JP2006194394A - Hose - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hose for suitably transporting a carbon dioxide refrigerant which has high gas barrier quality under high temperature and pressure conditions, 150°C or more and 10MPa or more. <P>SOLUTION: The hose comprises a base material and a layer formed of an alloy which has super plasticity at room temperature. The base material is a rubber layer or a rubber composition layer, and the alloy which has super plasticity at room temperature is a Zn-Al alloy layer with a β-phase of an average crystal grain size of 0.05μm or less finely dispersed in an α-phase or a α'-phase of an average crystal grain size of 5μm or less. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a hose having a layer made of an alloy having superplasticity at room temperature, and particularly to a hose having a high gas barrier property even under high temperature and pressure.

Conventionally, specified CFC-12 has been used as a refrigerant for air conditioning systems in automobiles, but its use has been banned from the viewpoint of conservation of the global environment, and now HFC-134a is widely used as a substitute for CFC. It is used. However, this alternative chlorofluorocarbon also has the problem that, from the viewpoint of the impact on the global environment, the ozone depletion coefficient is zero, but the global warming coefficient is high, which can cause global warming. Yes.
For this reason, the conversion to a refrigerant with a low global warming potential has been studied, and as one of them, development using carbon dioxide (CO ₂ ) as the refrigerant is underway. However, in an air conditioner system using carbon dioxide, usage conditions become severe, and a refrigerant transport hose attached to an automobile cooling device using carbon dioxide as a refrigerant has a high temperature (for example, 150 ° C.) which is said to be in a supercritical state. Low permeability to the refrigerant gas under the conditions of high pressure (for example, about 10 MPa or more). Metal pipes can be applied as satisfying such conditions. However, in automobile applications, ride comfort is important, so vibration absorption performance is required, and hoses using rubber materials have been developed. For example, resin or rubber Although a hose in which a metal layer is laminated on a material has been proposed, there is a problem that the metal layer cannot follow the bending of the hose and breaks. Nylon may be used to improve gas barrier properties, but nylon has a large carbon dioxide permeation amount in a supercritical state, and inner-shell butyl rubber (IIR) is a shell ethylene-propylene-diene terpolymer. The conventional rubber tube of rubber (EPDM) is inferior in long-term high-temperature heat resistance, and even when organic fibers such as polyethylene terephthalate (PET) are used as reinforcing fibers, the pressure resistance in the supercritical state is not sufficient, Reinforcing with organic fibers has been technically difficult from the viewpoint of shape stability of the crimped portion.
As a solution to these problems, for example, Patent Document 1 describes a hose which is modified into a resin layer and / or a rubber layer and combined with a metal foil, and Patent Documents 2 to 4 describe a resin layer and / or A hose is described in which a layer in which a metal layer is laminated on a rubber layer has a bellows shape. And further gas barrier property, high temperature heat resistance, and high pressure resistance were desired rather than these hoses. Further, hoses with improved gas barrier properties and heat / pressure resistance performance have been desired rather than these hoses.

JP 2003-277897 A JP 2003-56760 A JP 2003-74761 A JP 2004-156672 A

  The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a hose having a high gas barrier property even under high temperature and pressure.

  As a result of intensive studies to achieve the above object, the present inventors may refer to a layer made of an alloy having superplasticity at room temperature, which is excellent in gas barrier properties (hereinafter referred to as “room temperature superplastic alloy layer”). The present invention has been completed by finding that the above-mentioned problems can be solved by forming a hose using the following method.

