JPS63302037A - Hose - Google Patents

Abstract

PURPOSE:To obtain a hose which is free from a leak of fluid and superior in durability, by combining an inner pipe constituted of an inner layer of polyamide resin and an outer layer of rubber possessing 100% modulus of 14-40kgf/ cm<2> with an other pipe constituted of a reinforcement layer and rubber possessing 100% modulus of 20-50kgf/cm<2> which is higher than that of the foregoing outer layer. CONSTITUTION:An inner pipe 1 constituting a hose is constituted of an inner layer 4 composed of polyamide resin coming into contact directly with a carrying medium and an outer layer 5 composed of rubber covering the circumference of the inner layer 4. On the other hand, rubber constituting the outer layer 5 of the inner pipe 1 is constituted by making use of the rubber whose 100% modulus falls within a range of 15-40kgf/cm<2>. The rubber having 100% modulus of 20-50kgf/cm<2>, which is higher than that of the rubber constituting the outer layer 5 of the inner pipe 1, is used for an outer pipe 3 of the hose. Thus a reinforcement layer 2 is formed on the inner pipe 1, on which the outer pipe 3 made of rubber is formed and the rubber is vulcanized through heating. A hose, which is free from a leak of fluid and superior in durability, is obtained.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention is designed to fit a hose to an object such as a transportation pipe, and to attach a metal fitting to a hose by caulking a portion, the caulking portion becomes effective. The inner tube of the hose comes into close contact with the target object, completely preventing the leakage of gases such as refrigerant and/or fluids such as lubricating oil and hydraulic oil from the part that is crimped by this metal fitting. Regarding hoses.

[Conventional technology]

Conventionally, in order to improve the gas permeability of a hose for transporting refrigerant or fuel, a hose is known in which the inner tube is made of a laminate having a two-layer structure of a rubber layer and a resin layer.

In the case of an inner tube made of a laminate having such a two-layer structure, the resin layer is generally formed on the inner surface of the hose that comes into direct contact with gas etc., taking into consideration chemical resistance, heat resistance, etc. However, the modulus of this resin layer is generally about 10 to 50 times that of the inner tube rubber layer and the rubber outer tube of the pose.
0 times, so even if the metal fittings are attached and swaged, it is difficult to get a good fit.Also, in order to maintain the adhesion of the swaged portion of the metal fittings, if swaged too strongly, the rubber layer of the outer or inner tube of the bows may be damaged. This has the drawback that the deformation or damage may be significant, and gas and/or fluid such as lubricating oil or hydraulic oil may leak from the deformed or damaged portion. Furthermore, due to poor caulking properties of the metal fittings, there were disadvantages in that the metal fittings were easily pulled out (pulling resistance) or the hose tube was easily canted (tube cut resistance).

In order to eliminate the above-mentioned drawbacks, methods have been proposed such as applying an adhesive or forming a coating rubber layer on the metal fittings, but these methods are complicated and do not have sufficient effects, so they are not put into practical use. has not yet been achieved.

[Purpose of the invention]

The purpose of the present invention is to provide excellent low permeability to refrigerants and fuels,
Eliminates the disadvantages of hoses with a resin layer on the inner tube that exhibits heat resistance, such as gas and/or fluid leakage when fittings are attached, damage to the hose, and resistance to pull-out or tube cuts. Our goal is to provide a hose that is highly durable and easy to use.

C Structure of the Invention] An object of the present invention is to provide a hose consisting of an inner tube, a reinforcing layer, and an outer tube, in which the inner tube has an inner layer made of polyamide resin and a The rubber constituting the outer tube consists of at least two outer layers made of rubber having a modulus of 10%.
100% modulus is within the range of 20 to 50 Kgf/cm2 and higher than that of the rubber forming the outer layer of the inner tube.
% modulus can be achieved by using a hose made of rubber.

Hereinafter, the present invention will be described in detail with reference to the drawings.

FIG. 1 is a partially cutaway perspective view of the low permeability hose of the present invention. In the figure, ■ is an inner tube, 2 is a reinforcing layer, and 3 is an outer tube. It has a two-layer structure.

The inner tube 1 constituting the hose of the present invention is directly connected to the transport medium.
It is composed of at least two layers: an inner layer 4 in contact with the inner layer 4 made of polyamide resin, and an outer layer N5 made of rubber covering the inner layer 4.

