JPH10130433A - Thermoplastic elastomer composition for high-pressure, flexible hose - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an olefinic thermoplastic elastomer compsn. which has adhesion to a polyester fiber and particularly adhesion good enough to withstand stress created by cyclic deformation under a high temp. of 120 deg.C, and to provide a laminate, particularly a resin hose, comprising the olefinic thermoplastic elastomer compsn. as an adhesive layer or a constituent layer. SOLUTION: The thermoplastic elastomer compsn. and the laminate, particularly resin hose, comprising the thermoplastic elastomer compsn. as an adhesive layer or a constituent layer comprises the following components (A), (B), and (C): Component (A), an olefinic thermoplastic elastomer compsn. having a structure comprising an olefinic thermoplastic resin (a) as a matrix and a particle of an EPDM vulcanized rubber compsn. (b) finely dispersed in the matrix, the olefinic thermoplastic elastomer compsn. comprising 85 to 20wt.% olefinic thermoplastic resin and 15 to 80wt.% ethylene/propylene/diene copolymer rubber; (EPDM) vulvanized rubber compsn; Component (B), a polyester compolymer resin; and Component (C), an epoxy-contg. thermoplastic resin. The content of the component (A) is 90 to 50 pts.wt., the content of the component (B) is 10 to 50 pts.wt., and the content of the component (C) is 1 to 10 pts.wt. based on 100 pts.wt. in total of the components (A) and (B). The thermoplastic elastomer compsn. has excellent adhesion to an olefinic thermoplastic resin, a polyester resin and a polyester fiber.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an olefin-based thermoplastic elastomer composition having adhesiveness to polyester fiber, and particularly to adhesiveness capable of withstanding stress caused by repeated deformation at a high temperature of 120.degree. , In particular, a resin hose.

[0002]

2. Description of the Related Art Conventionally, in bonding an olefin-based thermoplastic elastomer composition and polyester fiber, a technique for stably bonding the two, particularly a high-temperature adhesive property capable of withstanding stress due to repeated deformation at a high temperature of 120 ° C. An olefin-based thermoplastic elastomer composition having the following has not been known. This is because the olefin-based thermoplastic elastomer composition is a non-polar substance and has a low surface energy, whereas the polyester fiber has a polarity, so that generally the adhesion between the two is poor, and the strength of the joint cannot be maintained especially at high temperatures. That's why. In order to solve this problem, for example, a formulation using a so-called primer and an adhesive system / adhesive resin has been proposed. However, a strong bond that can withstand repeated deformation at a high temperature such as 120 ° C. is obtained. Adhesive prescription,
Further, an olefin-based thermoplastic elastomer composition has not been known yet. Particularly in a hose, a dynamically vulcanized olefin-based thermoplastic elastomer composition has properties suitable for an outer tube material constituting a hose, and a polyester fiber has properties suitable as a reinforcing fiber layer material constituting a hose. There is no known adhesive prescription, particularly a strong adhesive prescription capable of withstanding stress due to repeated deformation at a high temperature such as 120 ° C., which is the use environment of a high-pressure flexible hose, and an olefin-based thermoplastic elastomer composition. Also, a hose combining these materials is not known.

[0003]

Accordingly, an olefin-based thermoplastic elastomer composition having an adhesive property to polyester fibers and an adhesive property capable of withstanding stress caused by repeated deformation at a high temperature such as 120 ° C., and A laminate using the above-mentioned thermoplastic elastomer composition and polyester fiber has been desired.

[0004]

The inventors of the present invention have made intensive studies and succeeded in inventing an olefin-based thermoplastic elastomer composition having good adhesion to polyester fibers and excellent heat resistance. It has been confirmed that a hose using a thermoplastic elastomer composition also has excellent properties, and the present invention has been completed.

That is, a first object of the present invention is to provide the following components A, B and C with 90 to 50 parts by weight of component A, 10 to 50 parts by weight of component B, and 100 parts by weight of the sum of components A and B, respectively. The present invention provides a thermoplastic elastomer composition having excellent adhesion to an olefin-based thermoplastic resin, a polyester-based thermoplastic resin, and a polyester-based fiber, which is contained in a proportion of 1 to 10 parts by weight of component C. Component A: having a structure in which particles of the EPDM vulcanized rubber composition (b) are finely dispersed using the olefin-based thermoplastic resin (a) as a matrix,
20% by weight, and an EPDM vulcanized rubber composition 15 to 80
An olefin-based thermoplastic elastomer composition containing 0.1% by weight. Component B: polyester copolymer resin. Component C: an epoxy group-containing thermoplastic resin. In the thermoplastic elastomer composition, the epoxy group-containing thermoplastic resin preferably contains at least 60 to 95% by weight of an ethylene monomer component and 0.5 to 15% by weight of a glycidyl methacrylate component.

A second object of the present invention is to provide a laminate obtained by melting and bonding at least the thermoplastic elastomer composition of the present invention and polyester fibers. In the laminate, the thermoplastic elastomer composition of the present invention and the polyester fiber may be melt-bonded via a polyester copolymer resin.

A third object of the present invention is to provide a hose having at least an outer tube in contact with a polyester fiber reinforcing layer, wherein at least the innermost layer of the outer tube is the thermoplastic elastomer composition of the present invention, and at least a polyester fiber reinforcing layer. A hose in which the adhesive layer is a polyester copolymer resin, and at least the innermost layer of the outer tube is the thermoplastic elastomer composition of the present invention, and In a hose in which at least a polyester fiber reinforcing layer is joined to an outer tube via an adhesive layer, the adhesive layer is the thermoplastic elastomer composition of the present invention, and at least the innermost layer of the outer tube is made of an olefin-based thermoplastic resin. A hose which is a thermoplastic elastomer composition having an EPDM vulcanized rubber composition as a matrix as a domain is provided. To.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The olefinic thermoplastic resin (component a) used as a matrix in the component A includes olefin homo- or copolymers, that is, ethylene, propylene, 1-butene, 1-pentene, 3-methyl-butene, 1-hexene, Homo- or copolymers such as 3-methyl-1-pentene, 4-methyl-1-pentene and 1-octene, and further,
A copolymer of an olefin homopolymer or a copolymer with another thermoplastic resin is preferably exemplified.