That is, the present invention provides the following hose.
(1) A hose comprising a base material and a layer made of an alloy having superplasticity at room temperature.
(2) The hose according to (1), wherein an alloy having superplasticity at room temperature is deposited on the base material.
(3) The hose according to (1), wherein a thin film made of an alloy having superplasticity at room temperature is incorporated and laminated on the base material.
(4) The hose according to any one of (1) to (3), wherein the base material is a rubber layer or a rubber composition layer.
(5) The hose according to any one of (1) to (4), comprising a rubber layer or a rubber composition layer, a layer made of an alloy having superplasticity at room temperature, and a metal wire layer.
(6) The rubber material of the rubber layer or rubber composition layer is hydrogenated nitrile rubber (HNBR), chlorosulfonated polyethylene rubber (CSM), acrylic rubber (ACM), ethylene-acrylic rubber (AEM), silicone rubber, and The hose according to any one of (1) to (5), comprising at least one selected from fluororubber.
(7) The alloy having superplasticity at room temperature is a Zn-Al alloy containing Zn: 30 to 80% by mass, the balance being Al and inevitable impurities, and an α phase having an average crystal grain size of 5 μm or less The hose according to any one of the above (1) to (6), which is a Zn—Al alloy having a structure in which a β phase having an average crystal grain size of 0.05 μm or less is finely dispersed in an α ′ phase.
(8) The alloy having superplasticity at room temperature is a Zn-Al alloy containing Zn: 75 to 99% by mass, the balance being Al and inevitable impurities, and an α phase having an average crystal grain size of 5 μm or less The above (1), which is a Zn—Al alloy having a main structure of α ′ phase and β phase, and a structure in which β phase having an average crystal grain size of 0.05 μm or less is finely dispersed in the α phase or α ′ phase. The hose according to any one of to (6).
(9) The hose according to any one of (1) to (8), wherein the thin film made of the alloy having superplasticity at room temperature has a thickness of 10 nm to 5 μm.
(10) The hose according to any one of (1) to (9), which is used in an environment having a temperature of 150 ° C. or higher and a pressure of 10 MPa or higher.
(11) The hose according to any one of (1) to (10), which is for transporting carbon dioxide refrigerant.

  The hose of the present invention has a high gas barrier property even at a high temperature and high pressure of, for example, 150 ° C. or higher and 10 MPa or higher.

The hose of the present invention has a base material and a layer made of an alloy having superplasticity at room temperature.
The base material is not limited as long as it is a conventionally known base material, but those that can be used at high temperatures are preferable, and there are a resin layer made of a thermoplastic resin that can be used at 150 ° C. or higher, and a rubber layer made of a rubber material. And preferred. A rubber material is preferable because of its vibration absorption effect.
Examples of the thermoplastic resin include heat-resistant thermoplastic resins having a melting point of 200 ° C. or higher that can be used at 150 ° C. or higher, such as polyamide, polyester, polyolefin, etc., preferably polyaramid, nylon MXD6, polyethylene-2, Fluorine-containing resins such as 6-naphthalate and various fluorine-containing polyolefins, polymethylpentene (TPX) and the like, particularly preferably fluorine-containing resins and polymethylpentene. Specific examples of the fluororesin include, for example, polytetrafluoroethylene (PTFE), tetrafluoroethylene / ethylene copolymer (ETFE), tetrafluoroethylene / perfluoroethylene copolymer (PFA), and polyvinylidene fluoride. Ride (PVdF), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), polychlorotrifluoroethylene (PCTFE), and the like.

The rubber material is preferably one that can be used under high temperature and high pressure. For example, hydrogenated nitrile rubber (HNBR), chlorosulfonated polyethylene rubber (CSM), acrylic rubber (ACM), ethylene-acrylic rubber (AEM), Examples thereof include silicone rubber and fluororubber.
These resins and rubber materials may be used alone or in combination of two or more.