Examples of such polyamide resins include nylon 6
, nylon 11, nylon 12, nylon 6-66 copolymer, and nylon 6/nylon 66/polyolefin blend resin. Here, in the case of blend resin, 40
~80 parts by weight of nylon 6 and/or nylon 6-
66 copolymer, 5 to 30 parts by weight of nylon 11 and 1
A resin composition consisting of 0 to 40 parts by weight of a polyolefin resin is preferable because it provides a good balance between permeability and flexibility of the resin layer. Examples of polyolefin resins include polyethylene, polypropylene, and copolymers thereof.

The thickness of this inner layer 4 is preferably in the range of 0.05 to 0.80 mm, preferably 0.08 to 0.50 mm.

On the other hand, the rubber constituting the outer layer of the inner tube must be constructed using a rubber whose 100% modulus is within the range of 15 to 40 Kgf/cm2, and this 100% modulus is smaller than 15 Kgf/cm2. When this happens, the rubber layer deforms greatly during crimping, and is pushed out to the end of the metal fitting.
This is undesirable because the rubber layer swells into a protrusion at the end of the metal fitting (bulge phenomenon), and if it exceeds 40 Kgf/cm, the amount of deformation of the rubber layer during tightening is small, causing damage to the inner layer of the inner tube. A sufficient amount of strain cannot be applied, and the inner layer of the inner tube does not follow the groove shape of the metal fitting sufficiently, resulting in the existence of a space, which may cause gas or fluid to leak through this space. That's why I don't like it.

The outer hose tube is 0 to 2 thicker than the rubber constituting the outer layer of the inner tube.
0gf/cm" It must be made of rubber with a high modulus. Its 100% modulus is 0 to 2.
0 Kgf/cm2 If it is not high, the amount of strain given to the outer layer rubber of the inner tube and the inner layer resin layer of the inner tube during tightening is not sufficient.
Similarly, this is not preferable because gas or fluid leaks. This outer tube preferably has a 100%
It is preferable to use a rubber having a modulus.

The thickness of the outer layer of the inner tube is preferably within the range of 0.5 to 3 mm, and the thickness of the outer tube is also preferably within the range of 0.5 to 3 fflln.

The rubber constituting the outer layer of the inner tube having characteristics such as the above-mentioned 100% modulus may include various rubbers that contribute to the flexibility of the hose, such as nitrile butadiene rubber (NBR).
, chlorosulfonated polyethylene (C3M), ethylene propylene diene terpolymer rubber (EPDM),
Butyl rubber (1111), chlorinated butyl rubber (CI-1)
1R), brominated butyl rubber (Br-11R), hydrin rubber (CI(R, CI(C), acrylic rubber (A
CM), chloroprene rubber (CR), etc.

Preferably, butyl rubber mli'), chlorinated butyl rubber (C7!-Ill?), and brominated butyl rubber (B7!
-IIR), chlorosulfonated polyethylene rubber (C
SM), ethylene propylene diene terpolymer rubber (E
PDM), hydrin rubber (CIIR, CHC), etc. are preferred.

On the other hand, the rubber constituting the outer tube includes ethylene propylene diene terpolymer rubber (EPDM), chloroprene rubber (CR), and chlorosulfonated polyethylene rubber (C
3M), hydrin rubber (CHR, CIC), butyl rubber (TIR), chlorinated butyl rubber (CI-IIR), brominated butyl rubber (Br-+1R), and the like.

An example of the method for manufacturing the hose of the present invention will be described below.

First, a resin tube is formed by extruding a thin layer of resin forming the inner tube inner layer 4 of the hose from the extrusion head of a resin extruder onto a mandrel that has been previously coated with a mold release agent and dried. The mandrel on which the resin tube has been formed is passed through a rubber molding machine, and rubber is extruded onto the resin tube to form the inner tube outer layer 5 made of rubber. In order to make the laminated structure of the inner tube inner layer 4 and the inner tube outer layer 5 that constitute this inner tube 1 into a composite structure that is more integrated, an adhesive is applied to effectively bond each layer, and the structural Along with integration, the mechanical strength, durability, etc. of the hose can be improved.

