JP5012961B2 - Rubber / resin composite hose - Google Patents

Description

  The present invention relates to a rubber / resin composite hose.

Conventionally, a fluid and transport hose represented by a liquid propane gas hose (LPG hose) and a car air conditioner hose generally uses a resin-rubber laminate in which a resin material and a rubber material are combined. As the bonding technique, use of an adhesive, surface treatment of a resin material, and the like have been generally performed. However, in order to obtain a good adhesion state, it is necessary to carry out these treatments under certain conditions, which causes problems such as an increase in the number of work steps and an increase in production costs. Therefore, the applicant of the present application has so far made fusion bonding of ultra-high molecular weight polyethylene (PE) and rubber at a temperature higher than the melting point of ultra-high molecular weight PE, so that the molecular chains of both substances are entangled with each other. It has been proposed to bond by melt melting that occurs (Patent Document 1). Further, adhesion between polyamide resin and rubber has been proposed (Patent Documents 2 to 4). Further, the applicant of the present application has previously proposed Patent Document 5 regarding the adhesion between polyamide resin and rubber.
However, all are bonding techniques between limited materials, and a technique for bonding a resin material and a rubber material applicable to a wider range has been demanded.

Japanese Patent Publication No. 07-117179 Japanese Patent No. 3899718 Japanese Patent No. 2589238 Japanese Patent No. 338398 JP 2002-79614 A

  Then, an object of this invention is to provide the rubber / resin composite hose which is excellent in the adhesiveness of a resin layer and a rubber layer.

  As a result of earnest research to solve the above-mentioned problems, the inventor has an inner tube, and the inner tube includes a resin layer as the innermost layer and a rubber layer adjacent to the innermost layer. Rubber / a resin composition containing a resin containing at least an ionomer having a carboxylic acid metal salt, and a rubber composition containing a rubber containing at least an epoxidized rubber. The present inventors have found that the resin composite hose has excellent adhesiveness between the resin layer and the rubber layer, and completed the present invention.

That is, this invention provides the following 1-13.
1. An inner tube, the inner tube includes a resin layer as an innermost layer and a rubber layer adjacent to the innermost layer;
The material used for the resin layer is a resin composition containing a resin containing at least an ionomer having a carboxylic acid metal salt,
A rubber / resin composite hose, wherein the material used for the rubber layer is a rubber composition containing rubber containing at least epoxidized rubber.
2. In the resin, the amount of the ionomer is 10 to 100% by mass in the total amount of the resin,
2. The rubber / resin composite hose according to 1 above, wherein the amount of the epoxidized rubber is 10 to 100% by mass in the total amount of the rubber.
3. 3. The rubber / resin composite hose according to 1 or 2 above, wherein the epoxidized rubber is an epoxidized natural rubber.
4). 4. The rubber / resin composite hose according to any one of 1 to 3, wherein the epoxidized rubber has an epoxidation rate of 2 to 75 mol%.
5. The rubber / resin composite hose according to any one of the above 1 to 4, wherein the rubber further contains acrylonitrile butadiene rubber (NBR).
6). 6. The rubber / resin composite hose according to any one of 1 to 5, wherein the resin further contains polyamide.
7). The above 6 wherein the polyamide is at least one selected from the group consisting of polyamide 6, polyamide 11, polyamide 12, polyamide 4-6, polyamide 6-6, polyamide 6-10, polyamide 6-12 and polyamide MXD-6 The rubber / resin composite hose described in 1.
8). 8. The rubber / resin composite hose according to any one of 1 to 7, wherein the rubber composition further contains a thiuram vulcanization accelerator and / or a sulfenamide vulcanization accelerator and an alkylphenol formaldehyde resin.
9. 9. The rubber / resin composite hose according to any one of 1 to 8, wherein an adhesive layer is not provided between the resin layer and the rubber layer.
10. 10. The rubber / resin composite hose according to any one of 1 to 9, wherein the resin layer and the rubber layer are directly bonded.
11. 11. The rubber / resin composite hose according to any one of 1 to 10 above, which has a reinforcing layer and an outer layer on the outside of the inner tube.
12 12. The rubber / resin composite hose as described in 11 above, wherein the material used for the reinforcing layer is brass plated wire.
13. The manufacturing method of the rubber / resin composite hose which manufactures the rubber / resin composite hose in any one of said 1-12 by carrying out the vulcanization adhesion of the said resin layer and the said rubber layer at least.

The rubber / resin composite hose of the present invention is excellent in adhesiveness between the resin layer and the rubber layer.
The rubber / resin composite hose obtained by the method for producing a rubber / resin composite hose of the present invention is excellent in adhesion between the resin layer and the rubber layer.

FIG. 1 is a perspective view schematically showing an example of the rubber / resin composite hose of the present invention by cutting out each layer of the hose.

The present invention will be described in detail below.
The rubber / resin composite hose of the present invention has an inner tube, and the inner tube includes a resin layer as an innermost layer and a rubber layer adjacent to the innermost layer, and a material used for the resin layer is And a resin composition containing a resin containing at least an ionomer having a carboxylic acid metal salt, wherein the material used for the rubber layer is a rubber composition containing a rubber containing at least an epoxidized rubber. And a composite hose.

