JP2003336774A - Hose and method for manufacturing hose - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hose and a method for manufacturing the hose which improve the barrier properties of refrigerant gas and dynamic durability including vibration resistance, and maintain or improve the hose flexibility even by using a CO<SB>2</SB>refrigerant. <P>SOLUTION: The hose consists of: an inner tube 4 formed such that a rubber layer 3 is formed on the outside of a resin layer tube 2; an barrier layer 6 where a stainless steel foil 5 on both surfaces of which a vulcanized adhesive is applied is spirally wound on the outside of the inner tube 4; a fiber reinforcing layer 7 situated on the outside of the barrier layer 6; and skin rubber 8 formed on the outside of the fiber reinforcing layer 7. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a hose and a method for manufacturing the hose. More specifically, it relates to a hose used for automobiles and the like, for example, used for transporting a refrigerant, and a method for manufacturing the hose.

[0002]

2. Description of the Related Art Conventionally, in a composite flexible hose used for transporting a refrigerant gas for a car air conditioner, a CO ₂ refrigerant, or a refrigerant gas for a contact freezer, the inner tube is generally made of a composite structure of a resin layer and a rubber layer. ing. The thin resin layer provided in the innermost layer secures gas permeation resistance, and the outer rubber layer secures flexibility, vibration absorption and moisture permeation resistance as a hose.

Generally, as a resin forming the innermost layer of a composite rubber hose for a car air conditioner and other refrigerants, a polyamide (PA) type resin is mainly used. This polyamide includes PA6, PA66, PA6 and PA6.
6 copolymers, PA11, PA12, PA11 and PA1
There are copolymers, modified products, blends of PA and blends of PA with olefin. The rubber on the outside of the inner tube may be butyl rubber, chlorinated butyl rubber, brominated butyl rubber, or the like.

However, since all of these inner tube materials are polymeric materials, their barrier properties in a high temperature atmosphere are insufficient. As means for improving the barrier property, JP-A-2-209224 and JP-A-2-209225 are known.
Japanese Patent Application Laid-Open No. 2-138586, Japanese Patent Application Laid-Open No. 2-1
13191, JP-B-63-13812, JP-A-11-264488, JP-A-11-2644.
No. 88, Japanese Patent Application Laid-Open No. 2000-241572, and the like have been proposed.

In the above-mentioned JP-A-2-209224 and JP-A-2-209225, a metal or metal compound thin film is formed on the outer periphery of the inner tube resin by sputtering or ion plating to improve the barrier property. ing. The method requires a vacuum chamber, and film-shaped ones can be continuously formed. However, if it is cylindrical, it is difficult to uniformly form a thin film of metal or metal compound due to the construction method, and it is also difficult to continuously process it. Furthermore, in the case of dry plating film,
The flexibility of the membrane itself is insufficient, the hose cannot follow the expansion when the inner tube tube diameter is expanded due to vibration or internal pressure of the hose, and there is a possibility that cracks will occur and the barrier property will be impaired.

Further, in Japanese Patent Laid-Open No. 2-138586, an aluminum laminate layer consisting of an aluminum thin layer, a fiber intermediate layer and an adhesive layer is provided on the outer periphery of a hose consisting of an inner tube, a reinforcing layer and an outer tube layer. However, since the refrigerant that has permeated the inner tube passes through the reinforcing layer (between the fibers) and leaks from the crimped portions at both ends, the effect of the barrier layer provided on the outer periphery of the outermost layer may be reduced. .

Further, in Japanese Patent Laid-Open No. 2-113191, a laminated sheet made of a plastic film and a metal thin film is used for the first barrier layer, and in order to prevent leakage from the lap portion of the aluminum laminated layer, A barrier layer is provided. However, since the inner tube and the aluminum laminate layer are not adhered to each other, the refrigerant that has permeated from the inside may stay between the inner tube and the aluminum laminate layer, which may cause swelling.

Further, in Japanese Examined Patent Publication No. 63-13812, an aluminum laminate tape having both surfaces coated with low molecular weight polyethylene is vertically wound on a nylon tube having a thickness of 1.5 mm, and the outer layer is extruded, and At the extrusion temperature, adhesion of the overlap portion, partial adhesion of the nylon tube and polyethylene, and adhesion of the outer layer linear polymer are simultaneously performed. However, the thickness of the nylon tube is thick and the flexibility is extremely poor. Therefore, in order to ensure flexibility, if the wall thickness of the nylon tube is reduced, the overlapping part will be formed at one place on the circumference of the tube, and the flexibility when bending the hose may differ depending on the bending direction. . In addition, since the aluminum laminate tape is simply coated with polyethylene, which is formed by so-called extrusion lamination, the adhesion between the aluminum film and nylon and the adhesion between the aluminum film and polyethylene are not sufficient, and the refrigerant that has permeated from inside has a polyethylene layer and aluminum. Stay between the film and
There is a fear of swelling.