For example, chlorinated rubber adhesive, phenolic resin adhesive, HR
A rubber layer can be formed after applying an adhesive such as an H-based adhesive by coating, spraying, or the like.

A reinforcing layer 2 is formed by appropriately braiding reinforcing threads onto the inner tube 1 thus formed using a braiding machine, and then rubber is extruded onto this reinforcing layer 2 using a rubber extruder. , forming a rubber outer tube 3. Next, in order to vulcanize the rubber layers constituting the inner tube outer layer 5 and outer tube 3 formed on the mandrel, the rubber layers constituting the inner tube outer layer 5 and the outer tube 3 are vulcanized under pressure within a temperature range of 130 to 170'C, preferably 140 to 160'C. Heat.

After this vulcanization is completed, the hose of the present invention can be obtained by cooling and pulling out the mandrel.

〔Example〕

Hereinafter, the effects of the present invention will be specifically explained using Examples and Comparative Examples.

In addition, the flexibility and metal fitting mountability were measured by the following method.

Hose flexibility: Bend the hose along an arc with a radius 10 times the outer diameter of the hose, and start measuring the bending radius from 10 times the bending radius (1, OD), and sequentially measure the bending stress up to 3 times the bending radius (n・2).

As a result, from the obtained plot curve of bending force and bending radius, the value of the prescribed radius (4 times) is calculated as 8.

Fig. 2 shows the metal fitting socket 1 in the measurement method of fitting fitting property.
FIG. 2 is a sectional view showing a state in which a hose 20 is gripped between a nipple (11) and a fitting (nipple). As shown in the figure, the outer tube of the hose 20 is in contact with the metal fitting socket 10, and the hose 20 is in contact with the metal fitting socket 10.
Attach the hose 2o to the nipple 11 so that the inner layer 4 of the inner tube of
After tightening to 50χ, in air at 120°C,
Aged for 168 hours. Then apply pressure 30 to this hose.
Nitrogen gas of Kgf/cm2 was sealed, and the presence or absence of nitrogen gas leakage (airtightness) was checked after 5 minutes.

Examples 1 to 9 100X modulus (M-100) is 35Kgf/c
The outer tube of the hose was made using butyl rubber-1 (IIR-1) of 100 m'' and chloroprene rubber (CR) of 43 kgf/cm2, and the inner layer and outer layer of the hose were shown in Table 1. It was made from resin and rubber having the same thickness and modulus.

Note that all of the reinforcing layers used were rayon braids made by braiding rayon.

The characteristics of the obtained pose were measured and are also shown in Table 1.

In the table, N-6 is Toshi ■ nylon 6 resin (CM-104
1), N-11 is nylon 11 resin (B
ESNOTL), POL is polyolefin, N-6/N
-117POL has a blend ratio of N-6/N-1
A three-way blend of nylon 6, nylon 11 and polyolefin with 1/POL=59°6/27.5/14.9, where IIR indicates butyl rubber.

Further, in the table, the respective compounding compositions of the inner layer rubber of the inner tube and the rubber of the outer tube are as shown in the following Tables 2 to 7.

Comparative Examples 1 to 6 Butyl rubber-2 (I
IR-2) and M-100 of 271 gf/cm2, or chlorinated butyl rubber (C5M) with M-100 of 24 Kgf/cm2.
The outer tube of the hose was made using the hose (I-IIR), and the inner layer and outer layer of the hose were made from resins and rubbers having the thickness and modulus shown in Table 1, respectively.

In each case, a rayon braid obtained by braiding rayon was used as the reinforcing layer.

In addition, as the inner layer rubber of the inner tube and the outer tube rubber, Example 1
Similarly to 9 to 9, rubbers having the compounding compositions shown in Tables 2 to 7 were used, and are shown in Table 1, respectively.

The properties of the obtained hose were measured and are also shown in Table 1.

