JPH10219036A - Wear-resistant, thermoplastic elastomer composition, its production, and hose using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic elastomer composition, excellent in resistance to wear and suitable for the external tube of a resin hose for high pressure use. SOLUTION: This wear-resistant, thermoplastic elastomer composition comprises (A) at least one type of silicone selected from among organosiloxanes and modifications thereof, (B) a thermoplastic copolyester elastomer, (C) a rubber composition containing acrylic rubber, and (D) a vulcanizer for the rubber composition, having a structure in which the vulcanized rubber particles of the rubber composition are finely dispersed in the thermoplastic resin; wherein the amount of silicone(s) (A) is 0.1 to 10 pts.wt. per 100 pts.wt. of the thermoplastic resin (B) and rubber composition (C) altogether, and the weight ratio of the thermoplastic resin (B) to rubber composition (C) is (30-90):(70-10).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic elastomer composition having excellent abrasion resistance, a method for producing the same, and an abrasion resistance and heat-softening property suitable for use in construction machines and the like using the same for an outer tube. And a high-pressure hose excellent in flexibility and the like.

[0002]

2. Description of the Related Art High pressure resin hoses used in construction machines and the like are required to have improved abrasion resistance, heat softening resistance, flexibility and the like. In particular, hose outer tubes are strongly demanded to improve wear resistance, heat softening resistance, flexibility, weather resistance, and the like.
In particular, regarding the abrasion resistance, the surface of the outer tube of the hose is liable to be rubbed and abraded with an adjacent member such as a metal due to vibration or swing in an environment in which the hose is used. Conventionally, a thermoplastic resin such as an ether-based polyurethane having wear resistance has been used for such a hose outer tube, but it is insufficient for long-term use. For this reason, an improvement by a polymer structure has been studied, but has a drawback such as impairing flexibility. As described above, a thermoplastic elastomer composition excellent in abrasion resistance, heat-resistant softening property, flexibility, and the like, which can be suitably used as a hose outer tube, has not been obtained to date.

[0003]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art and reduces the coefficient of friction of the outer tube of the hose, thereby improving the abrasion resistance of the hose surface, the softening resistance to heat, and the flexibility. It is an object of the present invention to provide a thermoplastic elastomer composition suitable for a high-pressure resin hose having excellent properties and the like. Another object of the present invention is to provide a method for producing the thermoplastic elastomer composition and a hose using the same as an outer tube.

[0004]

According to the present invention, (A)
At least one silicone selected from organosiloxanes and modified products thereof, (B) a thermoplastic copolyester elastomer, (C) a rubber composition containing an acrylic rubber, and (D) a vulcanizing agent for the rubber composition. The present invention provides a thermoplastic elastomer composition having a structure in which vulcanized rubber particles of the rubber composition are finely dispersed in a thermoplastic resin and having excellent wear resistance.

According to the present invention, when the thermoplastic elastomer composition is produced, a thermoplastic resin (B), a rubber composition (C) and a vulcanizing agent (D) are blended to remove silicone. There is provided a method for producing a thermoplastic elastomer composition comprising producing a thermoplastic elastomer composition containing other compounding components, and then incorporating silicone (A) into the composition.

According to the present invention, there is further provided a hose using the thermoplastic elastomer composition for an outer tube, the hose having at least an inner tube, a reinforcing layer, and an outer tube.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION As the silicone used as component (A) of the thermoplastic elastomer of the present invention, organosiloxanes, preferably polydimethylsiloxane and its modified products, preferably methyl methacrylate (MMA), ethylene vinyl It is a graft-modified product such as acetate (EVA) or polyethylene (PE). As the organosiloxanes, alkylsiloxanes are typical, and more specifically, fluoromethylpolysiloxane,
Examples include dimethylsiloxane, polydimethylsiloxane, and alkylarylsiloxanes (preferably, methylstyrylsiloxane, methylstyrylpolysiloxane, methylphenylsiloxane, polymethylphenylsiloxane, and the like).

The amount of the silicone (A) is not particularly limited, but is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the total of the thermoplastic copolyester elastomer (B) and the rubber composition (C). Parts by weight, more preferably 0.5 to 10 parts by weight.

The thermoplastic copolyester elastomer used as the component (B) of the thermoplastic elastomer composition in the present invention is known as a multi-block copolymer having a polyester and a polyether as main repeating units. Uses such a known thermoplastic copolyester elastomer. Typical examples of such a thermoplastic copolyester elastomer include, for example, the following.

The thermoplastic copolyester elastomer used in the present invention may be a random or multi-block copolymer comprising repeating units of polyester and polyether, polyester, repeating units of (poly) lactone and polyether or repeating units of polyester and polyimide ether. A polyester, including copolyetherester elastomers, (poly) lactone-modified copolyetherester elastomers and copolyetherimide ester elastomers.

[0011] Suitable thermoplastic copolyetherester elastomers and (poly) lactone-modified copolyetherester elastomers are prepared by conventional esterification / polycondensation processes by (i) at least one diol, (ii) at least one diol. (Iii) at least one long-chain ether glycol and, if necessary, (iv) at least one lactone or polylactone.