  The rubber / resin composite hose of the present invention is a resin composition in which the material used for the resin layer contains a resin containing at least an ionomer having a carboxylic acid metal salt, and the material used for the rubber layer is made of epoxidized rubber. By being a rubber composition containing at least the rubber to be included, the resin layer and the rubber layer can be bonded, and the adhesiveness between the resin layer and the rubber layer is excellent. Further, the resin layer and the rubber layer can be directly bonded without performing an adhesion treatment (for example, application of an adhesive, surface treatment of the resin layer) between the resin layer and the rubber layer.

  The inventors of the present application consider that the adhesion between the resin layer and the rubber layer is caused by the reaction between the metal carboxylate and the epoxy group of the epoxidized rubber. Note that the above mechanism is the inventor's inference, and even if the mechanism of the present invention is other than the above, it is within the scope of the present invention.

The rubber / resin composite hose of the present invention has an inner tube. The inner tube includes a resin layer as the innermost layer and a rubber layer adjacent to the innermost layer.
The rubber / resin composite hose of the present invention may be mentioned as one of preferred embodiments that further has a reinforcing layer and an outer layer outside the inner tube. The reinforcing layer can be adjacent to the rubber layer.

In the rubber / resin composite hose of the present invention, the resin layer and the rubber layer can be directly bonded.
In the present invention, the resin layer and the rubber layer are preferably bonded directly from the viewpoint of reducing manufacturing steps and excellent productivity.
Moreover, in this invention, from a viewpoint of reducing a manufacturing process and being excellent in work environment and productivity, it is mentioned as one of the preferable aspects that it does not have an adhesive bond layer between a resin layer and a rubber layer. .
Moreover, in this invention, it is mentioned as one of the preferable aspects that a surface treatment agent is not given to the surface of a resin layer from a viewpoint of reducing a manufacturing process and being excellent in productivity.

The thickness of the innermost layer (resin layer) is preferably 0.05 to 1.00 mm from the viewpoint of the flexibility and productivity of the hose.
The thickness of the rubber layer is preferably 0.5 to 6.0 mm from the viewpoint of the flexibility and productivity of the hose.
The thickness of the inner tube is preferably 0.6 to 7.0 mm.
The thickness of the outer layer is preferably 1.0 to 4.0 mm from the viewpoint of the flexibility and productivity of the hose.

An example of a preferred embodiment of the rubber / resin composite hose of the present invention will be described with reference to the accompanying drawings. The present invention is not limited to the attached drawings.
FIG. 1 is a perspective view schematically showing an example of the rubber / resin composite hose of the present invention by cutting out each layer of the hose.
In FIG. 1, the rubber / resin composite hose 1 has an inner tube 6, and further has a reinforcing layer 7 on the inner tube 6 and an outer layer 9 on the reinforcing layer 7. The inner tube 6 includes the resin layer 3 in the innermost layer and the rubber layer 5 adjacent to the resin layer 3 (innermost layer).

The innermost layer will be described below.
In the present invention, the innermost layer is a resin layer. The material used for the resin layer is a resin composition containing a resin containing at least an ionomer having a carboxylic acid metal salt.
In the present invention, when the innermost layer is a resin layer, it is excellent in permeation resistance and oil resistance to liquids and gases.

The resin composition used in the production of the innermost layer will be described below.
In the present invention, the resin composition used is a composition containing a resin containing at least an ionomer having a carboxylic acid metal salt.

The ionomer will be described below.
The ionomer contained at least in the resin contained in the resin composition is not particularly limited as long as it is a polymer having a carboxylic acid metal salt.
Examples of the metal of the carboxylic acid metal salt in the ionomer include sodium, zinc, and magnesium. Among these, zinc is preferable because the metal is more excellent in the adhesion between the resin layer and the rubber layer.
Examples of the ionomer include a resin in which molecules of an ethylene-methacrylic acid copolymer are crosslinked with metal ions (for example, zinc ions).

  The ionomer is not particularly limited for its production. For example, a conventionally well-known thing is mentioned. The ionomers can be used alone or in combination of two or more.

In the present invention, the resin contains at least an ionomer.
Examples of the polymer other than ionomer that can be contained in the resin include polyamide and polyolefin.

Among these, from the viewpoint of excellent gas permeation resistance, oil resistance, and mechanical strength, the resin preferably further contains polyamide.
Polyamide is polyamide 6, polyamide 11, polyamide 12, polyamide 4-6, polyamide 6-6, polyamide 6-10, polyamide 6-12 and polyamide from the viewpoint of superior gas permeation resistance, oil resistance and mechanical strength. It is preferably at least one selected from the group consisting of MXD-6.
Polymers other than ionomers are not particularly limited for their production. For example, a conventionally well-known thing is mentioned. Polymers other than ionomers can be used alone or in combination of two or more.

