JPH10128885A - Hose - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hose having excellent oil resistance, flexibility and cold resistant heat resistance as well as excellent heat resistant softening properties, heat resistant aging characteristics and high durability. SOLUTION: In the hose having at least an inner tube, a reinforcing layer and an outer tube, inner and outer tube material is formed of thermoplastic elastomer having a structure that vulcanized rubber particles of acrylic rubber composition is dispersed in matrix of thermoplastic copolyester elastomer and containing 30 to 90wt.% of the thermoplastic copolyester elastomer component and 70 to 10wt.% of the vulcanized rubber component of the acrylic rubber. Reinforcing layer material is formed of polyester fiber. An adhesive layer made of thermoplastic resin composition containing aromatic dicarboxylic acid as dicarboxylic acid for constituting the polyester and 50wt.% or more of thermoplastic polyester copolymer resin having 3.0MPa or more of Young's modules at 120 deg.C is disposed between the layer and the outer tube.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hose having a specific thermoplastic elastomer composition as an inner / outer tube and a polyester fiber reinforcing layer, and more particularly to a hose having a specific adhesive layer between the reinforcing layer and the outer tube. The present invention relates to a hose exhibiting excellent durability due to excellent heat-softening resistance and heat-aging resistance.

[0002]

BACKGROUND OF THE INVENTION The present inventors have previously provided at least an inner tube, a reinforcing layer and an outer tube, wherein the inner tube contains an acrylic group and an epoxy group in a matrix of a thermoplastic copolyester elastomer. The acrylic rubber composition has a structure in which vulcanized rubber particles are dispersed, and contains a thermoplastic copolyester elastomer component in an amount of 30 to 90% by weight and a vulcanized rubber component of the acrylic rubber composition in an amount of 70 to 10% by weight. Vulcanized rubber particles of an acrylic rubber composition, wherein the reinforcing layer is made of polyester fiber or the like, and the outer tube contains an acrylic group and an epoxy group in a matrix of a thermoplastic copolyester elastomer. Wherein the thermoplastic copolyester elastomer component is 30 to 90% by weight, and the vulcanized rubber of the acrylic rubber composition Min is a thermoplastic elastomer containing 70 to 10 wt%, proposed a hose arranged adhesive layers of at least reinforcing layer and the outer tube (Japanese Patent Application No. 8-23
No. 903), the use of the inner and outer tube materials of the hose improves the flexibility (normal temperature and low temperature), oil resistance and cold resistance of the hose, and allows production without the need for a vulcanization step. A hose that can reduce costs has been provided.

[0003] However, in the hose, a urethane-based cold-setting adhesive or the like is used as the adhesive layer. In this case, since the adhesive is of a reactive type, the hose is not used. There is a drawback that the heat curing progresses due to heat, the adhesive layer becomes hard, and the reinforcing layer is broken due to the filament breakage of the fiber of the reinforcing layer, and the durability is low. When a polyester hot-melt adhesive resin is used instead, the adhesive resin is incompatible with heat-fusibility, is inferior in heat-softening property, and has durability (high-temperature impact pressure test:
A hose satisfying 120 ° C. and 27.5 MPa) cannot be obtained.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to select a specific material for the adhesive layer in the hose having the above-mentioned structure, thereby providing a high durability which is further excellent in heat softening resistance and heat aging resistance. It is another object of the present invention to provide a hose used for a high-pressure fluid or the like.

[0005]

According to the present invention, there is provided at least an inner tube, a reinforcing layer, and an outer tube, wherein the inner tube contains an acrylic group and an epoxy group in a matrix of a thermoplastic copolyester elastomer. A thermoplastic elastomer having a structure in which vulcanized rubber particles of an acrylic rubber composition are dispersed, and containing 30 to 90% by weight of the thermoplastic copolyester elastomer component and 70 to 10% by weight of the vulcanized rubber component of the acrylic rubber. The composition, wherein the reinforcing layer is made of polyester fiber, and the outer tube is formed by dispersing vulcanized rubber particles of an acrylic rubber composition containing an acrylic group and an epoxy group in a matrix of a thermoplastic copolyester elastomer. 30 to 90% by weight of the thermoplastic copolyester elastomer component, and vulcanized rubber of the acrylic rubber. A thermoplastic elastomer composition containing 70 to 10% by weight of a component, wherein at least a hose in which an adhesive layer is disposed between the reinforcing layer and the outer tube, wherein the dicarboxylic acid constituting the polyester is an aromatic dicarboxylic acid It is an acid and has a Young's modulus at 120 ° C. of 3.0.
5 MPa or more of a thermoplastic polyester copolymer resin
A hose comprising a thermoplastic resin composition containing 0% by weight or more is provided.