The diols (i) used in the preparation of the copolyetherester elastomers and their (poly) lactone modifications include saturated and unsaturated aliphatic and cycloaliphatic dihydroxy compounds and aromatic dihydroxy compounds. 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-octylundecanediol. , 1,2-, 1,
3- and 1,4-dihydroxycyclohexane, 1,
Diols having 2 to 15 carbon atoms such as 2-, 1,3- and 1,4-cyclohexanedimethanol, butynediol, hexenediol and the like can be mentioned. 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-
Examples include diols having 6 to 19 carbon atoms such as dihydroxynaphthalene, 4,4'-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 the production of the copolyetherester elastomers and their modified (poly) lactones are aliphatic, cycloaliphatic and / or alicyclic.
Or an aromatic dicarboxylic acid. These dicarboxylic acids are preferably of low molecular weight, ie having a molecular weight of about 350 or less, but higher molecular weight ones, especially dimer acids, can also be used.

Representative examples of 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-ethylspernic 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, phenanthenedicarboxylic acid, anthracenedicarboxylic acid, Included are 4,4'-sulfonyldibenzoic acids, and their halo and C1-C12 alkyl, alkoxy, and aryl-substituted derivatives. 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 copolyetherester elastomer and its modified (poly) lactone, aromatic dicarboxylic acids and mixtures of two or more aromatic dicarboxylic acids, and aromatic dicarboxylic acids and fatty acids Mixtures with aromatic and / or cycloaliphatic 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. When using a mixture of dicarboxylic acids or their esters,
It is preferred that at least about 60 mole%, especially at least about 80 mole%, based on the total amount of dicarboxylic acid, is the same dicarboxylic acid. In particular, those in which dimethyl terephthalate accounts for about 60 mol% or more of the dicarboxylic acid mixture are best.

The long-chain ether glycol (iii) used in the production of the thermoplastic copolyetherester elastomer and its (poly) lactone modified product is preferably about 400
Poly (oxyalkylene) glycols and copoly (oxyalkylene) glycols having a molecular weight of from about 12,000. 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 from about 10 to about 50% by weight.

Among them, copolyether ester 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 prepared 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 include (i) one or more aliphatic or alicyclic diols having 2 to 15 carbon atoms, (ii) one or more aliphatic, Alicyclic or aromatic dicarboxylic acids or their ester derivatives,
And (iii) from 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)
The weight ratio of dicarboxylic acid (ii) to about 0.25 to about 2.
0, preferably in the range of about 0.4 to about 1.4.

The diol (i) used in the production of the polyetherimide ester includes saturated and unsaturated aliphatic and alicyclic dihydroxy compounds and aromatic dihydroxy compounds. Preferably, these diols have a low molecular weight, ie, a molecular weight of about 250 or less.

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 is from 2 to 8 diols. Having carbon atoms). If more than one diol is used, at least about 6 based on the total diol content,
It is preferred that 0 mol%, more preferably at least 80 mol%, 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 for 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 4 to 18 carbon atoms. However, higher molecular weight dicarboxylic acids, especially dimer acids, can also be used.

Among the aliphatic, cycloaliphatic and aromatic dicarboxylic acids used in the production of the polyetherimide esters,
Preference is given to aromatic dicarboxylic acids and mixtures of two or more aromatic dicarboxylic acids, and mixtures of aromatic dicarboxylic acids with aliphatic and / or cycloaliphatic dicarboxylic acids,
Aromatic dicarboxylic acids alone are 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 acid is best.

The polyoxyalkylenediimide diacid (iii) used for the production of the above polyetherimide ester is a high molecular weight diacid having an average molecular weight of more than about 700, preferably more than about 900. These diacids have two adjacent carboxyl groups or anhydride groups, and further carboxyl groups, which must be esterifiable and preferably not imidizable. ) Is produced by imidizing one or more tricarboxylic acid compounds containing a high molecular weight polyoxyalkylenediamine.

In the present invention, the rubber composition used as the component (C) of the thermoplastic elastomer composition includes:
Acrylic rubber (ACM) or a rubber composition containing acrylic rubber is used. Examples of such an acrylic rubber include the following, and the raw material rubber (for example, a diene rubber and a hydrogenated product thereof (for example, a diene rubber) containing the acrylic rubber as a main component and generally used for hoses in the past. NR, IR, epoxidized natural rubber, SBR, B
R (high cis and low cis BR), NBR, hydrogenated NB
R, hydrogenated SBR), olefin rubbers (eg, ethylene propylene rubber (EPDM, EPM), maleic acid-modified ethylene propylene rubber (M-EPM), IIR, isobutylene and aromatic vinyl or diene monomer copolymer, acrylic rubber (ACM), ionomer), halogen-containing rubber (for example, brominated product of Br-IIR, Cl-IIR, isobutylene paramethylstyrene copolymer (BI
MS), CR, hydrin rubber (CHR), chlorosulfonated polyethylene (CSM), chlorinated polyethylene (C
M), maleic acid-modified chlorinated polyethylene (MC
M)), sulfur-containing rubber (eg, polysulfide rubber),
Fluorine rubber (for example, vinylidene fluoride rubber, fluorine-containing vinyl ether rubber, fluorine-containing phosphazene rubber), thermoplastic elastomer (for example, styrene-based elastomer, olefin-based elastomer, ester-based elastomer, urethane-based elastomer, polyamide-based elastomer), etc. Can be mentioned. ) Can be used.

