JPH10231963A - Hose consisting of brass-plated wire reinforcing layer and thermoplastic elastomer composition and manufacture thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hose and its manufacturing method, in which an inner, outer pipe, and a reinforcing layer are adhered strongly, which has a good durability and high flexibility, and excels in these traits even with a high pressure. SOLUTION: A hose is composed of an inner pipe 2, at least one reinforcing layer 3, and an outer pipe 4, wherein the inner pipe 2 and outer pipe 4 contain a thermoplastic elastomer composition consisting of a dispersion of elastomer component at least part of which is bridged in a thermoplastic resin, and the reinforcing layer 3 is made from brass-plated wires, and maleic acid denatured polyolefin thermoplastic resin is set between the reinforcing layer 3 and inner pipe 2 and between the layer 3 and outer pipe 4.

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 strong bond between a thermoplastic elastomer composition and a brass-plated wire reinforcing layer, and having excellent durability and flexibility.

[0002]

2. Description of the Related Art A plastic hose in which an inner tube, a reinforcing layer, and an outer layer are laminated in this order in a tubular shape. The inner tube is made of a resin such as nylon, polyester elastomer, polyacetal, urethane, etc. A plastic hose having a polyolefin resin layer having a functional group between each layer using a galvanized hard steel wire or the like is disclosed in
No. 97948. In addition, a steel wire whose surface has been treated with a triazine thiol derivative to improve corrosion resistance and adhesion to rubber,
It is disclosed in Japanese Patent Publication No. 7-122225. However, heretofore, there is no known example in which these techniques have been applied to a thermoplastic elastomer composition in which a crosslinked elastomer is dispersed in a thermoplastic resin. On the other hand, a wire-reinforced plastic hose having two layers of wire reinforcing layers sandwiching an adhesive sheet or a synthetic resin sheet coated with an epoxy resin or the like between the inner layer of the hose and the outer jacket. A method for manufacturing a wire-reinforced plastic hose for bonding a wire to a bonding sheet and a jacket is disclosed in Japanese Patent Application Laid-Open No. 54-159468. These hoses are hoses using resins such as nylon, polyester, and polyurethane for the inner and outer tubes,
Further, the present invention is a manufacturing method for such a resin hose. However, hoses using nylon, polyester, polyurethane or the like have insufficient flexibility and durability. Until now, a wire reinforced hose using a thermoplastic elastomer composition in which a crosslinked elastomer is dispersed in a thermoplastic resin has not been known, and a wire reinforced hose using a flexible and highly durable thermoplastic resin has been known. Development is desired.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to firmly adhere an inner tube, an outer tube and a reinforcing layer, to provide good durability and high durability. An object of the present invention is to provide a hose having flexibility and excellent in these properties even under high pressure, and a method for producing the hose.

[0004]

That is, the present invention relates to a hose having an inner tube, at least one reinforcing layer, and an outer tube, wherein the inner tube and the outer tube have at least the thermoplastic resin contained therein. A thermoplastic elastomer composition comprising a partially crosslinked elastomer component dispersed therein, wherein the reinforcing layer is a brass-plated wire, between the reinforcing layer and the inner tube, and between the reinforcing layer and the outer tube. And a hose having a maleic acid-modified polyolefin-based thermoplastic resin.

[0005] It is preferable that the brass-plated wire is a brass-plated wire treated with a sulfur-containing triazine compound.

Further, in the method of manufacturing a hose, after covering the reinforcing layer, the brass-plated wire is heated by high-frequency induction heating to bond the maleic acid-modified polyolefin-based thermoplastic resin to the brass-plated wire. Provided is a method for manufacturing a hose.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The hose of the present invention is a hose having at least an inner tube, a reinforcing layer, and an outer tube, and each layer is joined by an adhesive layer. The inner pipe and the outer pipe may each be formed in one or more layers, and the reinforcing layer may be in one layer or in multiple layers.
The hose of the present invention will be described based on one embodiment example shown in the accompanying drawings. FIG. 1 is an explanatory front view showing the hose of the present invention with each layer cut away. Hose 1
It has an inner pipe 2, a reinforcing layer 3, and an outer pipe 4, and has an adhesive layer 5 between the reinforcing layer and the inner pipe and between the reinforcing layer and the outer pipe.
6. The inner tube 2 and the outer tube 4 of the hose 1 of the present invention contain a thermoplastic elastomer composition in which an elastomer component at least partially cross-linked is dispersed in a thermoplastic resin. The bonding layers 5 and 6 between the inner tube and the outer tube and the reinforcing layer contain a maleic acid-modified polyolefin resin.

The thermoplastic elastomer composition contained in the inner tube 2 and the outer tube 4 is a thermoplastic elastomer composition obtained by crosslinking at least a part of an elastomer component obtained by dispersing an elastomer component in a thermoplastic resin matrix phase. There is no particular limitation as long as it exists.

