JP2000018446A - Multilayer tubular body for cooler hose and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cooler hose which shows Freon (R) resistance, Freon (R) gas barrior property, and in heat aging resistance for a long period of time. SOLUTION: A multilayer tubular body for a cooler hose is composed of a core layer and a rubber layer having braid fiber and component made of rubber and/or thermoplastic resin of low temperature embrittlement temperature minus 20 deg.C or lower. An innermost layer of the core layer is at least made of polyphenylene sulfide resin having thickness of 0.5 mm or lower.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pressure-resistant cooler hose using a PPS resin as a core tube and a method for manufacturing the same.

[0002]

2. Description of the Related Art Various pressure hoses such as hydraulic hoses and hydraulic hoses, vacuum hoses, cooler piping hoses, and fuel piping tubes, brake tubes, air conditioner piping tubes, radiator hoses, control cable liners, etc. used for the automobile industry. Uses many hoses and tubes. In particular, various hoses and tubes used in the automotive industry are required to have extremely high performance such as high strength at high temperatures and long-term heat resistance, chemical resistance, gas barrier properties, and flexibility.
Various methods such as adding a reinforcing material or a filler or forming a multilayer structure based on a synthetic rubber have been adopted.

Polyamide resin tubes are used as engineer plastics for these tubular bodies because of their excellent mechanical strength, chemical resistance, heat resistance and gas barrier properties.

[0004] However, since the polyamide-based single-layer hose has a high water vapor permeability, when used as a cooler hose material, the cooling effect is easily reduced due to the freezing of water, which is not preferable.

[0005] In addition, due to the workability of parts and the flexibility of layout, hose flexibility and high pressure resistance that can withstand the internal pressure of the refrigerant in a high-temperature atmosphere are required, and it is difficult to design a single-layer polyamide hose. It is.

As a method for improving the water vapor permeability and the flexibility of a tube, for example, JP-A-59-97377 discloses a hose in which an outer layer is made of a condensation polymer-based flexible resin, an inner layer is made of a polyamide resin, and an intermediate layer is made of a polyolefin resin. However, when used as a cooler hose for an automobile, the pressure resistance is insufficient.

Furthermore, Japanese Patent Application Laid-Open No. Sho 61-2521 proposes a hose in which the inner layer is made of a polyamide resin and the sheath tube is made of rubber reinforced with fiber. There is a problem that the polyamide resin is deteriorated to cause seal leakage, and a cooler hose with higher performance is required.

[0008]

DISCLOSURE OF THE INVENTION The present invention has been achieved as a result of studying the improvement of the above-mentioned problems as an object, and has as its object the purpose of the present invention is to improve the freon resistance, the freon gas barrier property, and the long-term heat aging. The purpose of the present invention is to provide a hose having excellent properties.

[0009]

That is, the present invention provides: Core layer and rubber and / or low temperature embrittlement temperature -20 ° C
A multilayer tubular body for a cooler hose comprising the following thermoplastic resin component and a rubber layer comprising blade fibers, wherein at least the innermost layer of the core layer is made of a polyphenylene sulfide-based resin having a thickness of 0.5 mm or less. 1. a multilayer tubular body for a cooler hose, 2. The multilayer tubular body for a cooler hose as described in 1 above, wherein the core layer further has a thermoplastic resin layer different from the innermost layer of the polyphenylene sulfide-based resin. A thermoplastic resin mandrel is formed by laminating a coating layer of a polyphenylene sulfide-based resin having a thickness of 0.5 mm or less on the outer peripheral surface of the thermoplastic resin round bar in a non-adhered state, and an adhesive layer on the outer peripheral surface of the mandrel. Through, to form a sheath tube by coating the braid fiber and rubber or thermoplastic resin, to obtain an integral body of the mandrel and the sheath tube, pull out the round bar from the integral body, the polyphenylene sulfide-based resin 3. A method for producing a multilayer tubular body for a cooler hose, wherein the coating layer is left as a core tube inside the sheath tube. Supplying the thermoplastic resin to the hopper of the first extruder,
A rod-shaped flow of the thermoplastic resin is formed in a die, a round bar of the thermoplastic resin is formed while cooling with a sizing device, and a polyphenylene sulfide-based resin formed into a tubular flow by a second extruder is formed on the surface thereof. 4. The method for producing a multilayer tubular body for a cooler hose according to the above item 3, wherein the mandrel is formed by laminating outside the die. Supplying the thermoplastic resin to the hopper of the first extruder,
The thermoplastic resin is formed into a rod-like flow in a die, and a round bar of the thermoplastic resin is formed while being cooled by a sizing device, and a PPS resin formed into a tubular flow by a second extruder is laminated on the surface thereof. 5. The multilayer tubular body for a cooler hose according to the above item 3 or 4, wherein a mandrel is formed by laminating thermoplastic resins other than the above-mentioned PPS-based resin which have been formed into a tubular flow by a third extruder. 5. manufacturing method of The thermoplastic resin other than the PPS resin laminated on the round bar is made of a polyamide resin, a saturated polyester resin, a polyurethane resin, or a polyolefin resin.
It is a manufacturing method of the multilayer tubular body for cooler hoses described.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The multilayer tubular body for a cooler hose of the present invention comprises a core layer and a rubber layer, and at least the innermost layer of the core layer is made of a polyphenylene sulfide resin.