The acrylic rubber used as a rubber component of the thermoplastic elastomer composition of the present invention is a crosslinkable rubber having an acryl group and an epoxy group as a main chain or a side chain in a molecule. A copolymer rubber containing acrylate and / or methacrylate as a copolymer component can be given. The epoxy group-containing (meth) acrylate copolymer or the epoxy group-containing (meth) acrylate copolymer rubber used in the present invention comprises (1) alkyl (meth) acrylate and / or alkoxy (meth) acrylate substitution. A multicomponent copolymer obtained by polymerizing an alkyl ester, (2) an epoxy group-containing monomer, and (3) another ethylenically unsaturated monomer copolymerizable with these (1) and (2), if necessary. It is a polymer rubber.

The alkyl (meth) acrylate (1) used in the production of the epoxy group-containing (meth) acrylate copolymer rubber has the following formula:

[0035]

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(Wherein, R ₁ is an alkyl group having 1 to 18 carbon atoms, and R ₂ represents hydrogen or a methyl group). Specific examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and n- Pentyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-methylpentyl (meth) acrylate, n-octyl (meth) acrylate, 2-
Ethylhexyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, n-octadecyl (meth) acrylate, and the like, among which ethyl (meth) acrylate, n-propyl (meth) acrylate, Preferred are n-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and n-octyl (meth) acrylate.

The (meth) acrylic acid alkoxy-substituted alkyl ester (1) has the following formula:

[0038]

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Wherein R ₃ is hydrogen or a methyl group;
₄ represents an alkylene group having 1 to 18 carbon atoms, and R ₅ represents an alkyl group having 1 to 18 carbon atoms). Specific examples of such alkyl (meth) acrylates include 2
-Methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (n-propoxy)
Ethyl (meth) acrylate, 2- (n-butoxy) ethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 3-ethoxypropyl (meth) acrylate, 2- (n-propoxy) propyl (meth) acrylate, 2- (n-butoxy) propyl (meth) acrylate and the like.

Examples of the epoxy group-containing monomer used for producing the epoxy group-containing (meth) acrylate copolymer rubber include allyl glycidyl ether, glycidyl methacrylate, glycidyl acrylate, and the compounds shown below (each of the following formulas). In the formula, R ₆ represents hydrogen or a methyl group).

[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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If necessary, 2-cyanoethyl (meth) acrylate may be used as the monomer to be copolymerized with the alkyl (meth) acrylate or the alkoxy-substituted alkyl (meth) acrylate (1) and the epoxy group-containing monomer. A) cyano-substituted alkyl (meth) acrylates such as acrylate, 3-cyanopropyl (meth) acrylate and 4-cyanobutyl (meth) acrylate; amino-substituted alkyl (meth) acrylates such as diethylaminoethyl (meth) acrylate; Fluorine-containing (meth) acrylates such as 1-trifluoroethyl (meth) acrylate; hydroxy-substituted alkyl (meth) acrylates such as hydroxyethyl (meth) acrylate; alkyl vinyl ketones such as methyl vinyl ketone; vinyl ethyl ether , Vinyl or allyl ether such as allyl methyl ether, styrene, α-methyl styrene, chlorostyrene, vinyl aromatic compounds such as vinyl toluene, acrylonitrile, vinyl nitrile such as methacrylonitrile, acrylamide, methacrylamide, N-methylol acrylamide and the like Vinyl amide and ethylene, propylene, vinyl acetate and the like. The acrylic rubber used in the present invention is preferably an acrylic rubber comprising acrylic acid and an alkyl component having an alkyl component of C _{3 to} C _18. For example, 25% by weight of butyl acrylate, propyl acrylate, dodecyl acrylate, and hexadecyl acrylate may be used. The content is more preferably 30 to 60% by weight.

As a specific component constitution of the rubber containing an acrylic group and an epoxy group (acrylic rubber), from the viewpoint of heat resistance, alkyl (meth) acrylate or alkoxyalkyl (meth) acrylate (1)
A copolymer rubber composed of ethyl acrylate alone and composed of glycidyl methacrylate as an epoxy group-containing monomer is, from the viewpoint of cold resistance, an alkyl (meth) acrylate or an alkoxy alkyl (meth) acrylate (1). A copolymer rubber composed of ethyl acrylate, butyl acrylate and methoxyethyl acrylate, and a glycidyl methacrylate as an epoxy group-containing monomer is preferably exemplified. Furthermore, in terms of the balance between heat resistance and cold resistance, it is preferable to select the type and amount of the alkyl (meth) acrylate or the alkoxyalkyl (meth) acrylate (1). Further, the epoxy group-containing monomer component, in the crosslinking of the copolymer rubber,
An epoxy group is used for a crosslinking reaction, and is usually 1 to 20.
What contains 1.5% by weight, preferably 1.5% by weight to 15% by weight, more preferably 2% by weight to 10% by weight is suitably used in the vulcanization reactivity dynamically performed during kneading described later.