According to a preferred embodiment of the present invention, the thermoplastic polyester copolymer resin in the adhesive layer has a melt viscosity of 1000 Pa at a temperature of 230 ° C. and a shear rate of 50 to 200 s ^−1. S or less, the thermoplastic polyester-based copolymer resin in the adhesive layer further comprises a repeating unit of polyester and polyether or a repeating unit of polyester and polyimide ether, and the repeating unit of the polyester is 40 A hose is provided that is a thermoplastic block copolyester elastomer containing at least mole%.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic elastomer composition constituting the inner tube and the outer tube of the hose according to the present invention comprises a thermoplastic copolyester elastomer in an amount sufficient to provide thermoplasticity, and a thermoplastic copolyester elastomer in rubbery elasticity. A sufficient amount of at least a portion thereof is made of a blend with a vulcanized acrylic rubber, and a thermoplastic copolyester elastomer component at least partially forms a continuous phase (matrix phase) in which a discontinuous phase (dispersed phase) is contained. Means that at least a part of the vulcanized acrylic rubber is present in the rubber component. In addition, what is called a salami structure in which a thermoplastic resin is further dispersed in the discontinuous phase (rubber phase) may be used.

[0008] The thermoplastic copolyester elastomer, which is the first component of the thermoplastic elastomer composition of the present invention, is known as a multi-block copolymer having polyester and 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 includes a random and multi-block copolymer comprising a repeating unit of polyester and polyether, a repeating unit of polyester, (poly) lactone and polyether or a repeating unit of polyester and polyimide ether. A polyester, including copolyetherester elastomers, (poly) lactone-modified copolyetherester elastomers and copolyetherimide ester elastomers.

[0010] 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 production 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 use in the preparation of the copolyetherester elastomers and their (poly) lactone modifications are aliphatic, cycloaliphatic and / or cycloaliphatic.
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 (poly) lactone-modified product, 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 of suitable poly (oxyalkylene) glycols are 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 added to 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 their (poly) lactone modified products include copolyesters in which the dicarboxylic acid component is terephthalic acid, the diol component is 1,4-butanediol, and the long-chain ether glycol is poly (tetramethylene ether) glycol. Ether ester elastomers are preferred.

The polyetherimide ester elastomers 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 polyoxyalkylenediimide 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 above 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 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 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 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 in 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.

The acrylic rubber used as the rubber component of the thermoplastic elastomer composition of the present invention is a crosslinkable rubber having an acrylic 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:

[0033]

Embedded image

(Wherein, R ₁ represents 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:

[0036]

Embedded image

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).

[0039]

Embedded image

[0040]

Embedded image

[0041]

Embedded image

[0042]

Embedded image

[0043]

Embedded image

[0044]

Embedded image

[0045]

Embedded image

[0046]

Embedded image

[0047]

Embedded image

[0048]

Embedded image

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 thermoplastic elastomer composition of the present invention comprises:
30 to 90% by weight of a thermoplastic copolyester elastomer and acrylic rubber: 70 to 10% by weight (total of 100
% By weight), preferably 30 to 80% by weight: 70 to 20% by weight. If the blending amount of the thermoplastic copolyester elastomer is too large, flexibility is impaired, which is not preferable.On the contrary, if the blending amount is too small, the mechanical strength decreases and the rubber phase becomes a matrix phase and the fluidity during extrusion processing is impaired. Is not preferred.

The thermoplastic elastomer composition according to the present invention contains, as a third component, a crosslinking agent compound having at least one of a carboxyl group and a carboxylic anhydride group as a carboxyl group in the molecule. Is preferred. 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 acid anhydrides include (partial) carboxylic acid anhydrides of these polycarboxylic acids.

The preferred amount of the crosslinking agent compound is 0.5 to 20 parts by weight per 100 parts by weight of the acrylic rubber component.
More preferably, it is 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.