The resin layer or the rubber layer may be a resin composition layer and a rubber composition layer in which a softener or other resin is blended as necessary. The softening agent is blended to reduce the hardness of the resin or rubber. The softener is not particularly limited and can be selected and used from those conventionally used as a softener for resins and rubbers. However, a low molecular weight substance having a number average molecular weight of less than 20000 can be used. In terms of physical properties, those having a viscosity at 100 ° C. of 5 × 10 ² Pa · s or less, particularly 1 × 10 ² Pa · s or less are preferable. Further, from the viewpoint of molecular weight, the number average molecular weight is preferably less than 20,000, particularly 10,000 or less, particularly 5000 or less. As such a softening agent, usually a liquid or liquid at room temperature is preferably used.
The softener having such properties can be appropriately selected from, for example, various rubber or resin softeners such as mineral oil and synthetic. Here, examples of mineral oils include process oils such as naphthenic and paraffinic oils. Among them, non-aromatic oils, especially mineral oil-based paraffinic oils, naphthenic oils, or synthetic polyisobutylene oils are mentioned. One or two or more selected from oils having a number average molecular weight of 450 to 5000 is preferable.

In addition, these softeners may be used individually by 1 type, and may mix and use 2 or more types if mutual compatibility is favorable.
Although the compounding quantity of these softeners does not have a restriction | limiting in particular, It is 1-1000 mass parts normally with respect to 100 mass parts of resin or rubber | gum, Preferably it is chosen in the range of 1-500 mass parts. If this amount is 1 part by mass or more, sufficient reduction in hardness can be achieved, and the resulting molded product has sufficient flexibility, and if it is 1000 parts by mass or less, the softener does not bleed, and the molded product. The mechanical strength of is sufficient. In addition, it is preferable to select the compounding quantity of this softener suitably in the said range according to the kind of resin or rubber | gum, and the other component added to it.

The resin or rubber used in the present invention can be blended with a polyphenylene ether resin as desired for the purpose of improving the compression set of the molded body.
As the polyphenylene ether resin, known ones can be used. Specifically, poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4- Phenylene ether), poly (2,6-diphenyl-1,4-phenylene ether), poly (2-methyl-6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4- And a polyphenylene such as a copolymer of 2,6-dimethylphenol and a monovalent phenol (for example, 2,3,6-trimethylphenol or 2-methyl-6-butylphenol). Ether copolymers can also be used. Of these, poly (2,6-dimethyl-1,4-phenylene ether) and a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferable. Dimethyl-1,4-phenylene ether) is preferred.
The compounding quantity of polyphenylene ether resin can be suitably selected in the range of 10-250 mass parts with respect to 100 mass parts of resin or rubber | gum. When the blending amount is 250 parts by mass or less, the hardness of the resulting molded body is not excessively high and is moderate, and when it is 10 parts by mass or more, the effect of improving the compression set of the molded body obtained by blending is sufficient. It becomes.

Further, the resin or rubber used in the present invention includes clay, diatomaceous earth, silica, talc, barium sulfate, calcium carbonate, magnesium carbonate, metal oxide, mica, graphite, aluminum hydroxide and other flake-like inorganic additives, Mix various metal powders, glass powders, ceramic powders, granular or powdered solid fillers such as granular or powdered polymers, other various natural or artificial short fibers, long fibers (various polymer fibers, etc.) Can do.
Moreover, weight reduction can be attained by mix | blending an organic hollow filler which consists of a hollow filler, for example, inorganic hollow fillers, such as a glass balloon and a silica balloon, a polyvinylidene fluoride, a polyvinylidene fluoride copolymer, etc. Furthermore, in order to improve various physical properties such as weight reduction, it is possible to mix various foaming agents, and it is also possible to mix gas mechanically during mixing.

In addition to the above components, additives such as known resin components can be used in combination with the resin or rubber used in the present invention in order to improve various properties.
As the resin component, for example, a polyolefin resin or a polystyrene resin can be used alone or in combination. By adding these, the workability and heat resistance of the resin composition or rubber composition can be improved.
Examples of the polyolefin resin include polyethylene, isotactic polypropylene, a copolymer of propylene and a small amount of other α-olefin (for example, propylene-ethylene copolymer, propylene / 4-methyl-1-pentene copolymer). Coalesced), poly (4-methyl-1-pentene), polybutene-1, and the like. When isotactic polypropylene or a copolymer thereof is used as the polyolefin resin, those having an MFR (JIS K7210) of 0.1 to 50 g / 10 min, particularly 0.5 to 30 g / 10 min can be preferably used. .