The mixing ratio of the thermoplastic copolyester elastomer (B) and the rubber composition (C) used in the present invention is preferably (B) :( C), and is 30 to 90:70 to 10
(Weight ratio), more preferably 30-80: 70-20. If the blending ratio of B is too small, the mechanical strength is reduced, and the rubber phase becomes a matrix phase, which impairs the fluidity during extrusion or the like.

In the present invention, the vulcanizing agent used as the component (D) of the thermoplastic elastomer composition is any vulcanizing agent generally used for vulcanizing the acrylic rubber or the acrylic rubber-containing composition. As a specific example, it is preferable to mix a crosslinking agent compound having at least one of a carboxyl group and a carboxylic anhydride group as a carboxyl group in the molecule. Typical examples of such a crosslinking agent compound include, for example, the following compounds.

The crosslinking agent of the present invention is not particularly limited as long as it is a compound having two or more carboxyl groups and / or one or more carboxylic anhydride groups in the molecule. Preferably, aliphatic, cycloaliphatic and aromatic polycarboxylic acids, their (part) carboxylic anhydrides, and the (part) of these compounds with (poly) alkylene glycols
Esterified products are used. As the crosslinking agent, those having a molecular weight of 5,000 or less are preferable.

Specific examples of the aliphatic polycarboxylic acid include:
Examples include succinic acid, glutaric acid, pimelic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, dodecenylsuccinic acid, and butanetetracarboxylic acid. Specific examples of the alicyclic polycarboxylic acid include cyclopentane dicarboxylic acid, cyclopentane tricarboxylic acid, cyclopentane tetracarboxylic acid, cyclohexane dicarboxylic acid, cyclohexane tricarboxylic acid, methyl cyclohexane dicarboxylic acid, tetrahydrophthalic acid, endomethylene tetrahydrophthalic acid And methylendomethylenetetrahydrophthalic acid.
Specific examples of the aromatic polycarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, and pyromellitic acid. Specific examples of (partial) carboxylic anhydrides include these polycarboxylic (partial) carboxylic anhydrides. The amount of the vulcanizing agent used, vulcanizing conditions, etc. can be the same as before.

That is, the preferable amount of the crosslinking agent compound is 0.5 to 2 per 100 parts by weight of the acrylic rubber component.
0 parts by weight, more preferably 1 to 15 parts by weight. The addition of such a crosslinking agent compound is preferred because the acrylic rubber dispersed phase is crosslinked and the mechanical strength is improved and the set resistance is improved.

(A) at least one silicone selected from organosiloxanes and modified products thereof, (B) a thermoplastic copolyester elastomer,
In producing (C) a rubber composition containing an acrylic rubber and (D) a thermoplastic elastomer composition containing a vulcanizing agent for the rubber composition, other components except the silicone (A) are compounded. Then, it is suitably manufactured by blending silicone (A).

The components of the thermoplastic elastomer composition used in the present invention are, as described above, a thermoplastic copolyester elastomer and an acrylic rubber, and such a thermoplastic copolyester elastomer composition comprises at least one of the rubber components constituting the same. The parts are cross-linked.
Such a thermoplastic copolyester elastomer composition,
Usually, using a Banbury mixer, Brabender mixer or other kneading extruder (two-screw kneading extruder), etc.
For example, maintaining the melt of the thermoplastic copolyester elastomer and the acrylic rubber in these devices,
It can be manufactured by adding a vulcanizing agent (crosslinking agent) while kneading and dispersing the rubber phase finely, and kneading at a temperature that promotes crosslinking until the crosslinking of the rubber phase is completed.

That is, the thermoplastic elastomer composition produced in this manner advances the vulcanization of the rubber while masticating the thermoplastic resin and the rubber composition, that is, the vulcanization proceeds dynamically. Dynamic vulcanization (Dynamic Cure or Dy
(Namic Vulcanization). By utilizing such a manufacturing method, the obtained thermoplastic elastomer composition has a vulcanized rubber phase in which at least a part thereof becomes a discontinuous phase is finely dispersed in a thermoplastic resin phase in which at least a part thereof becomes a continuous phase. This thermoplastic elastomer composition exhibits the same behavior as the vulcanized rubber, and at least the continuous phase is a thermoplastic resin phase. Is possible.

Such a thermoplastic elastomer composition 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 diameter is preferably 50 μm or less, and more preferably 10 to 1 μm.

The kneading conditions, the type of vulcanizing agent used,
The amount and vulcanization 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.

A method for producing such a thermoplastic elastomer composition of the present invention will be described below. In the production of the thermoplastic elastomer composition of the present invention, first, a resin and a rubber composition are added, melt-kneaded, and then a vulcanizing agent is added under kneading,
This can be done by dynamically vulcanizing the rubber.

The composition of the present invention may further comprise, if necessary,
Compounding agents such as a reinforcing agent, a softening agent and an antioxidant can be added, and the compounding agent for the rubber component may be added during the kneading, but the compounding agent other than the vulcanizing agent is added before the kneading. It is better to mix them in advance. The compounding agent for the resin component may be mixed in advance before the kneading, or may be added during the kneading.

