
6), nylon 6/66/610 copolymer (N6 / 66
/ 610), nylon MXD6, nylon 6T, nylon 6 / 6T copolymer, nylon 66 / PP copolymer, nylon 66 / PPS copolymer, polyester resin (eg polybutylene terephthalate (PBT), polyethylene terephthalate (PET) ), Polyethylene isophthalate (PEI), polybutylene terephthalate / tetramethylene glycol copolymer, PET / PEI copolymer, polyarylate (PAR), polybutylene naphthalate (PBN), liquid crystal polyester, polyoxyalkylene diimide diacid / Aromatic polyesters such as polybutylene terephthalate copolymers), polynitrile resins (eg polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile / styrene copolymers (AS), methacryloyl) Tolyl / styrene copolymer, methacrylonitrile / styrene / butadiene copolymer),
Poly (meth) acrylate-based resin (for example, polymethylmethacrylate (PMMA), polyethylmethacrylate),
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 resins (eg cellulose acetate, acetic acid) Cellulose butyrate), fluorinated resins (eg polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polychlorofluoroethylene (PCT)
FE), tetrafluoroethylene / ethylene copolymer (E
TFE, imide resin (for example, aromatic polyimide (P
I)) etc. can be mentioned.

As described above, these thermoplastic resins must have a specific gas (air) permeability coefficient, Young's modulus and blending amount. It has flexibility of Young's modulus of 500 MPa or less and air permeability coefficient of 25 × 10 ^-12 cc · cm / cm ² ·.
Materials with a sec / cmHg or less have not yet been industrially developed and have an air permeability coefficient of 25 × 10 ⁻¹² cc · cm /
If it exceeds cm ² · sec · cmHg, the gas permeation resistance as the polymer composition for tires and the gas permeation resistance as a gas permeation resistant polymer composition for hoses is lowered, and the air permeation preventive layer of the tire or The hose does not function as a gas permeation preventive layer. Further, when the blending amount of these thermoplastic resins is less than 10% by weight, the gas permeation resistance similarly decreases, and it cannot be used as a gas (air) permeation preventive layer for tires and hoses. Absent.

The elastomer component blended as the component (B) in the thermoplastic elastomer composition according to the present invention is
Air permeability coefficient is 25 × 10 ^-12 cc · cm / cm ² · sec · cm
Any elastomer having a Young's modulus of 500 MPa or less or more than Hg, any blend thereof, or a reinforcing agent or filler generally added to the elastomer for improving dispersibility or heat resistance of the elastomer.
Crosslinking agent, softening agent, antiaging agent, an elastomer composition containing a necessary amount of a compounding agent such as a processing aid, and the compounding amount is the total of the polymer components including the thermoplastic resin and the elastomer component constituting the air permeation preventive layer. It is 10% by weight or more, preferably 10-85% by weight, based on the total weight of the amount.

The elastomer constituting such an elastomer component is not particularly limited as long as it has the above-mentioned air permeability coefficient and Young's modulus, but examples thereof include the following.

Diene rubbers and hydrogenated products thereof (eg, 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)), butyl rubber (II
R), isobutylene and aromatic vinyl or diene monomer copolymer, acrylic rubber (ACM), ionomer,
Halogen-containing rubber (eg Br-IIR, CI-IIR,
Brominated isobutylene paramethylstyrene copolymer (Br-IPMS), chloroprene rubber (CR), hydrin rubber (CHC, CHR), chlorosulfonated polyethylene (CSM), chlorinated polyethylene (CM), maleic acid modified chlorinated polyethylene (M-CM)), silicone rubber (for example, methyl vinyl silicone rubber, dimethyl silicone rubber, methylphenyl vinyl silicone rubber), sulfur-containing rubber (for example, polysulfide rubber), fluororubber (for example, vinylidene fluoride-based rubber, fluorine-containing vinyl ether-based rubber) , Tetrafluoroethylene-propylene rubber, fluorine-containing silicon rubber, fluorine-containing phosphazene rubber), thermoplastic elastomer (for example, styrene elastomer, olefin elastomer, polyester elastomer) Urethane elastomers, polyamide elastomers), and the like.

According to the present invention, an epoxidized product of a block copolymer composed of a vinyl aromatic compound and a conjugated diene compound and / or a partially hydrogenated product thereof is further used as the third component (C) for imparting adhesion. 3 to 50% by weight, preferably 5 to 20% by weight, is added to the thermoplastic resin composition as the component (A). If this blending amount is too small, the adhesion to the opposite rubber component will not be sufficient, and conversely if it is too large, the air permeability coefficient will be too large and the elastic modulus will be too low, which is not practical. Further, according to the present invention, a thin film containing the third component, which is the adhesiveness imparting component (C) as a main component, is used to form a thermoplastic elastomer composition layer and a rubber composition layer comprising the components (A) and (B). It is used to join the rubber / thermoplastic elastomer laminate by interposing it therebetween. The thin film used as the bonding layer has a thickness of 5 to 200 μm, preferably 10 μm to 100 μm.

Examples of the vinyl aromatic compound constituting the polymer block mainly containing a vinyl aromatic compound used in the third component (C) according to the present invention include styrene, α-methylstyrene and vinyltoluene. , P-t-
One kind or two or more kinds can be selected from butyl styrene, divinyl benzene, P-methyl styrene, 1,1-diphenyl styrene and the like, and among them, styrene is preferable. Further, as the conjugated diene compound, for example, butadiene,
Isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, piperidine, 3-butyl-1,
One or two or more types are selected from 3-octadiene, phenyl-1,3-butadiene and the like, and among them, butadiene, isoprene and a combination thereof are preferable.