As the thermoplastic resin used as the thermoplastic resin matrix phase, various thermoplastic resins or compositions thereof can be used. That is, it may be a single thermoplastic resin or composition, or a composition comprising a mixture thereof. Specifically, polyolefin-based resins (for example, high-density polyethylene (HDPE), ultra-high molecular weight polyethylene (UHMWP)
E), isotactic polypropylene, syndiotactic polypropylene, ethylene propylene copolymer resin), polyamide resin (for example, nylon 6 (N
6), nylon 66 (N66), nylon 46 (N4
6), nylon 11 (N11), nylon 12 (N1
2), nylon 610 (N610), nylon 612
(N612), nylon 6/66 copolymer (N6 / 6
6), nylon 6/66/610 copolymer (N6 / 66
/ 610), nylon MXD6 (MXD6), nylon 6T, nylon 6 / 6T copolymer, nylon 66 / PP
Copolymer, nylon 66 / PPS copolymer), polyester resin (for example, polybutylene terephthalate (P
BT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), PET / PEI copolymer, polyarylate (PAR), polybutylene naphthalate (PBN), liquid crystal polyester, polyoxyalkylenediimide diacid / polybutyrate Aromatic polyesters such as terephthalate copolymer), polynitrile resins (eg, polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile / styrene copolymer (AS), methacrylonitrile / styrene copolymer, methacrylonitrile / Styrene / butadiene copolymer), polymethacrylate resins (eg, polymethyl methacrylate (PMMA), polyethyl methacrylate), polyvinyl resins (eg, vinyl acetate (EV)
A), polyvinyl alcohol (PVA), vinyl alcohol / ethylene copolymer (EVOH), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinyl chloride / vinylidene chloride copolymer, vinylidene chloride / methyl acrylate copolymer Coalesce), cellulosic resin (eg, cellulose acetate, cellulose acetate butyrate), fluororesin (eg, polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polychlorofluoroethylene (PCTFE), tetrafluoroethylene / ethylene) Copolymer (ETFE)), imide-based resin (for example, aromatic polyimide (PI)), thermoplastic elastomer (for example, styrene-based elastomer, olefin-based elastomer, polyester-based elastomer, urethane-based elastomer) and the like. Door can be.

[0010] The elastomer component dispersed in the thermoplastic resin matrix phase is at least partially crosslinked. As the elastomer component, diene rubbers and hydrogenated products thereof (for example, N
R, IR, epoxidized natural rubber, SBR, BR (high cis BR and low cis BR), NBR, hydrogenated NBR, hydrogenated SBR), olefin rubber (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), halogen-containing rubber (for example, Br)
-IIR, Cl-IIR, bromide of isobutylene paramethylstyrene copolymer (Br-IPMS), CR, hydrin rubber (CHR), chlorosulfonated polyethylene (CSM), chlorinated polyethylene (CM), maleic acid-modified chlorination Polyethylene (M-CM), silicone rubber (eg, methyl vinyl silicone rubber, dimethyl silicone rubber, methyl phenyl vinyl silicone rubber), sulfur-containing rubber (eg, polysulfide rubber), fluoro rubber (eg, vinylidene fluoride rubber, fluorine-containing rubber) Vinyl ether rubber, tetrafluoroethylene-propylene rubber, fluorine-containing silicon rubber, fluorine-containing phosphazene rubber), thermoplastic elastomer (for example, styrene-based elastomer, olefin-based elastomer, ester-based elastomer, Urethane-based elastomer, polyamide-based elastomer) and the like.

In particular, olefin-based rubbers (compositions) such as EPM-based rubbers and EPDM-based rubbers (or rubber compositions containing them) are kneaded at the time of kneading by the method for producing the thermoplastic elastomer composition of the present invention described below. It is suitably used for reasons such as good thermal stability at the time of molding such as extrusion molding and injection molding using the thermoplastic elastomer composition of the present invention. Among them, EPM and / or EPDM which are binary or ternary copolymers having ethylene and propylene or some diene components such as dicyclopentadiene, ethylidene norbornene and 1,4-hexadiene, and furthermore, Maleic acid-modified EPM and / or EPDM obtained by modifying EPM and / or EPDM with maleic anhydride or the like can be suitably used. Specifically, Mitsui Petrochemical Company's Mitsui EPT4
070 etc. can be used.