As the polystyrene resin, those obtained by either a radical polymerization method or an ionic polymerization method can be suitably used as long as they are obtained by a known production method. The number average molecular weight of the polystyrene resin is preferably selected from the range of 5,000 to 500,000, more preferably 10,000 to 200,000, and the molecular weight distribution [ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw / Mn) ] Is preferably 5 or less.
Examples of the polystyrene resin include polystyrene, styrene-butadiene block copolymer having a styrene unit content of 60% by mass or more, rubber-reinforced polystyrene, poly α-methylstyrene, polypt-butylstyrene, and the like. May be used alone or in combination of two or more. Furthermore, a copolymer obtained by polymerizing a mixture of monomers constituting these polymers can also be used.
Moreover, the said polyolefin resin and polystyrene resin can also be used together. For example, when a polystyrene resin is used in combination as compared with the case of adding a polyolefin resin alone, the hardness of the resulting molded product tends to increase. Therefore, the hardness of the obtained molded body can be adjusted by selecting these blending ratios. In this case, the ratio of polyolefin resin / polystyrene resin is preferably selected from the range of 95/5 to 5/95 (mass ratio).

  When these resin components are used in combination, the blending amount is preferably about 0 to 100 parts by mass with respect to 100 parts by mass of the resin or rubber. For example, in the case of a polyolefin resin, 0.1 to 50 parts by mass is particularly preferred. Is more preferable. If the blending amount of the resin component is 100 parts by mass or less, the hardness of the resulting molded body will not be too high. In addition, when using polyolefin resin as a resin component, it is more preferable to mix | blend especially the above-mentioned softener in the range of 1-500 mass parts with respect to 100 mass parts of copolymers (thermoplastic elastomer).

  In addition, the resin or rubber used in the present invention includes other additives such as a flame retardant, an antibacterial agent, a hindered amine light stabilizer, an ultraviolet absorber, an antioxidant, a colorant, silicone oil, silicone as necessary. Various adhesive elastomers such as polymers, coumarone resins, coumarone-indene resins, phenol terpene resins, petroleum hydrocarbons, rosin derivatives and other tackifiers (tackfire), Rheostomer B (trade name: manufactured by Riken Vinyl Co., Ltd.), Hybler (trade name: manufactured by Kuraray Co., Ltd., a block copolymer in which polystyrene blocks are connected to both ends of a vinyl-polyisoprene block), Norex (trade name: manufactured by Nippon Zeon Co., Ltd., obtained by ring-opening polymerization of norbornene Norbornene) and the like can be used in combination.

  The silicone polymer has a weight average molecular weight of 10,000 or more, preferably 100,000 or more. The said silicone polymer improves the surface adhesiveness of the molded object using resin or rubber | gum. As the silicone polymer, a general-purpose thermoplastic polymer such as polyethylene, polypropylene, or polystyrene blended at a high concentration can be used in order to improve the handleability. In particular, a blended product with polypropylene has good workability and physical properties. As such a material, for example, a commercially available silicone concentrate BY27 series general-purpose type commercially available from Toray Dow Corning Silicone Co., Ltd. may be used. By blending the silicone polymer, the surface condition of the molded body can be improved, but the miscibility between the silicone polymer and the resin or rubber used in the present invention is not always good. This can be easily imagined because the chemical composition of each polymer is significantly different. Accordingly, the silicone polymer may be separated depending on the content of the blend and the molding conditions of the molded body. In that case, the state can be improved by using a polymer having a relatively good miscibility with the resin or rubber, for example, a graft polymer obtained by chemically bonding a silicone polymer to a polyolefin resin. . As such a material, you may use what is marketed as a BY27 series graft type from Toray Dow Corning Silicone Co., Ltd., for example.