The kneading machine used for producing the thermoplastic elastomer composition of the present invention 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 in consideration of kneading of the resin component and the rubber component and dynamic vulcanization of the rubber component. Further, two or more types of kneaders may be used to knead sequentially. The conditions for melt kneading are as follows:
The kneading temperature is, for example, 180 to 350 ° C., particularly 180 to 350 ° C.
The temperature is preferably 300 ° C., but is not particularly limited as long as it is not lower than the temperature at which the thermoplastic copolyester elastomer component melts. The shear rate during kneading is 1000 to 800
It is preferably ^{0 s -1} , especially 1000 to 5000 s ^-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
Preferably, it is 5 minutes. The shear rate is calculated by dividing the product obtained by multiplying the circumference of the circle drawn by the screw tip by the number of revolutions 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.

When the thermoplastic elastomer composition is produced by such a production method, the relationship between the viscosity and the volume fraction of the thermoplastic elastomer used and the acrylic rubber composition at the time of melt-kneading are mutually related, 180 ° C during kneading
It is preferable to make the relationship of the following formula within the range of -350 ° C and the shear rate of 1000-8000 s ^-1 . η ₂ / η ₁ <4.0 (η ₁ / η ₂ ) (φ ₂ / φ ₁ ) <1.0 where η ₁ : viscosity of the thermoplastic copolyester elastomer at the time of melt-kneading η ₂ : acrylic rubber composition Viscosity during melt-kneading of the product φ ₁ : Volume fraction of the thermoplastic copolyester elastomer φ ₂ : Volume fraction of the acrylic rubber composition By kneading within the range of the above formula, the rubber ratio is widely controlled, and preferably high. Realization of rubber ratio is possible, and
A thermoplastic elastomer composition that is flexible and has high elongation at break can be obtained. The method of compounding the silicone (A) according to the present invention is as follows: (1) The component (B),
A method for producing the thermoplastic elastomer composition of the present invention, in which the component (A) is added simultaneously with the kneading of the component (C), and then the component (D) is added and dynamic vulcanization is performed. Note that a part or the whole amount of the component (A) may be added to the component (C) in advance. (2) Using the twin-screw kneading extruder according to the above method, the component (B),
(C) is kneaded, then the component (D) is added and dynamic vulcanization is performed to obtain a pellet of the thermoplastic elastomer composition not containing the component (A), which is then extruded by a single screw extruder or the like. In the process, the components (A) and pellets of the thermoplastic elastomer composition not containing the component (A) are supplied in a predetermined quantitative ratio and molded to obtain the thermoplastic elastomer composition of the present invention. There is a method, and it can be manufactured by any method. In particular, the second method can efficiently disperse in the phase of the component (B) constituting the matrix phase of the thermoplastic elastomer composition. This is a more preferable production method because the concentration of (A) can be increased.

The hose according to the present invention comprises at least an inner tube,
It comprises a reinforcing layer and an outer tube, and is constituted by using the thermoplastic elastomer according to the present invention for the outer tube. As the inner tube material, similarly to the conventional hose, for example, a commonly used thermoplastic resin and thermoplastic elastomer, and a composition thereof, but are not particularly limited, polyolefin resin, polyamide resin, Thermoplastic resins such as polyester-based resins and their compositions, polyolefin-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, polyester-based thermoplastic elastomers, thermoplastic elastomers such as polyurethane-based thermoplastic elastomers and their compositions, and furthermore, Examples thereof include a thermoplastic elastomer composition in which a rubber composition containing a vulcanized rubber composition in a thermoplastic resin and a thermoplastic elastomer is dispersed in particles. In particular, the thermoplastic elastomer composition containing no component (A) of the present invention is suitably exemplified as an inner tube material.

The reinforcing layer of the hose according to the present invention is made of various fibers conventionally used for hoses.
Polyester fibers which are excellent in affinity with the inner and outer tubes used in the present invention and which are excellent in economy, flexibility, strength and modulus are particularly selected and used.

In the present invention, the interlayer between the inner tube and the reinforcing layer and / or
Alternatively, for the adhesive layer used between the reinforcing layer and the outer tube, various adhesive compositions conventionally used widely for hoses can be used, and specifically, a urethane-based adhesive is used. Can be. When an adhesive thermoplastic resin is used, a polyester copolymer resin or the like can be used. In any case, the thickness of the adhesive layer is not particularly limited, but is preferably 10 to 500, respectively.
μm.

In order to produce the hose according to the present invention, first, a thermoplastic elastomer obtained by dispersing a vulcanized acrylic rubber in a thermoplastic copolyester elastomer (component (B of the present invention) ), (C),
(D) of a thermoplastic elastomer composition), an inner tube of a hose is manufactured, a normal adhesive is applied to the outer surface of the inner tube as necessary, and a reinforcing polyester fiber is braided or spirally formed thereon. Winding, further forming an adhesive layer by extrusion molding using, for example, a thermoplastic polyester copolymer resin, and immediately thereafter, a general method of coating the thermoplastic elastomer composition again as an outer tube can be used. . Of course, when manufacturing the outer tube, the adhesive layer and the outer tube may be co-extruded, or a method in which the adhesive layer is once cooled after extrusion and then the outer tube is extruded. Is also good. The thickness of the adhesive layer is not particularly limited, but is preferably 10 to 500 μm.