In particular, a polyolefin resin is preferably used. In the case of a polyolefin resin, a polypropylene (PP) resin, especially a polypropylene resin having an isotactic, syndiotactic, or atactic stereochemical structure, a block or random containing 1 to 50% by weight of an ethylene component, and the like. Of ethylene
With a propylene copolymer resin, the softening temperature is 110 ° C or higher,
Those having a melting temperature of 160 ° C. or less are preferably used. Further, among polyolefin resins satisfying the above conditions, MI at 230 ° C. and a load of 2.16 kg is preferable.
(Melt index) 0.5 to 40, particularly 1 to 20
Are preferred. Further, a functional group-modified polyolefin resin obtained by modifying the above polyolefin resin with a functional group such as maleic anhydride is also preferably exemplified. These polyolefin resins may be used alone or in combination.

Similarly, the EPDM vulcanized rubber composition (component b) used as a domain in the component A is obtained by partially vulcanizing EPDM. The EPDM includes ethylene and propylene, and furthermore, some dicyclopentadiene and ethylidene. E which is a terpolymer having some diene components such as norbornene and 1,4-hexadiene
PDM and maleic acid-modified EPDM obtained by modifying these EPDM with maleic anhydride or the like can be suitably used.

The olefin-based thermoplastic elastomer composition used as the component A in the present invention comprises an olefin-based thermoplastic resin (component a) as a matrix and an EPDM vulcanized rubber composition (component b) dispersed as a dispersed phase (domain). And at least a part of the component b is vulcanized. Such a configuration is preferably such that a thermoplastic resin constituting the component a and a rubber composition constituting the component b (a component basically excluding a vulcanizing agent) are previously twin-screw kneaded extruder or the like. The rubber composition is dispersed in a thermoplastic resin that forms a continuous phase by melt-kneading, and a vulcanizing agent is continuously added in this state (under kneading) to dynamically vulcanize the rubber composition during kneading. It can be formed by performing. The type of vulcanizing agent, dynamic vulcanizing conditions (temperature, time) and the like may be appropriately determined according to the component b 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 sulfur-based 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) in the component b) may be used. Examples of the organic peroxide-based vulcanizing agent include benzoyl peroxide, t-butyl hydroperoxide, 2,4-dichlorobenzoyl peroxide, 2,5-dimethyl-2,5-di (t-butyl peroxide). Oxy) hexane, 2,5-dimethylhexane-2,5-
Di (peroxyl benzoate) and the like are exemplified, and for example, about 1 to 15 phr may be used. Further, examples of the phenolic resin-based vulcanizing agent include bromide of an alkylphenol resin, and a mixed crosslinking agent containing a halogen donor such as tin chloride and chloroprene and an alkylphenol resin. For example, about 1 to 20 phr is used. I just need. In addition, zinc white (about 5 phr), magnesium oxide (about 4 phr), litharge (10 to 20 phr)
phr), 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)
Is exemplified.

[0013] If necessary, a vulcanization accelerator may be added. Examples of the vulcanization accelerator include common vulcanization accelerators such as aldehyde / ammonia, guanidine, thiazole, sulfenamide, thiuram, dithioate, and thiourea, for example, 0.5 to 2 phr. The degree may be used.

Specifically, the aldehyde / ammonia vulcanization accelerator includes hexamethylenetetramine and the like; the guanidine vulcanization accelerator includes diphenylguanidine and the like; and the thiazole vulcanization accelerator includes dibenzo. Thiazyl disulfide (DM), 2-mercaptobenzothiazole and its Zn salt, cyclohexylamine salt 2
-(4'-morpholinodithio) benzothiazole and the like;
Examples of the sulfenamide vulcanization accelerator include cyclohexylbenzothiazolylsulfenamide (CBS) and N
-Oxydiethylene benzothiazolyl-2-sulfenamide, Nt-butyl-2-benzothiazolylsulfenamide, 2- (thymorpholinyldithio) benzothiazole and the like; as a thiuram-based vulcanization accelerator Include tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide, tetramethylthiuram monosulfide (TMTM), dipentamethylenethiuram tetrasulfide, and the like; Dithiocarbamate, Zn-
Thiourea includes diethyldithiocarbamate, Zn-di-n-butyldithiocarbamate, Zn-ethylphenyldithiocarbamate, Te-diethyldithiocarbamate, Cu-dimethyldithiocarbamate, Fe-dimethyldithiocarbamate, pipecoline pipecolyldithiocarbamate and the like; Examples of the system vulcanization accelerator include ethylene thiourea and diethyl thiourea.

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). (About 4 phr) may be used.

The compounding amount of the olefinic thermoplastic resin (component a) and the EPDM vulcanized rubber composition (component b) in component A is as follows: component a: component b is 85 to 20% by weight: 15 to 80% by weight. Yes, preferably component a: component b is 80 to 20% by weight: 20 to 80% by weight. If the compounding amount of the component a is too large, the flexibility is impaired, and if it is too small, the mechanical strength is reduced and the processability is deteriorated, which is not preferable.

Examples of the polyester-based copolymer resin blended as the component B in the present invention include a polyester-based random copolymer and a polyester-based multi-block copolymer having polyester and polyether as main repeating units.

As the polyester random copolymer, a known thermoplastic copolyester resin is used. Such a thermoplastic copolyester resin is produced from (i) at least one or more diols and (ii) at least one or more dicarboxylic acids by a conventionally employed esterification / polycondensation method.