[0012] The elastomer component in the thermoplastic elastomer composition of the present invention is at least partially crosslinked. The method of crosslinking the elastomer component is as follows:
The method is not particularly limited, and may be according to a conventionally known method.For example, a thermoplastic resin component and an elastomer component containing no crosslinking agent are melt-kneaded in a twin-screw kneading extruder or the like, and the elastomer is contained in the thermoplastic resin matrix phase. It can be formed by adding a crosslinking agent for crosslinking the elastomer component while dispersing the component as a disperse phase (domain) and dynamically crosslinking during kneading. In addition, as the dynamic crosslinking, in addition to the above method, a crosslinking is performed at a temperature of 150 to 300 ° C. using a crosslinking agent such as a sulfur-based, organic peroxide-based, metal oxide-based, phenolic resin, or quinone dioxime. You can also.

The type of the crosslinking agent and the dynamic crosslinking conditions (temperature and time) may be appropriately determined according to the composition of the elastomer component, and are not particularly limited. As the crosslinking agent, those described above can be used. More specifically, as the sulfur-based crosslinking agent, powdered sulfur, precipitated sulfur, highly dispersible sulfur, surface-treated sulfur, insoluble sulfur, dimorpholine Examples thereof include sulfide and alkylphenol disulfide. The addition amount is, for example, elastomer 100
About 0.5 to 4 parts by weight based on parts by weight may be used.
Further, as the organic peroxide-based crosslinking agent, benzoyl peroxide, t-butyl hydroperoxide, 2,2
4-dichlorobenzoyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane,
Examples thereof include 2,5-dimethylhexane-2,5-di (peroxyl benzoate).
About 1 to 15 parts by weight may be used for 00 parts by weight. Further, examples of the phenolic resin-based crosslinking agent include brominated alkylphenol resins, and mixed cross-linking systems containing a halogen donor such as tin chloride and chloroprene and an alkylphenol resin. About 1 to 20 parts by weight may be used. In addition, zinc white (about 5 parts by weight), magnesium oxide (about 4 parts by weight), litharge (about 10 to 20 parts by weight), p-quinonedioxime, p-dibenzoylquinonedioxime, tetrachloro-p- Benzoquinone, poly-p-dinitrosobenzene (about 2 to 10 parts by weight),
Methylene dianiline (about 0.2 to 10 parts by weight) is exemplified.

[0014] If necessary, a crosslinking accelerator may be added. Examples of the crosslinking accelerator include general crosslinking accelerators such as aldehyde / ammonia, guanidine, thiazole, sulfenamide, thiuram, dithioate, and thiourea. It is sufficient to use about parts by weight.

Specifically, hexamethylenetetramine or the like is used as the aldehyde / ammonia-based crosslinking accelerator; diphenylguanidine is used as the guanidine-based crosslinking accelerator; dibenzothia is used as the thiazole-based crosslinking accelerator. Zirdisulphide (DM), 2-mercaptobenzothiazole and its Zn salt, cyclohexylamine salt 2
-(4'-morpholinodithio) benzothiazole and the like;
Examples of sulfenamide-based crosslinking accelerators include cyclohexylbenzothiazolylsulfenamide CBS), N-
Oxydiethylene benzothiazolyl-2-sulfenamide, Nt-butyl-2-benzothiazolylsulfenamide, 2- (thymopolynyldithio) benzothiazole and the like; , Tetramethyl thiuram disulfide (TMTD), tetraethyl thiuram disulfide, tetramethyl thiuram monosulfide (TMTM), dipentamethylene thiuram tetrasulfide, and the like; dithioate-based crosslinking accelerators include Zn-dimethyl dithiocarbamate; Zn-diethyldithiocarbamate, Zn-di-n-butyldithiocarbamate, Zn-ethylphenyldithiocarbamate, Te-diethyldithiocarbamate, Cu-dimethyldithiocarbamate, Fe-dimethyldithiocarbamate, pipecoli Pi Pekori Le dithiocarbamate and the like. Examples of the thiourea-based vulcanizing Bridge accelerator, ethylene thiourea, diethyl thiourea and the like; are disclosed, respectively.

As the bridging accelerating auxiliary, a general rubber auxiliary can be used in combination. For example, zinc white (about 5 parts by weight), stearic acid, oleic acid and Zn salts thereof ( About 2 to 4 parts by weight).

[0017] In addition to the above, the elastomer component needs an antioxidant, an antioxidant, an ultraviolet absorber, a coloring agent such as a pigment or a dye, another plasticizer, and a reinforcing agent such as carbon black or silica. May be included according to In addition, various compounding agents (excluding a crosslinking agent) to the thermoplastic resin component and the elastomer component may be added during kneading of the thermoplastic resin component and the elastomer component, or may be previously mixed before kneading. Good.

