JP2002079614A - Rubber/resin composite and low permeable hose using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a rubber/resin composite high in bonding strength and excellent in cooling medium impermeability, and a low permeable hose using the same. SOLUTION: The rubber/resin composite is obtained by bonding a rubber composition, which contains 1-30 pts.wt. of a phenolic resin with respect to 100 pts.wt. of a rubber crosslinkable by the phenolic resin, and a polyamide resin, which is a resin alone having an amide bond or a mixture of 90 wt.% or more of the resin having the amide bond and 10 wt.% or less of a polyolefinic resin and/or a polyester resin, by vulcanization. This rubber/resin composite is used in the production of the low permeable hose.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber / resin composite, and more particularly, to a rubber / resin composite having high bonding properties and excellent refrigerant permeation resistance, and low permeation using the same. It relates to a sex hose.

[0002]

2. Description of the Related Art In recent years, as a hose for transporting a refrigerant used in a car air conditioner or the like, a laminate of a resin and rubber, which is a combination of a resin material such as polyamide having low gas permeability and a rubber material, is generally used. It has come to be. In such a laminate of rubber and resin, if the adhesion between the rubber material and the resin material is poor, gas or liquid stays at the bonding interface, and the resin in that portion swells. Therefore, conventionally, it has been generally performed to use an adhesive or perform a surface treatment on a resin material. However, in order to obtain a good adhesion state, it is necessary to perform these treatments under certain conditions, which not only increases the number of working steps, but also makes continuous production of hoses difficult, resulting in high production costs. .

On the other hand, Japanese Patent Application Laid-Open No. 8-34886 discloses that a rubber component containing a modified polybutadiene obtained by graft polymerization of a monomer such as butyl rubber or halogenated butyl rubber or an unsaturated carboxylic acid is added to a vulcanized resin such as an alkylphenol formaldehyde resin. A rubber composition containing an agent, and a resin composition containing 90 to 50% by volume of a polyamide resin and 10 to 50% by volume of an ethylene / propylene / diene terpolymer obtained by modifying a monomer such as an unsaturated carboxylic acid by graft polymerization. It is disclosed that by vulcanizing, a laminate of rubber and resin can be obtained without using an adhesive or the like. The publication suggests that the commonality of the modified substances contained in the rubber material and the resin material may contribute to the adhesion. However, when the rubber composition is composed of multiple components as described above, there is a problem that the rubber properties are easily damaged after vulcanization. In addition, when the resin composition contains the above-mentioned modified product, there is a concern that the gas permeation resistance may decrease.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to a rubber which is capable of firmly joining a resin material having low gas permeability and a rubber material without using an adhesive or the like, and which has excellent rubber properties after vulcanization. An object of the present invention is to provide a resin / resin composite and a low-permeability hose using the rubber / resin composite and having excellent refrigerant permeability and flexibility.

[0005]

Means for Solving the Problems In bonding a rubber material and a resin material such as a polyamide resin, the present inventors have proposed that a phenolic resin such as a halogenated phenol resin, a phenol resin, a resorcin resin and a cresol resin is used as a rubber component. Not only acts as a vulcanizing agent, but also has a high reactivity to amide bonds. The present inventors have found that they can do so, and have reached the present invention.

That is, the present invention relates to a rubber composition containing 1 to 30 parts by weight of the phenolic resin based on 100 parts by weight of a rubber crosslinkable with the phenolic resin, and a resin having an amide bond alone or the amide resin. Provided is a rubber / resin composite obtained by vulcanizing and bonding a polyamide resin which is a mixture of not less than 90% by weight of a resin having a bond and not more than 10% by weight of a polyolefin resin and / or a polyester resin. Here, the rubber crosslinkable with the phenolic resin is preferably butyl rubber, halogenated butyl rubber, or a halogenated copolymer rubber of an isomonoolefin and p-alkylstyrene. Further, it is preferable that the phenolic resin is at least one selected from the group consisting of a halogenated phenol resin, a phenol resin, a resorcin resin and a cresol resin. Further, the resin having an amide bond is preferably at least one selected from the group consisting of nylon 6, nylon 66, nylon 11, and nylon 12.