The method for producing the resin or rubber composition according to the present invention is not particularly limited, and a known method can be applied. For example, each of the above components and optionally used additive components are melt kneaded using a heating kneader, such as a single screw extruder, twin screw extruder, roll, Banbury mixer, plastic bender, kneader, high shear mixer, etc. Furthermore, it can be easily produced by adding a crosslinking agent such as an organic peroxide, a crosslinking aid or the like, if necessary, or by simultaneously mixing these necessary components and heating and kneading them.
In addition, a thermoplastic material prepared by kneading a polymer organic material and a softener is prepared in advance, and this material is further mixed with one or more types of polymer organic materials that are the same type or different from those used here. You can also
Furthermore, the resin or rubber used in the present invention can be crosslinked by adding a crosslinking agent such as an organic peroxide, a crosslinking aid or the like.
In the present invention, the substrate is preferably a rubber layer or a rubber composition layer.
Moreover, the thickness of the said base material is about 0.2-3.0 mm normally, Preferably it is 0.3-2.0 mm.

The alloy having superplasticity at room temperature used in the present invention (hereinafter referred to as “room temperature superplastic alloy”) is not particularly limited, and any one of conventionally known room temperature superplastic alloys is appropriately selected. be able to. Here, superplasticity means the following. That is, many eutectics such as Al-33% Cu (eutectic), Zn-22% Al (eutectoid), Sn-38% Pb (eutectic), or alloys close thereto, have fine grains. In a state, the elongation until breakage may show a large plastic deformation of about 1000%. This is called superplasticity. The large deformation is said to be due to the viscous shear deformation of the grain boundary and the movement of diffusion movement or grain boundary dislocation in the vicinity of the grain boundary. Superplastic alloys are used as raw materials when large deformation is required, such as drawing.
Examples of the room temperature superplastic alloy used in the present invention include the following alloys.
(1) A Zn-Al alloy containing 30 to 80% by mass of zinc, the balance being aluminum and inevitable impurities, and having an average crystal grain size in an α phase or α 'phase having an average crystal grain size of 5 µm or less Zn—Al alloy having a structure in which a β phase of 0.05 μm or less is finely dispersed.
(2) Zn-Al alloy containing 75 to 99% by mass of zinc, with the balance being aluminum and inevitable impurities, with an average crystal grain size of 5 μm or less, α phase or α ′ phase, and β phase as the main structure A Zn—Al alloy having a structure in which a β phase having an average crystal grain size of 0.05 μm or less is finely dispersed in the α phase or the α ′ phase.
The alloys (1) and (2) are Zn—Al alloys described in JP-A-11-222463, and the elongation at room temperature is a value exceeding 160%.
In the hose of the present invention, the thickness of the thin film made of room temperature superplastic alloy is usually about 10 nm to 5 μm, preferably 50 nm to 1 μm, from the viewpoint of desired required characteristics, balance of repeated deformation and balance of economy. is there.

The hose of the present invention preferably has a reinforcing layer in addition to the base material and the room temperature superplastic alloy layer. As this reinforcing layer, metal wires and organic fibers such as steel wires, stainless wires, polyethylene terephthalate fibers (PET), polyethylene naphthalate fibers (PEN), nylon fibers, aramid fibers, and other carbon fibers can be used. Among these, metal wires such as steel wires and stainless steel wires are preferable. By providing this reinforcing layer, high pressure resistance and flexibility as a hose can be improved.
Moreover, the thickness of the said reinforcement layer is about 0.2-6.0 mm normally, Preferably it is 0.4-4.0 mm.

In the present invention, it is preferable that an outer surface layer is further formed on the outer side of the reinforcing layer to protect the reinforcing layer, whereby the hose can be made highly durable. Examples of the material for the outer surface layer in this case include the resin or rubber of the base material, or the same as the composition thereof.
The thickness of the outer surface layer is usually about 0.3 to 3.0 mm, preferably 0.5 to 1.5 mm.