The polyphenylene sulfide (PPS) resin used in the present invention is a PPS resin or a resin composition containing the same. As the PPS resin used in the present invention, any PPS resin that can be produced by a known method can be used. When a resin composition containing a PPS resin is used, the composition preferably contains 50% by volume or more of the PPS resin, and more preferably 75% by volume or more of the PPS resin.
It is desirable to include it in the system resin. Examples of the resin other than the PPS resin to be contained in the resin composition include a polyamide resin, a polyester resin, a polyolefin resin, a polyurethane resin, and an elastomer resin thereof. At least one of these resins may be used as a blend. Among these, polyamide resins, polyolefin resins, polyamide alastomers, and polyolefin elastomers are particularly effective from the viewpoints of heat aging resistance, freon gas barrier properties, and the like.

Although the thickness of the PPS resin can be freely selected according to the required characteristics depending on the application, it is preferably 0.5 mm or less, particularly preferably in the range of 0.1 to 0.4 mm. PPS
If the thickness of the resin is too thick, the flexibility tends to be insufficient, and if the thickness of the PPS resin is too thin, the Freon barrier properties tend to be poor.

In the present invention, the core layer (core tube) may be a single layer of only the PPS resin layer. However, if at least the innermost layer is a PPS resin layer, the core layer (core tube) is formed of a PPS resin layer. It is also preferable to form a multilayer structure of two or more layers by laminating layers made of a thermoplastic resin in order to increase the impact resistance of the cooler hose.

Examples of the thermoplastic resin to be laminated include polyamide resins, saturated polyester resins, polyurethane resins, and polyolefin resins.

Specific examples of the polyamide resin include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polytetramethylene adipamide (nylon 46), and polyhexamylylene sebacamide (nylon 6). Nylon 610), polyhexamelylene dodecamide (nylon 612), polydodecaneamide (nylon 1
2) Polyundecaneamide (nylon 11), polyhexamethylene terephthalamide (nylon 6T), polyxylylene adipamide (nylon XD6), and mixtures or copolymers thereof.

Of these, nylon 6, nylon 66,
Nylon 11, nylon 12, and copolymers thereof are preferred in terms of heat resistance, moldability, and economy.

The degree of polymerization of the polyamide resin is not particularly limited, and the relative viscosity measured at 25 ° C. in a 98% concentrated sulfuric acid solution is in the range of 1.5 to 7.0, particularly 2.0 to 6.5. Are preferred.

The saturated polyester resin is at least 6
An aromatic polyester obtained from a dicarboxylic acid in which 0 mol% is terephthalic acid and an aliphatic diol. As dicarboxylic acids other than terephthalic acid, azelaic acid,
Sebacic acid, adipic acid, aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as dodecanedicarboxylic acid, isophthalic acid,
An aromatic dicarboxylic acid such as naphthalenedicarboxylic acid, or an alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid, alone or in a mixture. Examples of the aliphatic diol include ethylene glycol, propylene glycol, 1,4-butanediol, trimethylene glycol, hexamethylene glycol, and the like.

