JP5723520B2 - Refrigerant transfer hose - Google Patents

Description

  The present invention relates to a refrigerant transfer hose.

Since HFC134a currently used as a refrigerant for car air conditioners has a large global warming potential (GWP), HFO1234yf, which has a low global warming potential, is a promising candidate for a new refrigerant. . For example, Patent Document 1 has been proposed as a composition containing a refrigerant such as HFO1234yf and a lubricating oil.
Conventionally, a laminated structure of a resin and rubber having an innermost layer made of a polyamide resin material is generally used for a rubber hose for a car air conditioner in order to suppress permeation of the refrigerant.

JP 2009-74017 A

However, the present inventor applied a refrigerant composition containing a fluorine-based compound having a double bond such as HFO-1234yf and a lubricating oil as a refrigerant to a conventional rubber hose for a car air conditioner. It has been found that the innermost layer has low durability.
Then, an object of this invention is to provide the hose for refrigerant | coolant transfer excellent in durability.

  As a result of earnest research to solve the above problems, the present inventors have found that the refrigerant transfer hose having the innermost layer obtained by using the polyamide resin composition containing the polyamide and the acid sealing agent is excellent in durability. The headline and the present invention were completed.

That is, this invention provides the following 1-9.
1. A refrigerant transfer hose having an innermost layer obtained by using a polyamide resin composition containing polyamide and an acid sealant.
2. 2. The refrigerant transfer hose according to 1 above, wherein the acid sealing agent is at least one selected from the group consisting of a carbodiimide compound, an epoxy compound, an amine compound, an isocyanate compound, and an alcohol.
3. 3. The refrigerant transfer hose according to 2 above, wherein the carbodiimide compound is polycarbodiimide.
4). The refrigerant transfer according to 2 or 3, wherein the epoxy compound is at least one selected from the group consisting of an epoxy group-containing (meth) acrylic polymer, epoxy group-containing polystyrene, epoxidized soybean oil, glycidyl ester, and glycidyl ether. For hose.
5. 5. The refrigerant transfer hose according to any one of 2 to 4, wherein an epoxy equivalent of the epoxy compound is 140 to 3300 g / equivalent.
6). The refrigerant transfer hose according to any one of 1 to 5, wherein the amount of the acid sealing agent is 0.1 to 10 parts by mass with respect to 100 parts by mass of the polyamide.
7). The above 1-6, wherein the polyamide is at least one selected from the group consisting of polyamide 6, polyamide 11, polyamide 12, polyamide 4-6, polyamide 6-6, polyamide 6-10, polyamide 6-12 and polyamide MXD6. The refrigerant transfer hose according to any one of the above.
8). 8. The refrigerant transfer hose according to any one of 1 to 7, which is used for a refrigerant-containing composition containing a fluorine-based compound having a double bond as a refrigerant.
9. The fluorine compound is 1,2,3,3,3-pentafluoropropene, 1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene, 1,2,3, 9. The refrigerant transfer hose according to 8 above, which is at least one fluoropentene selected from the group consisting of 3-tetrafluoropropene and 3,3,3-trifluoropropene.

  The refrigerant transfer hose of the present invention is excellent in durability.

FIG. 1 is a perspective view schematically showing an example of the refrigerant transfer hose of the present invention by cutting out each layer of the hose.

The present invention will be described in detail below.
The refrigerant transfer hose of the present invention is
It is a hose having an innermost layer obtained by using a polyamide resin composition containing polyamide and an acid sealing agent.