The block copolymer referred to herein is a block copolymer composed of a polymer block containing a vinyl aromatic compound as a main component and a polymer block containing a conjugated diene compound as a main component, and a vinyl aromatic compound. And the conjugated diene compound has a copolymerization ratio of 5/95 to 70/30, particularly 1
Polymerization ratios of 0/90 to 60/40 are preferred. The weight average molecular weight of the block copolymer used in the present invention is 1
50,000 to 400,000, preferably 50,000
The range is 250,000. The molecular structure of the block copolymer may be linear, branched, radial or any combination thereof. Furthermore,
The unsaturated bond of the conjugated diene compound of the block copolymer is
The hydrogenation of the conjugated diene compound may be partially hydrogenated, and the degree of unsaturation of the conjugated diene compound is 5% or more, preferably 10%.
That is all.

In the present invention, the epoxy-modified block copolymer used in the present invention is obtained by epoxidizing the above block copolymer. The epoxy-modified block copolymer in the present invention can be obtained by reacting the block copolymer with an epoxidizing agent such as hydroperoxides and peracids in an inert solvent. Examples of the peracids include formic acid, peracetic acid, perbenzoic acid, trifluoroperacetic acid and the like. Of these, peracetic acid is the preferred epoxidizing agent. At the time of epoxidation, a catalyst can be used if necessary. For example, in the case of peracid, an alkali such as sodium carbonate or an acid such as sulfuric acid can be used as a catalyst. In the case of hydroperoxide,
A mixture of tungstic acid and caustic soda with hydrogen peroxide,
Alternatively, an organic acid may be used in combination with hydrogen peroxide, or molybdenum hexacarbonyl may be used in combination with tertiary butyl hydroperoxide to obtain a catalytic effect.

The material of the rubber layer to which the gas (air) permeation preventive layer in the rubber / thermoplastic elastomer laminate according to the present invention is adhered is not particularly limited, and has conventionally been generally used as a rubber material for tires or hoses. It can be any rubber material. Examples of such rubber include diene rubbers such as NR, IR, BR, SBR, NBR, hydrogenated NBR (HNBR), butyl rubber,
Halogenated butyl rubber, halide of isobutyne-P-methylstyrene copolymer (X-IPMS), chloroprene rubber (CR), chlorinated polyethylene rubber (CM),
Carbon black for chlorosulfonated polyethylene rubber (CSM), ethylene-propylene copolymer rubber (EPM), ethylene-propylene-diene ternary copolymer rubber (EPDM), ethylene methyl acrylate copolymer rubber (EMA), styrene elastomer, etc. A rubber composition containing a reinforcing agent, a softening agent such as process oil, a plasticizer and a vulcanizing agent, a vulcanization aid and an antiaging agent, and a processing aid.

The composition ratio of the specific thermoplastic resin component (A) and the elastomer component (B) constituting the thermoplastic elastomer composition is determined by the film thickness, air permeation resistance,
It may be appropriately determined depending on the balance of flexibility, but the preferable range is (A) / (B) ratio of 10/90 to 90/10, and more preferably 15/85 to 80/20.

As described above, the thermoplastic elastomer composition according to the present invention contains the thermoplastic resin component (A) and the elastomer component (B) having a specific air permeability coefficient and Young's modulus as essential constituent components. This is illustrated in the graph of FIG. 1, where component (A) corresponds to region X, component (B) corresponds to region Y, and the resulting thermoplastic elastomer composition corresponds to region Z. To do.
In the present invention, the thermoplastic resin A ₁ belonging to the component (A)
~ A _n are determined and their average value Aav (= ΣφiAi
(I = 1 to n), where φi is the weight% of Ai). This point Aav and air permeability coefficient is 25 × 10 ^-12 cc
cm / cm ² · sec · cmHg, Young's modulus of 500 MPa is connected to a point P by a straight line, and the straight line AavP is extrapolated below the straight line, and the air permeability coefficient is 25 × 10 ^-12 cc · cm / cm ² · sec ・
In the region S of cmHg or more, the average value Bav (= ΣφiBi (i) of the elastomer components (B) and B _{1 to} B _n belonging to the Y region
= 1 to n), where φi is a weight percentage of Bi), and a thermoplastic elastomer composition in the target region Z can be obtained by mixing with an appropriate blending.

The pneumatic tire having the air permeation preventive layer produced by using the rubber / thermoplastic elastomer laminate of the present invention will be described in more detail below. The air permeation prevention layer of the pneumatic tire according to the present invention can be arranged at an arbitrary position inside the tire, that is, inside or outside the carcass layer, or at another position. In short, the object of the present invention is achieved by arranging the tire so as to prevent transmission and diffusion of air from the inside of the tire and maintain the air pressure inside the tire for a long period of time.

FIG. 2 is a meridional direction half cross-sectional view illustrating a typical example of the arrangement of the air permeation preventive layer of a pneumatic tire.
In FIG. 2, a carcass layer 2 is mounted between a pair of left and right bead cores 1, 1 and an inner liner layer 3 is provided on the inner surface of the tire inside the carcass layer 2. FIG.
In the figure, 4 indicates a sidewall.

