JP2002248702A - Low permeation film and low permeation hose - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a low permeation hose which uses a deposition film of a metallic substance for a barrier layer, is light weight, flexible, and fluid-non- permeable, excellent in deposited film performance, and excellent in the chemical stability of a deposition substance. SOLUTION: In the deposition film, on a thin film resin layer, at least two kinds of metal oxide different in deposition film characteristics, preferably alumina indicating deposition film characteristics of high barrier properties and silica indicating deposition film characteristic of so-called barrier properties enduring stretching are deposited multi-dimensionally, and the deposition film characteristics are developed synergistically. The deposition film is incorporated into the low permeation hose as a low permeation layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low-permeability membrane and a low-permeability hose, and more particularly, to a flexible low-permeability membrane exhibiting excellent low-permeability to a liquid or a gas, and using the low-permeability membrane. More particularly, the present invention relates to a low-permeation hose suitable for a fuel hose, a refrigerant hose, a supercharger hose, and the like for an automobile.

[0002]

2. Description of the Related Art In recent years, fuel-impermeable hoses have been demanded for fuel hoses used in automobiles and the like in consideration of environmental concerns. In particular, hoses for transporting gaseous fuels such as hydrogen fuel for fuel cell vehicles are required to have a high degree of low permeability. For refrigerant hoses for transporting refrigerant used in air-conditioning systems for automobiles, refrigerant hoses for electric compressors used in electric vehicles and hybrid cars, etc., hoses with low refrigerant permeability are strongly demanded from the viewpoint of system maintenance and environmental considerations.

[0003] Conventionally, for example, a hose for transporting fuel is constituted by using NBR / PVC (blended rubber of acrylonitrile / butadiene rubber and polyvinyl chloride) or, in some cases, a multi-layered hose comprising a rubber layer or the like. A low-permeability layer using a resin having a relatively low permeability such as EVOH or PA is provided in the inside. However, in the case of a hose using only a rubber layer or a resin layer which is an organic material, the severe It is considered difficult to meet the requirement for transparency.

Therefore, a hose or a tube using a metal tube or a metal layer is to be studied. However, since metal pipes are rigid, for example, when considering piping for automobiles,
In many cases, the assembling work at the time of piping is difficult, and it is not possible to expect a reduction in stress due to engine vibration or vibration during running of a car, and it is against the demand for weight reduction.

[0005] On the other hand, when a resin film laminate layer including a metal foil or a vapor deposition layer of metal or the like is incorporated in a rubber hose or the like, a reduction in weight and flexibility are expected while maintaining a sufficiently low permeability. it can. However, in a hose incorporating a metal foil laminate layer, when repeatedly subjected to high pressure by a high pressure as a refrigerant hose for a compressor, or when subjected to repeated displacement or large displacement based on engine vibration as a hose connected to an engine part, It is known that the tube wall is stretched due to the diameter expansion or deformation of the hose, and the metal foil may be pulled and broken. When the metal foil breaks, the barrier properties rapidly decrease. In a vapor deposition layer of a metal or the like, although low permeability to liquid or gas is slightly inferior to a metal foil laminate layer, a high level of low permeability can still be secured, and the hose tube wall is stretched. However, there is an advantage that the barrier property does not sharply decrease because the phenomenon of breakage does not occur.

[0006]

However, the metal deposited layer has a problem in that the metal is chemically unstable and thus easily undergoes a chemical change. For example, in a fuel hose, when water vapor mixed with gasoline or hydrogen fuel permeates the resin film of the laminate layer, the metal may corrode and lose the inherent properties of the deposited film, which may cause a problem that the barrier property is reduced. is there.

On the other hand, in the course of studying a vapor-deposited layer having a higher performance as a low-permeability layer such as a hose, the present inventors have found the following. First, metal oxide deposited layers generally exhibit low transmission and flexibility comparable to the corresponding metal deposited layers, and, of course, are chemically stable. Secondly, based on higher performance, the deposited layer of metal oxide will exhibit different properties with respect to low permeability, flexibility, etc. depending on the material to be deposited. Third
When two or more metal oxides are simultaneously vapor-deposited,
The performance advantages of both metal oxides surface synergistically.