As the polyester-based multi-block copolymer, a known thermoplastic copolyester elastomer is used. Typical examples of the thermoplastic copolyester elastomer include the following. The thermoplastic copolyester elastomer used in the present invention is a repeating unit of polyester and polyether,
Copolyetherester elastomers, (poly) lactone-modified copolyetherester elastomers and copolyetherimide esters, which are polyester, random and multiblock copolyesters comprising repeating units of (poly) lactone and polyether or repeating units of polyester and polyimide ether Elastomers are included. Suitable thermoplastic copolyetherester elastomers and (poly) lactone-modified copolyetherester elastomers are prepared by conventional esterification / polycondensation methods by (i) at least one diol, (ii) at least one dicarboxylic acid. acid,
It is produced from (iii) at least one long-chain ether glycol and, if necessary, (iv) at least one lactone or polylactone.

The diol (i) used for the production of the copolyester resin, the copolyetherester elastomer and its (poly) lactone modified product includes a saturated and unsaturated aliphatic or alicyclic dihydroxy compound and an aromatic dihydroxy compound. Include. These diols preferably have a low molecular weight, ie, a molecular weight of about 300 or less. Specific examples of the aliphatic and alicyclic diols include ethylene glycol, propanediol, butanediol, pentanediol, 2-methylpropanediol, 2,2-dimethylpropanediol, hexanediol, decanediol, and 2-octylundecane. 2 to 15 diols such as diol, 1,2-, 1,3- and 1,4-dihydroxycyclohexane, 1,2-, 1,3- and 1,4-cyclohexanedimethanol, butynediol, hexenediol and the like. A diol having a carbon atom is exemplified. Particularly preferred diols are 1,4-butanediol and mixtures of 1,4-butanediol with hexanediol or butynediol. Specific examples of the aromatic diol include resorcinol, hydroquinone, 1,5-dihydroxynaphthalene, 4,4 ′
Diols having 6 to 19 carbon atoms such as -dihydroxydiphenyl, bis (p-hydroxyphenyl) methane and 2,2-bis (p-hydroxyphenyl) propane.

Particularly preferred diols are saturated aliphatic diols having 2 to 8 carbon atoms and mixtures of such saturated aliphatic diols, and mixtures of such saturated aliphatic diols and unsaturated diols. . When two or more diols are used, it is preferred that the same diol occupies at least about 60 mol%, especially at least 80 mol%, based on the total amount of diol. The most preferred diol mixtures are those in which the majority is 1,4-butanediol.

The dicarboxylic acids (ii) suitable for use in the production of the copolyester resins, copolyetherester elastomers and modified (poly) lactones thereof include aliphatic, cycloaliphatic and / or aromatic dicarboxylic acids. . These dicarboxylic acids are preferably of low molecular weight, that is, those having a molecular weight of about 350 or less,
Higher molecular weight ones, especially dimer acids, can also be used.

Representative examples of the aliphatic and alicyclic dicarboxylic acids include sebacic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4
-Cyclohexanedicarboxylic acid, adipic acid, glutaric acid, succinic acid, oxalic acid, azelaic acid, diethylmalonic acid, allylmalonic acid, 4-cyclohexene-1,2-
Dicarboxylic acid, 2-ethylsuberic acid, tetramethylsuccinic acid, cyclopentanedicarboxylic acid, decahydro-
1,5-naphthalenedicarboxylic acid, 4,4′-bicyclohexyldicarboxylic acid, decahydro-2,6-naphthalenedicarboxylic acid, 4,4-methylenebis (cyclohexanedicarboxylic acid), 3,4-furandicarboxylic acid, and 1, 1-cyclobutanedicarboxylic acid, as well as dimer acids thereof. Among these, cyclohexanedicarboxylic acid, sebacic acid, glutaric acid and adipic acid are preferred.

Representative examples of aromatic dicarboxylic acids include terephthalic acid, phthalic acid, isophthalic acid, bis-benzoic acid such as bis (p-carboxyphenyl) methane, oxybis (benzoic acid), ethylene-1,2-bis (P-
Substituted dicarboxy compounds having two benzene nuclei such as (oxybenzoic acid), 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, phenanthylenedicarboxylic acid, anthracenedicarboxylic acid, 4,4'-Sulfonyldibenzoic acid and their halo and C1-C12 alkyl, alkoxy, and aryl group-substituted derivatives are included. As long as the object of the invention is not attained, other aromatic dicarboxylic acids, such as p-
A hydroxy acid such as (β-hydroxyethoxy) benzoic acid can be used in combination.

Among the dicarboxylic acids used for producing the copolyester resin, the copolyetherester elastomer and the (poly) lactone modified product thereof, aromatic dicarboxylic acids, mixtures of two or more aromatic dicarboxylic acids, and aromatic dicarboxylic acids; Mixtures of dicarboxylic acids with aliphatic and / or alicyclic dicarboxylic acids are preferred, with aromatic dicarboxylic acids alone being particularly preferred. Among the aromatic dicarboxylic acids, aromatic dicarboxylic acids having 8 to 16 carbon atoms, in particular, benzenedicarboxylic acids such as phthalic acid, terephthalic acid and isophthalic acid, and dimethyl esters thereof, are preferred. Dimethyl is best. If a mixture of dicarboxylic acids or their esters is used, it is preferred that at least about 60 mol%, especially at least about 80 mol%, based on the total amount of dicarboxylic acids, is the same dicarboxylic acid. Above all,
It is best for dimethyl terephthalate to account for at least about 60 mole percent of the dicarboxylic acid mixture.

The long-chain ether glycol (iii) used for the production of the thermoplastic copolyetherester elastomer and its (poly) lactone modified product is preferably about 40%.
Poly (oxyalkylene) glycols and copoly (oxyalkylenes) having a molecular weight of 0 to about 12,000
Glycol. Preferred poly (oxyalkylene) units have a molecular weight of about 900 to about 4,000, and are derived from long chain ether glycols having a carbon to oxygen ratio of about 1.8 to about 4.3, excluding side chains. Is done.