In the present invention, the method for producing the thermoplastic elastomer composition constituting the gas (air) permeation preventive layer is such that the thermoplastic resin component constituting the components (A) and (C) and the elastomer (in the case of rubber, it is not The vulcanizate) component (B) is melt-kneaded with a biaxial kneading extruder or the like to disperse the elastomer component (B) as a dispersed phase (domain) in the thermoplastic resin forming a continuous phase (matrix). When the elastomer component is vulcanized, the vulcanizing agent and optionally a vulcanization aid 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 are preferably mixed in advance before the kneading. The kneader used for kneading the thermoplastic resin component and the elastomer component is not particularly limited, and examples thereof include a screw extruder, a kneader, a Banbury mixer, and a twin-screw kneading extruder. Above all, it is preferable to use a twin-screw kneading extruder for the kneading of the thermoplastic resin component and the elastomer component and the dynamic vulcanization of the elastomer component. In addition, 2
Kneading machines of more than one kind may be used and kneading may be sequentially performed. As a condition for melt-kneading, the temperature may be equal to or higher than the temperature at which the thermoplastic resin component melts. The shear rate during kneading is 10
It is preferably from 00 to 7500 Sec ^-1 . The total kneading time is preferably 30 seconds to 10 minutes, and when a vulcanizing agent is added, the vulcanization time after the addition is preferably 15 seconds to 5 minutes. The thermoplastic elastomer composition produced by the above method is then formed into a film by extrusion molding or calender molding. The method of forming a film may be a method of forming a normal thermoplastic resin or thermoplastic elastomer into a film.

The vulcanizing agent, vulcanizing aid, vulcanizing conditions (temperature, time), etc. in the case of dynamically vulcanizing may be appropriately determined according to the composition of the elastomer component to be added, and are not particularly limited. Not something. 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. About 4 phr [parts by weight per 100 parts by weight of the rubber component (polymer)] can be used. Examples of organic peroxide-based vulcanizing agents include benzoyl peroxide, t-butyl hydroperoxide, 2,4-bichlorobenzoyl peroxide, 2,5-dimethyl-2,5-di (t-butyl). (Peroxy) hexane, 2,5-dimethylhexane-2,5-
Di (peroxylbenzoate) and the like are exemplified, and for example, about 1 to 20 phr can be used. Further, examples of the phenol resin-based vulcanizing agent include brominated alkylphenol resins and mixed cross-linking systems containing a halogen donor such as tin chloride and chloroprene and an alkylphenol resin. Can be. Others, zinc white (about 5 phr), magnesium oxide (about 4 phr), litharge (10-20 ph)
r about), p-quinone dioxime, p-dibenzoylquinone dioxime, tetrachloro-p-benzoquinone, poly-p-dinitrosobenzene (about 2 to 10 phr), methylene dianiline (about 0.2 to 10 phr). Can be illustrated. If necessary, a vulcanization accelerator may be added. As vulcanization accelerators, aldehyde / ammonia,
General vulcanization accelerators such as guanidine, thiazole, sulfenamide, thiuram, dithioate and thiourea can be used, for example, in an amount of about 0.5 to 2 phr. Specifically, the aldehyde / ammonia-based vulcanization accelerator is hexamethylenetetramine, etc., the guanidine-based vulcanization accelerator is diphenylguanidine, etc., and the thiazole-based vulcanization accelerator is dibenzothiazyldisulfide ( DM), 2-mercaptobenzothiazole and its Zn salt, cyclohexylamine salt, etc., and sulfenamide vulcanization accelerators include cyclohexylbenzothiazylsulfenamide (CBS) and N-oxydiethylenebenzothiazyl-2-. Sulfenamide, N
Examples of thiuram-based vulcanization accelerators include tetramethylthiuram disulphide (TMTD), tetraethylthiuram disulphide, tetra-t-butyl-2-benzothiazole sulfenamide and 2- (thymolpolynyldithio) benzothiazole. Examples of dithioate vulcanization accelerators such as methyl thiuram monosulfide (TMTM) and dipentamethylene thiuram tetrasulfide include Zn.
-Dimethyldithiocarbamate, Zn-diethyldithiocarbamate, Zn-di-n-butyldithiocarbamate, Zn-ethylphenyldithiocarbamate, Te-
Diethyldithiocarbamate, Cu-dimethyldithiocarbamate, Fe-dimethyldithiocarbamate, pipecoline pipecolyldithiocarbamate, and the like. Thiourea-based vulcanization accelerators include ethylenethiourea and diethylthiourea. As a vulcanization accelerating auxiliary, a general rubber auxiliary may be used in combination, for example, zinc white (about 5 phr), stearic acid, oleic acid and Zn salt thereof (about 2 to 4 phr). Etc. can be used.

In the thin film thus obtained, at least a part of the elastomer component (B) is dispersed as a discontinuous phase (domain) in the continuous phase (matrix) of the thermoplastic resin components (A) and (C). Take structure. By adopting a dispersion structure in such a state, it is possible to impart a balance between flexibility and air permeation resistance, and it is possible to obtain effects due to rubber elasticity such as improved heat distortion resistance and improved water resistance, and Since the thermoplastic resin can be processed, it can be made into a film by a usual resin molding machine, that is, extrusion molding or calender molding.