[0008] Based on the above findings, the present invention has a high performance in light weight, flexibility and low permeability.
In addition, it is necessary to solve the problem of providing a low-permeation film using a vapor-deposited film that is stable against contact with water vapor and the like, and further providing a lightweight, flexible, and stable low-permeation hose having the low-permeation film. Make it an issue.

[0009]

Means for Solving the Problems (Structure of the First Invention) According to the structure of the first invention (the invention described in claim 1) for solving the above problems, a metal oxide is deposited on a resin thin film layer. A low-permeability film using one or more layers of a vapor-deposited film,
The above-mentioned deposited film is a low-permeation film in which two or more kinds of metal oxides having different deposited film characteristics are multi-source deposited.

(Structure of the Second Invention) The structure of the second invention (the invention described in claim 2) for solving the above-mentioned problem is as follows.
The vapor-deposited film according to the first aspect of the present invention is a binary vapor-deposited metal oxide exhibiting a vapor-deposited film characteristic (A) having a high barrier property and a metal oxide exhibiting a vapor-deposited film characteristic (B) called a barrier property against elongation. This is a low-permeation membrane.

[0011] Here, "the characteristics of a deposited film having high barrier properties" means:
At least the initial barrier property refers to a deposited film property that is high, and other deposited film properties are not limited, particularly when the initial barrier property is significantly reduced due to deformation of a hose incorporating a deposited film or elongation of a hose tube wall portion. In addition, the effect of the binary vapor deposition of the present invention is remarkable. In addition, the “vapor-deposited film property referred to as barrier property against elongation” refers to a vapor-deposited film property in which the barrier property is at least slightly reduced with respect to elongation, and other vapor-deposited film properties are not limited. Is relatively low, the effect of the binary vapor deposition of the present invention is remarkable.

(Structure of the Third Invention) In order to solve the above problems,
The configuration of the third invention of the present application (the invention described in claim 3) is as follows:
Metal oxidation exhibiting the characteristics of the deposited film (A) according to the second invention.
The material is alumina (Al₂O₃), And the steam of (B)
Silica (SiO₂ )
Low permeability membrane.

(Structure of Fourth Invention) The structure of the fourth invention (the invention described in claim 4) for solving the above-mentioned problem is as follows.
A low-permeation hose comprising one or more low-permeability layers using the low-permeation membrane according to the first to third aspects.

(Structure of Fifth Invention) The structure of the fifth invention (the invention according to claim 5) for solving the above-mentioned problem is as follows.
The low-permeation hose according to the fourth aspect, wherein the low-permeability layer is formed by spirally winding or vertically winding the tape-shaped low-permeability film.

(Structure of the Sixth Invention) The structure of the sixth invention (the invention according to claim 6) for solving the above problems is as follows.
The low-permeability layer according to the fourth invention is the same as the first invention to the tubular resin thin film layer extruded as a hose component.
A low-permeation hose obtained by performing multi-source vapor deposition according to the third invention.

(Structure of Seventh Invention) The structure of the seventh invention of the present application (the invention according to claim 7) for solving the above problems is as follows.
The low-permeation hose according to any of the fourth to sixth inventions is a low-permeation hose having the multilayer structure of any one of the following (1) to (6) including the low-permeation layer. (1) Inner rubber layer / low permeability layer / outer rubber layer (2) Inner rubber layer / low permeability layer / intermediate rubber layer / reinforcement layer / outer rubber layer (3) Resin thin film layer / intermediate rubber layer / Low transmission layer / Rubber outer tube layer (4) Resin thin film layer / Intermediate rubber layer / Low transmission layer / Intermediate rubber layer / Reinforcement layer / Rubber outer tube layer (5) Low transmission layer / Rubber outer tube layer (6) Low transmission Layer / Intermediate Rubber Layer / Reinforcing Layer / Rubber Outer Tube Layer (Constitution of Eighth Invention)
The invention (invention of claim 8) is characterized in that the low permeation hose according to the fourth invention to the seventh invention is a fuel hose, a refrigerant hose or a supercharger hose to which a liquid or a gas is transported. Is a low permeability hose.