[0071]

EXAMPLES The present invention will be further described with reference to Reference Examples, Examples and Comparative Examples, but it is needless to say that the scope of the present invention is not limited to these Examples and Comparative Examples.

Reference Examples, Examples 1 to 11 and Comparative Examples 1 to 2 A thermoplastic elastomer composition having the composition (parts by weight) shown in Table I was prepared using the silicone addition time shown in Table I as follows. The abrasion resistance, heat softening resistance and flexibility (hardness) of the obtained composition were measured as follows, and the results were shown in Table I.
It was shown to. First, the compounding agent other than the acrylic rubber and the vulcanizing agent is put into a closed rubber Banbury mixer for rubber and kneaded, and then formed into a sheet using a rubber roll,
Pellets were formed with a rubber paytizer. Next, the thermoplastic copolyester elastomer, the rubber pellets, and the compatibilizing agent are charged into a twin-screw kneading extruder, and after kneading, the thermoplastic copolyester elastomer and the vulcanizing agent are continuously added thereto. The rubber component dispersed as a domain in the matrix consisting of the compatibilizer was dynamically vulcanized. For the kneading conditions, the kneading temperature is, for example,
220-300 ° C., residence time 30 for the part where dynamic vulcanization is performed
And a shear rate of 1000-2500 sec- ¹ .
After the completion of the dynamic vulcanization, the mixture is continuously discharged into a strand form from the twin-screw kneading extruder, and after cooling with water, cut into a length of about 3 mm (about 2 mm in diameter) with a cutter to obtain a pellet-shaped thermoplastic elastomer composition. Was.

[0073]

[Table 1]

[0074]

[Table 2]

[0075]

[Table 3]

[Table I Footnotes] * 1 Esten 58212: Kyowa Hakko Kogyo Co., Ltd. * 2 SP-100: Dow Corning Asia Co., Ltd. * 3 SP-110: Dow Corning Asia Co., Ltd. * 4 SP-300: Dow Corning Asia Co., Ltd. * 5 Hytrel 5556: Toray Dupont Co., Ltd. * 6 E (ethylene) = 67% by weight, MA (methyl acrylate) = 30% by weight, GMA ( (Glycidyl methacrylate) = 3
% By weight * 7 EA (ethyl acrylate) = 40% by weight, BA (butyl acrylate) = 32% by weight, MEA (methoxyethyl acrylate) = 19% by weight, GMA (glycidyl methacrylate)
* 9 Seat SO: manufactured by Tokai Carbon Co., Ltd. * 9 Irganox 1010: manufactured by Japan Ciba Geigy Co., Ltd. * 10 manufactured by Mitsui Toatsu Fine Co., Ltd.

(Preparation of Specimen) Pellets of the thermoplastic elastomer composition were formed into a 2.0 mm thick sheet at 230 ° C. for 5 minutes at a pressure of 2.9 MPa using a commonly used resin press forming machine. did.

Measurement method a) Abrasion resistance = pico abrasion test A pico abrasion test described in JIS standard (JIS K 6264) was performed. A predetermined test piece was prepared by press molding, and a load of 44 N (4.49) was obtained using the obtained test piece.
kgf), the rotation speed is 60 times / minute, the rotation speed is 20 times forward rotation,
Twenty reversals were repeated twice each, under a total of 80 conditions. The obtained abrasion volume is 100 times the abrasion volume of the reference example.
It was expressed by an index. B) Heat softening resistance = 120 ° C Young's modulus No. 3 dumbbell shape according to JIS (JIS K 625)
The test piece of 1) was produced by a punching machine. About the obtained test piece, Young's modulus at 120 ° C according to JIS standard
(MPa) was measured. C) Flexibility = hardness No. 3 dumbbell shape according to JIS (JIS K 625)
The test piece of 1) was produced by a punching machine. The type A durometer hardness (JIS K6253) of the obtained test piece was measured in accordance with JIS standards.