Japanese Patent Laid-Open No. 11-264488 proposes spirally winding an aluminum laminate film and melt-bonding the rubber between the films and the inner tube rubber to the laminate film at the vulcanization temperature of the rubber. There is a possibility that the gas that has permeated from the inner surface will stay between the laminate film and the inner tube rubber and swell at the actual use temperature level of the hose due to its low adhesive strength.

Further, in consideration of the thermal decomposition starting temperature, the vulcanization temperature of a general rubber is 200 ° C. or lower, and a resin material (heat seal material) capable of melt adhesion at the vulcanization temperature.
Needless to say, the melting point of is less than 200 ° C. Although melt-bonding with PET resin is also described in the description, the melting point of PET resin is 250 ° C. to 260 ° C. level, and it is very difficult to melt-bond simultaneously with vulcanization of rubber.

Therefore, the applicants of the present invention, Japanese Patent Laid-Open No. 2001-24
In Japanese Patent No. 1572, it is proposed to spirally wrap an aluminum laminate film and vulcanize and bond an inner tube rubber and a laminate film using a vulcanizing adhesive. According to this method, vulcanization of rubber at 200 ° C. or lower is performed. It was found that the adhesive strength with rubber can be increased at a temperature and the gas permeation resistance can be secured.

However, when this rubber hose is used for transporting a refrigerant gas for a car air conditioner, CO ₂ is used as a refrigerant.
When a refrigerant is used, the refrigerant gas passing through the rubber hose has a high temperature and high pressure as compared with the case of using a conventional alternative CFC refrigerant or the like. On the other hand, the adhesive force between the aluminum film and the resin film constituting the laminate film weakens at high temperatures. Therefore, the hose is repeatedly pressurized under high pressure,
In addition, peeling occurs at the interface between these films due to repeated stress due to vibration of the automobile engine, etc., and the peeled portion becomes the leakage path of the refrigerant, and further, the strength of the aluminum foil itself is low, so vibration This causes problems such as cracks in the aluminum foil.

[0013]

SUMMARY OF THE INVENTION In view of the above circumstances, therefore, the present invention is to maintain or improve the flexibility of a hose even when a CO ₂ refrigerant is used, while at the same time, it is a refrigerant gas barrier property and vibration durability. It is an object of the present invention to provide a hose capable of improving the dynamic durability including the above and a method for producing the hose.

[0014]

According to the invention of claim 1, an inner tube made of a single-layer rubber tube, a single-layer resin tube, or a resin layer tube provided with a rubber layer on the outside, and an outer side of the inner tube. A metal foil selected from the group consisting of an iron foil, a steel foil, a stainless steel foil and a titanium alloy foil in a spiral or longitudinally wound barrier layer, and a fiber reinforcing layer provided outside the barrier layer, A hose made of an outer rubber provided on the outer side of the fiber reinforcing layer.

According to the second aspect of the present invention, a single-layer rubber tube, a single-layer resin tube, or an inner tube made of a resin layer tube provided with a rubber layer on the outer side, and an iron foil or a steel foil on the outer side of the inner tube. , A stainless steel foil, and a barrier layer formed by winding a metal foil selected from the group consisting of titanium alloy foil in a spiral shape or in a vertical direction, a rubber layer provided on the outer side of the barrier layer, and on the outer side of the rubber layer. A hose comprising a fiber-reinforced layer provided and an outer rubber provided outside the fiber-reinforced layer.

The invention according to claim 3 is the hose according to claim 1 or 2, characterized in that the metal foil has a thin film of a metal or a metal compound formed on at least one surface thereof.

The invention of claim 4 is characterized in that a vulcanizing adhesive is applied to both surfaces of the metal foil.
The hose according to any one of 1.

The hose according to any one of claims 1 to 3, wherein the overlapping portions of the metal foil are vulcanized and bonded to each other at a vulcanization temperature of the hose with a vulcanizing adhesive. Is.

The invention according to claim 6 is the hose according to any one of claims 1 to 3, wherein the resin layer tube of the inner tube is formed of a polyamide resin or a resin composition containing a polyamide resin as a main component. is there.