Representative examples of suitable poly (oxyalkylene) glycols include poly (ethylene ether) glycol, poly (propylene ether) glycol, poly (tetramethylene ether) glycol, ethylene oxide end-capped poly (propylene ether) glycol and majority A random or block copolymer of ethylene oxide and propylene oxide, including copoly (propylene ether-ethylene ether) glycol having a poly (ethylene ether) skeleton, and tetrahydrofuran and a small amount, such as ethylene oxide, propylene oxide or methyl tetrahydrofuran. Second
Or a block copolymer of the above (used at a ratio of carbon to oxygen not exceeding about 4.3). Formaldehyde and, for example, 1,4-
Polyformal glycols made by reacting diols such as butanediol and 1,5-pentanediol are also useful. Particularly preferred poly (oxyalkylene) glycols are poly (propylene ether) glycol, poly (tetramethylene ether) glycol and copoly (propylene ether-ethylene ether) glycol with a majority of polyethylene ether skeleton.

If necessary, one or more lactones or polylactones (iv) can be blended with these copolyetheresters. A polylactone-modified copolyetherester elastomer of this type is disclosed in U.S. Pat. No. 4,569,973.

Lactones (i) suitable for use in the present invention
As v), ε-caprolactone is particularly preferred,
Substituted lactones substituted at the α, β, γ, δ or ε position with a lower alkyl group such as a methyl group or an ethyl group can also be used. Further, as a block unit of the copolyetherester used in the present invention, a homopolymer or a copolymer of the monomer and another copolymerizable monomer and a polylactone including a hydroxy-terminated polylactone can be used.

In general, suitable copolyetherester elastomers and (poly) lactone modifications thereof include the amount of (iii) the long-chain ether glycol component or (iii) in the copolyetherester or (poly) lactone modification. The total amount of the long-chain ether glycol component and (iv) lactone component is from about 5 to about 80% by weight. A more preferred composition is one in which the amount of (iii) the long-chain ether glycol component or the total amount of the (iii) component and (iv) the lactone component is about 10 to about 50% by weight.

Among them, copolyetherester elastomers and (poly) lactone modified products thereof are copolymers containing terephthalic acid as a dicarboxylic acid component, 1,4-butanediol as a diol component, and poly (tetramethylene ether) glycol as a long-chain ether glycol. Ether ester elastomers are preferred.

The polyetherimide ester elastomer used in the present invention can be made from one or more diols, one or more dicarboxylic acids, and one or more high molecular weight polyoxyalkylene diimide diacids. The preparation of such polyetherimide ester elastomers is described in U.S. Pat. No. 4,556,705.

The polyetherimide ester elastomer used in the present invention is produced by a method commonly used for producing polyesters, for example, a method of producing a random or block copolymer by an esterification and condensation reaction. Can be. Thus, polyetherimide esters can generally be characterized as the reaction product of a diol and an acid.

Preferred polyetherimide ester elastomers used in the present invention are (i) one or more aliphatic or alicyclic diols having 2 to 15 carbon atoms, and (ii) one or more aliphatic or alicyclic diols. It can be prepared from cyclic or aromatic dicarboxylic acids or their ester derivatives, and (iii) one or more polyoxyalkylenediimidodiacids. The amount of polyoxyalkylenediimide diacid used will generally depend on the desired properties of the resulting polyetherimide ester. Generally, polyoxyalkylenediimidodiic acid (iii
) To the dicarboxylic acid (ii) weight ratio ranges from about 0.25 to about 2.0, preferably from about 0.4 to about 1.4.

The diol (i) used in the production of the above polyetherimide ester includes saturated and unsaturated aliphatic and alicyclic dihydroxy compounds and aromatic dihydroxy compounds. These diols have low molecular weight,
That is, those having a molecular weight of about 250 or less are preferred.

Particularly preferred diols are saturated aliphatic diols, mixtures thereof and mixtures of one or more saturated aliphatic diols with one or more unsaturated aliphatic diols, provided that each diol has from 2 to 8 Having a carbon atom). If more than one diol is used, at least about 60 based on the total diol content,
It is preferred that mole%, more preferably at least 80 mole%, is the same diol. Particularly preferred diols are those having 1,4-butanediol as a main component, and the most preferred diol is 1,4-butanediol alone.

The dicarboxylic acid (ii) used in the production of the above polyetherimide ester is selected from aliphatic, alicyclic and aromatic dicarboxylic acids and their ester derivatives. Preferred dicarboxylic acids have a molecular weight of less than about 300 or have from 4 to 18 carbon atoms. However, higher molecular weight dicarboxylic acids,
In particular, dimer acids can also be used.

Among the aliphatic, cycloaliphatic and aromatic dicarboxylic acids used in the production of polyetherimide esters, aromatic dicarboxylic acids and mixtures of two or more aromatic dicarboxylic acids, and aromatic dicarboxylic acids and aliphatic and A mixture with an alicyclic dicarboxylic acid is preferred, and an aromatic dicarboxylic acid alone is particularly preferred. Among the aromatic dicarboxylic acids, aromatic dicarboxylic acids having 8 to 16 carbon atoms, in particular, benzenedicarboxylic acids such as phthalic acid, terephthalic acid and isophthalic acid, and dimethyl esters thereof, are preferred. Dimethyl is best.

The polyoxyalkylenediimide diacid (iii) used in the production of the polyetherimide ester is a high molecular weight diacid having an average molecular weight of greater than about 700, preferably greater than about 900. These diacids comprise two adjacent carboxyl groups or anhydride groups and further carboxyl groups (the other carboxyl group must be esterifiable and preferably not imidizable). ) Is produced by imidizing one or more tricarboxylic acid compounds containing a) with a high molecular weight polyoxyalkylenediamine. Component B in the thermoplastic elastomer composition of the present invention imparts polarity to the olefin-based thermoplastic elastomer composition of the present invention, and contributes to improving the adhesion to the polyester-based thermoplastic resin and polyester fiber.