The ratio of the thermoplastic resin component forming the thermoplastic resin matrix phase of the thermoplastic elastomer composition to the elastomer component is not particularly limited, but is preferably based on the weight of the thermoplastic resin. Is 10 to 90% by weight. When the blending amount of the thermoplastic resin is large, the flexibility of the obtained thermoplastic elastomer composition is reduced. On the other hand, if the amount is too small, the melt fluidity of the thermoplastic elastomer composition decreases, and molding processing becomes difficult. If the amount is too small, the thermoplastic resin component as a continuous phase contains the elastomer as a dispersed phase (domain). The components cannot be physically wrapped and tend to be difficult to knead.

The thermoplastic elastomer composition may contain a petroleum softener and a plasticizer generally called process oil or extender oil. Petroleum softeners are used to reduce the viscosity of the polymer used during processing, reduce the hardness of the crosslinked or processed product, or control physical properties such as high and low temperature properties. Petroleum-based softeners are obtained by refining heavy oils, and are roughly classified into alkylaromatic oils, alkylnaphthenic oils, and paraffinic oils depending on the contained components, and have compatibility with the polymer used. Depending on the type of the thermoplastic resin component and the elastomer component, a suitable one of these or a mixture thereof may be used. In addition, as one embodiment of the process oil, generally, high-boiling esters or liquid compounds similar to a polymer having a chemical structure can be suitably used as a plasticizer used for rubber and thermoplastic resin.

These plasticizers are so-called phthalate plasticizers such as dioctyl phthalate (DOP), dibutyl phthalate (DBP), diisodecyl phthalate (DIDP), diisononyl phthalate (DINP), dioctyl adipate (DOP); Epoxidized plasticizers such as epoxidized soybean oil and epoxidized fatty acid esters; and chlorinated plasticizers such as chlorinated fatty acid esters and chlorinated paraffins; and tricresyl phosphate (TCP); Phosphoric plasticizers such as tri-β-chloroethyl phosphate (TCEP); adipic plasticizers such as dioctyl adipate (DOA) and didecyl adipate (DDA); and sebacic plasticizers such as dibutyl sebacate (DBS). An azelaic acid such as dioctyl azelate (DOZ) Plasticizer; triethyl citrate (T
A citric acid plasticizer such as EC); and a polyester plasticizer such as polypropylene and adipate (PPA) can be suitably used individually or in a blended state. It is not particularly limited as long as it is a plasticizer having heat resistance, a softener,
Preferably, the weight loss on heating shown in JIS K6220 is 10
A low-volatility plasticizer and a softener of 1% or less at 0 ° C. for 3 hours are preferable as exhibiting good hot-time characteristics. As the softener and plasticizer exhibiting such properties, any of the above softeners and plasticizers may be used as long as they satisfy the above-mentioned heating loss, and particularly preferably, high-boiling aroma softeners and paraffin-based softeners. Softener Naphthenic softener, DIDP, DT
Phthalate plasticizers such as DP, epoxy plasticizers such as epoxidized soybean oil, and phosphate plasticizers such as TCEP can be suitably used.

The above process oil can be added in an amount of 5 to 100 parts by weight, preferably 5 to 80 parts by weight, based on 100 parts by weight of the sum of the thermoplastic resin component and the elastomer component. If the amount is less than 5 parts by weight, sufficient flexibility cannot be obtained and 1
If the amount is more than 00 parts by weight, mixing with the thermoplastic resin component and the elastomer component becomes difficult.

In addition to the above constitution, for example, when the thermoplastic resin component and the elastomer component have different compatibility in the thermoplastic elastomer composition of the present invention, both may be made compatible with each other by using a compatibilizer. By mixing the compatibilizer into the system, the interfacial tension between the thermoplastic resin component and the elastomer component is reduced, and as a result, the particles of the elastomer dispersed phase become finer, so that the properties of both components are more effectively expressed. Will be. Such a compatibilizer is generally a copolymer having a structure of both or one of a thermoplastic resin component and an elastomer component, or an epoxy group, a carbonyl group, a halogen group, an amino group capable of reacting with the thermoplastic resin component or the elastomer component. The copolymer may have a structure having a group, an oxazoline group, a hydroxyl group and the like. These may be selected according to the kind of the thermoplastic resin component or the elastomer component to be mixed, and those usually used include styrene-ethylene-butylene block copolymer (SEBS) and its maleic acid modified product, E
Modified maleic acid of PM and EPDM, EPDM / styrene or EPDM / acrylonitrile graft copolymer and its maleic acid modified product, styrene / maleic acid copolymer, reactive phenoxy resin and the like can be mentioned.

The thermoplastic elastomer composition may further include a vulcanization accelerator, an antioxidant, an antioxidant, an ultraviolet absorber, a coloring agent such as a pigment or a dye, another plasticizer, a carbon black, A reinforcing agent such as silica and a processing aid may be added and kneaded as necessary.