Next, using the thermoplastic elastomer composition obtained in each example as an outer tube, a hose having an inner diameter of 9.5 mm and an outer diameter of 17.5 mm consisting of the following inner tube, adhesive layer and reinforcing layer was formed by a conventional method. Manufactured. Inner tube: thermoplastic elastomer composition (parts by weight) thermoplastic copolyester elastomer Hytrel 5556 (manufactured by Toray DuPont) EMA-GMA 14.43 Composition E (ethylene) = 67% by weight MA (methyl acrylate) = 30% by weight % GMA (glycidyl methacrylate) = 3% by weight Acrylic rubber Composition EA (ethyl acrylate) = 40% by weight BA (butyl acrylate) = 32% by weight MEA (methoxyethyl acrylate) = 19% by weight GMA (glycidyl methacrylate) = 9% by weight % FEF grade carbon black (Seast SO Tokai Carbon Co., Ltd.) 40.00 Anti-aging agent Irganox 1010 (Nippon Ciba Geigy Co., Ltd.) 3.33 Crosslinking agent Butanetetracarboxylic acid (Mitsui Toatsu Fine Co., Ltd.) 1.60 Reinforcement layer : Polyester fiber Adhesive layer: Inner tube / reinforcing interlayer adhesive layer = moisture-curable urethane adhesive Thailand Ito 7411 (manufactured by Lord Far East) Reinforcing layer / adhesive layer between outer tubes = thermoplastic polyester-based copolymer resin composition thermoplastic copolyester elastomer 50 parts by weight block copolymer composition terephthalic acid = 30 mol% isophthalic acid = 12 mol% 1,4-butanediol = 38 mol% Polytetramethylene glycol = 20 mol% Thermoplastic polyurethane elastomer 50 parts by weight ESTEN 58212 (manufactured by Kyowa Hakko Kogyo Co., Ltd.) Inner tube extrusion Resin extrusion using inner tube material It was extruded into a hollow shape having an inner diameter of 9.5 mm and a thickness of 1.0 mm by a machine to form an inner tube. Reinforcing layer braid After a moisture-curable urethane-based adhesive was applied thereon, a reinforcing fiber layer was formed using a polyester fiber by a braiding machine. Adhesive layer formation A moisture-curable urethane-based adhesive was applied thereon, or a thermoplastic polyester-based copolymer resin was molded by a resin extruder to form an adhesive layer. Outer tube extrusion Using the outer tube material shown in Table I, 1.0 mm
To form an outer tube.

The performance (abrasion resistance, heat softening resistance and flexibility) of the hose thus obtained was measured as follows, and the results are shown in Table I.

Measurement method a) Abrasion resistance = abrasion resistance test Abrasion resistance is determined by rubbing the outer tube surface of the hose by reciprocating motion of each part 13 of the tester shown in FIG. The number of reciprocations (ten thousand times) of the corner portion 13 before performing was measured. In this tester, the hose under test 11 is fixed by passing through the shaft core 12, the corner 13 comes into contact with the surface of the outer tube of the hose 11 under test so as to be pushed by the weight 14, and the corner 1
3 is an arm 17 by a cylinder 15 and a piston 16
The arm 17 is rotatably stopped by a pin 18 on a piston 16. Corner 13 is 9
At an angle of 0 °, the tip is a circular arc with a radius of 0.4 mm.
The corner 13 presses the surface of the outer tube of the hose 11 under test at 14.7 N (1.50 kgf). B) Heat-softening resistance = high-temperature destruction test (120 ° C.) A predetermined metal fitting was attached to both ends of the hose, and a high-temperature destruction test of the hose was performed as described below. JIS standard (JI
SK 6349) was carried out at a temperature of 120 ° C. Measure the pressure that led to the destruction,
It was evaluated as a burst pressure (MPa). C) Flexibility = bending stiffness The sample hose is bent along arcs of various radii and the bending force (N) is measured. Specifically, the sample hose outer diameter of 10
The measurement is started from the double bending radius, the bending radius is sequentially changed up to three times, and the bending force (N) is measured. From this measurement result, a graph showing the relationship between the bending force and the bending radius is created, and the bending force at the specified radius (four times) is read from the obtained graph and is defined as the bending stiffness (N) of the hose.