In the present invention, the acid sealing agent can seal or capture the acid (hereinafter sometimes referred to as “sealing or the like”). An acid sealing agent seals an acid by reacting with an acid.
The acid is not particularly limited as long as it is a compound having at least one acid group (for example, carboxy group). Examples thereof include acids such as carboxylic acid, phosphoric acid and sulfonic acid; partial esters of acids. Partial esters include those having at least one acid group and at least one ester.
Specific examples of the acid include, for example, a carboxylic acid present in the innermost layer, a carboxylic acid such as a carboxylic acid generated by hydrolysis of a lubricant such as an ester oil in the refrigerant-containing composition; Examples include phosphoric acid produced by hydrolysis of the phosphoric acid ester-based additive contained; sulfonic acid.
Examples of the carboxylic acid present in the innermost layer include a carboxylic acid bonded to the end of the polyamide, and a carboxylic acid generated by hydrolysis of the polyamide under the influence of alteration of the refrigerant-containing composition.
As phosphoric acid, for example, a highly acidic phosphoric acid moiety produced by hydrolysis of an additive such as a triaryl phosphate ester contained in a lubricant such as an ester oil contained in a refrigerant-containing composition Examples include esters.
The acid sealing agent seals the carboxylic acid bonded to the end of the polyamide, and the carboxylic acid generated by hydrolysis of the polyamide under the influence of alteration of the refrigerant-containing composition, the acid generated from the refrigerant-containing composition. By sealing or capturing, the polyamide can be prevented from being hydrolyzed. The present inventors consider that the suppression of the hydrolysis of the polyamide increases the durability of the innermost layer, and as a result, the refrigerant transfer hose of the present invention is excellent in durability.
In addition, the said mechanism is a guess of this inventor, and even if a mechanism differs, it is in the scope of the present invention.

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

The refrigerant transfer hose of the present invention includes an inner tube, a reinforcing layer, and an outer layer, and the inner tube has one of the preferred embodiments including an innermost layer (inner surface resin layer) and a rubber layer.
The thickness of the innermost layer is preferably 0.05 to 0.3 mm from the viewpoint of superior durability and flexibility.
The thickness of the rubber layer is preferably 1.0 to 2.0 mm from the viewpoint of being excellent in durability and excellent in flexibility.
The thickness of the reinforcing layer is preferably 0.5 to 1.5 mm from the viewpoints of superior durability and flexibility.
The thickness of the outer layer is preferably 0.5 to 1.5 mm from the viewpoints of better weather resistance and excellent flexibility.

The innermost layer will be described below.
The innermost layer of the refrigerant transfer hose of the present invention is obtained by using a polyamide resin composition containing polyamide and an acid sealant.

The acid sealant will be described below.
The acid sealing agent is not particularly limited as long as it is a compound capable of sealing an acid (including a partial ester).
In addition to sealing the acid, the acid sealing agent can capture, for example, the acid generated from the refrigerant-containing composition.

Examples of the functional group capable of reacting with an acid included in the acid sealing agent include a carbodiimide group, an epoxy group, an amino group, an isocyanate group, and a hydroxy group.
Examples of the acid sealing agent include carbodiimide compounds, epoxy compounds, amine compounds, isocyanate compounds, and alcohols.
Of these, carbodiimide compounds and epoxy compounds are preferred from the viewpoint of superior durability.
Moreover, it is preferable that an acid sealing agent is a solid on normal temperature (23 degreeC) conditions from a viewpoint that it is excellent in handling.

From the viewpoint that the acid sealing agent can at least seal the carboxylic acid that the polyamide has, it is possible to at least seal the carboxylic acid (including the partial ester) as one of preferred embodiments. It is done.
In the present invention, an acid sealing agent that seals at least carboxylic acid is referred to as a “carboxylic acid sealing agent”.
Examples of the carboxylic acid sealing agent include carbodiimide compounds, epoxy compounds, amine compounds, isocyanate compounds, and alcohols.
When the acid sealant is a carboxylic acid sealant, the carboxylic acid sealant can seal phosphoric acid, sulfonic acid, and these partial esters in addition to carboxylic acid.
The following description regarding the acid sealant shall be applied to the carboxylic acid sealant.

The carbodiimide compound as the acid sealing agent is not particularly limited as long as it is a compound having a carbodiimide group (—N═C═N—). Examples thereof include polycarbodiimide and monocarbodiimide.
Of these, polycarbodiimide is preferable from the viewpoint of superior durability.

  The polycarbodiimide that can be used in the present invention is not particularly limited as long as it has a plurality of carbodiimide groups in a molecular chain (for example, a polymer main chain). The polycarbodiimide can be obtained, for example, by condensing an arbitrary organic diisocyanate, and a known technique can be used for the method. For example, what is obtained by decarbonation gas condensation reaction of organic diisocyanate can be used.

Examples of polycarbodiimides include poly [1,1-dicyclohexylmethane (4,4-diisocyanate)] and a cyclohexylamine urea adduct.
As a commercially available product of polycarbodiimide, for example, “Carbodilite HMV-8CA”, “Carbodilite LA-1” manufactured by Nisshinbo Co., Ltd., which are fine granular polycarbodiimide compounds at room temperature, are easily available and easy to operate. It is mentioned as a preferable aspect in terms of surface.