The method for producing the thermoplastic elastomer composition constituting the gas (air) permeation preventive layer comprising the thermoplastic resin component (A) and the elastomer component (B) as another method in the present invention is the same as above. Depending on the method and conditions, the thermoplastic component (A) and the elastomer (unvulcanized product in the case of rubber) component (B) are melt-kneaded in a twin-screw kneading extruder or the like, and then formed into a film. The thin film thus obtained has a structure in which the elastomer component (B) is dispersed as a discontinuous phase (domain) in the continuous phase (matrix) of the thermoplastic resin component (A).

Further, the adhesiveness-imparting composition layer of the component (C) can be kneaded and molded alone to form a film in the same manner as the above-mentioned composition, and in the case of a single composition, it can be used as it is for a resin. It can be formed into a film with an extruder, placed between the air permeation preventive layer and the rubber composition layer facing at least one surface, and molded into a laminate structure. In addition, as another aspect of the method for forming a laminate of a gas (air) permeation preventive layer comprising components (A) and (B) and an adhesion imparting layer comprising component (C), a gas (air) permeation preventive layer composition is provided. And the adhesiveness imparting layer composition are separately extruded at the same time using different resin extruders, and a common sheeting die is provided at the tips of the two extruders to form a multilayer film, which is previously integrated. It is also possible to make a laminated sheet which is used as a multilayer film and is used for forming a tire.

In the method of manufacturing a pneumatic tire having an air permeation preventive layer comprising a thin film of the thermoplastic elastomer composition according to the present invention, the inner liner layer 3 is disposed inside the carcass layer 2 as shown in FIG. Explaining an example of the case, in the first embodiment, the thermoplastic elastomer composition ((A) + (B) + (C)) of the present invention is extruded in advance into a thin film having a predetermined width and thickness, Cylinder can be stuck on the tire molding drum. Further, in the second aspect, the thermoplastic elastomer composition ((A) + (B)) which constitutes the air permeation preventive layer of the present invention and the thermoplastic resin or the thermoplastic resin composition which constitutes the adhesion imparting layer in advance. (C) is extruded into a thin film with a predetermined width and thickness, and the thin film is stuck to a cylinder on a tire molding drum. In both modes, a carcass layer made of unvulcanized rubber, a belt layer, a tread layer, and other members used in ordinary tire manufacturing are sequentially laminated on top of that, and the drum is removed to obtain a green tire. Next, by heating and vulcanizing the green tire according to a conventional method, a desired lightweight pneumatic tire can be manufactured. In addition, also when providing an air permeation prevention layer on the outer peripheral surface of a carcass layer, it can be performed according to this.

The hose having the gas permeation preventive layer produced by using the rubber / thermoplastic elastomer laminate of the present invention will be described in more detail. The gas permeation preventive layer of the hose according to the present invention can be arranged at any position inside the hose, for example, inside, in the middle, outside of the inner rubber layer, or at any other position. That is, a low permeability hose can be obtained by arranging it so as to prevent permeation and diffusion of low molecular components such as air or hydrocarbon compounds from the inside of the hose and to minimize leakage from the inside of the hose to the outside. The object of the invention is achieved.

FIG. 3 is a schematic sectional view illustrating a typical example of the arrangement of the gas permeation preventive layer of the low permeability hose. As shown in FIG. 3, the low-permeability hose 9 includes an inner pipe inner layer 5, an inner pipe outer layer 6, a reinforcing layer 7, and an outer pipe 8 made of rubber. The gas permeation preventive layer is provided as the inner pipe inner layer 5 inside the rubber inner pipe outer layer 6.

The hose of the present invention is not limited to the constitution of the illustrated example, and the inner pipe may be constituted by one layer or three or more layers,
Also, the outer tube may be composed of a plurality of layers. Further, if necessary, the fiber reinforcing layer may be formed of a plurality of layers. In any case, at least one layer of the inner tube and / or the outer tube is formed of the thermoplastic elastomer of the present invention. That is, the hose of the present invention can be used in various configurations according to the application.
It may be the hose structure disclosed in each of the gazettes of No. -125885 and No. 63-302086.

Where to use the thermoplastic elastomer of the present invention may be determined according to the application of the hose and required characteristics. For example, if the fluorocarbon permeation resistance is more important, it is preferable to form at least a part of the inner tube (particularly the innermost layer) from the thermoplastic elastomer of the present invention, and if the water permeation resistance is more important, at least It is preferable to form a part (especially the outermost layer) of the outer tube with the thermoplastic elastomer of the present invention. Further, in the hose of the present invention, a pipe (or layer) which does not utilize the thermoplastic elastomer of the present invention
The various materials used for a well-known hose can be used for all.

Examples of the reinforcing layer include a braiding layer formed of a reinforcing steel wire such as a brass-plated steel wire or a reinforcing thread that is usually used, a linear (spiral), a net-like, or a film-like reinforcing layer. . As the reinforcing yarn, any of natural fiber, synthetic fiber and the like may be used. Specifically, it is preferable to use yarns of vinylon, aliphatic polyamide, aromatic polyamide, nylon, rayon, polyamide, polyester or the like. Particularly, rayon and polyester are more preferable.