Examples of preferred saturated polyesters include:
Polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexylene dimethylene terephthalate, and the like, among which having a suitable mechanical strength, polybutylene terephthalate or
Terephthalic acid is 60 mol% or more, preferably 70 mol%
A copolymer polyester comprising the above, a dicarboxylic acid component containing dodecanedicarboxylic acid and / or isophthalic acid, and a 1,4-butanediol component is particularly preferred.

Polybutylene terephthalate (hereinafter PBT)
The degree of polymerization of the copolymerized polyester is not particularly limited, and the relative viscosity of a 0.5% orthochlorophenol solution measured at 25 ° C. is in the range of 0.5 to 2.5,
Particularly, those having a range of 0.8 to 2.0 are preferable. The degree of polymerization of polyethylene terephthalate is not particularly limited, either.
It is preferable that the intrinsic viscosity measured in (1) is in the range of 0.54 to 1.5, particularly 0.6 to 1.2.

The polyurethane resin used here is a chain polymer comprising a polyisocyanate and a diol. Specific examples of the polyisocyanate include 2,4-tolylene diisocyanate, hexanetylene diisocyanate, meta-xylene diisocyanate, and the like. And 4,4 '
-Diphenylmethane diisocyanate. There are two types of diols: polyester type and polyether type. Specific examples of the former include organic acids such as phthalic acid, adipic acid, dimerized linoleic acid and maleic acid and glycols such as ethylene, propylene, butylene and diethylene. However, specific examples of the latter include polyoxypropylene glycol, poly (oxypropylene) poly (oxymethylene) glycol, poly (oxybutylene) glycol, and poly (oxytetramethylene).
Glycols and the like are each generally used. The degree of polymerization of these polyurethanes is not particularly limited.
The melt viscosity at 0 ° C. and a shear rate of 10 / sec is 10
Those having a poise of 100 to 100,000 are used.

Specific examples of the polyolefin resin used here include low, medium and high density polyethylene, polyethylene-polypropylene copolymer, polypropylene, ethylene-vinyl acetate copolymer, modified polyolefin, and elastomers thereof. The modified polyolefin means a copolymer obtained by copolymerizing or graft copolymerizing 0.1 to 10% of an unsaturated carboxylic acid or a glycidyl compound as a monomer component of ethylene and / or propylene, or a derivative thereof, Examples of the unsaturated carboxylic acid of the copolymerization component include unsaturated monomers such as acrylic acid, methacrylic acid, maleic acid, and fumaric acid, dicarboxylic acids, and amides, esters, metal salt compounds, and anhydrides thereof.

Examples of the glycidyl compound as a copolymer component include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and the like. Among them, glycidyl methacrylate is preferably used.

These polyolefin resins are excellent in moisture-proof properties, and furthermore, low in terms of flexibility and low-temperature impact resistance, medium-density polyethylene, heat-resistant in terms of polypropylene, high-density polyerylene, and interlayer. From the viewpoint of adhesiveness, a modified polyolefin is particularly desirable.

In the present invention, the rubber layer comprises rubber and / or
Alternatively, it is composed of a component (hereinafter, sometimes referred to as a rubber component) composed of a thermoplastic resin having a low-temperature embrittlement temperature of −20 ° C. or lower and blade fibers. The low-temperature embrittlement temperature is AS
It can be measured according to TM D746.

The rubber used in the present invention and / or the thermoplastic resin having a low embrittlement temperature of -20 ° C. or lower include chlorinated polyethylene rubber, chlorosulfonated polyethylene rubber, chloroprene rubber, and ethylene-propylene-diene ternary copolymer. Combination, vinyl chloride resin, thermoplastic polyurethane can be used, but other rubber or thermoplastic resin may be used.

The blade fibers used in the present invention include:
Polyester fiber, polyamide fiber, aramid fiber, P
PS fiber is typical, but other synthetic fibers can also be used.

The rubber layer of the multilayer tubular body for a cooler hose of the present invention constitutes the outer layer of the core layer, and the rubber component layer /
It can be arranged like a blade fiber / rubber component layer or a blade fiber layer / rubber component layer. Each rubber component layer may be a single layer or a multilayer.