A brass-plated wire is used for the reinforcing layer in the hose of the present invention. The brass-plated wire can be formed by braiding, for example, into a blade shape or a spiral shape. The brass-plated wire of the reinforcing layer is preferably treated with a sulfur-containing triazine compound represented by the following formula.

[0025]

Embedded image

Wherein R is -OR ', -SR', -NH
R ′, —N (R ′) ₂ , R ′ is H, an alkyl group, an alkenyl group, a phenyl group, a phenylalkyl group, an alkylphenyl group, or a cycloalkyl group;
Li, K, 1 / 2Mg, 1 / 2Ba, 1 / 2Ca, aliphatic primary, secondary or tertiary amine, quaternary ammonium salt, or phosphonium salt. Specifically, 1,
3,5-triazine-2,4,6-trithiol, 1,
3,5-triazine-2,4,6-trithiol diethanolamine, 6-dibutylamino-1,3,5-triazine-2,4-dithiol, 6-dibutylamino-
Examples thereof include 1,3,5-triazine-2,4-dithiol / monoethylenediamine, 6-dibutylamino-1,3,5-triazine-2,4-dithiol / monoethanolamine and the like.

When the surface of the brass-plated wire is treated with the above sulfur-containing triazine compound, the corrosion resistance of the wire,
And the adhesion to the elastomer composition is improved. A method of treating the surface of a brass-plated wire with the above sulfur-containing triazine compound (hereinafter referred to as triazine treatment)
Is not particularly limited, and may be according to a conventionally known method disclosed in Japanese Patent Publication No. 7-122225 or the like. For example, a method of drawing a wire in a lubricant containing a sulfur-containing triazine compound, a method of immersing a wire and a counter electrode in a solution of a sulfur-containing triazine compound, and applying a voltage between the two can be exemplified.

The hose of the present invention has an adhesive layer containing a maleic acid-modified polyolefin-based thermoplastic resin between the reinforcing layer and the inner tube and between the reinforcing layer and the outer tube. When there are a plurality of reinforcing layers for improving the hose durability, at least one of the reinforcing layers may be provided with an adhesive layer containing the maleic acid-modified polyolefin-based thermoplastic resin of the present invention. Here, as the polyolefin resin to be modified, for example, polypropylene resin (PP) such as isotactic, syndiotactic or random or block copolymer with ethylene or the like,
High density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (L-LDP
E) and other general polyolefin resins such as an ethylene-ethyl acrylate copolymer (EEA) and an ethylene-methyl acrylate copolymer (EMA) can be used.

The method for modifying these polyolefin resins with maleic acid or maleic anhydride is not particularly limited, and can be carried out by a conventionally known method. Using an extruder or a twin-screw kneading extruder, it can be obtained by adding and kneading maleic acid, or further maleic anhydride and peroxide to polypropylene, and performing a grafting reaction. The maleic acid modification rate is preferably 0.1 to 10% by weight in terms of maleic acid groups.

In order to obtain a suitable adhesion in the present invention, 1
It is preferably a maleic acid-modified resin of a polyethylene resin having a melt index of 30 g / 10 minutes or less measured at 90 ° C., a load of 2.16 kgf, an orifice diameter of 1 mm, and a measurement time of 10 minutes.
More preferably, it is 0.5 / 10 minutes.

As the adhesive layer of the present invention, a resin obtained by blending an epoxy-modified polyolefin-based resin and a polyester-based resin in addition to the maleic acid-modified polyolefin-based thermoplastic resin can be used. It can be appropriately determined within a range where the effect as the polyolefin-based thermoplastic resin is not impaired.