The epoxy group-containing thermoplastic resin blended as the component C in the present invention includes, for example, a copolymer resin or a copolymer rubber containing an epoxy group-containing acrylate and / or methacrylate as a copolymer component. Such epoxy group-containing (meth) acrylate copolymer resin or epoxy group-containing (meth) acrylate copolymer rubber includes (1) alkyl (meth) acrylate and / or alkoxy-substituted alkyl (meth) acrylate, ( 2) a multi-component copolymer resin or multi-component copolymer obtained by polymerizing an epoxy group-containing monomer and (3) another ethylenically unsaturated monomer copolymerizable with these (1) and (2). It is rubber.

Among them, it is preferable to use an epoxy group-containing thermoplastic resin containing at least 60 to 95% by weight of a component derived from an ethylene monomer and 0.5 to 15% by weight of a component derived from glycidyl methacrylate. It is preferable to contain 65 to 90% by weight of a component from a monomer and 1 to 15% by weight of a component from glycidyl methacrylate.

In the thermoplastic elastomer composition of the present invention, the components A: B are blended in a weight ratio of 90 to 50:10 to 50, and the component C is added to 100 parts by weight of the sum of the components A and B.
1 to 10 parts by weight. Preferably, A: B is 90
C is preferably 2 to 8 parts by weight based on 100 to 100 parts by weight of A + B in the range of 60 to 10 to 40. This is because by setting the mixing ratio, the adhesiveness with the polyolefin-based thermoplastic resin, the polyester-based thermoplastic resin, and the polyester fiber is excellent.

In the method for producing the thermoplastic elastomer composition according to the present invention, a known method for producing a thermoplastic resin composition can be used, but a batch-type production method may be used. Using a twin-screw kneading extruder, etc., which continuously supplies and melts the thermoplastic resin, transfers while mixing and kneading, and sequentially adds and kneads the rubber composition and vulcanizing agent to produce an elastomer composition. Although a continuous production method may be used, components B and C are mixed after sufficiently kneading and dynamically vulcanizing components a and b to obtain component A. Hereinafter, an example of a preferred method for producing the thermoplastic elastomer composition of the present invention will be described.

In the production of the thermoplastic elastomer composition, the machine used for kneading the components a, b and B, C is not particularly limited, but includes a screw extruder, a kneader, a Banbury mixer, a twin screw kneading extruder, and the like. Is exemplified. Above all, a melt of component a (thermoplastic resin) and component b (rubber composition) is maintained in these devices, and while the rubber phase is finely kneaded and dispersed, a vulcanizing agent (crosslinking agent) of component b is further added. In consideration of dynamic vulcanization in which kneading is performed at a temperature that promotes crosslinking until the crosslinking of the rubber phase is completed, it is preferable to use a twin-screw kneading extruder. Further, two or more types of kneaders may be used to knead sequentially. That is, the component A produced in this manner is used for dynamic vulcanization (Dynamic vulcanization) in which vulcanization of a rubber proceeds while masticating a thermoplastic resin and a rubber composition. Cure or Dynamic
Vulcanization). By using such a manufacturing method,
The obtained thermoplastic elastomer composition is in a state where at least a part thereof is in a state in which a vulcanized rubber phase which is at least partly a discontinuous phase is finely dispersed in a thermoplastic resin phase which is a continuous phase. Since the composition exhibits the same behavior as the vulcanized rubber, and at least the continuous phase is a thermoplastic resin phase, it can be processed according to the thermoplastic resin at the time of molding.

Hereinafter, an example of the production method will be more specifically illustrated based on kneading usually performed by a twin-screw kneading extruder. First, the pelletized component a is charged from the first charging port of the twin-screw kneading extruder, mixed by a twin-screw, melted and heated.

On the other hand, for the component b, a rubber kneading machine such as a Banbury mixer is used, and if necessary, a reinforcing agent, an antioxidant, a processing aid and the like are added to the rubber component and kneaded. No, as a so-called masterbatch, molded into a sheet with a thickness of 2 to 2.5 mm using a rubber roll, etc.,
This sheet is prepared by pelletizing with a rubber pelletizer. As described above, after the component a is melted and heated in the twin-screw kneading extruder, the component b thus pelletized in advance is charged from the second inlet of the twin-screw kneading extruder, and the component a is added to the component a. Disperse b. When component b is added, a processing aid such as stearic acid, zinc stearate and wax may be used in combination. In this case, component b and stearic acid or the like may be mixed by a Banbury mixer or the like, and then pelletized as described above and then charged into the twin-screw kneading extruder component.

Thereafter, a vulcanizing agent or a vulcanizing aid is charged from the third input port of the twin-screw kneading extruder.
The component b is vulcanized (dynamically vulcanized). By performing vulcanization in this manner, vulcanization is performed in a state where component b is sufficiently dispersed in component a, and while component b is in a sufficiently fine state. Then, a component A in which the component b at least partially vulcanized as a dispersed phase (domain) is stably dispersed is prepared. Such a thermoplastic elastomer composition (component A) comprises at least a part of a thermoplastic resin as a continuous phase and at least a part of a rubber composition as a discontinuous phase, and comprises a vulcanized rubber composition which is a discontinuous phase. The particle size of the product is preferably 50 μm or less,
Further, the thickness is more preferably from 10 to 1 μm. By using such component A, favorable results can be obtained in terms of melt fluidity, rubber elasticity and the like of the obtained thermoplastic elastomer composition (molded product) of the present invention.

The thermoplastic elastomer composition of the present invention comprises:
The olefin-based thermoplastic resin composition (component A) produced as described above is extruded into a strand by a twin-screw kneading extruder, pelletized by a resin pelletizer, and melted together with components B and C using the pellets. It is manufactured by kneading. Thereafter, using an extruder or a simple extruder having a melt extrusion mechanism, a general resin injection molding machine or a simple injection molding machine, it is possible to extrude or injection mold into molds having various shapes.