The method of manufacturing the hose of the present invention is not particularly limited, and various known manufacturing methods can be used. For example, in the case of the hose 9 shown in FIG. 3, the inner tube inner layer 5 is extruded by a resin extruder having a crosshead structure on a mandrel coated with a release agent in advance, and a rubber extruder is used. To extrude the rubber inner tube outer layer 6 and form a fiber reinforcing layer 7 by braiding a reinforcing yarn on the rubber inner tube outer layer 6 using a braiding machine. Further, a rubber outer tube 8 for rubber is similarly formed thereon. It may be extrusion-molded with a rubber extruder having a crosshead structure. Also, between the inner pipe / reinforcing layer / outer pipe layers,
Adhesion may be appropriately performed with an adhesive or the like. After that, the rubber layer is vulcanized using a vulcanizing can or the like, and after cooling, the mandrel is finally pulled out to obtain the hose 9 of the present invention shown in FIG. Although the mandrel is used in the method for manufacturing the hose described above, the low-permeability hose of the present invention may be manufactured without using the mandrel unless strict dimensional accuracy is required.

The thermoplastic elastomer composition of the present invention, the method for producing the same, the tire and the low-permeability hose have been described above, but the present invention is not limited to the above examples and does not depart from the gist of the present invention. Of course, various improvements and changes may be made.

The gas permeation preventive layer according to the present invention has an air permeation coefficient of 25 × 10 ⁻¹² cc · cm / cm ² · sec · cmHg or less,
It is preferably 5 × 10 ⁻¹² cc · cm / cm ² · sec · cmHg or less. Air permeability coefficient of 25 × 10 ^-12 cc ・ cm / cm ²・
By setting sec · cmHg or less, the thickness of the gas (air) permeation preventive layer can be reduced to 1/2 or less of the thickness of the conventional air permeation preventive layer.

On the other hand, the Young's modulus is 1 to 500 MPa, preferably 10 to 300 MPa, and the thickness is 0.02 to 1.0 mm, preferably 0.05 to 0.5 mm. Young's modulus is 1 MPa
If it is less than 500 MPa, handling is difficult due to wrinkles during tire molding or hose molding. On the contrary, if it exceeds 500 MPa, tire deformation or hose deformation during running cannot be followed, which is not preferable.

[0045]

EXAMPLES The present invention will be described in more detail below with reference to Examples, but it goes without saying that the present invention is not limited to the following Examples. The evaluation methods used in the following Examples 1 to 5 and Comparative Examples 1 and 2 are as follows.

Film air permeation coefficient measurement method: JIS K7126 “Plastic film and sheet gas permeation test method (method A)” was followed. Test piece: The film sample prepared in each example was used. Test gas: Air (N ₂ : O ₂ = 8: 2) Test temperature: 30 ° C

Method for Measuring Freon Gas Permeability Coefficient In a stainless steel cup 10 as shown in FIG. 4, half the volume of freon gas (HFC134a, code 1) was used.
Put 1). The upper opening of the cup 10 is covered with a sample sheet 12 obtained by cutting the sample sheet, a sintered metal plate 13 is placed on the upper portion thereof, and a bolt 15 and a nut 16 are tightened via a fixing member 14. This cup is left under an atmosphere of 100 ° C., and after 24 hours, the total weight is measured,
The amount of decrease is calculated and the gas permeation coefficient is calculated by the following formula. Gas permeability coefficient [(mg ・ mm) / (24hr ・ cm ² )] ＝ (M ・
t) / (T · A) However, in the above formula, A = permeation area [cm ² ]: T = test time [day]: M = reduced weight [mg]: t = thickness of test piece [mm ]:

The Young's modulus of the film was measured according to JIS K6301 "Vulcanized rubber physical test method". Specimen: A film sample prepared by extrusion molding in each example was placed in parallel with the resin flow direction during extrusion according to JIS.
I punched it out with No. 3 dumbbell. A tangent was drawn on a curve in the initial strain region of the obtained stress-strain curve, and the Young's modulus was determined from the slope of the tangent.

Adhesive force measuring method between rubber and film The method was based on JIS K6301 "Physical test method for vulcanized rubber". Test piece: A sheet-shaped unvulcanized rubber composition was laminated on a film sample prepared by extrusion molding in each example, and 1
Vulcanize using a press molding machine at 80 ° C. × 10 minutes × 2.3 MPa. The obtained rubber / film laminate was cut into a 25 mm width pouch. Test method: The above test piece is 50 mm / at an angle of 180 °
A peeling test was conducted by pulling at a peeling speed of a minute.

Examples 1 to 4 and Comparative Examples 1 to 2 A modified butyl rubber of Br-isobutylene-p-methylstyrene copolymer (Br-IPMS) was mixed with the following various compounding agents to form a closed type Banbury mixer for rubber. The mixture was kneaded in the inside and then formed into a rubber sheet having a thickness of 2.5 mm using a rubber roll to prepare a masterbatch.

Masterbatch formulation (unit: parts by weight) ──────────────────────────── Br-IPMS (EXXPRO 89-4) ^{1 )} 100 carbon black (GPF) ²⁾ 60 stearic acid 1 petroleum hydrocarbon resin ³⁾ 10 paraffinic process oil ⁴⁾ 10 ─────────────────────── ────── Note 1) EXXPRO 89-4: Exon Butyl (Exxon Chemical) 2) GPF: Seast V (Tokai Carbon) 3) Escoletz 1102 (Esso) 4) Machine oil 22 (Showa Shell Sekiyu)

The masterbatch was pelletized with a pelletizer for rubber, and the pellets were used to mix 2 parts of the components (A) and (C) with the masterbatch component (B) at various compounding ratios (parts by weight) shown in the table. The mixture was kneaded with a shaft kneader, and further used as a vulcanizing agent during biaxial kneading so that 5 parts by weight of Zinc Hua No. 3 and 2 parts by weight of zinc stearate were added to 100 parts by weight of the polymer component of the rubber composition. The rubber masterbatch component dispersed as a dispersed phase (domain) in the resin matrix during the kneading and the continuous charging was dynamically vulcanized.
The thermoplastic elastomer composition mixed by a twin-screw kneader is extruded into a strand, the thermoplastic elastomer composition is further pelletized by a resin pelletizer, and the pellet is used to attach a T-die for sheeting. A film having a width of 350 mm and a thickness of 0.1 mm was produced by the resin extruder described above. The air permeability coefficient, Freon gas permeability coefficient and Young's modulus of the obtained film were measured.