The rubber layer and the core layer may be provided with an adhesive layer therebetween. The adhesive used for the adhesive layer is a flexible epoxy type,
An adhesive such as a silicone adhesive can be used.

The multilayer tubular body for a cooler hose of the present invention comprises:
It can be manufactured by the following method.

That is, a coating layer of a polyphenylene sulfide resin having a thickness of 0.5 mm or less is laminated on the outer peripheral surface of the round rod of the thermoplastic resin in a non-adhered state to form a thermoplastic resin mandrel. Via an adhesive layer on the outer peripheral surface, coat the blade fiber and rubber or thermoplastic resin to form a sheath tube, obtain an integral body of a mandrel and a sheath tube, pull out the round bar from the integral body, It can be manufactured by leaving a coating layer of polyphenylene sulfide resin as a core tube inside a sheath tube.

[0032] The thermoplastic resin mandrel can be specifically manufactured by using a plurality of extruders. That is, the thermoplastic resin is supplied to the hopper of the first extruder, the thermoplastic resin flows in a die in a die, and a round bar of the thermoplastic resin is formed while being cooled by a sizing device. It can be manufactured by forming a mandrel by laminating a polyphenylene sulfide-based resin formed into a tubular flow by a second extruder outside a die.

The thermoplastic resin is supplied to the first extruder to form a rod-shaped flow in the die, and the thermoplastic resin is cooled while being cooled by a sizing device having an outer shape corresponding to the inner diameter of the desired PPS resin core tube. After a round bar is formed, a continuous method is preferred in which a PPS resin formed into an annular flow by a second extruder is laminated outside the die to a desired thickness and cooled on the outer surface thereof, but a thermoplastic resin round bar is prepared in advance. In addition, a method of laminating a PPS resin again may be used.

When a thermoplastic resin layer is provided on the core layer, the thermoplastic resin is supplied to the hopper of the first extruder, and the rod-shaped flow of the thermoplastic resin is formed in the die. Form a round bar of thermoplastic resin while cooling,
A mandrel is formed by laminating a PPS resin formed into a tubular flow by a second extruder on the surface thereof and laminating a thermoplastic resin other than the PPS resin formed into a tubular flow by a third extruder. Can be formed.

The single-layer or multi-layer tube used in the core hose of the present invention has a width of 12.56 m.
m, cut into strips with a length of 100 mm and span 3
In the bending test at 0 mm, it is desirable that the load for bending 3 mm is 500 g or less. If the bending deflection load is 500 g or more, sufficient flexibility as a cooler hose cannot be obtained, which is not preferable.

As the round bar of the thermoplastic resin used in the present invention, those having excellent flexibility and heat resistance are preferable. For example, plasticized nylon 1 containing a plasticizer in an amount of about 10 to 30% is preferably used.
1 and 12, polyester amide resins, polyetherester amide resins, copolyester resins and other thermoplastic resins can be used.

Here, the round bar may be a column having a completely circular cross section or a slightly elliptical cross section. Further, a hollow body having a thickness that does not hinder the production of the hose of the present invention may be used. The thickness of the PPS resin laminated on the surface of the thermoplastic resin can be freely selected according to the required characteristics depending on the application, but is preferably 0.5 mm or less, particularly preferably in the range of 0.1 to 0.4 mm. PP
If the thickness of the S-based resin exceeds 0.5 mm, the flexibility is insufficient, which is not preferable. The PPS resin has a thickness of 0.1
If it is less than mm, effective freon barrier properties cannot be obtained.

What is important in the structure of the thermoplastic resin mandrel of the present invention is that the PPS resin and the thermoplastic resin round bar are in non-adhesive contact with each other. Note that PP
The S resin is a resin having low adhesiveness to other thermoplastic resins. An effective non-adhesive mandrel molding method includes applying a mold releasing agent, a lubricant and the like to a round bar.

As an example of a method for manufacturing the cooler hose of the present invention, an adhesive is applied to the outer periphery of the above-mentioned thermoplastic mandrel and then coated with rubber, and then a braided layer of a braid fiber is formed. After coating
The hose of the present invention can be obtained by adopting a method in which only the round bar of the thermoplastic resin is removed and the coating layer of the PPS resin is left as a core tube.