Further, the present invention provides a low-permeability hose having at least a layer composed of the rubber / resin composite. Here, it is preferable to have a layer made of an aluminum foil or a vapor-deposited film between any surfaces of the resin layers constituting the rubber / resin composite or between the resin layers.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. The rubber / resin composite of the present invention is characterized in that a rubber composition and a polyamide resin are vulcanized and bonded. The rubber composition of the present invention comprises a rubber component and at least one selected from the group consisting of a halogenated phenolic resin, a phenolic resin, a resorcinol resin and a cresol resin (in the present invention, these resins are collectively referred to as “phenolic resin”). "
).

The rubber component of the present invention is not particularly limited as long as it can be crosslinked by the phenolic resin. For example, acrylonitrile butadiene rubber (NBR),
Butyl rubber (IIR), ethylene propylene diene rubber (EPDM), chlorosulfonated methyl polyethylene (CSM), brominated butyl rubber (BIIR), chlorinated butyl rubber (ClIIR), isomonoolefin and p-
Halogenated copolymer rubbers with alkylstyrene can be mentioned. These may be used alone or as a mixture of two or more. However, if the rubber composition contains multiple components, the rubber properties may be impaired. It is preferred that Among these, halogenated butyl rubber such as butyl rubber, brominated butyl rubber or chlorinated butyl rubber, or brominated isobutylene-p-methylstyrene copolymer rubber (BIM
It is preferable to use S), and it is particularly preferable to use halogenated butyl rubber or BIMS alone. This is because butyl rubber, halogenated butyl rubber and BIMS are excellent in weather resistance, heat resistance, water resistance and gas permeability, and halogenated butyl rubber and BIMS have the effect of further increasing the vulcanization rate.

The rubber component is mixed with a phenolic resin to form a rubber composition. The phenolic resin of the present invention,
It can act as a vulcanizing agent for the rubber component and can crosslink the rubber component by heating. In addition, since the phenolic hydroxyl group of the phenolic resin has a high reactivity with respect to the amide bond, the adhesiveness with the polyamide resin is excellent. Therefore, in the present invention, excellent adhesiveness can be obtained without the need to use an adhesive or perform a surface treatment on the polyamide resin for bonding the rubber and the resin. As the phenolic resin, a halogenated phenol resin, a phenol resin, an alkylphenol resin and the like can be preferably used among the above. In particular, when the halogenated phenol resin is used, the vulcanization time can be reduced because of its high reactivity. In addition, since vulcanization can be performed even at a relatively low temperature, there is no possibility that the rubber properties are impaired by heating. Examples of the halogenated phenol resin include a brominated phenol formaldehyde resin and a chlorinated phenol formaldehyde resin.

In the rubber composition of the present invention, the amount of the phenolic resin is in the range of 1 to 30 parts by weight based on 100 parts by weight of the rubber component. Preferably it is in the range of 2 to 20 parts by weight, more preferably 3 to 15 parts by weight. If the amount of the phenolic resin is less than 1 part by weight, the adhesive strength to the polyamide resin is reduced, and if the amount is more than 30 parts by weight, the physical properties of the rubber are impaired.

The above-mentioned rubber composition may contain a rubber compounding agent which is generally used, for example, a reinforcing agent such as carbon, a filler, a softening agent, a lubricant, an anti-aging agent, a processing aid, a vulcanization accelerator and the like. Can be blended in an appropriate amount as needed.

The polyamide resin used in the present invention is a resin having an amide bond alone or a mixture of a resin having an amide bond and a polyolefin resin and / or a polyester resin. Examples of the resin having an amide bond include nylon 6, nylon 66, nylon 11, nylon 12, nylon 610, nylon 612, nylon 6/66, nylon 6/66/610, and a mixture thereof. Examples of the polyolefin-based resin include polyolefin-based resins such as polyethylene, polypropylene, and polybutylene. Examples of the polyester resin include polybutylene terephthalate, polyethylene terephthalate, polyethylene isophthalate, PET / PEI copolymer, polyarylate, polybutylene naphthalate, liquid crystal polyester, polyoxyalkylenediimidic acid / polybutylate terephthalate copolymer, and the like. No.