A sheet-like (2 mm thick) rubber composition prepared by compounding the rubber composition (I) or (II) shown below was laminated on the obtained film (0.1 mm thick), and 180 ° C. × 10 minutes ×
Vulcanization adhesion was performed using a press molding machine at 2.3 MPa, and the obtained rubber / film laminate was cut into pieces of 25 mm width. A peel test was conducted by pulling the test piece at an angle of 180 ° at a peel speed of 50 mm / min.

Compounding of Rubber Composition (I) Parts by Weight Natural Rubber RSS # 3 80 SBR 20 Nipol 1502 FEF Carbon Black 50 manufactured by Nippon Zeon Co., Ltd. HTC # 100 Chubu Carbon Co., Ltd. Stearic Acid 2 beads Stearate NY Nippon Oil & Fats Manufactured by ZnO 3 No. 3 Zinc white sulfur 3 Powdered sulfur Karuizawa Smelter Vulcanization accelerator (BBS) 1 Nt-butyl-2-benzothiazylsulfenamide aroma oil 2 Desolex 3 Showa Shell Sekiyu KK Made

Compounding of rubber composition (II) parts by weight brominated butyl rubber 100 exon bromobutyl 2244 exon chemical carbon black HAF 30 Seast N Tokai carbon ZnO 3 Zinc Hua No. 3 Shodo chemical sulfur 2 powder sulfur Karuizawa refining Tosho DM 1 NOXCELLER DM Ouchi Shinko Chemical Stearic acid 1 beads Stearic acid NY NOF CORPORATION

The results are shown in Table 1.

[Table 1]

As is clear from Examples 1 to 4 and Comparative Examples 1 and 2, the rubber component (B) was contained in the matrix of the thermoplastic resin component (A), and the epoxy-modified SBS was used as the third component.
It can be seen that the system containing the resin satisfies the target region in terms of the air permeability coefficient and the flexibility and has sufficient adhesive force with the rubber of the compound (1) assuming the tire. On the other hand, similarly, it can be seen that the brominated butyl rubber composition of the compound (II) in the case of the low permeability hose also has sufficient adhesive force. In addition, as shown in FIG. 5, the air permeability coefficient and the HFC134a
The gas permeability coefficient is in a proportional relationship, and it is possible to evaluate the air permeability coefficient in a hose having a low gas permeability with respect to a low molecular weight component.

Example 5 Using the same rubber masterbatch pellets prepared in Examples 1 to 4, the components (A) and (B) were kneaded in a twin-screw kneader at the following blending ratios, Further, the same amount of the same vulcanizing agent was added to dynamically vulcanize the rubber masterbatch component dispersed as a dispersed phase in the resin matrix during kneading. The thermoplastic elastomer composition mixed by a twin-screw kneader is extruded into a strand shape, the thermoplastic composition is further pelletized by a pelletizer for resin, and the pellet is used to extrude for resin with a T-die attached. Machine width 350
A film having a thickness of 200 mm and a thickness of 200 μm was prepared. Blending of thermoplastic elastomer composition (unit: parts by weight) ──────────────────────────────── A N11 (BMN 0 ¹⁾ ) 10 N6 / 66 (CM6001 ²⁾ ) 30 ──────────────────────────────── B Br-IPMS ( EXXPRO 89-4 ³⁾ ) 60 ──────────────────────────────── Note ¹⁾ Atochem ²⁾ Toray ( ³⁾ Exxon Chemical Co., Ltd.

Next, a rubber composition having the following composition was used to form a sheet having a thickness of 1 mm with a roll mixer. Compounding of rubber composition (unit: parts by weight) ─────────────────────────── SBR (Nipol 1502) 40 Nippon Zeon Co., Ltd. Made NR (RSS No. 3) 60 Carbon black GPF 45 Seast V Tokai Carbon Co., Ltd. ZnO 4 No. 3 Zinc flower Stearic acid 2 beads Stearic acid NY Nippon Oil & Fat Co. Aroma oil 3 Desolex No. 3 Showa Shell Petroleum Co., Ltd. Sulfur 2.5 Powdered sulfur Karuizawa Smelter ─────────────────────────── Furthermore, pellets of ESBS 015 (epoxy equivalent 1025) are used for resin. It was formed into a film having a thickness of 50 μm using a T-die extruder.

The ESBS 015 film prepared above was sandwiched between a thermoplastic elastomer film and a rubber sheet to be laminated, and vulcanized and adhered by using a press molding machine at 180 ° C. × 10 minutes × 2.3 MPa. Then, the obtained rubber / ESBS 015 film / thermoplastic elastomer film laminate was cut into a 25 mm-width laminate. This test piece was pulled at a peeling speed of 50 mm / min at an angle of 180 ° and a peeling test was conducted. The result showed that the peeling force was 1
It was 90 N / 25 mm.