In the resin, since the content of the ionomer is related to the adhesiveness, the content of the ionomer is preferably 10 to 100% by mass, and more preferably 20 to 100% by mass in the total amount of the resin.
When the resin contains a polymer other than an ionomer, the amount of the polymer other than the ionomer (for example, polyamide) can be 90% by mass or less based on the total amount of the resin. The amount of the polymer other than the ionomer is preferably 10 to 90% by mass, more preferably 40 to 90% by mass based on the total amount of the resin, from the viewpoint of improving gas permeation resistance, oil resistance and mechanical strength. preferable.

  The resin composition can contain additives as long as it does not impair the purpose of the present invention. Examples of additives include fillers, reinforcing agents, anti-aging agents, vulcanizing agents, vulcanization accelerators, vulcanization activators, plasticizers, pigments (dyes), tackifiers, lubricants, dispersants, and processing agents. Auxiliaries are mentioned.

  The resin composition is not particularly limited for its production. For example, a method of mixing an ionomer, a polymer other than an ionomer, and an additive, which can be used as necessary, using a twin-screw kneading extruder may be mentioned. The mixing temperature is preferably set to a temperature equal to or higher than the melting point of the resin or near the melting point.

The rubber layer will be described below.
In the present invention, the rubber layer is adjacent to the innermost layer. The material used for the rubber layer is a rubber composition containing rubber containing at least epoxidized rubber.

The rubber composition used in the production of the rubber layer will be described below.
In the present invention, the epoxidized rubber contained in the rubber contained in the rubber composition is not particularly limited as long as it is a rubber having an epoxy group. The epoxidized rubber is preferably an epoxidized natural rubber from the viewpoint that it is superior in adhesion between the resin layer and the rubber layer.

Since the epoxy group in the epoxidized rubber is involved in the adhesion between the resin layer and the rubber layer, the epoxidation rate is preferably 2 to 75 mol%, and more preferably 20 to 75 mol%. The epoxidation rate means the ratio of the number of epoxidized out of the total number of double bonds in the raw rubber (for example, natural rubber) before epoxidation.
Epoxidized rubber is not particularly limited for its production. For example, a conventionally well-known thing is mentioned. Epoxidized rubbers can be used alone or in combination of two or more.

In the present invention, the rubber includes at least an epoxidized rubber.
Examples of rubbers other than the epoxidized rubber that can be included in the rubber include acrylonitrile butadiene rubber (NBR), natural rubber (NR), butadiene rubber (BR), styrene-butadiene copolymer rubber (SBR), and polyisoprene rubber. (IR), butyl rubber (IIR), chlorobutyl rubber (Cl-IIR), bromobutyl rubber (Br-IIR), chloroprene rubber, ethylene-propylene copolymer rubber, styrene-isoprene copolymer rubber, styrene-isoprene-butadiene copolymer Examples include polymer rubber, isoprene-butadiene copolymer rubber, and chlorosulfonated polyethylene.

The rubber preferably further contains acrylonitrile butadiene rubber (NBR) from the viewpoint of excellent adhesion between the resin layer and the rubber layer and excellent oil resistance.
The rubber other than the epoxidized rubber is not particularly limited for production. For example, a conventionally well-known thing is mentioned. Rubbers other than the epoxidized rubber can be used alone or in combination of two or more.

In the rubber, the amount of the epoxidized rubber is excellent due to the adhesion between the resin layer and the rubber layer, and is preferably 10 to 100% by mass in the total amount of the rubber. However, in consideration of various physical properties such as cold resistance, 20 More preferably, it is -70 mass%.
When rubber | gum contains rubbers other than epoxidized rubber, the quantity of rubber | gum (for example, acrylonitrile butadiene rubber) other than epoxidized rubber can be 90 mass% or less in rubber | gum whole quantity. The amount of rubber other than the epoxidized rubber is preferably 30 to 90% by mass, and 50 to 90% by mass based on the total amount of rubber from the viewpoint that the adhesiveness between the resin layer and the rubber layer is excellent and the oil resistance is excellent. More preferably.

In the present invention, the rubber composition is more excellent in adhesiveness between the resin layer and the rubber layer, excellent in vulcanization adhesion between the rubber layer and the reinforcing layer, and further excellent in adhesiveness between the rubber layer and the reinforcing layer. It is preferable to contain a thiuram vulcanization accelerator and / or a sulfenamide vulcanization accelerator. In addition, the rubber composition is more excellent in the adhesion between the resin layer and the rubber layer, more excellent in vulcanization adhesion between the rubber layer and the reinforcing layer, and more excellent in adhesion between the rubber layer and the reinforcing layer. It is preferable to contain a resin. The rubber composition is further excellent in adhesion between the resin layer and the rubber layer, excellent in vulcanization adhesion between the rubber layer and the reinforcement layer, and further excellent in adhesion between the rubber layer and the reinforcement layer. It preferably contains a sulfur accelerator and / or a sulfenamide vulcanization accelerator, and an alkylphenol formaldehyde resin.
In the present invention, when the rubber composition further contains a thiuram vulcanization accelerator and / or a sulfenamide vulcanization accelerator and an alkylphenol formaldehyde resin, the rubber composition is more excellent in adhesion between the resin layer and the rubber layer. The layer and the reinforcing layer can be directly bonded more firmly.
Further, the rubber composition further contains a thiuram vulcanization accelerator and / or a sulfenamide vulcanization accelerator (particularly, a sulfenamide accelerator), so that the rubber composition can be used at a high temperature (for example, 40 to 120 ° C. and 70 ° C. are preferred embodiments.) The adhesive property between the resin layer and the rubber layer is bonded to the resin layer and the rubber layer using a current adhesive (for example, a phenol resin adhesive). It can be equal to or higher than that of