Operation and effect of the present invention (operation and effect of the first invention) Since the low-permeation film of the first invention uses a vapor-deposited film in which a metal oxide is vapor-deposited on a resin thin film layer, it has a sufficiently low resistance to liquids and gases. While maintaining the transparency, it can be expected to secure lightness and flexibility. Moreover, compared to a metal foil laminate film, for example, the phenomenon of tensile breakage of the vapor-deposited layer does not occur, so that the barrier property does not suddenly decrease, and the vapor-deposited layer is chemically stable, such as water. There is an advantage that the barrier property is not impaired by contact with the metal.

Further, since two or more kinds of metal oxides exhibiting different deposition film characteristics are multi-sourced,
The performance advantages of both metal oxides are synergistically and simultaneously exhibited, resulting in a very excellent barrier layer. For example, when a metal oxide exhibiting a high barrier property of a deposited film and a metal oxide exhibiting a deposited property of a barrier property against elongation are binary-deposited, a high barrier property and a deposited film are incorporated. A vapor deposited layer whose barrier property is not significantly reduced by the deformation of the hose or the elongation of the wall of the hose tube (that is, the elongation of the vapor deposition film based on these) is formed.

(Function / Effect of Second Invention) When the low-permeation membrane is used for a fuel hose or a refrigerant hose for an automobile, for example,
As in the second invention, it is possible to binary-deposit a metal oxide exhibiting a vapor-deposited film characteristic (A) having a high barrier property and a metal oxide exhibiting a vapor-deposited film characteristic (B) called a barrier property against elongation. Particularly preferred.

As described above, when the deposited film characteristic (A) is significantly reduced due to the deformation of the hose incorporating the deposited film or the elongation of the hose tube wall, and / or the deposited film characteristic (B) In the case where the initial barrier property of the present invention is relatively low, the effect of the binary vapor deposition of the present invention is particularly remarkable.

(Function and Effect of Third Invention) Alumina is particularly preferred as a metal oxide exhibiting a high barrier property of a deposited film, and silica is particularly preferred as a metal oxide exhibiting a highly flexible deposited film property. It is suitable.

(Operation / Effect of the Fourth Invention)
One or two low permeability layers using the low permeability film according to the third invention
The low-permeability hose having more than one layer is excellent in low permeability, light weight, and flexibility, and particularly, since the properties of each metal oxide film multi-deposited on the low-permeability film are synergistically and simultaneously exhibited. Excellent hose.

(Function / Effect of Fifth Invention) First invention to third invention
In forming the low-permeability layer of the low-permeation hose using the low-permeability membrane according to the present invention, the tape-shaped low-permeability membrane is formed by spirally winding or vertically wrapping the tape. Is particularly preferred.

(Function / Effect of the Sixth Invention) In forming the low permeability layer of the low permeability hose, the first invention to the third invention are applied to a tubular resin thin film layer extruded as a hose component.
Performing multi-source vapor deposition according to the present invention is particularly preferable for forming a seamless, high-barrier, low-permeability layer.

(Function / Effect of the Seventh Invention) The content of the multilayer structure of the non-permeable composite hose is not limited.
For example, any of the multilayer structures described in (1) to (6) of the seventh invention can be arbitrarily selected.

(Function and Effect of Eighth Invention) Fourth Invention to Seventh Invention
The use of the low permeability hose according to the invention is not limited, but it can be particularly preferably used as a fuel hose, a refrigerant hose or a supercharger hose for transporting a liquid or gas.

[0026]

Next, embodiments of the first to eighth inventions will be described. In the following, simply "the present invention"
When it says, it points out 1st invention-8th invention collectively.

[Application Field of Low Permeation Hose] The low permeation hose of the present invention can be used without limitation as a non-permeation hose for transporting liquids or gases for various uses, for example, for automobiles. , A hose for a refrigerant, a hose for a supercharger, or the like, particularly when the refrigerant or the fuel has a high permeability like carbon dioxide or hydrogen.

In addition, including the above-mentioned various hoses,
It is preferably used for a hose that requires lightness, a hose that requires flexibility, a hose that undergoes repeated displacement or large displacement, a hose for transporting a fluid having high permeability, and the like.

[Structure of Low Permeability Hose] Although the structure of the low permeability hose of the present invention is not limited, it is usually a multi-layer hose, and any one of the layers or the innermost layer or the outermost layer according to the present invention may be used. One or two or more low permeability layers are provided.
More preferably, the low transmission layer is located between any layers of the multilayer structure.