According to a seventh aspect of the invention, the rubber layer of the inner pipe is
At least one selected from the group consisting of butyl rubber, chlorinated butyl rubber, brominated butyl rubber, nitrile rubber, chlorosulfonated polyethylene rubber and chloroprene rubber.
The hose according to any one of claims 1 to 3, which is made of a kind of rubber.

According to the invention of claim 8, the thickness of the metal foil is 3
The hose according to any one of claims 1 to 3, which has a thickness of -50 µm.

In a ninth aspect of the present invention, the vulcanizing adhesive is mainly composed of a halogenated polymer to which a crosslinking agent is added or a mixture of a resol type phenol resin and an aldehyde-modified product of polyvinyl alcohol. The hose according to item 4.

A tenth aspect of the invention is a single-layer rubber tube,
An inner tube made of a single-layer resin tube or a resin layer tube provided with a rubber layer on the outer side, and an iron foil on the outer side of the inner tube,
A barrier layer in which a metal foil selected from the group consisting of steel foil, stainless steel foil, and titanium alloy foil is spirally or longitudinally wound, a fiber reinforcing layer provided outside the barrier layer, and the fiber reinforcing It is a method of manufacturing a hose which is composed of an outer rubber provided on the outer side of the layer and is vulcanized and bonded to each other by vulcanization.

[0024] The invention of claim 11 is a single-layer rubber tube,
An inner tube made of a single-layer resin tube or a resin layer tube provided with a rubber layer on the outer side, and an iron foil on the outer side of the inner tube,
A barrier layer formed by spirally or vertically winding a metal foil selected from the group consisting of steel foil, stainless steel foil, and titanium alloy foil, a rubber layer provided outside the barrier layer, and a rubber layer of the rubber layer. This is a method for producing a hose, which comprises a fiber-reinforced layer provided on the outer side and an outer rubber provided on the outer side of the fiber-reinforced layer, and these are vulcanized to be vulcanized and bonded to each other.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION A hose and a method for manufacturing the hose according to the present invention will be described below with reference to the accompanying drawings.

FIG. 1 is a partially cutaway perspective view showing an embodiment of the hose of the present invention.

As shown in FIG. 1, a hose 1 according to an embodiment of the present invention comprises an inner tube 4 having a rubber layer 3 on the outer side of a resin layer tube 2 and stainless steel on the outer side of the inner tube 4. A barrier layer 6 in which a high-strength metal foil 5 such as a foil is wound in a spiral shape, a fiber reinforcement layer 7 provided outside the barrier layer 6, and an outer rubber 8 provided outside the fiber reinforcement layer 7. It can be manufactured by vulcanizing and adhering these to each other with a vulcanizing adhesive.

The resin layer tube 2 is formed of a polyamide resin or a resin composition containing a main component of the polyamide resin, for example, 60% by weight or more and a balance of ethylene / α-olefin / non-conjugated diene rubber. preferable. As the rubber layer 3, butyl rubber (IIR), chlorinated butyl rubber, brominated butyl rubber,
It is preferably formed of at least one rubber selected from the group consisting of nitrile rubber, chlorosulfonated polyethylene rubber and chloroprene rubber.

In the present embodiment, the inner tube is formed of the resin layer tube 2 and the rubber layer 3, but the present invention is not limited to this, and the resin layer tube 2 is not limited to this. Instead of the inner tube 4 provided with the rubber layer 3 on the outside,
It can be an inner tube of a single-layer rubber tube or a single-layer resin tube.

As the metal foil 5, high-strength metal foil such as iron foil, steel foil, and titanium alloy foil can be used in addition to stainless steel foil. Incidentally, the above-mentioned JP-A-11-26448.
No. 8 discloses that a single layer of aluminum or copper foil having a thickness of 3 to 70 μm is used instead of using an aluminum laminated film. However, since aluminum and copper have low strength, there is a problem that if the aluminum foil or copper foil single layer is used to maintain the strength, the thickness of the foil becomes too thick and the flexibility of the tube product decreases. Therefore, conventionally, a resin film having flexibility is attached to an aluminum foil to maintain the flexibility and increase the strength. On the other hand, when the metal foil 5 having high strength as in the present invention is used, the strength of the single layer of the metal foil 5 can be kept thinner than that of the aluminum foil without using a laminated film, so that the flexibility of the tube product is improved. It does not interfere. The metal foil 5 has a wall thickness of 3 to 50 μm, and preferably 7 to 30 μm. This is because when the wall thickness is thinner than 3 μm, many pinholes are generated in the metal foil 5 and the barrier effect is lowered, and when the wall thickness is thicker than 50 μm, the flexibility of the metal foil 5 decreases and the hose 1 becomes flexible. Because it lowers. Further, the width of the metal foil 5 is 1 to 2 of the outer diameter of the inner tube 4 when spirally wound.
It is 5 times, and preferably 1.2 to 1.5 times. This is because if the width of the metal foil 5 is smaller than the outer diameter of the inner tube 4 to be wound, the productivity is reduced, and if it exceeds 2.5 times the outer diameter of the inner tube 4, the winding work becomes difficult and wrinkles and scrapes are generated. This is because it tends to occur. In the case where the metal foil 4 is wound vertically, the width of the metal foil 4 is approximately the same as or slightly longer than the outer peripheral length of the inner tube 4.