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 has 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 allows the vulcanization of the rubber to proceed 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.

The 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 contain additives such as a reinforcing agent, 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 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 a thermoplastic elastomer composition is produced by such a production method, the relationship between the viscosity and the volume fraction of the thermoplastic elastomer to be 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 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 adhesive layer used between the reinforcing layer and the outer tube in the present invention particularly contains, in the present invention, the dicarboxylic acid constituting the polyester is an aromatic dicarboxylic acid.
A thermoplastic resin composition containing 50% by weight or more of a thermoplastic polyester copolymer resin having a Young's modulus at 20 ° C. of 3.0 MPa or more is selected and used. As such a thermoplastic polyester-based copolymer resin, terephthalic acid as an aromatic dicarboxylic acid, further containing isophthalic acid,
Block copolyetherester elastomers containing 1,4-butanediol as the diol and poly (tetramethylene ether) glycol as the long-chain ether glycol are particularly preferred. Regarding the hot Young's modulus of the thermoplastic polyester-based copolymer resin, those having a Young's modulus of 3.0 to 500 MPa measured at a temperature of 120 ° C. and a tensile speed of 500 mm / min can be preferably used,
Further, those having a pressure of 5.0 to 200 MPa can be more preferably used. If the hot Young's modulus is less than 3.0 MPa, the strength of the adhesive layer will be insufficient, and it will not be able to withstand the pressure during use. And this is 500MPa
In the case of a super hose, since the adhesive layer is rigid, the hose body is also rigid, which impairs flexibility. Furthermore, if the adhesive layer becomes too rigid, the ability to follow the deformation at the bonding interface with the outer tube will be poor, leading to breakage near the bonding interface.

Regarding the melt viscosity of the thermoplastic polyester copolymer resin used in the adhesive layer according to the present invention,
The melt viscosity measured at 0 ° C. and any one of the shear rates of 50 to 200 s ⁻¹ is preferably 1 to 1000 Pa · s, and more preferably 10 to 500 Pa · s. If the melt viscosity is less than 1 Pa · s,
The extrudability of the adhesive layer becomes worse and the impregnation property of the reinforcing layer becomes excessive, and the reinforcing layer performance is deteriorated due to the hardening of the reinforcing layer.
As the extrusion moldability of the adhesive layer deteriorates, the amount of impregnation into the reinforcing layer decreases extremely, and the adhesion to the reinforcing layer deteriorates.

As a method for forming the adhesive layer of the present invention, extrusion molding is preferably exemplified. In the extrusion molding, regarding the timing of forming the outer tube, (1) a method in which the outer tube is extruded simultaneously with the outer tube, and (2) a method in which the outer tube is extruded immediately after the adhesive layer is extruded (before the temperature of the adhesive layer returns to room temperature). , And (3) a method of once cooling and then extruding the outer tube after forming the adhesive layer, which can be formed by any method. However, from the balance of adhesiveness, dimensional stability and productivity, The method (2) is a more preferable method.

In order to manufacture the hose according to the present invention, first, a hose is prepared by using a thermoplastic elastomer composition obtained by dispersing a vulcanized product of acrylic rubber in the thermoplastic copolyester elastomer by known extrusion molding. After manufacturing an inner tube, applying an ordinary adhesive as necessary to the outer surface thereof, wrapping a reinforcing polyester fiber thereon in a braid or spiral form, and furthermore, a specific thermoplastic polyester-based copolymer resin according to the present invention. A general method of forming an adhesive layer by extrusion molding using the above method and immediately thereafter covering the outer tube again by the thermoplastic elastomer extrusion molding can be used. Of course, as described above, when manufacturing the outer tube, the adhesive layer and the outer tube may be simultaneously extruded, or the adhesive layer may be cooled once after extrusion, and then the outer tube may be extruded. May be adopted.
The thickness of the adhesive layer is not particularly limited, but is preferably 10 to 500 μm.

[0069]

EXAMPLES The present invention will be further described with reference to the following examples, but it goes without saying that the scope of the present invention is not limited to these examples.