The composition of the present invention may contain additives such as a reinforcing material, a softening agent and an antioxidant, if necessary. The compounding agent for the rubber component may be added during the kneading, but the compounding agent other than the vulcanizing agent is preferably mixed in advance before the kneading. The compounding agent for the resin component may be mixed in advance before the kneading, or may be added during the kneading. The kneading conditions, the type and amount of the vulcanizing agent to be used, the vulcanizing conditions (temperature, etc.) may be appropriately determined according to the blending of the rubber composition to be added and the blending amount of the rubber composition.
There is no particular limitation.

The conditions for melt-kneading the components a and b are as follows: a kneading temperature of, for example, 150 to 350 ° C.
The temperature is preferably 0 to 300 ° C., but is not particularly limited as long as the temperature is equal to or higher than the temperature at which the olefin-based thermoplastic resin component melts. The shear rate during kneading is 1000-8000
It is preferably in seconds ^-1 , especially 1000 to 5000 seconds ^-1 . The residence time of the entire melt kneading is 30 seconds to 10 minutes, and the residence time (vulcanization time) after adding the vulcanizing agent is 15 seconds to 5 minutes.
Minutes is preferred. The shear rate is calculated by dividing the product obtained by multiplying the circumference of the circle drawn by the tip of the screw cross section by the number of rotations of the screw for one second by the gap at the tip. That is, the shear rate is a value obtained by dividing the tip speed by the tip gap. Here, the residence time in the part where dynamic vulcanization is performed is
Multiply the total volume of the part to be dynamically vulcanized by the filling factor and divide it by the volumetric flow rate to calculate.

As the conditions for melt-kneading the components A, B and C, the kneading temperature is, for example, 150 to 350 ° C.
In particular, the temperature is preferably from 150 to 300 ° C., and the shear rate during kneading is from 10 to 8000 sec ⁻¹ , particularly from 50 to 500 ° C.
It is preferably 0 sec- ¹ .

The thermoplastic elastomer composition of the present invention comprises:
The adhesiveness to polyester fibers is improved, and the oil resistance and heat resistance properties of the dynamically vulcanized olefin-based thermoplastic elastomer composition are not impaired. As a result, a laminate using an olefin-based thermoplastic elastomer composition and polyester fibers, which were conventionally difficult to use together while having excellent properties, can be produced,
Here, the thermoplastic elastomer composition of the present invention can be used not only as a structural layer but also as an adhesive layer.
Therefore, according to the present invention, it is possible to provide a thermoplastic elastomer composition that can withstand stress due to repeated deformation at a high temperature such as 120 ° C. and a laminate using the elastomer composition and polyester fibers. Also,
Since the thermoplastic elastomer composition of the present invention has excellent adhesiveness to a polyolefin resin, it may be bonded to a resin containing a polyolefin resin as a main component.

The second aspect of the present invention is a laminate obtained by melting and bonding at least the thermoplastic elastomer composition of the present invention to polyester fibers. Here, the thermoplastic elastomer composition of the present invention may be directly melt-bonded to the polyester fiber, or may be bonded via a polyester copolymer resin or the like.

In the case where the thermoplastic elastomer composition of the present invention is directly melt-bonded to a polyester fiber, the composition of the present invention forms a structural layer and does not have an adhesive layer between the polyester fiber and the reinforcing layer. And a laminate in which an adhesive layer made of the composition of the present invention is interposed between a polyester fiber reinforcing layer and a structural layer made of another resin or composition. In the latter case, examples of other resins and compositions include a polyolefin-based thermoplastic resin, a polyester-based thermoplastic resin, and an EPDM / polypropylene-based thermoplastic elastomer composition. The EPDM / polypropylene-based thermoplastic elastomer composition includes Component A used in the thermoplastic elastomer composition of the present invention.

When the composition of the present invention adheres to a polyester fiber layer via an adhesive layer, the adhesive layer is formed by mixing a polyester copolymer resin, a modified olefin thermoplastic resin and a polyester copolymer resin. Although what consists of a composition etc. is mentioned, a polyester-type copolymer resin is used suitably. As the polyester-based copolymer resin, component B used in the thermoplastic elastomer composition of the present invention is exemplified.

In the laminate of the present invention, in one laminate,
Examples include those in which the composition of the present invention is used for both the adhesive layer and the structural layer, those in which the composition of the present invention is used in a plurality of structural layers or adhesive layers, and those having a repeating structure.

Specific examples of the laminate include a belt, a tire,
Examples include molds and hoses, but are not limited to the above examples as long as they have a layered structure. As an example of the laminate using the thermoplastic elastomer composition of the present invention, a hose is particularly preferable. Hereinafter, the present invention will be described in more detail with reference to examples of hoses.
The present invention is not limited to the following specific examples, and the outer tube and the inner tube may have a multilayer structure, or may have an adhesive layer, a reinforcing layer, or a multilayer structure.

One example of the hose of the present invention has a structure as shown in FIG. 1, and the hose 1 has an inner tube 2, an adhesive layer 3,
It comprises a reinforcing layer 4, an adhesive layer 5, and an outer tube 6. The composition of the present invention can be used for the inner tube 2, the adhesive layer 3, the adhesive layer 5, and the outer tube 6.

In addition to the composition of the present invention, the outer tube 6 may be appropriately selected from compositions (resins) that can be used for high-pressure flexible hoses. In the case of a multilayer structure, the innermost layer) is preferably the thermoplastic elastomer composition of the present invention. As another composition constituting the outer tube 6, a polyolefin-based thermoplastic resin, a polyester-based copolymer resin, an EPDM / polypropylene-based thermoplastic elastomer composition, or the like is suitably used. The EPDM / polypropylene-based thermoplastic elastomer composition includes Component A used in the thermoplastic elastomer composition of the present invention. Examples of the adhesive layer 5 include a polyester copolymer resin, a composition formed by mixing a modified olefin thermoplastic resin and a polyester copolymer resin, and the like, and a polyester copolymer resin is preferably used. . As the polyester-based copolymer resin, component B used in the thermoplastic elastomer composition of the present invention is exemplified.