Further, it is also preferable to form a metal or metal compound thin film such as a plating layer on at least one surface of the metal foil 5. As a result, the pinholes in the metal foil 5 can be closed and the barrier effect can be improved. Further, the effect of improving the corrosion resistance of the metal foils 5 and the effect of increasing the adhesiveness between the metal foils 5 can be expected. Unlike the film formation on the outer circumference of the inner tube resin as in the above-mentioned JP-A-2-209224 and JP-A-2-209225, the film-like metal foil 5 surface is subjected to a sputtering or ion plating method. A uniform film can be easily formed by such means. In addition, the metal foil 5 and the plating film cooperate to form the hose 1.
Follows the elongation when the diameter of the inner tube 4 swells due to vibration or the internal pressure of the hose, so that the occurrence of cracks is prevented.

The vulcanizing adhesive comprises a halogenated polymer such as chlorinated polyolefin and a cross-linking agent, and the polyolefin of the chlorinated polyolefin is polyethylene,
Selected from the group consisting of polypropylene, ethylene-propylene copolymer, ethylene-propylene-diene terpolymer, ethylene-propylene-hexadiene terpolymer, ethylene-propylene-dicyclopentadiene terpolymer and ethylene-propylene-ethylidene norbornene terpolymer. In addition, chlorosulfonated polyethylene, chlorinated natural rubber, polychloroprene, chlorinated polychloroprene, chlorinated polybutadiene,
Butadiene / halogenated cyclic conjugated diene adduct, chlorinated butadiene styrene copolymer, brominated poly (2,3-dichloro-1,3-butadiene), α-haloacrylonitrile and 2,3-dichloro-1,3 It is also possible to choose from the group consisting of chlorine- and bromine-containing synthetic rubbers, including copolymers of butadiene, polyvinyl butyral, chlorinated polyvinyl chloride, and mixtures thereof. Further, it is also possible to use a material containing a mixture of a resol-type phenol resin and an aldehyde-modified product of polyvinyl alcohol as a main component.

Such a vulcanizing adhesive may be applied to both sides of the metal foil 5 in advance, for example. After the metal foil 5 is wound around the inner pipe 4 in a spiral shape or vertically, the hose 1 is heated at a heating temperature for vulcanizing, whereby the overlap portion of the metal foil 5 can be vulcanized and adhered.
Furthermore, the metal foil 5 and the inner tube 4 and the reinforcing layer 7 can be bonded together. The vulcanization temperature of hose 1 is usually 1
It is about 30 to 190 ° C, preferably about 150 to 180 ° C. When the temperature of vulcanization adhesion is low, the adhesive strength tends to be insufficient due to insufficient reaction, and when it is high, the strength tends to be insufficient or the durability may be deteriorated due to thermal decomposition of the adhesive itself. .

Instead of adhering the metal foil 5 with a vulcanizing adhesive, the metal foil 5 may be vertically wrapped around the inner tube 4 and the abutting portions at both ends in the width direction of the metal foil 5 may be welded. As the welding method, laser welding such as YAG laser, spot welding, ultrasonic welding, friction welding and the like can be used.

As the fiber reinforcing layer 7, a layer reinforced by braiding braiding fibers such as fiber (polyester (PET)), nylon aramid, or the like in a braided or spiral shape can be used.

As the outer cover rubber 8, ethylene / propylene / diene copolymer (EPDM), butyl rubber, butyl chloride rubber or brominated butyl rubber can be used.

[0037]

As described above, according to the present invention, even if a CO ₂ refrigerant is used, the barrier layer is not peeled off or cracked in the barrier layer, so that the flexibility as a hose is maintained or improved. At the same time, the dynamic durability including the barrier property of the refrigerant gas and the vibration durability can be improved.

[Brief description of drawings]

FIG. 1 is a partially cutaway perspective view showing an embodiment of a hose of the present invention.