  The monocarbodiimide that can be used in the present invention is not particularly limited as long as it has one carbodiimide group. Specifically, for example, dimethylcarbodiimide, diethylcarbodiimide, diisopropylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, t-butylisopropylcarbodiimide, di-t-butylcarbodiimide, dicyclohexylcarbodiimide, diphenylcarbodiimide, 2,2,6,6-tetra Examples include methyldiphenylcarbodiimide, 2,2,6,6-tetraethyldiphenylcarbodiimide, 2,2,6,6-tetraisopropyldiphenylcarbodiimide, and di-β-naphthylcarbodiimide.

The epoxy compound will be described below.
The epoxy compound as the acid sealing agent is not particularly limited as long as it is a compound having one or more epoxy groups.
Examples of the epoxy compound include an epoxy group-containing (meth) acrylic polymer, an epoxy group-containing polystyrene, a polymer containing an epoxy group such as epoxidized soybean oil; a glycidyl ester (including a polymer and a monomer); glycidyl ether ( Polymer and monomer).

The epoxy equivalent of the epoxy compound is preferably 140 to 3300 g / equivalent from the viewpoint that it is superior in durability and the composition hardly causes gelation.
When the epoxy compound is a polymer containing an epoxy group, the epoxy equivalent is preferably 170 to 3300 g / equivalent from the viewpoint that the durability is excellent and the composition hardly causes gelation.
When the epoxy compound is a monomer containing an epoxy group, the epoxy equivalent is preferably 140 to 400 g / equivalent from the viewpoint that the durability is excellent and the composition hardly causes gelation.

Among them, an epoxy group-containing (meth) acrylic polymer and a glycidyl ether (including a polymer and a monomer) are preferable from the viewpoint that the epoxy compound is excellent in durability and the composition is hardly gelled.
In addition, an epoxy group-containing (meth) acrylic polymer (especially solid at room temperature) is preferred from the viewpoint that it is superior in durability and the composition hardly causes gelation.

The epoxy group-containing (meth) acrylic polymer will be described below.
The epoxy group-containing (meth) acrylic polymer as the acid sealing agent is not particularly limited as long as the main chain is a (meth) acrylic polymer and has at least one epoxy group.
In the present invention, (meth) acryl means one or both of acrylic and methacrylic.

The (meth) acrylic polymer as the main chain may be either a homopolymer or a copolymer.
Examples of the epoxy group-containing (meth) acrylic polymer include a methyl methacrylate / glycidyl methacrylate copolymer.

  The weight average molecular weight of the epoxy group-containing (meth) acrylic polymer is preferably 5,000 to 300,000 from the viewpoint that the durability is excellent, the composition is less likely to be gelled, and the handleability is excellent. More preferably, it is 8,000-250,000.

  Among them, the epoxy group-containing (meth) acrylic polymer is preferably a methyl methacrylate / glycidyl methacrylate copolymer from the viewpoint that it is excellent in durability, the composition hardly causes gelation, and is easy to handle.

The glycidyl ether will be described below.
The glycidyl ether as the acid sealing agent is not particularly limited as long as it is a compound having a glycidyloxy group.
Examples of the glycidyl ether include butyl-glycidyl ether, 2-ethylhexyl glycidyl ether, stearyl-glycidyl ether, allyl-glycidyl ether, phenyl-glycidyl ether, butylphenyl-glycidyl ether, butoxy-polyethylene glycol-glycidyl ether, glycidol, glycerin. Epichlorohydrin-0 to 1 mol adduct-polyglycidyl ether, ethylene glycol-epichlorohydrin-0 to 2 mol adduct-polyglycidyl ether, polyethylene glycol-diglycidyl ether, neopentyl glycol-diglycidyl ether, trimethylolpropane -Polyglycidyl ether.

A commercial item can be used as an epoxy compound.
Examples of commercially available products of epoxy group-containing polystyrene include Marproof G-1010S (styrene polymer, powder, weight average molecular weight 100,000, epoxy equivalent 1,700 g / equivalent, manufactured by NOF Corporation).
Examples of commercially available products of epoxidized soybean oil include Neusizer 510R (manufactured by NOF Corporation).
Commercially available epoxy group-containing (meth) acrylic polymers include, for example, Marproof G-0150M (acrylic polymer, powder, weight average molecular weight 8,000 to 10,000, epoxy equivalent 310 g / equivalent, NOF Corporation Manufactured), Marproof G-2050M (acrylic polymer, powder, weight average molecular weight 200,000-250,000, epoxy equivalent 340 g / equivalent, manufactured by NOF Corporation).