The hose of the present invention may have a mode in which the adhesive layer 5 is not provided. In this case, the outer tube 6 (the innermost layer when the outer tube has a multilayer structure) is the elastomer composition of the present invention.

The adhesive layer 5 may be made of the thermoplastic elastomer composition of the present invention. in this case,
Examples of the outer tube 6 include those made of a polyolefin resin, a polyester resin, an EPDM / polypropylene thermoplastic elastomer composition, and the like.

The reinforcing layer constituting the hose of the present invention is preferably a layer in which polyester fibers are braided or spirally braided.

As long as the characteristics of the hose of the present invention are not impaired, a material other than the composition of the present invention may be used for the inner tube. The substance constituting the inner tube may be the thermoplastic elastomer composition of the present invention, but is not particularly limited as long as it has flexibility and heat resistance not to impair the properties of the hose of the present invention.

The adhesive layer 3 can be appropriately selected from those other than the composition of the present invention in accordance with the inner tube. For example, the inner tube (when the inner tube has a multilayer structure, a layer in contact with the adhesive layer 3) is used. When it is made of a polyester-based copolymer resin or a thermoplastic elastomer composition containing a polyester-based copolymer resin, a urethane-based cold-setting adhesive, a polyester-based copolymer resin, or the like can be used.

In the composition of the present invention, the epoxy group-containing thermoplastic resin (component C) acts as a compatibilizer and contributes to the adhesion between the rubber particles dispersed in the olefinic thermoplastic resin and the thermoplastic resin interface. , Elongation, both the physical properties of tear are improved, whereby it is possible to obtain a thermoplastic elastomer composition having excellent elongation and tear properties and high breakage resistance, and also has a high adhesive strength when used as an adhesive layer. Obtainable. By using such a composition of the present invention, it becomes possible to produce a hose satisfying the hose impulse resistance.

Such a hose of the present invention can be easily produced by a method known per se, that is, by extruding a thermoplastic elastomer composition.

[0067]

EXAMPLES The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the scope of the examples.

(Thermoplastic Elastomer Composition) Component a (olefin-based thermoplastic resin), unvulcanized component b (rubber composition) and component B, component C, and each component constituting the vulcanized system shown below Using the compounding agent, as follows:
Various thermoplastic elastomer compositions shown in Table 1 below were produced. First, components other than the vulcanizing agent (crosslinking agent) among the respective components constituting the component b are charged into a closed rubber-type Banbury mixer and kneaded. A master batch was prepared by molding into a rubber sheet shape of 0.5 mm. The sheet of this master batch was pelletized by a pelletizer for rubber to prepare a pellet of the component b. Next, the component a and the pellet-shaped component b are charged into a twin-screw kneading extruder, and after kneading, a vulcanizing agent is continuously added thereto to disperse as a domain in a matrix composed of polyester and a compatibilizer. The rubber component is dynamically vulcanized. The kneading conditions are as follows: a kneading temperature of 160 to 200 ° C .;
９０90 sec, shear rate 1000-4000 sec ⁻¹ .
After the completion of the dynamic vulcanization, the mixture is continuously discharged in a strand form from the twin-screw kneading extruder, cooled with water, cut into a length of about 3 mm (about 2 mm in diameter) by a cutter, and then formed into a pellet-like thermoplastic elastomer composition (component A) was obtained. Further, the component A in the form of pellets
And components B and C are kneaded at a kneading temperature of 200 to 280 ° C. and a shear rate of 5
The mixture was melt-kneaded at 0 to 200 sec- ¹ to obtain pellets of the composition of the present invention in the same manner as described above. Thereafter, the thermoplastic elastomer composition pellets were molded into a sheet having a thickness of 2 mm at 200 ° C. for 5 minutes at a pressure of 2.9 MPa using a commonly used press molding machine for resin. Shape (JIS K6251), tearing crescent shape (JIS
K 6252). About the obtained test piece, the adhesiveness at the time of 120 degreeC at first was evaluated. Next, the tensile strength at room temperature, the elongation at break, and the tear strength crescent shape were measured according to JIS K6252 according to JIS K6251. Further, the elongation at break at 120 ° C. was measured as an index of high-temperature physical properties, and the elongation at break after standing at 120 ° C. for 336 hours was measured as an index of heat aging resistance. The results are shown in Table 1 below.

(Hose) Using the compositions shown in Table 1, various hoses were prepared as described below, and the impulse durability was evaluated in the lower part of Table 1. Inner tube extrusion The inner tube material is extruded by a resin extruder,
It is extruded with a die into a hollow shape having an inner diameter of 9.5 mm and a thickness of 1.0 mm to form an inner tube. The ACM / COPE composition shown in Table 2 was used as the resin for the inner tube. Adhesive layer formation As the adhesive, a solution obtained by diluting a urethane cold-setting adhesive (Tylite 7411: manufactured by Lord Far East Co.) 10 times with MEK was used. The adhesive was applied to the outer surface of the inner tube and allowed to air dry. Reinforcing layer braiding Two layers of a polyester fiber reinforcing layer material were braided with a braiding machine using a braiding machine to form a reinforcing fiber layer. Adhesive layer formation For the hose having an adhesive layer, Hytrel 2531 (Toray DuPont Co., Ltd.) is used as a polyester copolymer resin.
Or the respective compositions of the examples. Each resin (composition) was extruded onto the inner tube with a crosshead resin extruder at a thickness of 0.1 mm. Outer tube extrusion Using a crosshead resin extruder, each elastomer composition or EPDM / PP composition (component A) described in Table 1
Was extruded as an outer tube material at an outer diameter of 17.5 mm to form an outer tube.