When a resin having an amide bond is used as a polyamide resin in combination with one or both of a polyolefin resin and a polyester resin, the content of the resin having an amide bond in the mixture is used. Is preferably 90% by weight or more. This is because when the content of the resin having an amide bond is less than 90% by weight, the adhesive strength is reduced. When a polyolefin-based resin and a polyester-based resin are used in combination, it is preferable that the mixing weight percentage of these is 10% by weight or less.

In the rubber / resin composite of the present invention, a layer (rubber layer) composed of the rubber composition and a layer (resin layer) composed of a polyamide resin are laminated in an unvulcanized state. In the present invention, there is no need to interpose an adhesive layer or the like between the rubber layer and the resin layer. The rubber / resin composite of the present invention is not limited to a shape, and may be a joined body of different shaped bodies, and may be a film or a cylinder. Film-like rubber /
In the case of producing a resin composite, a polyamide resin is formed into a film, set in a mold, and a rubber composition is directly overlaid and laminated thereon.

The rubber / resin composite of the present invention comprises a rubber layer / tree
Two-layer structure of oil layer or three-layer structure of rubber layer / resin layer / rubber layer
It is preferable to use
Metal foil or vapor-deposited film may be provided between surfaces or resin layers.
No. Examples of metal foil include aluminum foil, copper foil, and gold foil.
Of these, aluminum foil is preferred, and the resin layer surface
An aromatic ester such as ethyl-m-aminobenzoate
Laminate using a tell-based adhesive or the like. As a deposited film
Is aluminum, copper, silver, gold, cobalt, iron, tin,
Metals such as nickel, lead, zinc, etc.
Gold component, SiO _Two, Silica, alumina and the like.
You. Of these, aluminum deposited films are preferred.
Alternatively, it can be deposited by a commonly used PVD method. Metal foil
Alternatively, the thickness of the deposited film is preferably 0.1 to 100 μm.
And a thickness of 1 to 30 μm is more preferable. Metal foil and evaporation
By having a membrane, the rubber / resin composite of the present invention can be cooled.
Excellent permeation resistance when used in hoses for transporting media.
Also, since it is laminated or deposited on the resin layer,
Excellent elongation at break of metal foils and vapor-deposited films.
There are no problems such as pinholes and cracks.

Therefore, the rubber / resin composite of the present invention has a three-layer structure of rubber layer / resin layer / metal foil or rubber layer / resin layer / deposited film, rubber layer / resin layer / metal foil / rubber layer or rubber. Four-layer structure of layer / resin layer / deposited film / rubber layer, four-layer structure of rubber layer / resin layer / metal foil / resin layer or rubber layer / resin layer / deposited film / resin layer, or rubber layer / resin layer / A five-layer structure of metal foil / resin layer / rubber layer or rubber layer / resin layer / deposited film / resin layer / rubber layer is preferable, and rubber layer / resin layer / aluminum foil / rubber layer or rubber layer / resin layer / aluminum A four-layer structure of a vapor deposition film / rubber layer or a five-layer structure of a rubber layer / resin layer / aluminum foil / resin layer / rubber layer or a rubber layer / resin layer / aluminum vapor deposition film / resin layer / rubber layer is more preferable. The film (rubber layer) made of the rubber composition has a thickness of 0.1%.
The thickness is preferably 4 to 4 mm, more preferably 0.5 to 2 mm. Further, the film (resin layer) made of a polyamide resin preferably has a thickness of 0.001 to 1 mm,
A thickness of 0.01 to 0.1 mm is more preferred. These thicknesses may be selected depending on the application, and may be beyond the above range as long as the effects of the present invention are not impaired.