The method of coating the outer peripheral surface of the thermoplastic resin mandrel or the blade fiber with a rubber component is optional. For example, a method of molding a rubber or a thermoplastic resin by an extrusion method, a method of spirally winding a tape, and the like are employed. I can do it.

The method of braiding the outer peripheral surface of the rubber with the braid fiber is arbitrary, and for example, a braiding method using a vertical braiding device or a horizontal braiding device can be adopted.

The braided layer of the rubber or thermoplastic resin and the braid fiber that coats and reinforces the outer peripheral surface of the PPS resin is not limited to the above-mentioned structure, but is optional. Coating and reinforcement may be applied in various layers such as rubber or thermoplastic resin.

Further, in order to tightly adhere the PPS resin layer to the rubber or the blade fiber, it is necessary to apply a flexible epoxy or silicone adhesive to the PPS resin layer and then reinforce the coating. preferable.

In this way, an integral product comprising the mandrel and the core layer of the hose is obtained. The monolith preferably comprises a rubber tube, a braided layer of blade fibers and a rubber tube. FIG. 1 is a conceptual side view showing a preferred embodiment in a partly longitudinal sectional view of an integrated body, and FIG. 2 is a conceptual transverse sectional view thereof. The monolithic material is disposed on the outer layer portion of the mandrel 7 composed of the round bar 6 and the PPS resin layer 5 in the order of the adhesive layer 4, the rubber coating layer 3, the synthetic fiber braided layer 2 and the rubber coating layer 1 from the inside.

FIG. 5 is a conceptual side view in which a part of an integral body is shown in an example in which a thermoplastic resin layer is further provided on a core layer, and FIG. 6 is a conceptual transverse sectional view thereof. .
In this integrated body, in the integrated body shown in FIGS.
A thermoplastic resin layer 5 'other than the S-based resin is provided.

In the present invention, a method of pulling out a thermoplastic resin round bar from an integral body is performed by applying a fluid pressure such as air or water to the end surface of the round bar.

Thus, a cooler hose is obtained. That is, the coating layer becomes the innermost layer of the hose, remains as a so-called core tube, and has a structure in which a rubber layer, a braided layer of blade fibers, and a rubber layer are sequentially laminated thereon. FIG. 3 is a conceptual side view in which a part of the cooler hose is longitudinally sectioned after the round bar 6 has been pulled out from the integral body shown in FIGS. 1 and 2, and FIG. 4 is a conceptual transverse sectional view thereof. FIG. 7 shows FIGS.
Is a conceptual side view of a partly vertical cross section of the cooler hose after a round bar has been pulled out of the one-piece object indicated by the symbol, and FIG. 8 is a conceptual horizontal cross-sectional view thereof.

By using a PPS resin for the inner layer of the cooler hose thus obtained, a hose excellent in chemical properties such as chemical resistance, freon gas barrier properties and long-term heat aging resistance can be obtained. Cooler hose,
It is useful for home air conditioner cooler hoses, refrigerator cooler hoses, and the like.

Hereinafter, the present invention will be further described with reference to examples.

[0050]

EXAMPLES "Flexibility" A tube having an outer diameter of Φ14 and an inner diameter of Φ11 was wound around a cylindrical rod of various diameters, and the minimum radius that could be wound without breaking was determined.

"Bending flexibility" A round bar was pulled out of a thermoplastic resin mandrel and had an inner diameter of 11 mm and a wall thickness of 0.1 to 0.5.
mm PPS resin tube, inner diameter 11 mm, PP
A 0.156 mm thick tube of S-based resin and a 0.4 mm thick tube of a thermoplastic resin other than PPS resin is 12.56 mm wide.
The actual load was measured when it was cut into a strip having a length of 100 mm and bent by 3 mm under the condition of a span of 30 mm using a three-point bending tester.

[Freon gas permeability] Outer diameter Φ14 × inner diameter Φ11 Cut the tube to 30 cm and put HFC in the hose.
134a is sealed in 10 g and left in a thermostat at 100 ° C.
The weight change was measured, and the permeation amount (g / m / 24 hr) was calculated.