The following can be pointed out about the configuration of the generally preferred multilayer structure of the low permeability hose. That is, the low permeability hose can include a resin layer, but is preferably a thin film resin layer. It is preferable to provide a resin thin film layer or rubber layer having resistance to the transport fluid on the inner peripheral side of the low permeability layer. The low-permeability hose preferably includes a reinforcing layer using a reinforcing thread or a wire, and the reinforcing layer is preferably provided on the outer peripheral side of the low-permeability layer. The outermost layer of the low permeability hose has at least one of water resistance, chemical resistance, and impact resistance.
It is preferable to provide a rubber outer tube layer made of excellent rubber on the element.

In view of the above, the particularly preferred multilayer structure in the low-permeation hose is described in the above (1) to (6) in the sixth invention.
The multilayer structure of (6) can be exemplified. Although the low transmission layer will be described later, other elements of the multilayer structure can be configured as follows.

The resin thin film layer can be provided inside the low permeability layer, or on both the inside and outside. When the resin thin film layer is provided inside the low-permeability layer, the non-permeability of the hose to refrigerant etc. is further improved, and when it is provided on both the inside and outside, the low-permeability layer is fixed and protected in a sandwich state in addition to the improvement in non-permeability can do. Preferred examples of the constituent material of the resin thin film layer include ethylene vinyl alcohol copolymer (EVOH), various polyamides (PA), polyethylene terephthalate (PET), polyethylene (PE), and polypropylene (PP). Is preferably about 200 μm or less.

The intermediate rubber layer reduces or absorbs the bending and deformation forces acting on the low-permeability hose so that the low-permeability layer does not reach the low-permeability layer. This is effective in avoiding problems.

As a constituent material of such an intermediate rubber layer, a rubber material having good non-permeability and flexibility to a refrigerant or the like and easily achieving good high-temperature adhesion to a low-permeability layer or a reinforcing layer, for example, butyl rubber (IIR), Halogenated IIR, ethylene-propylene rubber, ethylene-propylene-diene rubber (E
PDM) and nitrile rubber (NBR). The thickness of the intermediate rubber layer is arbitrary, for example, 0.2
About 1.0 mm.

As the reinforcing layer, for example, a wire blade layer,
The reinforcing yarn may be arbitrarily employed such as a braided winding, a spiral winding or a two-layer spiral winding in the opposite direction, and further an intermediate rubber layer interposed between the two spiral windings in the opposite direction. By providing the reinforcing layer, the low-permeability layer can be effectively protected from high-pressure repeated pressurization, repeated displacement, large displacement, etc. acting on the low-permeation hose.

As the constituent material of the outer tube layer, rubber is usually preferable, and particularly, for example, chloroprene rubber (CR), IIR, halogenated IIR, chlorosulfonated polyethylene rubber (CSM), EPDM, etc. having good weather resistance are preferable. Can be used.

[Low Permeation Layer] The low permeation layer is formed using the low permeation film according to the present invention, but the configuration is not limited. The low-permeability layer and the resin thin film layer or various rubber layers constituting the inner and outer circumferences thereof may be bonded by an adhesive layer. Representative configurations of the low transmission layer are those shown in the fifth invention and those shown in the sixth invention.

In the configuration according to the fifth aspect of the invention, a low-permeability layer is formed by spirally winding or vertically winding a tape-like low-permeability film. In this case, the formation efficiency of the low transmission layer is good. Spiral winding is a method in which a single tape-shaped low-permeability film is spirally wound while partially polymerizing to form a cylindrical low-permeability layer as a whole. The vertical wrapping is a method in which one tape-shaped low-permeability film is rolled round in the width direction and both edges in the width direction are polymerized to some extent to form a cylindrical low-permeability layer as a whole. In any of the above winding methods, it is preferable that the polymerized portion of the low-permeability film is bonded.

In the configuration according to the sixth aspect of the present invention, multi-source vapor deposition of metal oxide is performed on the outer periphery of an extruded cylindrical resin thin film layer as a hose component. Usually, a resin thin film layer is further extruded on the outer periphery thereof, and is adhered to the resin thin film layer on which the multi-source evaporation is performed by adhesion or heat fusion.
In the case of the configuration of the low transmission layer, since the low transmission layer has no joint as a whole, it has particularly high barrier properties.