An acid sealing agent can be used individually or in combination of 2 types or more, respectively.
The amount of the acid sealant is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polyamide, from the viewpoint that the durability is excellent and the composition hardly causes gelation. More preferably, it is 5 parts by mass.
When the acid sealing agent is a carbodiimide compound, it is preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the polyamide from the viewpoint that the durability is excellent and the composition hardly causes gelation. More preferably, it is 3 to 1 part by mass.
When the acid sealing agent is an epoxy compound, it is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polyamide from the viewpoint that the durability is excellent and the composition is less prone to gelation. More preferably, it is 5-5 mass parts.

The polyamide will be described below.
In the present invention, the polyamide contained in the polyamide resin composition is not particularly limited.
The polyamide is selected from the group consisting of polyamide 6, polyamide 11, polyamide 12, polyamide 4-6, polyamide 6-6, polyamide 6-10, polyamide 6-12 and polyamide MXD6 from the viewpoint of excellent refrigerant permeation resistance. At least one is preferred.
Even when the polyamide resin composition contains a polyamide (for example, polyamide 6) that is easily hydrolyzed, the refrigerant transfer hose of the present invention can exhibit excellent durability.
Polyamides can be used alone or in combination of two or more.

  The polyamide resin composition can contain additives as long as it does not impair the purpose of the present invention. Examples of the additive include a filler, a reinforcing agent, an anti-aging agent, a plasticizer, a pigment (dye), a tackifier, a lubricant, a dispersant, and a processing aid.

The production of the polyamide resin composition is not particularly limited. For example, the method of mixing polyamide and an acid sealing agent and the additive which can be used as needed using a biaxial kneading extruder is mentioned.
The mixing temperature is preferably 180 to 300 ° C, more preferably 200 to 280 ° C, from the viewpoint of excellent mixing processability.

The rubber layer will be described below.
In the present invention, the inner tube can have a rubber layer. When the inner tube has a rubber layer, the rubber layer is adjacent to the innermost layer.

The rubber composition used in the production of the rubber layer will be described below.
In the present invention, the rubber contained in the rubber composition is not particularly limited. Examples of rubber include acrylonitrile butadiene rubber (NBR), natural rubber (NR), butadiene rubber (BR), styrene-butadiene copolymer rubber (SBR), polyisoprene rubber (IR), butyl rubber (IIR), and chlorobutyl rubber. (Cl-IIR), bromobutyl rubber (Br-IIR), chloroprene rubber, ethylene-propylene copolymer rubber, styrene-isoprene copolymer rubber, styrene-isoprene-butadiene copolymer rubber, isoprene-butadiene copolymer rubber And chlorosulfonated polyethylene.

The rubber preferably contains butyl rubber (IIR) from the viewpoint of superior durability and excellent permeation resistance.
The rubbers can be used alone or in combination of two or more.

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

  In the present invention, the rubber composition is not particularly limited for its production. For example, a method of mixing (kneading) rubber and an additive that can be used as necessary using an open roll, a kneader, an extruder, a universal stirrer, and a batch kneader.

The reinforcing layer will be described below.
Since the refrigerant transfer hose of the present invention has a reinforcing layer, it can maintain strength and is excellent in pressure resistance and metal fitting tightening fixing force.

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

Among these, polyester fibers are preferable from the viewpoint of superior durability and cost performance with respect to predetermined required performance.
The reinforcing layer is not particularly limited with respect to its shape. For example, the thing of a blade shape and a spiral shape is mentioned.
The material of the reinforcing layer can be used alone or in combination of two or more.

The outer layer will be described below.
Since the refrigerant transfer hose of the present invention has the outer layer, the reinforcing layer can be protected and the moisture penetration resistance from the outside is excellent.