In the case of manufacturing a cylindrical rubber / resin composite, the above rubber composition is extruded on the outer periphery of a mandrel or the like to form a rubber layer, and then, a resin made of the above-mentioned polyamide-based resin is formed on the outer periphery. The resin layer is formed by winding the film into a spiral shape or a spiral shape. When a metal foil or a vapor-deposited film is provided on the surface of the resin layer, a film having the metal foil or the vapor-deposited film formed on the surface of the resin film is spirally or spirally wound around the rubber layer. When a metal foil or a vapor-deposited film is laminated between resin layers, a metal foil or a film provided with a vapor-deposited film may be wound in a spiral shape or a spiral shape between two resin films. After winding the resin film provided with the vapor-deposited film, only the resin film may be wound in a spiral shape or a spiral shape. When a rubber layer is further provided on the outer periphery of the resin layer formed as described above, the rubber composition is extruded to form a rubber layer in the same manner as described above. The thickness of each layer is
The range is preferably the same as in the case of molding into a film, and can be adjusted depending on the application.

Further, a film-shaped rubber / resin composite prepared in advance is spirally or wound around the outer periphery of a mandrel or the like, or on the outer periphery of a rubber layer formed by extruding the rubber composition on the outer periphery of a mandrel or the like. It is also possible to produce a cylindrical rubber / resin composite by winding in a shape. As the film-like rubber / resin composite, any of the above-mentioned ones can be used. In particular, a two-layer film-like rubber / resin composite in which a resin film and a sheet-like rubber composition are laminated is used. Then, there is no overlapping portion between the resin films, and the bonding can be made stronger, which is preferable.

When the film-like rubber / resin composite having a two-layer structure is wound directly on a mandrel or the like, it is preferable that the rubber layer be on the inner side. Preferably, the layers are formed to produce a cylindrical rubber / resin composite. On the other hand, when a rubber layer is formed in advance on the outer periphery of a mandrel or the like, the two-layer film-shaped rubber / resin composite is wound around the resin layer so that the cylindrical rubber / resin composite is formed. Preferably, a resin composite is produced. Further, from the viewpoint of permeation resistance, the film-like rubber / resin composite having the two-layer structure has a three-layer structure or a four-layer structure having a metal foil or a vapor-deposited film between any surfaces of the resin layers or between the resin layers. It is preferable to use the rubber / resin composite of the above. The film or cylindrical rubber / resin composite thus obtained is vulcanized and bonded by heating the whole.

As described above, according to the present invention, a rubber / resin composite having high peel strength can be obtained without using an adhesive or the like or subjecting the resin layer to surface treatment or the like. Although the reason for such excellent bonding properties is not clear, it is considered that the fact that the resin particles melted by heating can simultaneously or almost simultaneously penetrate the rubber composition where vulcanization has started also contributes to the adhesion. Further, according to the present invention, environmental problems caused by paint spots and solvents contained in the adhesive due to the use of the adhesive are eliminated, and furthermore, steps such as application of the adhesive and surface treatment of the resin layer can be omitted. Excellent workability. The thus obtained rubber / resin composite of the present invention can be used not only for refrigerant transport hoses requiring low gas permeability and power steering hoses, but also for LPG, LNG, oxygen, acetylene, argon or hydrogen. It can be applied to various uses such as gas hose.

Next, the configuration of the low-permeability hose using the rubber / resin composite of the present invention will be described in detail. The low permeability hose of the present invention may have at least a layer composed of the above-mentioned rubber / resin composite.
Examples of the hose include a resin composite, a reinforcement layer, and an outer tube. In this case, each layer may be formed as a single layer, or may be formed as a plurality of layers.

FIG. 1 is a perspective view of a low-permeability hose according to a preferred embodiment of the present invention, in which each layer of the hose is cut away. The hose 1 has the rubber / resin composite 2 of the present invention as the innermost layer, a reinforcing layer 3 on the upper layer, and an outer tube 4 on the upper layer. In the low permeability hose of the present invention, as the rubber / resin composite, any of the rubber / resin composites exemplified above can be used. Layer / resin layer / aluminum foil / rubber layer / rubber layer / resin layer / aluminum vapor deposition film / rubber layer, rubber layer / resin layer / aluminum foil /
It is particularly preferable to have a five-layer structure of resin layer / rubber layer or rubber layer / resin layer / aluminum deposition film / resin layer / rubber layer.