[Explanation of symbols]

1 hose 2 Resin layer tube 3 rubber layers 4 inner tube 5 metal foil 6 Barrier layer 7 Fiber reinforcement layer 8 outer rubber

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ identification code FI theme code (reference) B29K 77:00 B29K 77:00 105: 22 105: 22 (72) Inventor Keizo Saga Bessho-cho, Himeji City, Hyogo Prefecture Sado 1118 address stock Company Nichirin Himeji plant in the F-term (reference) 3H111 AA02 BA02 BA03 BA05 BA12 BA15 CB05 CB06 CB07 CC02 DA26 DB09 DB19 4F100 AB02B AB03B AB04B AB10 AB12B AB33B AK01A AK01B AK04A AK04B AK08A AK08B AK27A AK27B AK46A AK46B AK62 AL06A AL06B AN00A AN00E BA05 BA07 BA10A BA10E DA11 DG01D GB32 JD02B JK17 JL01 YY00B 4F213 AA12 AA29 AA45 AB03 AD03 AD08 AG08 AH17 WA15 WA17 WA34 WA38 WA43 WA54 WA87 WW01 WW21 WW01 WW01 WF01 WF05 WF01 WF05 WF01 WF05 WF21 WF01 WF01 WF05 WF01 WF05

Claims (11)

[Claims] 1. A single-layer rubber tube, a single-layer resin tube,
Alternatively, an inner tube made of a resin layer tube provided with a rubber layer on the outside and a metal foil selected from the group consisting of iron foil, steel foil, stainless steel foil and titanium alloy foil on the outer side of the inner tube are spiral-shaped. Alternatively, a hose including a barrier layer wound vertically, a fiber reinforcing layer provided outside the barrier layer, and an outer rubber provided outside the fiber reinforcing layer. 2. A single-layer rubber tube, a single-layer resin tube,
Alternatively, a spiral is formed of an inner tube made of a resin layer tube provided with a rubber layer on the outside and a metal foil selected from the group consisting of iron foil, steel foil, stainless steel foil, and titanium alloy foil on the outer side of the inner tube. -Shaped or longitudinally wound barrier layer, rubber layer provided outside the barrier layer, fiber reinforcement layer provided outside the rubber layer, and outer rubber provided outside the fiber reinforcement layer A hose consisting of. 3. The hose according to claim 1, wherein the metal foil has a metal or metal compound thin film formed on at least one surface thereof. 4. The hose according to any one of claims 1 to 3, wherein a vulcanizing adhesive is applied to both surfaces of the metal foil. 5. The hose according to claim 1, wherein the overlapping portions of the metal foil are vulcanized and bonded to each other at a vulcanization temperature of the hose with a vulcanizing adhesive. 6. The hose according to claim 1, wherein the resin layer tube of the inner tube is formed of a polyamide resin or a resin composition containing a polyamide resin as a main component. 7. The rubber layer of the inner tube is made of at least one rubber selected from the group consisting of butyl rubber, chlorinated butyl rubber, brominated butyl rubber, nitrile rubber, chlorosulfonated polyethylene rubber and chloroprene rubber. The hose according to any one of 1 to 3. 8. The hose according to claim 1, wherein the metal foil has a wall thickness of 3 to 50 μm. 9. The hose according to claim 4, wherein the vulcanizing adhesive is a halogenated polymer to which a crosslinking agent is added or a mixture of a resol-type phenol resin and an aldehyde-modified product of polyvinyl alcohol as a main component. . 10. An inner tube made of a single-layer rubber tube, a single-layer resin tube, or a resin layer tube provided with a rubber layer on the outer side, and an iron foil, a steel foil, a stainless steel foil on the outer side of the inner tube, And a barrier layer in which a metal foil selected from the group consisting of titanium alloy foil is spirally or longitudinally wound, a fiber reinforcing layer provided outside the barrier layer, and a fiber reinforcing layer provided outside the fiber reinforcing layer. A method of manufacturing a hose that is made of outer rubber and is vulcanized and bonded together by vulcanization. 11. An inner tube made of a single-layer rubber tube, a single-layer resin tube, or a resin layer tube provided with a rubber layer on the outside, and an iron foil, a steel foil, a stainless steel foil on the outside of the inner tube. And a barrier layer in which a metal foil selected from the group consisting of titanium alloy foil is spirally or longitudinally wound, a rubber layer provided outside the barrier layer, and a fiber reinforcement provided outside the rubber layer. A method for producing a hose comprising a layer and an outer rubber layer provided on the outer side of the fiber reinforced layer, which are vulcanized and bonded to each other by vulcanization.