Next, a method for manufacturing a hose according to the present invention will be described with reference to an embodiment shown in the accompanying drawings. FIG.
FIG. 1 is a schematic diagram showing an outline of a hose manufacturing process of the present invention. The hose of the present invention can be manufactured, for example, as follows. That is, as shown in FIG. 2, a thermoplastic elastomer composition for an inner tube is bonded from an extruder 8 for an inner tube onto a mandrel 7 to which a release agent is applied in advance, and an extruder 9 for an adhesive is further bonded thereon. The layers are simultaneously extruded in two layers and formed into a tube shape in the inner tube forming die 10 to form the inner tube 11. At this time, after extruding the inner tube in advance,
The adhesive layer may be extruded on the inner tube. Next, the inner tube 1
1 and the reinforcing layer 13 on the adhesive layer using the reinforcing layer forming machine 12.
The reinforcing layer 13 is formed by braiding a plurality of brass-plated wires into a spiral shape or a blade shape. The brass-plated wire is preferably treated with a sulfur-containing triazine compound before braiding. When this triazine treatment is performed, the corrosion resistance of the wire and the adhesiveness of the wire to the elastomer composition are further increased. Next, high frequency is applied to the hose on which the reinforcing layer 13 has been formed by the high frequency induction heating device 14, and the reinforcing wire of the reinforcing layer 13 is locally heated for 0.1 to 5 seconds. At this time, the reinforcing layer 13 made of brass-plated wire is
It is heated to 350 ° C. to melt the adhesive layer, and it is possible to make a sufficient bond. In addition, the heating of the wire of the reinforcing material can be performed not only by induction heating using a high-frequency furnace, but also by hot air heating or infrared heating. When the heat treatment is performed, the bonding layer and the wire are sufficiently bonded, and the durability of the hose is improved. In particular, when high-frequency induction heating is performed, only the surface of the adhesive layer that is in contact with the wire can be partially melted, and the reinforcing layer 13 and the adhesive layer can be physically and chemically firmly adhered to each other. Less deterioration. Furthermore, since the melting by heating is performed instantaneously, there is an advantage that the working efficiency is high. Finally, on the sufficiently heated reinforcing layer 13, similarly to the inner tube, an adhesive layer from the extruder for adhesive 16 is provided, and on the extruder 17 for the outer tube material, a thermoplastic elastomer composition for the outer tube is provided. Are simultaneously extruded in two layers to form an outer tube forming die 1
The outer tube 18 is formed in the shape of a hose in 5.
At the time of forming the outer tube, the outer layer 18 may be formed by first extruding the adhesive layer, and then extruding the thermoplastic elastomer composition for the outer tube. Further, in FIG. 2, the high-frequency induction heating of the brass-plated wire reinforcing layer 13 is performed before the outer tube 18 is formed. The adhesive layers are firmly bonded. By removing the mandrel 7 after forming the hose in this way, a desired hose is obtained.

The hose of the present invention obtained by the above-described manufacturing method has the following characteristics. In the method for producing a hose of the present invention, a post-vulcanization step is not necessary as in a hose such as a normal rubber hose, so that the production step can be simplified and is simpler than the production of a rubber hose. Since a post-vulcanization step is unnecessary, there is no shrinkage deformation due to heat during heating, and the dimensions of the hose can be easily maintained. Since a flexible thermoplastic elastomer composition is used for the inner pipe and the outer pipe instead of plastic, a flexible hose can be obtained even if a hard wire blade is used as a reinforcing layer. Since the maleic acid-modified polyolefin-based thermoplastic resin is used for the adhesive layer, the bonding between the inner tube and the outer tube and the reinforcing layer is strong, and the durability is excellent. The durability of the hose is improved by using a brass-plated wire having a higher strength than a conventionally used galvanized wire for the reinforcing layer. Furthermore, by treating the surface of the brass-plated wire with the sulfur-containing triazine compound, the corrosion resistance of the wire, the adhesion of the wire to the inner tube and the outer tube, and the durability of the hose are further improved. After the reinforcing layer is formed or after the outer tube is formed, the adhesive layer is heated, but by selecting high-frequency induction heating, heat is repelled or lost on the wire surface compared to heating methods such as infrared heating and hot air heating. Without heating, the adhesive layer can be heated and workability is good. In addition, the heating of the adhesive layer can be uniform.

Accordingly, the hose of the present invention can be used as a high-pressure hose that requires durability under long-term use in a high-temperature and high-pressure environment. For example, oil-resistant hoses for construction machinery and automobiles, power steering hoses, water It can be used as a jet hose or the like.

[0035]

The present invention will be described in more detail with reference to the following examples. Preparation of Thermoplastic Elastomer Using the rubber composition, thermoplastic copolyester elastomer, compatibilizer and crosslinking agent, the thermoplastic elastomer composition (ACM / ACM /
COPE). In the table, the unit is [parts by weight].

[0036] 1) Hytrel 5556, manufactured by DuPont 2) ACM / stearic acid / FEF grade carbon black / anti-aging agent (Irganox 1010, manufactured by Nippon Ciba Geigy) = 100/2/40 / 3.3 (weight ratio) 3) Butane Tetracarboxylic acid, manufactured by Mitsui Toatsu Fine 4) Bond First 7L, manufactured by Sumitomo Chemical

The rubber composition is prepared by putting ACM, stearic acid, carbon black and an antioxidant into a closed rubber Banbury mixer for rubber and kneading the mixture. It was made into a pellet with a pelletizer. Next, the thermoplastic copolyester elastomer, the rubber pellets, and the compatibilizer
After being charged into a shaft kneading extruder and sufficiently kneaded, a rubber component dispersed as a domain in a matrix composed of a thermoplastic copolyester elastomer was dynamically crosslinked by continuously charging a crosslinking agent. The kneading conditions are as follows: at a kneading temperature of 250 ° C. and a shear rate of 1000 sec ⁻¹ , after the completion of the dynamic crosslinking, continuously discharge the strand from the twin-screw kneading extruder, cool with water, and use a cutter to obtain a length of about 3 mm (diameter about 2mm)
To obtain a pelletized thermoplastic elastomer composition.