Description of Effects of Examples (Examples 1 to 5, Comparative Examples 1 and 2, Reference Example) This is an example which shows the dependency of the addition amount of the component (A) silicone and explains the addition effect of silicone. The reference example is a conventional resin hose in which an ether-based polyurethane thermoplastic elastomer is used for the outer tube. The effects of the present invention will be described based on the wear properties of the hose. Comparative Example 1 is a thermoplastic elastomer composition and a hose which do not contain the component (A) silicone of the present invention. The hose has the same abrasion as the reference example, and has poor abrasion resistance. However, the hardness of this thermoplastic elastomer composition at room temperature is lower than that of the ether-based polyurethane thermoplastic elastomer, and at 120 ° C.
Because of its excellent Young's modulus, it has low bending stiffness at room temperature, is flexible, has a high breaking pressure in a high-temperature breaking test, and has excellent heat-softening resistance. Examples 1 to 5 show components (A) of the present invention.
A thermoplastic elastomer composition and a hose containing polydimethylsiloxane as the silicone. In the production of the thermoplastic elastomer composition, the component (A) is added at the time of kneading the components (B) and (C). As shown in Example 1, the wear resistance was approximately doubled by the addition of 0.5 part by weight of silicone, and the effect of improving the wear resistance by the addition of the component (A) was found. Further, as compared with Comparative Example 1, the hardness at normal temperature and the Young's modulus at 120 ° C. are equivalent, and the flexibility and heat-softening resistance are equivalent to and superior to Comparative Example 1. Further, as shown in Examples 2 to 5, when the compounding amount of the silicone is increased, the abrasion resistance is further improved, while the flexibility and the heat-softening resistance are hardly changed, which is good. Comparative Example 2 is a thermoplastic elastomer composition and a hose containing 15 parts by weight of the silicone as the component (A), and has good abrasion resistance, flexibility and heat-softening resistance. No improvement in resistance is observed. That is, it is understood that the blending of the component (A) in an amount of more than 10 parts by weight has no improvement effect anymore, and that the blending of 10 parts by weight or less is appropriate in consideration of economy. (Examples 6 to 8) As the silicone of the component (A), MM
A thermoplastic elastomer composition containing A (methyl methacrylate) -modified polydimethylsiloxane and a hose. A method of adding the component (A) to the thermoplastic elastomer composition at the time of kneading the components (B) and (C) (Example 6)
And a method of adding a thermoplastic elastomer composition containing no component (A) at the time of extrusion molding after production (Examples 7 and 8)
It is due to. Since the MMA-modified polydimethylsiloxane can be formed in a pellet form, it can be supplied without contamination of a hopper or the like by post-addition in a single screw extruder or the like, and thus can be used more preferably. Example 6
Compared with Examples 1 to 5, it shows the same characteristics, and the component (A)
Using MMA-modified polydimethylsiloxane as
Abrasion improvement effect equivalent to polydimethylsiloxane, and
It was found that flexibility and heat-softening property were obtained. Furthermore,
In Examples 7 and 8 in which the component (A) was added later, Example 6 was used.
It can be seen from the comparison with that that the same wear resistance improving effect can be obtained with a smaller blending amount. This consists of the components (B), (C)
As compared with the method of adding the component (A) at the time of kneading, the component (A) is unevenly distributed in the phase of the component (B) forming the matrix phase, and as a result, the concentration of the component (A) on the wear surface is high. Is presumed to have been formed. Therefore, as a method for adding the component (A), a thermoplastic elastomer composition not containing the component (A) is produced, and the component (A) is blended by post-addition to obtain the thermoplastic elastomer composition of the present invention. Is a more preferable method. (Examples 9 to 11) As the silicone of the component (A),
A thermoplastic elastomer composition and a hose containing VA (ethylene vinyl acetate) -modified polydimethylsiloxane. The thermoplastic elastomer composition is prepared by a method of adding the component (A) at the time of kneading the components (B) and (C) (Example 9), and a method of extruding the thermoplastic elastomer composition containing no component (A). This is based on the method of adding at the time of molding (Examples 10 and 11). Since the EVA-modified polydimethylsiloxane can be formed in a pellet form, it can be supplied without contamination of a popper or the like by post-addition in a single screw extruder or the like, and thus can be used more preferably. Example 9 shows the same characteristics as those of Examples 1 to 5, and even if EVA-modified polydimethylsiloxane is used as the component (A), the abrasion improving effect and flexibility are the same as those of polydimethylsiloxane. It was found that heat softening resistance was obtained. Further, similarly to Examples 6 to 8, Examples 10 and 11, in which the component (A) was added later, showed the same wear resistance improving effect with a smaller amount than Example 9. Therefore,
As in Examples 6 to 8, as a method for adding the component (A),
It can be seen that the thermoplastic elastomer composition of the present invention is more preferably produced by producing a thermoplastic elastomer composition not containing the component (A) and then blending the component (A) by post-addition.

[0083]

According to the present invention, it is possible to provide a thermoplastic elastomer composition having excellent abrasion resistance, heat-softening resistance and flexibility, and a hose using the same for an outer tube, and a use environment in which vibrations and swings are severe. Can be used for a long period of time.

[Brief description of the drawings]

FIG. 1 is a schematic view of a testing machine used for a wear test of a hose of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Hose to be tested 2 ... Shaft core 3 ... Corner part 4 ... Weight 5 ... Cylinder 6 ... Piston 7 ... Arm 8 ... Pin

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Shigeru Yamauchi 2-1 Oiwake, Hiratsuka-shi, Kanagawa Yokohama Rubber Co., Ltd. Inside the Hiratsuka Factory (72) Inventor Susumu Hatanaka 2-1 Oiwake, Hiratsuka-shi, Kanagawa Yokohama Rubber Hiratsuka Factory

Claims (5)

[Claims] (A) at least one silicone selected from organosiloxanes and modified products thereof,
(B) a thermoplastic copolyester elastomer, (C) a rubber composition containing an acrylic rubber, and (D) a vulcanizing agent for the rubber composition, wherein the vulcanized rubber particles of the rubber composition are thermoplastic resin A thermoplastic elastomer composition having a structure finely dispersed therein and having excellent wear resistance. 2. The heat according to claim 1, wherein the amount of the silicone (A) is 0.1 to 10 parts by weight based on 100 parts by weight of the total of the thermoplastic resin (B) and the rubber composition (C). Plastic elastomer composition. 3. A thermoplastic resin (B) and a rubber composition (C)
(B) :( C) is from 30 to 90:70 to 10
The thermoplastic elastomer composition according to claim 1, which is (weight ratio). 4. A thermoplastic resin (B), a rubber composition (C) and a vulcanizing agent (D) are blended in producing the thermoplastic elastomer composition according to any one of claims 1 to 3. Then, a method for producing a thermoplastic elastomer composition comprising producing a thermoplastic elastomer composition containing other components other than silicone (A), and then incorporating silicone (A) therewith. 5. A hose having at least an inner tube, a reinforcing layer, and an outer tube, wherein the thermoplastic elastomer composition according to claim 1 is used for an outer tube.