Examples 1 to 8 and Comparative Examples 1 to 5 The inner tube, the adhesive layer, the reinforcing layer, the adhesive layer and the outer tube having an inner diameter of 9.5 mm having a structure (material and thickness) as shown in Table I,
A hose having an outer diameter of 17.5 mm was manufactured. Inner tube extrusion Using the inner tube material shown in Table I, an inner diameter of 9.
It was extruded into a hollow shape having a thickness of 5 mm and a thickness of 1.0 mm 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 shown in Table I was applied thereon, or a thermoplastic polyester-based copolymer resin shown in Table I 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. As the adhesive layer between the inner tube and the reinforcing layer, a Tylite 7411 moisture-curable urethane adhesive manufactured by Lord Far East Co., Ltd. was used. The urethane-based adhesive (Comparative Example 1) and the thermoplastic polyester-based copolymer resin (Comparative Examples 2 to 5 and Examples 1 to 5)
8) was used. The components of each composition used for the inner tube and the outer tube of Table I are as shown in Table II, and were manufactured as follows. First, a compounding agent other than the acrylic rubber and the vulcanizing agent was put into a closed rubber Banbury mixer for rubber and kneaded, and then formed into a sheet using a rubber roll, and then pelletized with a rubber pelletizer. . Then
The thermoplastic copolyester elastomer, the pelletized rubber, and the compatibilizer are charged into a twin-screw kneading extruder, and after kneading, the vulcanizing agent is continuously added thereto so that the thermoplastic copolyester elastomer and the compatibilizing agent are mixed. The rubber component dispersed as a domain in the matrix of the agent was dynamically vulcanized. The kneading conditions are, for example, a kneading temperature of 180 to 350 ° C., a residence time of 15 to 300 seconds in a part where dynamic vulcanization is performed, and a shear rate of 1000 to 8000 s ⁻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.

The physical properties (hardness, Young's modulus, and melt viscosity) of the adhesive layer shown in Table I were measured for the following test pieces based on the following measurement methods.

(Preparation of Specimen) The pellets of the thermoplastic elastomer composition were molded 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 molding machine. did.

(Measurement Method) A test piece having a JIS standard No. 3 dumbbell shape (JIS K6251) was prepared by a punching machine. About the obtained test piece, based on JIS standard,
The Young's modulus at 120 ° C. and type D durometer hardness (Shore D; JIS K 6253) were measured. The melt viscosity was measured by a capillary rheometer at a measurement temperature of 230 ° C., a shear rate of 122 s ⁻¹ , and an orifice diameter of 1 m.
m, capillary length 10 mm.

After these hoses were manufactured, fittings were attached to both ends of the hoses, and the hoses were subjected to an impulse durability test within a predetermined time shown in Table I as follows.

Impulse Test / Evaluation A test is performed in accordance with SAEJ188 type 1. Auto multi oil (Idemitsu), 60 at 120 ° C, pressure 27.5MPa
Give the impulse ten thousand times, and confirm whether the bracket has been removed or the main body has been broken. The evaluation criterion was set to 400,000 times, and a case where there was no abnormality was judged to be acceptable.

The results obtained are shown in Table I.

[0077]

[Table 1]

[0078]

[Table 2]

[0079]

[Table 3]

The following can be understood from the above results. Comparative Example 1 Comparative Example 1 is a hose made of a urethane-based room-temperature and moisture-curable adhesive which is conventionally used. It has not reached the endurance target number of 400,000 times, and the desired performance has not been obtained.

Comparative Examples 2 to 3 and Examples 1 to 7 Comparative Examples 2 to 3 are hoses using a thermoplastic polyester copolymer resin for the adhesive layer, and the dicarboxylic acid constituting the polyester is replaced by an aliphatic dicarboxylic acid. 120 ° C
Since the Young's modulus of the adhesive layer is less than 3.0 MPa, the adhesive layer is inferior in heat-resistant softening property, and metal fittings come off early and desired performance cannot be obtained. In Examples 1 to 7, the dicarboxylic acid constituting the polyester was an aromatic dicarboxylic acid, and the Young's modulus at 120 ° C. was 3.0 MPa or more. This is an example, and the desired number of durability is reached, and the desired performance is satisfied. From the comparison between the comparative example and the example, the dicarboxylic acid constituting the polyester is an aromatic dicarboxylic acid,
It can be seen that when the Young's modulus is 3.0 MPa or more, a desired hose endurance can be obtained. 230 ° C,
The melt viscosity at 122 s ^-1 was 1000 Pa · s or less in each case, and the effect of impregnating the reinforcing layer was obtained.