In the present invention, from the viewpoint of reducing production steps and excellent productivity, it is mentioned as one preferred embodiment that the rubber layer and the reinforcing layer are directly bonded.
Moreover, it is mentioned as one of the preferable aspects that it does not have an adhesive bond layer between a rubber layer and a reinforcement layer from a viewpoint of reducing a manufacturing process and being excellent in work environment and productivity.

The thiuram vulcanization accelerator will be described below.
In the present invention, the thiuram vulcanization accelerator that can be further contained in the rubber composition is not particularly limited as long as it is generally blended with rubber. For example, what is represented by following formula (1) is mentioned.

In the above formula ^(1), R 1 ~R ^4, respectively aliphatic hydrocarbon group having 1 to 18 carbon atoms, represents an alicyclic hydrocarbon group or an aromatic hydrocarbon group, x is an integer of 1 to 4 To express.

Examples of the aliphatic hydrocarbon group include linear alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an octyl group, a dodecyl group, and a stearyl group; an isopropyl group, an isobutyl group, and an s- Branched alkyl group such as butyl group, t-butyl group, isopentyl group, neopentyl group, t-pentyl group, 1-methylbutyl group, 1-methylheptyl group, 2-ethylhexyl group; vinyl group, allyl group, propenyl group , An alkenyl group such as but-2-en-1-yl (—CH ₂ —CH═CH—CH ₃ ), but-3-en-1-yl (—CH ₂ —CH ₂ —CH═CH ₂ ); Ethynyl group, propynyl group, but-2-yn-1-yl (—CH ₂ —C≡C—CH ₃ ), but-3-en-1-yl (—CH ₃ —CH ₂ —C≡CH), etc. Alkynyl group of And the like.
Examples of the alicyclic hydrocarbon group include a cyclohexyl group, a methylcyclohexyl group, and an ethylcyclohexyl group.
Examples of the aromatic hydrocarbon group include aralkyl groups such as benzyl group and phenethyl group; aryl groups such as phenyl group, tolyl group (o-, m-, p-), dimethylphenyl group and mesityl group.

  Specific examples of the thiuram vulcanization accelerator include tetramethylthiuram monosulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, tetrahexylthiuram disulfide, tetrakis (2-ethylhexyl) thiuram disulfide, tetrastearyl thiuram disulfide, And thiuram disulfide such as tetracyclohexyl thiuram disulfide and tetrabenzyl thiuram disulfide.

Among these, tetramethylthiuram monosulfide, tetraethylthiuram disulfide, tetrakis (2) are excellent in terms of adhesion between the resin layer and the rubber layer, excellent vulcanization adhesion between the rubber layer and the reinforcing layer, and excellent rubber properties. -Ethylhexyl) thiuram disulfide and the like are preferable.
The thiuram vulcanization accelerators can be used alone or in combination of two or more. The thiuram vulcanization accelerator is not particularly limited for its production. For example, a conventionally well-known thing is mentioned.

The amount of the thiuram-based vulcanization accelerator is excellent in the adhesiveness between the resin layer and the rubber layer, excellent in vulcanization adhesion between the rubber layer and the reinforcing layer, and excellent in adhesiveness between the rubber layer and the reinforcing layer. The amount is preferably 0.2 to 3.0 parts by mass, more preferably 0.25 to 2.75 parts by mass, with respect to 100 parts by mass of the rubber including the epoxidized rubber, and 0.3 to 2. More preferably, it is 5 parts by mass.
When the amount of the thiuram vulcanization accelerator is 0.2 parts by mass or more with respect to 100 parts by mass of the rubber containing the epoxidized rubber, the adhesiveness to the reinforcing layer (especially brass-plated steel wire) is excellent (specifically Is preferable because it has a high adhesive strength and a large amount of rubber.
When the amount of the thiuram vulcanization accelerator is 3.0 parts by mass or less with respect to 100 parts by mass of the rubber containing the epoxidized rubber, the scorch time becomes an appropriate length, which is excellent in extrusion processability.

The sulfenamide vulcanization accelerator will be described below.
In the present invention, the sulfenamide vulcanization accelerator that can be further contained in the rubber composition is not particularly limited as long as it is generally blended with rubber.
Examples of the sulfenamide-based vulcanization accelerator include N-cyclohexyl-2-benzothiazolylsulfenamide and Nt-butyl-2-benzothiazolylsulfenamide.