One preferred embodiment is that the outer layer that the refrigerant transfer hose of the present invention can have is a rubber layer.
The material of the outer layer that the refrigerant transfer hose of the present invention can have is not particularly limited. Examples of the material used for the outer layer include those similar to the rubber composition used for the rubber layer in the present invention, and other rubber compositions.
From the viewpoint of superior weather resistance, it is preferable to include an ethylene-propylene copolymer rubber, and from the viewpoint of excellent permeation resistance, it is preferable to include butyl rubber (IIR).

The production of the refrigerant transfer hose of the present invention is not particularly limited. For example, a method of laminating an innermost layer, a rubber layer, a reinforcing layer and an outer layer in this order on a mandrel, and then vulcanizing and adhering these layers can be mentioned.
Further, an adhesion treatment (for example, application of an adhesive, surface treatment to the innermost layer) can be performed between the innermost layer and the rubber layer. An adhesion treatment (for example, application of an adhesive) can be performed between the rubber layer and the reinforcing layer. When the outer layer is a rubber layer similar to the rubber layer of the inner tube, an adhesion treatment (for example, application of an adhesive) can be performed between the reinforcing layer and the outer layer.

In the present invention, the temperature of the polyamide resin composition when extruding the innermost layer is preferably 230 to 250 ° C. from the viewpoint of excellent workability.
The temperature during vulcanization is preferably 130 to 180 ° C. from the viewpoint of excellent rubber quality and economy.
The vulcanization time is preferably 30 to 120 minutes from the viewpoint of excellent rubber quality and economy.
Examples of the vulcanization method include press vulcanization, steam vulcanization, oven vulcanization (hot air vulcanization), and hot water vulcanization.

The refrigerant-containing composition that can be used for the refrigerant transfer hose of the present invention is not particularly limited. For example, the composition containing a refrigerant | coolant like a fluorine-type compound and a lubricant is mentioned.
Examples of the refrigerant contained in the refrigerant-containing composition include a fluorine-containing compound having a double bond; and saturated hydrofluorocarbons such as HFC-134a (structural formula: CF ₃ -CFH ₂ ).
Examples of the fluorine compound having a double bond include 1,2,3,3,3-pentafluoropropene, 1,3,3,3-tetrafluoropropene, and 2,3,3,3-tetrafluoropropene. _{(formula: CF 3 -CF = CH 2,} HFO-1234yf), 1,2,3,3- tetrafluoropropene include fluoropropene such as 3,3,3-trifluoropropene.

  Even if the refrigerant applied to the refrigerant transfer hose of the present invention is a fluorine-based compound having a double bond such as fluoropropene, the refrigerant transfer hose of the present invention contains polyamide and an acid sealing agent. By having the innermost layer obtained by using the polyamide resin composition, excellent durability can be exhibited.

  The lubricating oil contained in the refrigerant-containing composition is not particularly limited. For example, a conventionally well-known thing is mentioned.

  The refrigerant transfer hose of the present invention is a hose that can be used to transfer a refrigerant, and can be applied to a fluid transport hose such as an air conditioner hose (for example, a car air conditioner). Moreover, the refrigerant | coolant transfer hose of this invention can be used for the hose for warm water (for temperature control apparatuses) other than the hose for an air conditioner.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
<Evaluation>
Using the test specimen obtained as described below, the immersion test and the tensile test are conducted by the following method, and the test specimen after the tensile strength (T _B ), elongation (E _B ), and immersion test of the test specimen is obtained. The state of was evaluated. The results are shown in Table 1.
1. Preparation of Specimen 1 A polyamide resin composition obtained as described below was prepared using an electrothermal press at 230 ° C., and the sheet was 5 mm wide, 80 mm long, and 0.15 mm thick. The test piece was cut out, and this was designated as test specimen 1.

2. Immersion test The autoclave contains 50% by mass of a refrigerant-containing composition [HFO-1234yf (manufactured by Honeywell) as a refrigerant] and 50 masses of trade name: Atmos GU-10 (manufactured by Nippon Oil Corporation) as a lubricant % Of the refrigerant-containing composition containing 100% by weight of water] and the test body 1 obtained as described above were added, and the heating and pressurizing conditions at 135 ° C. An immersion test was performed under 168 hours.
After the immersion test, the test body 1 is lifted from the refrigerant-containing composition containing water, and the test body obtained after the immersion test is taken as the test body 2.

3. Tensile test Tensile test was carried out according to JIS K 7113, and the tensile strength (T _B ) and elongation (E _B ) at 23 ° C. were measured for specimen 1 and specimen 2 obtained as described above.