Although the hose of the present invention does not necessarily have to have a reinforcing layer, it is preferable to have a reinforcing layer because the tensile strength at break, the usable pressure range, and the fitting property of the fitting are improved. . The reinforcing layer may be formed in a blade shape or a spiral shape, and is not particularly limited. As the material used,
Yarns, wires and the like can be mentioned. As reinforcement yarn,
Examples include yarns made of vinylon fiber, rayon fiber, polyester fiber, nylon fiber, aromatic polyamide fiber, and the like. Examples of the reinforcing wire include a hard steel wire, and more specifically, a plus-plated wire or a zinc-plated wire for rust prevention and adhesion.

The outer tube is the outermost layer of the hose and is a layer for maintaining the weather resistance, heat resistance, water permeability and the like of the hose. From this viewpoint, butyl rubber, halogenated butyl rubber, ethylene propylene rubber, BIMS Etc. are preferred, but are not limited thereto. Outer tube 0.5 ~
A thickness of 3 mm is preferred, and a thickness of 1-2 mm is more preferred.

The low-permeability hose of the present invention is, for example, provided with a reinforcing thread or a reinforcing wire on the outer periphery of an unvulcanized rubber / resin composite formed in a cylindrical shape on the outer periphery of a mandrel or the like as described above. A reinforcing layer is formed by braiding a plurality of pieces into a spiral shape or a blade shape, and an outer tube is formed on the outer periphery by extrusion molding. Subsequently, the entire hose is heated. The heating temperature may be a temperature at which the rubber is vulcanized, preferably 120 ° C. or higher, more preferably 1 ° C. or more.
The temperature is 40 to 170 ° C., and the rubber layer is vulcanized by heating to join the resin layer and the adjacent rubber layer. After sufficiently cooling, the low permeability hose of the present invention is obtained by extracting from the mandrel.

The low-permeability hose of the present invention thus obtained has a resin layer made of a polyamide resin having low gas permeability, and an adhesive layer or the like is provided between the resin layer and the rubber layer. Can be firmly joined without intervening. Therefore, it is not necessary to define conditions such as spots of the adhesive and a dry state, and the workability is excellent. Further, in the present invention, since a metal foil or a vapor-deposited film contributing to refrigerant permeability resistance is provided on the surface of the resin layer, the metal foil or the vapor-deposited film is excellent in elongation at break, and follows the deformation of the hose. be able to. Furthermore, according to the present invention, the resin particles of the polyamide resin melted by heating can penetrate into the adjacent rubber layer almost simultaneously starting vulcanization. It can be solved and can be firmly joined.

[0028]

EXAMPLES The present invention will be described in more detail with reference to examples. Examples 1 to 7 (1) Rubber composition A chlorinated butyl rubber composition or a BIMS rubber composition was obtained using the raw materials shown below in the amounts shown in Table 1. Chlorinated butyl rubber: Chlorobutyl 1066, manufactured by Esso Chemical Co., Ltd. BIMS: MDX90-10, additive manufactured by Exxon Chemical Co., Ltd. Carbon black: Asahi No. 50, manufactured by Asahi Carbon Co., zinc oxide: No. 3, manufactured by Shodo Chemical Co., Ltd. Antioxidant: Antigen RD-GS, manufactured by Sumitomo Chemical Co., Ltd. Stearic acid Paraffin-based oil: machine oil, manufactured by Showa Shell Sekiyu KK Brominated phenol formaldehyde resin: tacky roll 250-1, manufactured by Taoka Chemical Industry Co., Ltd.

(2) Polyamide resin The following polyamide resin was used. Nylon 6: Toray Nylon 6, Toray Nylon 66: Toray Nylon 66, Toray Nylon 11: Rilsan N11, ATOCHEM Nylon 12: Rilsan N12, ATOCHEM

<Adhesion Test> A polyamide resin (nylon 6, nylon 66, nylon 11, or nylon 12) shown in Table 1 was formed into a film having a thickness of 0.5 mm.
Chlorinated butyl rubber composition or BIM obtained thereon
The S rubber composition was overlaid so as to have a thickness of 3.5 mm, set in a mold, and heated at 148 ° C. for 45 minutes with a press. After cooling, it was removed from the mold, and the interface between the resin layer and the rubber layer was peeled by hand to evaluate the adhesiveness. The results are shown in Table 1. In the table, ○ indicates no peeling, Δ indicates easy peeling, and × indicates no adhesion.