Among them, Nt-butyl-2 is superior in terms of adhesion between the resin layer and the rubber layer, excellent in vulcanization adhesion between the rubber layer and the reinforcement layer, and excellent in adhesion between the rubber layer and the reinforcement layer. -Benzothiazolylsulfenamide is preferred.
The sulfenamide vulcanization accelerators can be used alone or in combination of two or more. The sulfenamide vulcanization accelerator is not particularly limited for its production. For example, a conventionally well-known thing is mentioned.

The viewpoint that the amount of the sulfenamide vulcanization accelerator is superior to the adhesion between the resin layer and the rubber layer, excellent in the vulcanization adhesion between the rubber layer and the reinforcement layer, and excellent in the adhesion between the rubber layer and the reinforcement layer. Therefore, it is preferably 0.5 to 5.0 parts by mass, more preferably 0.6 to 4.0 parts by mass with respect to 100 parts by mass of the rubber containing the epoxidized rubber, and 0.7 to More preferably, it is 3.0 parts by mass.
When the amount of the sulfenamide-based vulcanization accelerator is 0.5 parts by mass or more with respect to 100 parts by mass of the rubber containing the epoxidized rubber, the adhesion to the reinforcing layer (especially brass-plated steel wire) is excellent (specifically In particular, the adhesive strength is high and the amount of rubber is increased), which is preferable because necessary physical properties can be expressed.
When the amount of the sulfenamide-based vulcanization accelerator is 5.0 parts by mass or less with respect to 100 parts by mass of the rubber containing the epoxidized rubber, the scorch time becomes an appropriate length and is excellent in extrusion processability and practicality. .

The alkylphenol formaldehyde resin will be described below.
In the present invention, the alkylphenol formaldehyde resin that can be further contained in the rubber composition is not particularly limited as long as it is generally blended with rubber as a vulcanizing agent. For example, a conventionally well-known thing is mentioned.

Of these, halogenated alkylphenol formaldehyde resins are preferred from the viewpoints of excellent adhesion between the resin layer and the rubber layer, excellent vulcanization adhesion between the rubber layer and the reinforcement layer, and excellent adhesion between the rubber layer and the reinforcement layer. A brominated alkylphenol formaldehyde resin is more preferable.
The alkylphenol formaldehyde resins can be used alone or in combination of two or more. The alkylphenol formaldehyde resin is not particularly limited for its production. For example, a conventionally well-known thing is mentioned.

The amount of the alkylphenol formaldehyde resin is superior from the viewpoint of adhesiveness between the resin layer and the rubber layer, excellent in vulcanization adhesion between the rubber layer and the reinforcing layer, and from the viewpoint of excellent adhesiveness between the rubber layer and the reinforcing layer. It is preferable that it is 1-10 mass parts with respect to 100 mass parts of rubber | gum containing this, It is more preferable that it is 2-8 mass parts, It is further more preferable that it is 3-7 mass parts.
When the amount of the alkylphenol formaldehyde resin is 1 part by mass or more with respect to 100 parts by mass of the rubber including the epoxidized rubber, the adhesiveness with the reinforcing layer (especially brass-plated steel wire) is excellent (specifically, adhesive strength and rubber) (Attachment becomes high) It is preferable.
When the amount of the alkylphenol formaldehyde resin is 10 parts by mass or less with respect to 100 parts by mass of the rubber including the epoxidized rubber, the hardness of the rubber becomes appropriate, the scorch time becomes an appropriate length, and extrusion processability and practicality Excellent and preferable.

In the present invention, the rubber composition can contain sulfur as a vulcanizing agent. The sulfur that the rubber composition can further contain is not particularly limited. For example, a conventionally well-known thing is mentioned. Specific examples include powdered sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur, and insoluble sulfur.
Sulfur can be used alone or in combination of two or more.

  The amount of sulfur is 1 with respect to 100 parts by mass of rubber containing epoxidized rubber from the viewpoint of good tensile properties after vulcanization (for example, 100% elongation tensile stress, tensile strength, etc.) and heat aging resistance. 0.5 to 3.0 parts by mass is preferred, and 1.7 to 2.5 parts by mass is more preferred.

  The rubber composition can contain additives as long as it does not impair the purpose of the present invention. Examples of additives include fillers, reinforcing agents, anti-aging agents, vulcanizing agents other than sulfur and alkylphenol formaldehyde resins, vulcanization accelerators other than thiuram vulcanization accelerators and sulfenamide vulcanization accelerators ( Examples thereof include dibenzothiazyl disulfide), vulcanization activators, plasticizers, pigments (dyes), tackifiers, lubricants, dispersants, and processing aids.

  In the present invention, the rubber composition is not particularly limited for its production. For example, rubber, thiuram vulcanization accelerator, sulfenamide vulcanization accelerator, alkylphenol formaldehyde resin, sulfur, additive, open roll, kneader, extruder, universal agitator that can be used as needed And a method of mixing (kneading) using a batch kneader.