4). Evaluation of the state of the test body before and after the immersion test The test body 1 and the test body 2 obtained as described above were bent, and the state of the test body before and after the immersion test was evaluated.

<Manufacture of polyamide resin composition>
Using each component shown in Table 1 in the amount (parts by mass) shown in the same table, these components were uniformly mixed using a biaxial kneading extruder to produce a polyamide resin composition.

Each component shown in Table 1 is as follows.
Polyamide 1: Polyamide 6 (trade name Zytel ST811HS, manufactured by DuPont)
Acid sealant 1: Carbodiimide-modified isocyanate (trade name Carbodilite LA-1, manufactured by Nisshinbo Chemical Co., Ltd.)
Acid sealant 2: Methyl methacrylate / glycidyl methacrylate copolymer (trade name Marproof G-2050M, weight average molecular weight 200,000 to 250,000, epoxy equivalent 340 g / equivalent, manufactured by NOF Corporation)

As is apparent from the results shown in Table 1, Comparative Example 1 containing no acid sealant was inferior in durability.
On the other hand, in Example 1 and Reference Example 1 , the decrease in tensile strength (T _B ) and elongation (E _B ) of the test specimen is suppressed, and it does not crack even after bending after the immersion test. Excellent.

<Manufacture of hoses>
Using a resin extruder on the surface of a thermoplastic resin mandrel having an outer diameter of 11 mm, the innermost layer was extruded to a thickness of 0.15 mm with the polyamide resin composition of Example 1 (extrusion temperature 240 ° C.), and the surface was thick. A tube rubber layer with a thickness of 1.2 mm (butyl rubber composition A shown below) is extruded to form two reinforcing layers in which PET (polyethylene terephthalate) fibers having a total yarn amount of 80,000 dtex are alternately wound in a spiral shape. Then, a 1.0 mm thick cover rubber layer (the same composition as the butyl rubber-based composition A was used) was extruded on the surface to form an extruded outer layer. The pentene resin is extruded into an outer skin, and the resulting tubular laminate is vulcanized for 100 minutes at 160 ° C. Then, the outer sheath and mandrel are removed from the tubular laminate to produce a hose. It was.

  Butyl rubber composition A (both tube rubber and cover rubber): 100 parts by weight of butyl rubber, 80 parts by weight of carbon black (HAF), 3 parts by weight of stearic acid, 10 parts by weight of paraffin oil, 2 parts by weight of zinc oxide, and brominated alkylphenol A composition containing 8 parts by mass of formaldehyde resin.

1 Refrigerant transfer hose 3 Innermost layer 5 Rubber layer 6 Inner tube 7 Reinforcement layer 9 Outer layer

Claims (5)

Containing a polyamide and a carbodiimide compound as an acid sealant,
An innermost layer obtained by using a polyamide resin composition in which the amount of the acid sealing agent is 0.1 to 2 parts by mass with respect to 100 parts by mass of the polyamide;
Used for a refrigerant-containing composition containing a fluorine-based compound having a double bond as a refrigerant ,
The fluorine compound is 1,2,3,3,3-pentafluoropropene, 1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene, 1,2,3, At least one fluoropropene selected from the group consisting of 3-tetrafluoropropene and 3,3,3-trifluoropropene,
Refrigerant transfer hose.   The refrigerant transfer hose according to claim 1, wherein the carbodiimide compound is polycarbodiimide.   The polyamide is at least one selected from the group consisting of polyamide 6, polyamide 11, polyamide 12, polyamide 4-6, polyamide 6-6, polyamide 6-10, polyamide 6-12 and polyamide MXD6. The hose for refrigerant transfer according to 2.   The refrigerant transfer hose according to claim 2, wherein the polycarbodiimide is a urea adduct of poly [1,1-dicyclohexylmethane (4,4-diisocyanate)] and cyclohexylamine.   Having only an inner tube, a reinforcing layer and an outer layer, the inner tube having only the innermost layer and the rubber layer,
  The reinforcing layer is at least one selected from the group consisting of polyester fiber, polyamide fiber, aramid fiber, vinylon fiber, rayon fiber, polyparaphenylenebenzobisoxazole fiber, polyarylate fiber and polyketone fiber,
  The refrigerant transfer hose according to claim 1, wherein the outer layer is a rubber layer.