Comparative Example 1 The adhesiveness was evaluated in the same manner as in the Example except that the amount of the brominated phenol formaldehyde resin was small.

Comparative Example 2 Nylon 11 (Rilsa) was used as a polyamide resin.
n, Adhesion was evaluated in the same manner as in Example, except that a mixture of 85% by weight of ATOCHEM and 15% by weight of polyethylene (Shorex, manufactured by Showa Denko KK) was used.

Comparative Examples 3-6 Magnesia- and thiirane-based accelerators (Suncellar MSP) were used in place of the brominated phenol formaldehyde resin.
O, manufactured by Sanshin Chemical Industry Co., Ltd.), and the adhesion was evaluated in the same manner as in Examples. The results are shown in Table 1.

[0034]

[Table 1]

<Manufacture of Polyamide Resin Film> Nylon 6 was used as the polyamide resin and had a thickness of 0.02 m.
m was formed to produce a resin film.

<Low Permeability Hose> Example 8 The chlorinated butyl rubber composition obtained in Example 1 was extruded with a rubber crosshead die-type extruder around the outer periphery of a mandrel having a diameter of 11 mm to a thickness of 0.1 mm. An innermost layer of 8 mm was formed. On the innermost layer, the resin film obtained above was spirally wound by half wrap to form a resin layer having a thickness of 0.04 mm. On the resin layer, the chlorinated butyl rubber composition was further extruded using a rubber crosshead die type extruder to form an inner tube outer layer having a thickness of 0.8 mm. Furthermore, a reinforcing material made of PET yarn is braided thereon (1.
(500d, 96), and a reinforcing layer was formed. On the reinforcing layer, the chlorinated butyl rubber composition obtained above was extruded using a rubber crosshead die-type extruder to have a thickness of 2 m.
m was formed. Thereafter, the entire hose was heated at 150 ° C. for 60 minutes. After confirming sufficient cooling, the mandrel was pulled out to obtain a low permeability hose of the present invention.

Example 9 In Example 8, instead of the resin film, an aromatic ester-based adhesive (ethyl-
m-aminobenzoate, manufactured by Nippon Kayaku Co., Ltd.), except that a resin film obtained by laminating an aluminum foil having a thickness of 0.01 mm using an aluminum foil as an outer layer was provided. A low permeability hose of the present invention was obtained in the same manner as in Example 8.

Example 10 In Example 8, in place of the resin film, a 0.01 mm-thick aluminum vapor-deposited film was formed on the surface of the resin film by a PVD method, and the resin film was used as the outer layer. A low-permeability hose of the present invention was obtained in the same manner as in Example 8, except that the aluminum vapor-deposited film was wound as described above.

Example 11 A resin film obtained by laminating an aluminum foil having a thickness of 0.01 mm using the aromatic ester-based adhesive between two resin films in place of the resin film in Example 8. And the low permeability hose of the present invention was obtained in the same manner as in Example 8, except that the aluminum foil was provided between the resin layers.

Example 12 The low permeability hose of the present invention was prepared in the same manner as in Example 11, except that the BIMS rubber composition obtained in Example 7 was used instead of the rubber composition. I got

Comparative Example 7 A low-permeability hose was obtained in the same manner as in Example 8, except that no resin layer was formed.

<Refrigerant Permeation Test> In the refrigerant permeation test, HFC134a was used as a refrigerant, and a method based on JRA2001 of JRA standard (Japanese refrigeration and air conditioning industry standard) was adopted. That is, out of four 50 cm long hoses, 3
0.6 ± 0.1 g of a refrigerant (HFC134a) was sealed in the book with a volume of 1 cm ³ of the hose, and the other one was sealed tightly empty. These four tubes were kept in a thermostat at 100 ° C. for 96 hours, and the weight was measured every 24 hours. At this time, it was confirmed that the internal pressure of the hose containing the refrigerant after 96 hours was maintained at the saturated vapor pressure at the test temperature. The refrigerant permeation amount was calculated by the following formula as a weight loss excluding a change in the weight of the hose from 24 hours to 96 hours. D = [(B / S1) − (C / S2)] × 100 In the formula, D is the refrigerant permeation amount [g / (m · 72 hr)], B is the weight loss of the refrigerant-enclosed hose [g / 72 hr)], C represents the weight loss of the refrigerant-unenclosed hose [g / 72 hr)], S1 represents the length of the refrigerant-enclosed hose [m], and S2 represents the length of the refrigerant-unenclosed hose [m]. The results are shown in Table 2 below.