<Evaluation of Impulse Durability> The following three types of hoses were prepared for each composition, and SAE J1
According to 88TYPE1, the temperature is 120 ° C. and the pressure is 20.
One million durability tests were performed at 6 MPa. A hose using a polyester copolymer resin as an adhesive layer between the outer tube made of the composition of each example and the reinforcing layer. A hose in which the outer tube made of the composition of each example and the reinforcing layer are directly melt-bonded. A hose in which an EPDM / PP composition corresponding to the component A is used for an outer tube, and an adhesive layer made of the composition of each example is interposed between the outer layer and a reinforcing layer. The number of times of destruction and the state of destruction of the hose that was destroyed at the end of 1,000,000 times were recorded. No more than one million tests were performed.

[0071]

[Table 1]

[0072]

[Table 2]

[0073]

[Table 3]

* EPDM / PP composition used Santoprene 201-64. 1) E; methylene 2) GMA; glycidyl methacrylate 3) MA; methyl acrylate ** Evaluation of adhesiveness during heating ○: 0.3 kgf / 25 mm or more ×: less than 0.3 kgf / 25 mm *** Metal: metal fitting missing I have. Main unit: The main unit has been destroyed.

[0075]

[Table 4]

The components shown in Table 1 are as follows. EPDM / PP composition: Santoprene 201-64
(AES Japan Co., Ltd.) COPE resin (Component B) (1): Byron GM-990
(Copolyester manufactured by Toyobo Co., Ltd.) COPE resin (Component B) (2): Hytrel 2551
(Copolyester manufactured by Dupont Toray) COPE resin (Component B) (3): Hytrel 2531
(Copolyester manufactured by Toray DuPont) EMA-GMA (component C) E (ethylene): 67% by weight GMA (glycidyl methacrylate): 3% by weight MA (methyl acrylate): 30% by weight E-GMA (component) C) E (ethylene): 88% by weight GMA (glycidyl methacrylate): 12% by weight

From the evaluation results, Comparative Example 1 in which the components B and C were not added was inferior in the adhesiveness to the polyester fiber and did not satisfy the characteristics required for a hose. Comparative Example 2
Since component C was not added, components A and B did not compatibilize with each other, so that phase separation occurred and sufficient strength could not be obtained. Comparative Example 3 was inferior in high-temperature characteristics because of the large amount of component B. Comparative Example 4 contained less component B,
Poor adhesion to PE resin (3) and polyester fiber. In Comparative Example 5, since the component C was small, phase separation occurred as in Comparative Example 2. Comparative Example 6 is a component C
Or too much, it was inferior in high temperature characteristics. On the other hand, all of Examples 1 to 8 belonging to the scope of the present invention were excellent in adhesiveness to polyester fiber and heat aging resistance, and had sufficient durability in the properties of a hose as a laminate. Further, in the adhesion between the thermoplastic elastomer composition of the present invention and the polyester fiber, a sufficient adhesive force is obtained in any case even with or without the polyester copolymer resin layer, and the laminate shows sufficient durability. I understand.
Furthermore, when the thermoplastic elastomer composition of the present invention was used as an adhesive layer, sufficient adhesiveness and heat aging were exhibited.

[0078]

According to the present invention, an olefin heat having good adhesiveness to polyester fiber, which has not existed conventionally, and particularly having adhesiveness to withstand stress due to repeated deformation at a high temperature such as 120 ° C. A laminate including a thermoplastic elastomer composition and a hose using the elastomer composition can be obtained.

[Brief description of the drawings]

FIG. 1 schematically shows a layer structure of a hose.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Hose 2 Inner tube 3 Adhesive layer 4 Reinforcement layer 5 Adhesive layer 6 Outer tube

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 67:00 63:00 33:14) (72) Inventor Takashi Sato No. 2-1, Oiwake, Hiratsuka-shi, Kanagawa Prefecture Yokohama Rubber Co., Ltd. Hiratsuka Factory

Claims (7)

[Claims] 1. The following components A, B and C are each represented by component A
90 to 50 parts by weight, 10 to 50 parts by weight of component B, 100 parts by weight of the sum of components A and B, and 1 to 10 parts by weight of component C, olefin-based thermoplastic resin, polyester-based thermoplastic resin and polyester A thermoplastic elastomer composition having excellent adhesion to a base fiber. Component A: An ethylene / propylene / diene copolymer rubber (E
PDM) Olefinic resin having a structure in which particles of vulcanized rubber composition (b) are finely dispersed and containing 85 to 20% by weight of olefinic thermoplastic resin and 15 to 80% by weight of EPDM vulcanized rubber composition Thermoplastic elastomer composition. Component B: polyester copolymer resin. Component C: an epoxy group-containing thermoplastic resin. 2. The epoxy group-containing thermoplastic resin contains at least 60 to 95% by weight of an ethylene monomer component,
2. The thermoplastic elastomer composition according to claim 1, which contains 0.5 to 15% by weight of a component derived from glycidyl methacrylate. 3. A laminate obtained by melting and bonding at least the thermoplastic elastomer composition according to claim 1 and polyester fibers. 4. A laminate obtained by melting and bonding at least the thermoplastic elastomer composition according to claim 1 to polyester fibers via a polyester copolymer resin. 5. A hose having at least an outer tube in contact with the polyester fiber reinforcing layer, wherein at least the innermost layer of the outer tube is the thermoplastic elastomer composition according to claim 1. 6. A hose in which at least a polyester fiber reinforcing layer is joined to an outer tube via an adhesive layer, wherein the adhesive layer is made of a polyester copolymer resin, and at least the innermost layer of the outer tube is as defined in claim 1. A hose which is the thermoplastic elastomer composition according to the above. 7. A hose in which at least a polyester fiber reinforcing layer is joined to an outer tube via an adhesive layer, wherein the adhesive layer is the thermoplastic elastomer composition according to claim 1, and at least the outer tube has A hose in which the innermost layer is a thermoplastic elastomer composition having a structure in which particles of an EPDM vulcanized rubber composition and domains are finely dispersed using an olefin-based thermoplastic resin as a matrix.