Preparation of Hose (Example 1) A thermoplastic elastomer composition (ACM / COPE) in which an acrylic rubber cross-linked to a copolymerized polyester resin prepared by the above method is dispersed, and an adhesive are placed on a polyester mandrel. Two layers were extruded to form an inner tube (9.5 mm in inner diameter), on which a brass-plated wire (0.25 mm in diameter) was braided to form a reinforcing layer, which was heated by infrared rays. . The heating temperature by infrared rays was 140 ° C., and the line speed was 0.5 m / min. Further, a thermoplastic elastomer composition (EPDM / PP, Santoprene 101) in which an adhesive and a partially crosslinked ethylene-propylene-diene copolymer rubber in a polypropylene resin are dispersed on the heated reinforcing layer.
-73, manufactured by AES Co., Ltd.
6.9 mm). Note that a maleic acid-modified polypropylene resin was used for the adhesive layer between the inner tube and the reinforcing layer and between the outer tube and the reinforcing layer.

Example 2 A thermoplastic elastomer composition (NBR / PP, in which acrylonitrile-butadiene rubber partially cross-linked to polypropylene resin is dispersed in an inner tube
A hose was produced in the same manner as in Example 1 except that Geolast 701-70, manufactured by AES was used. (Example 3) The same NBR /
A hose was prepared in the same manner as in Example 1, except that the PP elastomer composition was used, the maleic acid-modified high-density polyethylene (HDPE) resin was used for the adhesive layer, and induction heating was performed using a high-frequency furnace as a heating method. The high-frequency furnace had a secondary power of 15 kw, a heating temperature of 180 ° C., and a line speed of 5 kW.
m / min.

(Example 4) The same NBR / PP elastomer composition as used in Example 2 was used for the inner tube, and the maleic acid-modified linear low density polyethylene (LLDPE) was used for the adhesive layer.
Using a resin, except for performing hot air heating as a heating method,
A hose was produced in the same manner as in Example 1. The heating temperature by hot air heating was 120 ° C., and the line speed was 1 m / min. (Example 5) The same NBR /
A hose was produced in the same manner as in Example 1, except that a brass-plated wire treated with a triazine was used for the reinforcing layer using the PP elastomer composition. (Example 6) In the same manner as in Example 5, except for heating the reinforcing layer, induction heating was performed at a secondary power of 15 kw and a line speed of 5 m / min. The durability and bending hardness of the obtained hose were almost the same as those of Example 5, but the induction heating of Example 6 was bonded in 1/10 of the time of the infrared heating of Example 5. Sufficient adhesion between the reinforcing layer and the other layers via the layer was obtained.

(Conventional Example 1) An inner tube (inner diameter: 9.5 mm) was extruded with acrylonitrile / butadiene rubber onto a mandrel, and then brass-plated wire (diameter: 0.25 m)
m) was braided into a blade to form a reinforcing layer. Thereafter, an outer tube made of chloroprene rubber (outer diameter of 16.9 m)
m) is extruded at 150 ° C. (20 kg / cm
² ) Vulcanization bonding was performed under the conditions of × 45 minutes.

Comparative Example 1 Nylon 11 (Rilsan BE)
(SNOTL, manufactured by Atochem) and extruding two layers of adhesive,
An inner tube (inner diameter: 9.5 mm) was formed, and then a zinc-plated wire (diameter: 0.25 mm) was braided into a braid to form a reinforcing layer. Thereafter, this was induction-heated in a high-frequency furnace in the same manner as in Example 3. Furthermore, an adhesive and polyurethane (Esten 58311, manufactured by Kyowa Hakko Co., Ltd.)
Were extruded in two layers to form an outer tube (outer diameter: 16.9 mm). Note that a maleic acid-modified polypropylene resin was used for the adhesive layer between the inner tube and the reinforcing layer and between the outer tube and the reinforcing layer. (Comparative Example 2) Brass-plated wire (diameter 0.2)
5 mm), and a hose was produced in the same manner as in Comparative Example 1 except that infrared heating was performed as a heating method.

(Comparative Example 3) A thermoplastic elastomer composition (NBR / PP) in which acrylonitrile / butadiene rubber partially crosslinked with a polypropylene resin is dispersed in an inner tube.
And using a thermoplastic elastomer composition (EPDM / PP) in which an ethylene-propylene-diene copolymer rubber partially cross-linked to a polypropylene resin was dispersed in the outer tube. Produced. (Comparative Example 4) The inner tube was filled with the NBR / PP elastomer composition as in Comparative Example 3, and the outer tube was filled with EPDM / PPDM as in Comparative Example 3.
A hose was produced in the same manner as in Comparative Example 1, except that the PP elastomer composition, the brass-plated wire for the reinforcing layer, and the polypropylene (PP) resin for the adhesive layer were used.