[Impact resistance after heat aging] A tube having an outer diameter of Φ14 and an inner diameter of Φ11 was cut into 30 cm, left in a thermostat at 120 ° C. for 1,000 hours, cooled to 23 ° C.
A 00 g iron ball is dropped from a height of 30 cm, and the presence or absence of cracks in the tube is checked. Further, after cooling to −30 ° C. instead of 23 ° C., the iron ball was similarly dropped and the presence or absence of cracks in the tube was evaluated to evaluate the low-temperature impact resistance after heat aging.

Examples 1-4, Comparative Examples 1-2 Plasticized nylon 11 (manufactured by Toray Industries, Inc.) using a 40 mm extruder.
Rilsan BESNOP40TL into the hopper,
At a temperature between 210 ° C and 230 ° C, a rod-like flow was formed in the die at 210 ° C. Next, the rod-shaped material was extruded from a die, and cooled while sizing in a cooling tank to form a round bar having an outer diameter of 11 mm.

Next, the round bar was passed through a crosshead die attached to a 30 mm extruder, and a PPS resin (Torayna A670-X01 manufactured by Toray Industries, Inc. or Nylon 6 (Amilan CM1046 manufactured by Toray Industries, Inc.) was used. X0
6) at 280-310 ° C and 230-250 ° C, respectively.
At 280 ° C to 310 ° C.
As a circular flow from a crosshead die at 230 ° C., 230 ° C. to 250 ° C., 0.05 mm to 1.
The layers were laminated to a thickness of 0 and cooled in a cooling bath to obtain a mandrel. Next, an epoxy-based adhesive (Kemit TE2101 manufactured by Toray Industries, Inc.) was applied to the PPS mandrel, and the mandrel was passed through a crosshead die attached to a 40 mm extruder.
Diene copolymer rubber (Esprene 50 manufactured by Sumitomo Chemical Co., Ltd.)
1) was extruded at a temperature of 50 to 100 ° C., and the outer peripheral surface of the mandrel was coated to a thickness of 1.0 mm.
Using a horizontal braiding apparatus, a polyester fiber of 10 deniers of 500 denier having a braiding angle of 54
^. It was braided under the conditions of 44 'and a tension of 2 kg. Further, the outer peripheral surface is coated with an ethylene-propylene-diene copolymer having a thickness of 2.0 mm by an extruder having a thickness of 40 mm in the same manner as described above, and then the coated rubber is vulcanized at a temperature of 190 ° C. for 60 to 90 minutes. I made 30m one piece.

Then, 80 kg /
Apply a water pressure of ² cm and pull out only the round bar from
A hose having an S resin core and a nylon core tube was obtained.

As is clear from Table 1, the inner layer has a thickness of 0.5 mm.
By using the PPS resin with the following thickness, the permeability of the freon gas and the heat aging resistance are remarkably improved while maintaining the flexibility, and it is understood that the PPS resin is useful as a cooler hose.

Examples 5 to 8 Round bars were formed in the same manner as in Example 1. Insert the round bar 2
While passing through a multilayer crosshead die attached to a 30 mm extruder, PPS resin (Toray Co., Ltd. TORELINA A670-X01) was melt-extruded at a temperature of 280 ° C. to 310 ° C. for the inner layer, and nylon 11 ( Toray Co., Ltd. Rilsan BESN BK F15XN), PBT resin (Toray Co., Ltd., Trecon 5201X10), thermoplastic polyurethane resin (Sumitomo Badesche Urethane Industry Co., Ltd., Elastollan ET885), polyolefin resin (Mitsui Petrochemical (Mitsui Petrochemical) Milastoma-5030B), respectively.
Melt extrusion at a temperature of 0 ° C. to 260 ° C.
As a multilayer annular flow from a multilayer crosshead die at a temperature of .degree. C., it was laminated outside the die on the outer periphery of a round bar with the thickness shown in Table 1, and cooled in a cooling bath to obtain a mandrel. Then Examples 1 to
A hose was obtained in the same manner as in No. 4.

[0059]

[Table 1]

As is apparent from the results shown in Table 1, when the core tube is a thin PPS single layer, cracks occur in the low-temperature impact test. However, when the core tube is laminated with PPS using a thermoplastic resin other than the PPS resin, the low-temperature impact occurs. Is remarkably improved.