Specific examples of the layer structure of the hose of the present invention include the following structures, but are not limited thereto.
(1) Room temperature superplastic alloy layer / base material (2) Base material / room temperature superplastic alloy layer (3) Base material / room temperature superplastic alloy layer / base material (4) Room temperature superplastic alloy layer / base material / reinforcing layer / Outer surface layer (5) Base material / Room temperature superplastic alloy layer / Base material / Reinforcement layer / Outer surface layer In the present invention, among these, a rubber layer or a rubber composition layer (base material) and a room temperature superplastic alloy layer And a hose having a metal wire layer (reinforcing layer) is preferable.
More specifically, for example, a hose composed of room temperature superplastic alloy layer 1 / rubber layer 2 / wire reinforcing layer 3 / rubber layer 4 (see FIG. 1), rubber layer 5 / room temperature superplastic alloy layer 6 / rubber layer 7 A hose made of / wire reinforcing layer 8 / rubber layer 9 (see FIG. 2) is preferable.

  The shape of the hose of the present invention is not particularly limited, and can be a straight tube hose or a bent tube having a smooth tube shape, and the entire length in the axial direction or a part or most of the axial direction can be corrugated (bellows). ) And the other part may be a straight tube or a bent tube having a smooth tube shape. The corrugated shape may be a spiral shape in which the corrugated peaks are continuous, or the corrugated peaks may be independent for each mountain.

The base material in the present invention may be prepared from the resin or rubber or a composition thereof by a conventionally known method such as an extrusion molding method, an injection molding method, a calender molding method, a solution casting method, or the like.
The method for forming the room temperature superplastic alloy layer is not particularly limited, and may be formed by a conventionally known method, such as a vacuum deposition method, a sputtering method, an ion plating method, a plating method, a thermal spraying method, an injection method, etc. A known metal thin film laminating method can be applied, and in particular, a room temperature superplastic alloy formed by depositing a room temperature superplastic alloy layer on the base material or a film on the mandrel by vapor deposition or sputtering in advance. A method of laminating a thin film comprising the above into the substrate is preferred.
In addition, when the reinforcing layer is provided, the forming method is not particularly limited, and may be formed by a conventionally known method. For example, the wire is braided or spirally wound, and the braided (blade structure) layer or each other is formed. It is preferable that the layer is formed as a spiral layer wound in a pairing direction because pressure resistance is improved.
Further, when the outer surface layer is provided, the forming method is not particularly limited, and it may be formed by a conventionally known method. For example, a tube-shaped formed body is produced in the same manner as the base material, and is laminated. The method of doing is mentioned.

The hose of the present invention is used without limitation for transporting various fluids (liquid or gas) in various industrial fields, and is particularly suitable for a fluid transport hose for automobiles. For example, it can be preferably used for a liquid fuel hose, a gas fuel hose or a refrigerant hose for automobiles. More specifically, a fuel hose used for gasoline for gasoline vehicles or alcohol-mixed gasoline, a fuel hose used for hydrogen gas or methanol for fuel cell vehicles, a refrigerant hose used for chlorofluorocarbon or carbon dioxide, an air hose, etc. Also can be used arbitrarily.
Among these, the hose of the present invention can be used in a supercritical environment of a temperature of 150 ° C. or higher and a pressure of 10 MPa or higher, and is particularly suitably used for transporting carbon dioxide refrigerant used in an automobile cooler. be able to.