Examples of the tire of the present invention will be shown below. The evaluation methods used in Examples 6 to 10 and Comparative Examples 3 to 5 are as follows.

Inner liner layer durability test method 165SR13 A steel radial tire was prepared and
Mounted on a rim of × 4 1 / 2-J size, with air pressure of 200 kPa, mounted on a 1500cc class passenger car, applied a load equivalent to 4 passengers (65 kg / person), and traveled 20,000 km on an actual road I do. After running, remove the tire from the rim,
Visually observe the liner layer on the inner surface of the tire. If the liner layer has cracks and visible wrinkles, or if the liner layer has peeled or lifted, it is judged as rejected, and if not, it is judged as passed.

Air leak test method (pressure drop rate) Initial pressure of 200 kPa, room temperature of 21 ° C., no load, left for 3 months. The measurement interval of the internal pressure is set every four days, and the measured pressure Pt, the initial pressure Po, and the elapsed days t are regressed to the equation Pt / Po = exp (-αt) to obtain the α value. Using the obtained α, t = 30
(Day) is substituted, β = [1−exp (−αt)] × 100 to obtain an air pressure reduction rate β (% / month) per month.

Examples 6 to 10 and Comparative Examples 3 to 5 Steel radial tires having a tire size of 165SR13 were produced according to the conventional method.

The results are shown in Table 2.

[Table 2]

In Comparative Example 3, the adhesive strength was insufficient, so that
It is not possible to obtain sufficient durability of the air permeable layer. Comparative Example 4
Has a large air permeability, and even if the inner liner layer has the same thickness as that of Comparative Example 5, the pressure drop rate is large. That is, weight reduction cannot be realized. On the other hand, in all of Examples 6 to 10, the pressure drop rate was equal to or higher than that of Comparative Example 5, and the durability was at a practical level. It turns out that you can get tires.

Examples of the hose of the present invention will be shown below.
The evaluation methods used in Examples 11 to 15 and Comparative Examples 6 to 8 are as follows.

Adhesive strength of tube / thermoplastic elastomer Cut out to a width of 1 mm along the longitudinal direction of the hose, and the adhesive strength between the inner layer of the inner tube and the outer layer of the inner tube was measured using an autograph at a peeling speed of 50 mm / min. The obtained value was converted into N / 25 mm.

Gas Permeability JRA 200 (Japan Refrigeration and Air Conditioning Industry Association Standard) JRA 200
Same as 1. A refrigerant (HFC134a) is sealed in a fitting assembly hose having a hose length of 0.45 m, 0.6 ± 0.1 gram per 1 cm ³ of the hose internal volume. 96 at 100 ° C
After being left for an hour, the weight loss (gas permeation amount) between 24 hours and 96 hours is measured, and the value is converted to gf / m / 72 hours. Conventionally, the leak rate of CFC12 gas in rubber hose is 20
２５25 gf / m / 72 hours, and the refrigerant replacement cycle of the rubber hose is about 2 years. On the other hand, a replacement cycle of 10 years is required for maintenance-free operation. Therefore, in order to make maintenance free, it is necessary that the gas leakage amount is 5 gf / m / 72 hours or less regardless of the type of gas.

Impulse durability An impact pressure test (impulse test) in accordance with JIS K6375, page 7.7 was carried out. JIS as test oil
Using a mineral oil equivalent to the two types specified in K2213 (turbine oil), a rectangular wave with an oil temperature of 93 ° C and a maximum pressure of 200 kgf / cm ² was repeatedly added, and the number of times of failure was measured to determine the hose structure. When the inner tube inner layer was not broken due to the peeling failure, it was cut off at 200,000 times.

Hose Flexibility A hose is bent along an arc having a predetermined radius and the bending force is measured. The bending radius is 10 times the outer diameter of the hose (10
Starting from D), the bending force is sequentially measured up to 3 times (n = 2). From the curve obtained by plotting the relationship between the bending force and the bending radius obtained as a result, a numerical value at a specified radius (4 times) is read. Generally, the flexibility of conventional rubber hoses is at a level of 2.0 kgf, and some hose having a resin tube structure is at a level of 6 to 7 kgf. In the case of a hose having such a resin tube structure, when the hose is mounted on a device in a narrow space such as an engine room, the workability is obviously poor, and empirically, the bending force is 3.5 kg.
If it is less than f, workability will be good. Also, the vibration absorption has a correlation with the flexibility, but this relationship is non-linear, and when the bending force is about 3.5 kgf or more, the reaction force sharply increases and the vibration absorption becomes extremely poor. Therefore, the bending force of the hose is preferably 3.5 kgf or less, more preferably 2.0 kgf.

Examples 11 to 14 and Comparative Examples 6 to 8 Examples 1 to 4 were compared on a mandrel of nylon 11 having an outer diameter of 11 mm, which was previously coated with a release agent, using an extruder for resin having a crosshead. The thermoplastic elastomers of Examples 1 and 2 were extruded into a tube shape so that the inner diameter was 12 mm and the outer diameter was 150 μm. Further, after extruding the inner tube outer layer with a rubber extruder having a crosshead structure to a thickness of 2.0 mm,
A polyester fiber (Tetoron 1500d / 2, manufactured by Toray Industries) dip-treated with a resorcinol formalin condensate was braided, and an outer tube (thickness: 1.5 mm) was extruded and molded. After further wrapping nylon wrapping tape in a double layer and vulcanizing under pressure at 153 ° C. for 60 minutes in a vulcanizer,
The wrapping tape and mandrel were removed to obtain a hose.