[0061]

The cooler hose of the present invention is excellent in chemical properties such as chemical resistance, freon gas barrier properties and long-term heat aging resistance by using a PPS resin for the innermost layer of the core layer. It is extremely useful for hoses, household air conditioner cooler hoses, refrigerator cooler hoses, and the like.

[Brief description of the drawings]

FIG. 1 is a conceptual cross-sectional side view of a preferred embodiment of a single unit of a cooler hose of the present invention before a round bar is pulled out.

FIG. 2 is a conceptual cross-sectional view of the one-piece object of FIG.

FIG. 3 is a conceptual cross-sectional side view of a part of the cooler hose after a round bar is pulled out of the one-piece unit shown in FIGS.

FIG. 4 is a conceptual cross-sectional view of FIG.

FIG. 5 is a conceptual cross-sectional side view of a preferred embodiment of the integrated body before the round bar is pulled out in the cooler hose of the present invention.

FIG. 6 is a conceptual cross-sectional view of the integral body of FIG.

FIG. 7 is a conceptual cross-sectional side view of a part of the cooler hose after a round bar is pulled out of the one-piece unit shown in FIGS.

8 is a conceptual cross-sectional view of FIG.

[Explanation of symbols]

 1. Rubber coating layer 2. 2. Synthetic fiber braided layer Rubber coating layer 4. Adhesive layer 5 '. 4. Thermoplastic resin layer other than PPS 5. PPS resin layer Round bar 7. Mandrel

Continued on the front page F-term (reference) 3H111 AA02 BA11 BA15 CA53 CB06 CB09 CC02 DA07 DA14 DB09 DB25 EA02 EA15 EA17 4F100 AK01B AK01C AK03C AK41C AK46C AK48 AK51C AK53G AK57A AK75 E10 BA11 BA02 BA03 BA02 BA03 EH171 EH231 EJ912 GB48 GB51 JA20B JB01 JB16B JB16C JD02 JJ10 YY00A YY00B

Claims (6)

[Claims] A multilayer tubular body for a cooler hose comprising a core layer, a rubber and / or a component comprising a thermoplastic resin having a low-temperature embrittlement temperature of −20 ° C. or lower, and a rubber layer comprising a blade fiber, wherein at least the core layer has A multilayer tubular body for a cooler hose, wherein the innermost layer is a layer made of a polyphenylene sulfide-based resin having a thickness of 0.5 mm or less. 2. The multilayer tubular body for a cooler hose according to claim 1, wherein the core layer further has a thermoplastic resin layer different from the innermost layer of the polyphenylene sulfide resin. 3. An outer peripheral surface of a round bar of a thermoplastic resin having a thickness of 0.5 mm
A thermoplastic resin mandrel is formed by laminating a coating layer of a polyphenylene sulfide-based resin having the following thickness in a non-adhered state, and coating the outer surface of the mandrel with a blade fiber and a rubber or a thermoplastic resin through an adhesive layer. To form an integral body of the mandrel and the sheath tube, pull out the round bar from the integral body, and leave the coating layer of the polyphenylene sulfide resin as a core tube inside the sheath tube. A method for producing a multilayer tubular body for a cooler hose, comprising: 4. A thermoplastic resin is supplied to a hopper of a first extruder to form a rod-shaped flow of the thermoplastic resin in a die.
A round bar of thermoplastic resin is formed while cooling with a sizing device, and a mandrel is formed by laminating a polyphenylene sulfide resin formed into a tubular flow with a second extruder on the surface of the bar outside the die. The method for producing a multilayer tubular body for a cooler hose according to claim 3. 5. A thermoplastic resin is supplied to a hopper of a first extruder, a rod-like flow of the thermoplastic resin is formed in a die, and a round bar of the thermoplastic resin is formed while being cooled by a sizing device. A mandrel is formed by laminating a PPS resin formed into a tubular flow by a second extruder on the surface thereof and laminating a thermoplastic resin other than the PPS resin formed into a tubular flow by a third extruder. The method for producing a multilayer tubular body for a cooler hose according to claim 3 or 4, wherein: 6. The multilayer tubular body for a cooler hose according to claim 5, wherein the thermoplastic resin other than the PPS resin laminated on the round bar comprises a polyamide resin, a saturated polyester resin, a polyurethane resin, or a polyolefin resin. Production method.