The reinforcing layer will be described below.
Since the rubber / resin composite hose of the present invention has a reinforcing layer, it can maintain strength and has excellent pressure resistance.

The material of the reinforcing layer that the rubber / resin composite hose of the present invention can have is not particularly limited.
Examples of the material used for the reinforcing layer include polyester fiber, polyamide fiber, aramid fiber, vinylon fiber, rayon fiber, PBO (polyparaphenylene benzobisoxazole) fiber, polyketone fiber, polyarylate fiber, and polyketone fiber. Examples of such fiber materials include metal materials such as hard steel wires (for example, brass-plated wires and galvanized wires).

In particular, in a hose that requires high pressure resistance, a brass-plated wire (brass) is used from the viewpoint of excellent vulcanization adhesion between the rubber layer and the reinforcing layer and excellent adhesion between the rubber layer and the reinforcing layer. Plating wire) is preferred.
The brass plating wire is not particularly limited as long as it can be used for reinforcing the rubber hose.
The reinforcing layer is not particularly limited with respect to its shape. For example, the thing of a blade shape and a spiral shape is mentioned.
The material of the reinforcing layer can be used alone or in combination of two or more.

  When the reinforcing layer is a brass-plated wire, the rubber composition further comprises a thiuram vulcanization accelerator and a rubber composition from the viewpoint that adhesion to the brass-plated wire can be made possible while maintaining adhesion to the resin layer. It is preferable to contain a sulfenamide-based vulcanization accelerator and an alkylphenol formaldehyde resin.

The outer layer will be described below.
Since the rubber / resin composite hose of the present invention has an outer layer, it can protect the reinforcing layer and has excellent durability.

One preferred embodiment is that the outer layer that the rubber / resin composite hose of the present invention can have is a rubber layer.
The outer layer that the rubber / resin composite hose of the present invention can have is not particularly limited with respect to its material. Examples of the material used for the outer layer include a rubber composition used in the present invention and other rubber compositions.
The rubber contained in the rubber composition used when forming the outer layer is not particularly limited. For example, styrene butadiene rubber (SBR), acrylonitrile butadiene rubber (NBR), butyl rubber (IIR), ethylene propylene diene rubber (EPDM), hydrogenated NBR (HNBR), chloroprene rubber (CR), chlorosulfonated methyl polyethylene (CSM) , Chlorinated polyethylene (CM), brominated butyl rubber (BIIR), chlorinated butyl rubber (CIIR), and BIMS.

  The rubber / resin composite hose of the present invention is not particularly limited for its production. For example, a method of at least vulcanizing and bonding the resin layer and the rubber layer can be mentioned. More specifically, for example, a method of laminating a resin layer, a rubber layer, a reinforcing layer, and an outer layer in this order on a mandrel, and then vulcanizing and adhering these layers can be mentioned. In the present invention, the resin layer and the rubber layer are directly vulcanized and bonded without performing an adhesion treatment (for example, application of an adhesive, surface treatment on the resin layer) between the resin layer and the rubber layer. Can do.

The temperature during vulcanization is preferably 140 to 190 ° C. from the viewpoint of adhesion between the resin layer and the rubber layer and the development of rubber physical properties.
The vulcanization time is preferably 30 to 180 minutes from the viewpoints of adhesion between the resin layer and the rubber layer, rubber physical properties, and energy efficiency.
Examples of the vulcanization method include press vulcanization, steam vulcanization, oven vulcanization (hot air vulcanization), and hot water vulcanization.

In the rubber / resin composite hose of the present invention, the adhesive strength between the resin layer and the rubber layer is preferably 50 N / 25 mm or more.
In the present invention, the adhesive strength between the resin layer and the rubber layer is determined by the resin sheet obtained by using the resin composition (sheet thickness 0.2 mm) and the rubber sheet obtained by using the rubber composition (raw material). Sheet thickness of 2.5 mm), and press vulcanized at 148 ° C. for 60 minutes to produce a 25 mm wide sheet-shaped test piece, and the obtained sheet-shaped test piece was measured at room temperature using an autograph. Perform a peel test to peel the rubber layer from the resin layer at an angle of 180 degrees at a peel speed of 50 mm / min under conditions of (23 ° C.) or 70 ° C., and measure the adhesive strength (unit = N per 25 mm width). Is the value obtained by

  In the present invention, the adhesive strength between the rubber layer and the reinforcing layer (brass plating wire) is obtained by winding a brass plating wire in a spiral shape on an iron mandrel having an outer diameter of 25 mm, and using the rubber composition thereon. The rubber sheets (raw sheet thickness 2.5 mm) were bonded together, and this was vulcanized at 148 ° C. for 60 minutes to obtain a hose test piece. The rubber sheet of the obtained hose test piece The left and right rubbers are cut out so that the width of the rubber is 25 mm, and the adhesive between the remaining rubber part and the wire part is removed from the reinforcing layer at a peeling speed of 50 mm / min at room temperature (23 ° C.) using an autograph. It is a value obtained by conducting a peel test for peeling and measuring the adhesive strength (unit = N per 25 mm width).