Example 15 The inner tube inner layer and the adhesive layer (made by ESBC 015 Daicel Chemical Co., Ltd.) were formed on the same mandrel as above by using an extruder having two resin extruders and a crosshead structure at the tip. Inner tube inner layer / adhesive layer = 150 μm / 20 μm Except for extrusion molding, molding was performed in the same manner as above.

The results are shown in Table 3.

[Table 3]

The hoses of Examples 11 to 15 show excellent performances in adhesive strength, gas permeability, durability and flexibility.
A comparative example in which a composition not containing an epoxidized product of a block copolymer (C) composed of a vinyl aromatic compound and a conjugated diene compound or a hydrogenated product thereof is used for the inner layer of the inner tube, and further the structure does not have an adhesive layer. In Comparative Example 6 and Comparative Examples 7 and 8, breakage of the outer layer of the inner tube progresses from the film breakage caused by peeling of the inner layer of the inner tube during the impulse durability test. It can be seen that the hose of Comparative Example 8 has flexibility but is inferior in gas permeability due to the addition of a large amount of (C) adhesive thermoplastic resin.

[0076]

As described above, according to the present invention,
Provided is a rubber / thermoplastic elastomer laminate obtained by strongly adhering a thermoplastic elastomer composition using a thermoplastic resin as a gas permeation preventive layer in a continuous phase and an elastomer composition in a dispersed phase and a rubber composition. Therefore, this is used as an inner liner layer that retains good gas (air) retention in the tire and maintains flexibility while being highly adhesive to the rubber layer used for adhesion to the carcass material. It is possible to obtain a lightweight pneumatic tire, and by using this for a rubber hose structure, etc., it has resistance to air (gas) permeation and flexibility, and is highly durable. You can get a hose.

[Brief description of drawings]

FIG. 1 is a graph showing the relationship between the air permeability coefficient and Young's modulus of the thermoplastic resin component (A) and the elastomer component (B) according to the present invention and the thermoplastic elastomer composition of the present invention.

FIG. 2 is a meridional direction half cross-sectional view showing the structure of a pneumatic tire using the rubber / thermoplastic elastomer laminate of the present invention as an inner liner layer.

FIG. 3 is a sectional view of a hose in which the rubber / thermoplastic elastomer laminate of the present invention is used as an inner tube of the hose.

FIG. 4 is a cross-sectional view of a cup used for measuring the Freon gas permeation coefficient in the present invention.

FIG. 5 is a graph showing a correlation between an air permeability coefficient and a Freon gas permeability coefficient.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Bead core 2 ... Carcass layer 3 ... Inner liner layer 4 ... Side wall 5 ... Inner tube inner layer 6 ... Inner tube outer layer 7 ... Reinforcement layer 8 ... Outer tube 9 ... Low permeability hose 10 ... Cup 11 ... Freon gas 12 ... Sample sheet 13 ... Sintered metal plate 14 ... Fixing member 15 ... Bolt 16 ... Nut

Claims (5)

[Claims] (A) The air permeability coefficient is 25 × 10 ⁻¹² cc
・ Cm / cm ²・ sec ・ cmHg or less and at least one thermoplastic resin having a Young's modulus of more than 500 MPa based on the weight of all polymer components, 10% by weight or more, and (B) an air permeability coefficient of 25 × 10 ^-12 cc ・cm / cm ² · se
c. At least one elastomer component having a Young's modulus of 500 MPa or less and having a Young's modulus of 500 MPa or less is 10 wt% or more based on the weight of all polymer components, and the total amount (A) + (B) of the components (A) and (B) is the total polymer Included in an amount of 30% by weight or more per component weight,
Further, (C) the thermoplastic resin of the component (A) is added with an epoxidized product of a block copolymer composed of a vinyl aromatic compound and a conjugated diene compound and / or a partial hydrogenated product thereof in an amount of 3 to 50.
Including weight%, air permeability coefficient is 25 × 10 ^-12 cc · cm / cm ² · sec · cm
A rubber / thermoplastic elastomer laminate in which a thermoplastic elastomer composition having a Young's modulus of 1 to 500 MPa at a Hg or less is used as a gas permeation preventive layer, and a rubber composition layer is laminated on the layer. 2. The thermoplastic resin as the component (A) is a polyamide resin, a polyester resin, a polynitrile resin, a poly (meth) acrylate resin, a polyvinyl resin, a cellulose resin, a fluorine resin, and an imide. The rubber / thermoplastic elastomer laminate according to claim 1, which is at least one thermoplastic resin selected from the group of resin series. 3. The component (B) elastomer is selected from the group consisting of diene rubbers and hydrogenated products thereof, olefin rubbers, halogen-containing rubbers, silicone rubbers, sulfur-containing rubbers, fluororubbers and thermoplastic elastomers. The rubber / thermoplastic elastomer laminate according to claim 1 or 2, which is at least one elastomer. 4. The rubber / thermoplastic elastomer laminate according to claim 1, wherein the elastomer as the component (B) forms a discontinuous phase in the composition. 5. A thin film containing, as a main component, an epoxidized product of a block copolymer composed of a vinyl aromatic compound and a conjugated diene compound contained in the component (C) and / or a partially hydrogenated product thereof is used as the component (A). And a thermoplastic elastomer composition layer comprising (B) and a rubber composition layer, the rubber / thermoplastic elastomer laminate being laminated.