The resins used as the adhesive layer in the examples and comparative examples are as follows. PP: Tokuyama Corporation, RB121D maleic acid-modified PP; Mitsui Petrochemical Company, QB540 maleic acid-modified HDPE; Mitsui Petrochemical Company, HB50
0 Maleic acid-modified LLDPE; NB5 manufactured by Mitsui Petrochemical Co., Ltd.
50

The physical properties of the hoses manufactured in Examples 1 to 6, Conventional Example 1, and Comparative Examples 1 to 4 were measured and evaluated as follows. (1) Durability of hose The durability test was performed in accordance with SAE J188 type 1. Oil is auto-multi oil, temperature 100 ℃,
Impact pressure was repeatedly applied under the condition of a pressure of 140 kg / cm ² . The number of pressurizations for the hoses manufactured in Examples 1 to 6 and Comparative Examples 1 to 4 was determined assuming that the number of times until the abnormality occurred in the hose manufactured in Conventional Example 1 was 100. (2) Bending Hardness of Hose The hose was bent along an arc having a predetermined radius (bending radius), and the bending force (load required for bending) was measured.
The bending radius was measured from 10 times (10D) the hose radius, and the bending force was sequentially measured twice up to 3 times, and the average was taken. From the curve obtained by plotting the relationship between the bending force and the radius obtained as a result, the bending force at the specified radius (4 times, 4D) was read. Assuming that the bending force at the time of 4D of the hose manufactured in Conventional Example 1 is 100, Examples 1 to 6 and Comparative Examples 1 to 4
The bending force required for the hose manufactured in the above to deform similarly was shown as a relative value. Table 2 shows the results.

[0046]

[Table 1]

[0047]

[Table 2]

[0048]

According to the present invention, the inner tube and the outer tube of the hose contain a thermoplastic elastomer composition in which an elastomer component at least partially cross-linked is dispersed in a thermoplastic resin. Thereby, excellent flexibility is obtained as compared with the resin hose. Further, by using a maleic acid-modified polyolefin-based thermoplastic resin for the adhesive layer, a high adhesive strength is obtained, and the durability of the hose is improved. If brass-plated wire treated with triazine is used for the reinforcing layer,
Furthermore, if the high-frequency induction heating is performed as a heating method at the time of hose production, the bonding between the inner and outer tubes and the wire can be strengthened without taking much time, and the workability is high. .

[Brief description of the drawings]

FIG. 1 is a schematic view showing an example of the hose of the present invention.

FIG. 2 is a schematic view showing an example of a method for manufacturing a hose of the present invention.

DESCRIPTION OF SYMBOLS 1 Hose 2 Inner tube 3 Reinforcing layer 4 Outer tube 5, 6 Adhesive layer 7 Mandrel 8 Inner tube extruder 9 Adhesive extruder 10 Inner tube forming die 11 Inner tube 12 Reinforcing layer forming machine 13 Reinforcing layer 14 High-frequency induction heating device 15 Die for forming outer tube 16 Extruder for adhesive 17 Extruder for outer tube material 18 Outer tube

Continued on the front page (72) Inventor Jiro Watanabe 2-1 Oiwake, Hiratsuka-shi, Kanagawa Prefecture Yokohama Rubber Co., Ltd. Inside the Hiratsuka Factory (72) Inventor Tsuyoshi Kawaguchi 2-1 Oiwake, Hiratsuka-shi, Kanagawa Prefecture Yokohama Rubber Co., Ltd. (72) Inventor: Shigeru Yamauchi 2-1 Oiwake, Hiratsuka-shi, Kanagawa Yokohama Rubber Co., Ltd. Hiratsuka Factory

Claims (3)

[Claims] 1. A hose having an inner tube, at least one reinforcing layer, and an outer tube, wherein the inner tube and the outer tube have at least a part of a crosslinked elastomer component dispersed in a thermoplastic resin. Wherein the reinforcing layer is a brass-plated wire, and between the reinforcing layer and the inner tube, and between the reinforcing layer and the outer tube, a maleic acid-modified polyolefin-based thermoplastic resin. A hose comprising: 2. The hose according to claim 1, wherein said brass-plated wire is a brass-plated wire treated with a sulfur-containing triazine compound. 3. The method for manufacturing a hose according to claim 1, wherein the brass-plated wire is heated by high-frequency induction heating after coating the reinforcing layer, and the maleic acid-modified polyolefin-based thermoplastic resin and the brass wire are heated. A method for manufacturing a hose, comprising joining a plated wire.