[Low Permeation Film] The configuration of the low permeation film is not limited as long as one or more vapor-deposited films obtained by vapor-depositing a metal oxide on a resin thin film layer are used. The multiple vapor deposition according to the present invention may be performed on all of the one or two or more vapor-deposited films, or the multiple vapor deposition according to the present invention may be performed on a part of these vapor-deposited films.

The deposited film is formed by depositing a metal oxide on the resin thin film layer, preferably by adhering another resin thin film layer,
It is in a state of being sandwiched by the resin thin film layers from both sides. The resin thin film layers on which the metal oxide has been deposited may be bonded together with the deposited layer inside.

The constituent material of the resin thin film layer which is the base of the deposited film is not limited. However, when importance is placed on the non-permeability of the low-permeability membrane, PA, PET or EVOH is preferably used. When importance is attached to the adhesiveness between the low transmission layer and the inner or outer peripheral resin thin film layer or various rubber layers, it is preferable to use PE or PP.

The above PA, PET, EVOH, PE or P
Each of P is relatively flexible as a resin material, and is also preferable for securing flexibility for facilitating spiral winding or longitudinal wrapping of a low-permeability membrane and for securing flexibility of a low-permeability hose. From a similar point of view, the thickness of the low-permeability membrane is set to 5 to 100 μm.
m and the thickness of the entire low-permeation film is preferably 200 μm or less.

[Multi-source vapor deposition of metal oxide] In the multi-source vapor deposition of metal oxide according to the present invention, two or more kinds of metal oxides having different vapor-deposited film characteristics are simultaneously vapor-deposited on a resin thin film layer. These deposition materials are mixed. The method for that is not limited, for example,
Simultaneously evaporating metals by resistance heating method, electron beam method or other known means under oxidizing conditions for two or more metal species, or performing the same operation on an alloy of two or more metals Can be generated by

In the above multi-source vapor deposition, the total vapor deposition amount of the metal oxides and the vapor deposition amount ratio of each metal oxide are appropriately selected according to the purpose, and thus cannot be uniformly limited. As an example, in the case of binary deposition of the metal oxide exhibiting the deposited film characteristics of (A) and the metal oxide exhibiting the deposited film characteristics of (B), the deposition ratio of the former and the latter metal oxides Is 1:
The thickness is about 10 to 10: 1, and the total thickness of the deposited films of these metal oxides is about 10 to 10000 °.

The combination of the above-mentioned "two or more metal oxides" is not limited as long as the metal oxides exhibit different vapor deposition film characteristics from each other.
A combination of a metal oxide exhibiting high barrier property (A) (or capable of high-density vapor deposition) and a metal oxide exhibiting vapor deposition property (B), which is a barrier property against elongation, is used. preferable. A typical example of the metal oxide (A) which exhibits the properties of the deposited film (or can be deposited at a high density) is alumina. A typical example of the metal oxide exhibiting the characteristics of the deposited film (B) is silica.

It is to be noted that a combination of two or more metal oxides to be multi-source vapor-deposited is inappropriate, and the characteristics of both metal oxides may not always be synergistically exhibited. Binary deposition in such a case does not fall under the present invention.

[0048]

EXAMPLES [Preparation of Hose] The hoses according to Examples A to E shown in Table 1 at the end were prepared. Example C is an embodiment of the present invention. In Table 1, “film” refers to a PA6 resin thin film capable of forming a metal oxide vapor-deposited film and having a thickness of 15 μm.

The hose of Example A was a total rubber hose having an inner diameter of 5 mm, which was not provided with the above-mentioned film and was composed of only an EPDM rubber layer having a thickness of 4 mm. The hose including the hoses according to the following Examples B to E is a straight tube having a total length of 1 m. The hose of Example B has the above film layer provided on the inner periphery of the rubber layer. In the hose of Example C, a metal oxide was added to the above film.
A low-permeability film formed by original vapor deposition is provided on the inner periphery of the rubber layer.