Next, the present invention will be described in more detail using examples.
Example 1
A hose having the structure shown in FIG. 1 composed of the following first to fourth layers was manufactured by the following procedure.
First layer: Room temperature superplastic alloy vapor deposition layer 1 (Material: Zn: Zn-Al alloy containing 70% by mass with the balance being Al and unavoidable impurities, α phase or α 'phase having an average crystal grain size of 5 µm or less) A room temperature superplastic alloy which is a Zn-Al alloy having a structure in which a β phase having an average crystal grain size of 0.05 μm or less is finely dispersed, and a thickness of 10 μm)
Second layer: rubber layer 2 (material: acrylic rubber (ACM), thickness 1.5 mm)
3rd layer: wire layer 3 (material: brass-plated surface with main component Fe, thickness 0.33 mm, 120 implants, blade structure)
Fourth layer: outer rubber layer 4 (material: ACM, thickness 1.5 mm)
First, a tubular rubber layer 2 having an inner diameter of 15 mm and a thickness of 1.5 mm was formed using ACM as a rubber material. On the inner surface, the room temperature superplastic alloy was deposited to a thickness of 10 μm with a general-purpose vapor deposition apparatus to form a room temperature superplastic alloy vapor deposition layer 1. Thereafter, a wire made of Bridgestone Co., Ltd. having a thickness of 0.33 mm was knitted into a blade structure with a pitch of 69.8 mm on the outer surface of the rubber layer 2 to form a wire layer 3 covering the outer side of the rubber layer 2. . Using ACM as a rubber material, a tube-shaped outer rubber layer 4 having a thickness of 1.5 mm was formed and incorporated so as to cover the outer surface of the wire layer 3 to manufacture a hose.
The following evaluations (1) to (4) were performed on the obtained hose. As a result, (1) Gas permeation amount 1.0 g / m · day, (2) Pressure resistance 700 kg / cm ² or more, (3) Sealing performance 500,000 times or more, (4) Repeated pressurization performance 1 million times or more there were. Thus, the basic performance as a hose was satisfied while having excellent gas barrier properties.

<Evaluation method>
(1) Gas barrier properties After carbon dioxide is pressurized and sealed in a hose (10 MPa), the hose is left in an oven at 100 ° C., and the total weight is measured every 24 hours. The permeation amount (g / m · day) was calculated and evaluated by averaging the values after 48, 72 and 96 hours.
(2) Pressure resistance Internal pressure was applied by water pressure, and the pressure when the hose was broken was measured.
(3) Repeated bending performance (sealability)
A hose was attached to the U-shape, and bending was repeated with the shortest point being 150 mm and the longest point being 250 mm, and the number of repetitions until the internal pressure leaked from the hose was measured.
(4) Repetitive pressurization performance A hose with an exposed length of 500 mm is attached in a U shape with a bending radius of 75 mm, and the internal pressure is set to 0 to 15 MPa in one cycle and repeatedly pressurized at 30 cpm in an atmosphere of 150 ° C. The number of repetitions until the hose was broken was measured.

Example 2
A hose having the structure shown in FIG. 1 composed of the following first to fifth layers was manufactured by the following procedure.
First layer: inner rubber layer 5 (material: ACM, thickness 1.0 mm)
Second layer: Room temperature superplastic alloy film layer 6 (thickness 50 μm)
Third layer: intermediate rubber layer 7 (material: ACM, thickness 1.0 mm)
4th layer: wire layer 8 (material: brass-plated surface layer with main component Fe, thickness 0.33 mm, 120 implants, blade structure)
Fifth layer: outer rubber layer 9 (material: ACM, thickness 1.0 mm)
First, a tube having an inner diameter of 13 mm and a thickness of 1.0 mm was formed using ACM using the inner rubber layer 5 as a rubber material. Also, a room temperature superplastic alloy film layer 6 having an inner diameter of 14.0 mm and a thickness of 10 μm was formed by tape wrapping. Further, a tube having an inner diameter of 14.01 mm and a thickness of 1.0 mm was formed using ACM with the intermediate rubber layer 7 as a rubber material.
Thereafter, the inner rubber layer 5, the room temperature superplastic alloy film layer 6 and the intermediate rubber layer 7 were assembled in this order, and further, the outer surface of the intermediate rubber layer 7 was bridged by Bridgestone Corporation having a thickness of 0.33 mm. A wire layer 8 covering the outer side of the intermediate rubber layer 7 was formed by knitting a wire made into a blade structure with a pitch of 72.8 mm by a blader. Using ACM as a rubber material, a tube-shaped outer rubber layer 9 having a thickness of 1.0 mm was formed and incorporated so as to cover the outer surface of the wire layer 8 to manufacture a hose.
Evaluation of said (1)-(4) was performed about the obtained hose. As a result, (1) Gas permeation amount 1.0 g / m · day, (2) Pressure resistance 700 kg / cm ² or more, (3) Sealing performance 500,000 times or more, (4) Repeated pressurization performance 1 million times or more there were. Thus, the basic performance as a hose was satisfied while having excellent gas barrier properties.