  The rubber / resin composite hose of the present invention is, for example, a refrigerant transport hose [as the refrigerant, for example, carbon dioxide, HFC-134a (for car air conditioner). ]; It can be applied to a liquid propane gas hose (LPG hose).

  Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.

<Evaluation>
About the hose or laminated body obtained as follows, the adhesion between rubber and resin (rubber / resin adhesion 1 to 4) and the adhesion between the reinforcing layer and the rubber layer were evaluated by the following methods. The results are shown in Table 3, Table 4, Table 7, Table 8, Table 11, Table 11 and Table 12. The evaluation results for rubber / resin adhesion 1 to 4 are measured at room temperature unless otherwise specified. The adhesive strength of rubber / resin bonds 1 and 2 in Table 11 was measured under conditions of room temperature and 70 ° C.

1. Adhesiveness between rubber and resin (rubber / resin adhesion 1 to 4)
(1) Manufacture of test pieces used in rubber / resin bonding 1 (using adhesive)
Brush the resin sheet 1 obtained as follows with a phenol resin adhesive [trade name TY-PLY-BN (manufactured by Road Far East)] diluted 3-fold with methyl ethyl ketone (MEK)] After coating and drying, a resin sheet and a rubber sheet obtained as described below were bonded together, and this was press vulcanized at 148 ° C. for 60 minutes to obtain a sheet-like test piece.
In addition, about Example I-1, II-1, and III-1, the result of the rubber | gum / resin adhesion | attachment 1 is shown by the comparison reference.

(2) Manufacture of test piece used in rubber / resin adhesion 2 The resin sheet 1 obtained as described below and the rubber sheet obtained as described below are bonded together, and this is 148 ° C. for 60 minutes. Press vulcanized to obtain a sheet-like test piece. No adhesive was used for bonding.

(3) Manufacture of test piece used in rubber / resin bonding 3 The resin sheet 2 obtained as described below and the rubber sheet obtained as described below are bonded together, and this is 148 ° C. for 60 minutes. Press vulcanized to obtain a sheet-like test piece. No adhesive was used for bonding.

(4) Manufacture of a test piece used in rubber / resin adhesion 4 A resin sheet 3 (containing no ionomer) obtained as described below and a rubber sheet obtained as follows were bonded together. This was press vulcanized at 148 ° C. for 60 minutes to obtain a sheet-like test piece. No adhesive was used for bonding.

(5) Evaluation conditions and evaluation criteria for rubber / resin adhesion 1 to 4 About each obtained sheet-like test piece, rubber was peeled at a peeling speed of 50 mm / min at room temperature (23 ° C.) or 70 ° C. using an autograph. A peel test was conducted to peel the layer from the resin layer at an angle of 180 degrees, and the adhesive strength (unit = N / 25 mm) was measured. In addition, with rubber after the peel test (%, area ratio in which the rubber remains without being peeled from the resin layer) was visually determined, and the fracture state after the peel test was observed.
The evaluation criteria of the fracture status were: A: material breakage (thick material breakage), ○: material breakage, Δ: material breakage (thin material breakage), x: interface, cut: rubber cut.

2. Adhesion between reinforcing layer and rubber layer (hose wire bonding)
(1) Production of hose-shaped test piece First, a brass plating wire was wound in a spiral shape on an iron mandrel having an outer diameter of 25 mm to form a reinforcing layer. Next, an unvulcanized sheet having a thickness of 2.5 mm prepared from each of the obtained rubber compositions was bonded onto the reinforcing layer, and this was vulcanized for 60 minutes at 148 ° C. A test specimen was prepared.

(2) Evaluation method of hose-like test piece About each obtained hose-like test piece, the adhesive strength (unit = N per 25 mm width) and rubber attached when the rubber outer layer is peeled at a peeling speed of 50 mm / min (min) (Unit%, area ratio where the rubber remains without being peeled) was measured.

<Preparation of resin sheet 1>
30 parts by mass of ionomer (resin in which molecules of ethylene-methacrylic acid copolymer are cross-linked with zinc ions, trade name: Himilan 1706, manufactured by Mitsui DuPont Polychemical Co., Ltd.) and 70 masses of polyamide (11-nylon, manufactured by Arkema Co., Ltd.) Were mixed with a biaxial kneader and then extruded with a T-die extruder to produce a 0.2 mm thick sheet. The obtained sheet is referred to as “resin sheet 1”.

<Preparation of resin sheet 2>
50 parts by mass of an ionomer (resin in which molecules of ethylene-methacrylic acid copolymer are cross-linked with zinc ions: trade name Himilan 1706, manufactured by Mitsui DuPont Polychemical Co., Ltd.), and polyamide (11-nylon, manufactured by Arkema Co., Ltd.) 50 masses Were mixed with a biaxial kneader and then extruded with a T-die extruder to produce a 0.2 mm thick sheet. The obtained sheet is referred to as “resin sheet 2”.