[0043]

[Table 2]

[0044]

As described above, the rubber / resin composite of the present invention has excellent bonding properties between the rubber layer and the resin layer.
Excellent refrigerant resistance and elongation at break. Rubber of the present invention /
The resin composite is suitably used for various uses such as a hose for transporting a refrigerant, a gas hose for LPG and LNG, oxygen, and a gas for acetylene, and can be particularly suitably used for a hose for transporting a refrigerant for a car air conditioner.

[Brief description of the drawings]

FIG. 1 is a perspective view showing an example of a low permeability hose of the present invention.

[Explanation of symbols]

 Reference Signs List 1 hose 2 rubber / resin composite 3 reinforcing layer 4 outer tube

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 23/22 C08L 23/22 77/00 77/00 F16L 11/04 F16L 11/04 11/08 11 / 08 AB F25B 41/00 F25B 41/00 G // (C08L 23/22 (C08L 23/22 61:06) 61:06) (C08L 77/00 (C08L 77/00 23:00) 23:00) (C08L 77/00 (C08L 77/00 67:00) 67:00) (72) Inventor Hideyuki Oishi 2-1 Oiwake, Hiratsuka-shi, Kanagawa Yokohama Rubber Co., Ltd. Hiratsuka Factory (72) Inventor Yuji Kawamori Kanagawa 2-1 Oiwake, Hiratsuka-shi, Yokohama Inside the Hiratsuka Factory of Yokohama Rubber Co., Ltd. (72) Inventor Hiroaki Shibano 4-6-40 Higashi-Hachiman, Hiratsuka-shi, Kanagawa F-term in Hiratsuka Office, Yokohama Hidex Co., Ltd. 3H111 AA02 BA13 BA15 BA24 BA25 BA26 BA29 B A34 CA52 CB04 CB14 CB22 CC03 DA14 DB09 EA04 4F100 AB10C AB33C AK03A AK03B AK03J AK09A AK12A AK12J AK33A AK33H AK34A AK41B AK42 AK43 AK43G AK46B AK48B AK62B AK66B AL01A AL05B AN02A BA02 BA03 BA04 BA05 BA07 BA10A BA10B BA10C CA02A CA03A DA11 EH17 EH51 EH66 EH66C EJ06A EJ17 EJ42 JD01 JD05 JK06 JK08 JL11 YY00A YY00B 4J002 BB012 BB181 BB241 CC032 CC052 CC062 CC072 CF032 CL011 CL031 GF00

Claims (6)

[Claims] 1. A rubber 1 crosslinkable with a phenolic resin.
A rubber composition containing 1 to 30 parts by weight of the phenolic resin, and a resin having an amide bond alone,
Or 90% by weight or more of the resin having an amide bond and a polyolefin resin and / or a polyester resin 1
0% by weight or less of a polyamide resin,
Rubber / resin composite obtained by vulcanization bonding. 2. The rubber according to claim 1, wherein the rubber crosslinkable by the phenolic resin is butyl rubber, halogenated butyl rubber, or a halogenated copolymer rubber of isomonoolefin and p-alkylstyrene. Rubber / resin composite. 3. The rubber according to claim 1, wherein the phenolic resin is at least one selected from the group consisting of halogenated phenolic resins, phenolic resins, resorcinol resins and cresol resins.
Resin composite. 4. The resin according to claim 1, wherein the resin having an amide bond is at least one selected from the group consisting of nylon 6, nylon 66, nylon 11, and nylon 12. Rubber / resin composite. 5. A low-permeability hose having at least a layer constituted by the rubber / resin composite according to claim 1. 6. The low permeability hose according to claim 5, further comprising a layer made of an aluminum foil or a vapor-deposited film between any surface of the resin layers constituting the rubber / resin composite or between the resin layers.