Comparative Example 1
A hose was manufactured in the same manner as in Example 1 except that the room temperature superplastic alloy vapor deposition layer 1 was not provided.
The obtained hose was evaluated in the above (1) to (4). As a result, while (2) to (4) had the same performance as in Example 1, (1) the gas permeation amount was about 950 g / m. -The gas permeation amount was so large that it became day or more and the test itself was difficult.
Comparative Example 2
In Example 2, a hose was produced in the same manner except that instead of the room temperature superplastic alloy film layer 6, a tape-wrapped superplastic alloy film having a thickness of 10 μm was used.
The obtained hose was evaluated in the above (1) to (4). As a result, while (2) to (4) had the same performance as in Example 2, (1) the gas permeation amount was about 950 g / m. -The gas permeation amount was so large that it became day or more and the test itself was difficult.

  As described above in detail, the hose of the present invention has a high gas barrier property even under high temperature and high pressure of, for example, 150 ° C. or higher and 10 MPa or higher. For this reason, it is suitable for various hoses for automobiles, and in particular, it can be suitably used for transporting carbon dioxide refrigerant used in automobile coolers.

It is a figure explaining the structure of the hose of this invention. It is another figure explaining the structure of the hose of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Room temperature superplastic alloy vapor deposition layer 2 Rubber layer 3 Wire layer 4 Outer rubber layer 5 Inner rubber layer 6 Room temperature superplastic alloy film layer 7 Intermediate rubber layer 8 Wire layer 9 Outer rubber layer

Claims (11)

  A hose comprising a base material and a layer made of an alloy having superplasticity at room temperature.   The hose according to claim 1, wherein an alloy having superplasticity at room temperature is deposited on the base material.   The hose according to claim 1, wherein a thin film made of an alloy having superplasticity at room temperature is incorporated and laminated on the base material.   The hose according to any one of claims 1 to 3, wherein the base material is a rubber layer or a rubber composition layer.   The hose according to any one of claims 1 to 4, comprising a rubber layer or a rubber composition layer, a layer made of an alloy having superplasticity at room temperature, and a metal wire layer.   The rubber material of the rubber layer or rubber composition layer is hydrogenated nitrile rubber (HNBR), chlorosulfonated polyethylene rubber (CSM), acrylic rubber (ACM), ethylene-acrylic rubber (AEM), silicone rubber, or fluororubber. The hose according to any one of claims 1 to 5, comprising at least one kind selected from the inside.   The alloy having superplasticity at room temperature is a Zn-Al alloy containing Zn: 30 to 80% by mass, the balance being Al and inevitable impurities, and an average crystal grain size of 5 μm or less α phase or α ′ phase The hose according to any one of claims 1 to 6, which is a Zn-Al alloy having a structure in which a β phase having an average crystal grain size of 0.05 µm or less is finely dispersed.   The alloy having superplasticity at room temperature is a Zn-Al alloy containing Zn: 75 to 99% by mass, the balance being Al and inevitable impurities, and having an average crystal grain size of 5 μm or less, an α phase or an α ′ phase And a β-phase alloy having a structure in which a β phase having an average crystal grain size of 0.05 μm or less is finely dispersed in the α phase or α ′ phase. The hose described in Crab.   The hose according to any one of claims 1 to 8, wherein the thin film made of an alloy having superplasticity at room temperature has a thickness of 10 nm to 5 µm.   The hose according to any one of claims 1 to 9, which is used in an environment having a temperature of 150 ° C or higher and a pressure of 10MPa or higher. The hose according to any one of claims 1 to 10, which is used for transporting carbon dioxide refrigerant.

Images