Example 8 and Comparative Examples 4 and 5 Examples 8 and Comparative Examples 4 and 5 were obtained by blending a thermoplastic urethane elastomer with the thermoplastic polyester copolymer resin of Example 7; The Young's modulus at 120 ° C. tends to decrease with an increase in the amount of the elastomer blended.
Despite the Young's modulus at 3.0 ° C or higher being 3.0 MPa or more, the content of the thermoplastic polyester-based copolymer resin is less than 50% by weight. The desired performance is not obtained due to the loss. On the other hand, according to Example 8, it can be seen that the same system satisfies the desired performance if the content of the thermoplastic polyester copolymer resin is 50% by weight or more. The melt viscosity at 230 ° C. and 122 s ⁻¹ was 1
000 Pa · s or less, and the effect of impregnating the reinforcing layer is obtained.

Among the examples, Examples 5 to 8 are more preferable examples. That is, it has a Young's modulus at 120 ° C. of 3.0 MPa or more, contains 50% by weight or more of a thermoplastic polyester-based copolymer resin, and further comprises an aromatic dicarboxylic acid and a diol. (Examples 2 and 3 have less than 40 mol%). Examples 1 and 4 also show more preferable ranges of the Young's modulus and the melt viscosity, respectively. That is, in Example 1, the Young's modulus at 120 ° C. was 5.0 MPa.
In Example 4, the melt viscosity at 230 ° C. and 122 s ⁻¹ was more than 500 Pa · s.

[0084]

As described above, according to the present invention,
A composition comprising a thermoplastic copolyester elastomer and an acrylic rubber is used for the inner tube and the outer tube, and the reinforcing layer is made of polyester fiber, and the dicarboxylic acid constituting the polyester is aromatic between the reinforcing layer and the outer tube. By disposing a thermoplastic resin composition containing 50% by weight or more of a thermoplastic polyester-based copolymer resin having a Young's modulus at 120 ° C. of 3.0 MPa or more as an aromatic dicarboxylic acid as an adhesive layer, oil resistance, It is possible to obtain a hose which is excellent in flexibility, heat resistance against cold and heat, and also has high durability in heat hardening property and heat aging resistance. Therefore, the hose according to the present invention is particularly useful as a hose for high pressure fluids and the like.

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

Claims (3)

[Claims] At least an inner tube, a reinforcing layer, and an outer tube are provided,
The inner tube has a structure in which vulcanized rubber particles of an acrylic rubber composition containing an acryl group and an epoxy group are dispersed in a matrix of a thermoplastic copolyester elastomer.
0 to 90% by weight, the vulcanized rubber component of the acrylic rubber is 7
A thermoplastic elastomer composition containing 0 to 10% by weight, wherein the reinforcing layer is made of polyester fiber, and the outer tube is made of an acrylic rubber containing an acrylic group and an epoxy group in a matrix of a thermoplastic copolyester elastomer. A structure in which the vulcanized rubber particles of the composition are dispersed,
30 to 30 parts of the thermoplastic copolyester elastomer component
90% by weight, 70% by weight of the vulcanized rubber component of the acrylic rubber
A thermoplastic elastomer composition containing 10% by weight, wherein at least a hose in which an adhesive layer is disposed between the reinforcing layer and the outer tube, wherein the dicarboxylic acid constituting the polyester is an aromatic dicarboxylic acid; And 120
A hose comprising a thermoplastic resin composition containing 50% by weight or more of a thermoplastic polyester copolymer resin having a Young's modulus at 3.0 ° C. of 3.0 MPa or more. 2. The thermoplastic polyester copolymer resin in the adhesive layer has a temperature of 230 ° C. and a shear rate of 50 to 200 s.
Melt viscosity at any shear rate of ^-1 is 1000 Pa
The hose according to claim 1, which is not more than s. 3. The thermoplastic polyester copolymer resin in the adhesive layer comprises a repeating unit of a polyester and a polyether or a repeating unit of a polyester and a polyimide ether.
3. The hose according to claim 1, which is a thermoplastic block copolyester elastomer containing 0 mol% or more.