Here, the metal oxides which were binary deposited were alumina and silica, and the deposition amount ratio thereof was alumina: silica = 1: 1, and the thickness of these deposited films was 5 in total.
00 °. The hose of Example D is provided with a low-permeability film formed by vapor-depositing alumina on the above film on the inner periphery of the rubber layer. The thickness of the evaporated film is the total thickness of the evaporated film in Example C. Is equal to The hose of Example E is provided with a low-permeability film obtained by mono-depositing silica on the above film, provided on the inner periphery of the rubber layer. The thickness of the deposited film is the total thickness of the deposited film in Example C. Is equal to

[Evaluation of Hose] The hoses of Examples A to E were allowed to stand at 24 ° C. while continuously applying an internal pressure of 1 MPa with oxygen gas at 80 ° C. while crimping both ends with metal fittings. Next, the load state is further changed
It was kept for 4 hours, and the oxygen gas permeation amount during the 24 hours was measured.

For the hoses of each example, the oxygen gas permeation amount measurement as described above was performed by measuring the hose in its natural state (straight tube) (indicated as “No R” in Table 1),
200 (in a state where the hose is bent so as to have a radius of 200 mm to extend the deposited film), and similarly,
The measurement was performed at bending R120, bending R100, and bending R70.

The measured values are shown in Table 1 and are shown graphically in FIG. In the measurement of the hose of each example under each measurement condition, about 0.1 ml / day · MPa of oxygen gas leaked from the crimped portions at both ends of the hose, but a slight amount of oxygen gas leaked compared to the entire leak amount. Because of the amount of leakage
This leakage is included in the measurement.

[0054]

[Table 1]

[Brief description of the drawings]

FIG. 1 is a graph showing evaluation results of Examples.

Continued on the front page F-term (reference) 3H111 AA02 BA11 CB03 CB04 CB05 CB06 CB10 CB21 DA14 DB08 DB09 DB11 4F100 AA17B AA17C AA19B AA19C AA20B AA20C AK01A AN00D AN00E AN02 BA02 BA03 BA10 E10BA10 BA10 BA10 BA10 BA10 BA10 BA10 BA10 BA10 JD01C JK08B JK08C JL03 JM02A 4K029 AA11 AA25 BA44 BA46 BA50 BB02 BC00 BD00

Claims (8)

[Claims] 1. A low-permeation film comprising one or more vapor-deposited films obtained by vapor-depositing a metal oxide on a resin thin film layer, wherein the vapor-deposited films have different vapor-deposited film characteristics. A low-permeation film characterized by multi-layer metal oxide deposition. 2. The vapor-deposited film is a binary vapor-deposited metal oxide exhibiting a vapor-deposited film characteristic (A) having a high barrier property and a metal oxide exhibiting a vapor-deposited film characteristic (B) called a barrier property against elongation. The low-permeation membrane according to claim 1, wherein 3. The metal oxide exhibiting the properties of the deposited film (A) is alumina, and the metal oxide exhibiting the properties of the deposited film (B) is silica. Low permeability membrane. 4. A low-permeation hose comprising one or more low-permeability layers using the low-permeation film according to claim 1. Description: 5. The low-permeation hose according to claim 4, wherein the low-permeability layer is formed by spirally winding or vertically winding the tape-shaped low-permeability film. 6. The method according to claim 1, wherein the low-permeability layer is formed on a tubular resin thin film layer extruded as a hose component.
The low-permeation hose according to claim 4, wherein the multiple vapor deposition according to claim 3 is performed. 7. The low permeation hose according to claim 4, wherein the low permeation hose has a multi-layer structure including the low permeation layer described in any one of the following (1) to (6). Low permeability hose. (1) Inner rubber layer / low permeability layer / outer rubber layer (2) Inner rubber layer / low permeability layer / intermediate rubber layer / reinforcement layer / outer rubber layer (3) Resin thin film layer / intermediate rubber layer / Low transmission layer / Rubber outer tube layer (4) Resin thin film layer / Intermediate rubber layer / Low transmission layer / Intermediate rubber layer / Reinforcement layer / Rubber outer tube layer (5) Low transmission layer / Rubber outer tube layer (6) Low transmission Layer / intermediate rubber layer / reinforcement layer / rubber outer tube layer 8. The hose according to claim 4, wherein the low-permeation hose is a fuel hose, a refrigerant hose, or a supercharger hose for transporting a liquid or a gas. The low permeability hose described.