<Preparation of resin sheet 3>
Polyamide (11-nylon, manufactured by Arkema) was extruded using a T-die extruder to produce a 0.2 mm thick sheet. The obtained sheet is referred to as “resin sheet 3”.

<Production of rubber sheet>
A rubber sheet (unvulcanized) having a thickness of 2.5 mm was prepared from the rubber compositions A to C obtained as follows using a roll.

<Manufacture of rubber composition>
The components shown in Table 1, Table 5, and Table 9 below were used in the amounts (parts by mass) shown in the same table, and uniformly mixed using a closed kneader to produce rubber compositions. Let the obtained rubber composition be rubber composition A1-A10, rubber composition B1-B16, and rubber composition C1-C20.

Each component shown in Table 1 is as follows.

Each component shown in Table 5 is as follows.

Each component shown in Table 9 is as follows.

As is apparent from the results shown in Table 3, Table 4, Table 7, Table 8, Table 11, Table 11 and Table 12, Comparative Example I-1 using a rubber composition containing no epoxidized rubber In Comparative Examples II-1 and II-2 and Comparative Examples III-1 and II-2, the resin layer and the rubber layer did not adhere to each other. In Comparative Examples I-3 to 12, Comparative Examples II-3 to 18, and Comparative Examples III-3 to 22, which use a resin composition containing no ionomer, the resin layer and the rubber layer did not adhere to each other.
On the other hand, Example I-1-8, Example II-1-14, and Example III-1-18 are excellent in the adhesiveness of a resin layer and a rubber layer. Further, as is clear from Example I-1 (results of rubber / resin adhesion 1 to 3), the rubber / resin composite hose of the present invention has an adhesive property between the resin layer and the rubber layer (rubber / resin adhesion 2). 3) can be made equal to or more than the case where the resin layer and the rubber layer are bonded using the current adhesive (rubber / resin bonding 1). The same applies to Example II-1 and Example III-1.
In Examples II-1 to 14 and Examples III-1 to 18, the rubber composition further contains a thiuram vulcanization accelerator and / or a sulfenamide vulcanization accelerator, and an alkylphenol formaldehyde resin. Adhesion with a brass plating wire can be made possible while maintaining adhesiveness with the resin layer. Furthermore, in the case of a sulfenamide accelerator, the adhesive property between the resin layer and the rubber layer at a high temperature (for example, 50 to 120 ° C.) is changed from the current adhesive (for example, TY-PLY-BN: phenol resin system). It can be made equal to or more than when the resin layer and the rubber layer are bonded using an adhesive.

1 Rubber / resin composite hose 3 Resin layer (innermost layer)
5 Rubber layer 6 Inner tube 7 Reinforcement layer 9 Outer layer

Claims (13)

An inner tube, the inner tube includes a resin layer as an innermost layer and a rubber layer adjacent to the innermost layer;
The material used for the resin layer is a resin composition containing a resin containing at least an ionomer having a carboxylic acid metal salt,
A rubber / resin composite hose, wherein the material used for the rubber layer is a rubber composition containing rubber containing at least epoxidized rubber. In the resin, the amount of the ionomer is 10 to 100% by mass in the total amount of the resin,
2. The rubber / resin composite hose according to claim 1, wherein the amount of the epoxidized rubber in the rubber is 10 to 100 mass% in the total amount of the rubber.   The rubber / resin composite hose according to claim 1 or 2, wherein the epoxidized rubber is an epoxidized natural rubber.   The rubber / resin composite hose according to any one of claims 1 to 3, wherein an epoxidation rate of the epoxidized rubber is 2 to 75 mol%.   The rubber / resin composite hose according to any one of claims 1 to 4, wherein the rubber further contains acrylonitrile butadiene rubber (NBR).   The rubber / resin composite hose according to any one of claims 1 to 5, wherein the resin further contains polyamide.   The polyamide is at least one selected from the group consisting of polyamide 6, polyamide 11, polyamide 12, polyamide 4-6, polyamide 6-6, polyamide 6-10, polyamide 6-12 and polyamide MXD-6. 6. The rubber / resin composite hose according to 6.   The rubber / resin composite hose according to any one of claims 1 to 7, wherein the rubber composition further contains a thiuram vulcanization accelerator and / or a sulfenamide vulcanization accelerator and an alkylphenol formaldehyde resin.   The rubber / resin composite hose according to any one of claims 1 to 8, wherein an adhesive layer is not provided between the resin layer and the rubber layer.   The rubber / resin composite hose according to claim 1, wherein the resin layer and the rubber layer are directly bonded.   The rubber / resin composite hose according to claim 1, further comprising a reinforcing layer and an outer layer outside the inner tube.   The rubber / resin composite hose according to claim 11, wherein a material used for the reinforcing layer is a brass plating wire.   The manufacturing method of the rubber / resin composite hose which manufactures the rubber / resin composite hose in any one of Claims 1-12 by carrying out the vulcanization adhesion of the said resin layer and the said rubber layer at least.