Table 2 (I IR-1) 11R100 (manufactured by Esso Chemical Co., Ltd., Exxon Butyl 268) Carbon black 65 (manufactured by Showa Cabo Soto Co., Ltd., Showblank N220) AC polyethylene
7 stearic acid
3 Anti-aging agent 2 (Antage OD, Kawaguchi Chemical Department) Zinc white 5 Brominated phenol resin 12 (Takkirol 250-1, manufactured by Taoka Chemical Co., Ltd.) (Hereinafter, blank space) Table 3 (I IR-2) 1R100 (Eng.・7So Kagaku Co., Ltd., Exxon Butyl 268) Carbon Blank 65 (Showa Capo Soto Co., Ltd., Show Blank, N220) AC Polyethylene
7 stearic acid
3 Anti-aging agent
2 (Kawaguchi Chemical Department Antage OD) Softener (Fuji Kosan machine oil 22) 8 Zinc white
Tribrominated phenolic resin
12 (manufactured by Taoka Chemical Co., Ltd., Tasoquirol 250-1) (hereinafter, blank) Table 4 (CI-11R) CI-11R (chlorinated butyl rubber) 100 (manufactured by Esso Chemical Co., Ltd., chlorobutyl 1066) carbon blank
60 (manufactured by Showa Cabosoto Co., Ltd., show blank, N220) AC polyethylene
7 Stearic acid 2 Magnesia 1 Anti-aging agent 2 (Kawaguchi Chemical Department Antage OD) Softener (machine oil 22 manufactured by Fuji Kosan Co., Ltd.) 5 Accelerator TT
2 (manufactured by Sanshin Kagaku Kogyo Co., Ltd., Suncellar TT) Accelerator R2 (Kawaguchi Chemical Department Acta-MS-R) Table 5 (NBR) NBR100 (manufactured by Nippon Zeon Co., Ltd., Nisopol 1042) Carbon blank 80 (manufactured by Asahi Carbon Co., Ltd., Asahi #5
0) Stearic acid dizinc white
5 Anti-aging agent
2 (Kawaguchi Chemical Department Antige OD) Plasticizer (manufactured by Thiso Petrochemical Co., Ltd., DOP) 10 Sulfur 2 Accelerator TS
1 (Suncellar MS manufactured by Sanshin Chemical Industry) (Hereinafter, blank space) Table 6 (□ Sake groove) C5M
100 (manufactured by DuPont, Hypalon 40) Carbon black 60 (Asahi #50, manufactured by Asahi Carhon) Paraffin wax 1.5 (manufactured by Ohmukai Shinko Kagaku, Sunnock) Magnesia 4 Stearic acid 1 Softener
30 (manufactured by Fuji Kosan Co., Ltd., Fukol #
1000) Pentaerythritol
3 (manufactured by Nihon Kagaku Kogyo Co., Ltd., Neulyzer P) Accelerator TRA
2 (Sunseller TRA manufactured by Sanshin Chemical Industry) Table 7 (Danbon) CR100 (Manufactured by Showa Neoprene Co., Ltd., Neoprene) Carbon black 100 (Manufactured by Asahi Carbon Asahi 11
50) Magnesia 4 Stearic acid 3 Anti-aging agent 3G
3 (manufactured by Seiko Kagaku Co., Ltd., Osinon 3
C) Softener 20 (manufactured by Fuji Kosan Co., Ltd., Fukol 115ON) sulfur
1 accelerator rs
1 (Suncellar TS manufactured by Sanshin Chemical Industry) Accelerator D 1 (Suncellar D manufactured by Sanshin Chemical Industry) Zinc white 5 [Effects of the invention] In the hose according to the present invention, the inner layer of the inner tube is composed of resin. This product prevents poor adhesion (gas leakage) at the clamped part of the metal fittings caused by this, and improves and improves the pull-out resistance, tube force, and gutter resistance of the clamped part of the metal fittings, and prevents piping using hoses. This greatly improves the workability and safety of the system.

[Brief explanation of the drawing]

FIG. 1 is a partially cutaway perspective view showing one embodiment of the refrigerant transport hose of the present invention, and FIG.
FIG. 3 is a cross-sectional view of the hose with the metal fittings attached. I... Inner tube, 2... Reinforcement layer, 3... Outer tube, 4...
・Resin inner tube inner layer, 5...Rubber inner tube outer layer, 6...
Pull on the metal fitting), 7...Metal fitting socket, 20...Hose.

Claims (1)

[Claims] In a hose consisting of an inner tube, a reinforcing layer, and an outer tube, the inner tube has an inner layer made of polyamide resin and 15 to 4
Consisting of at least two layers, an outer layer consisting of rubber having a 100% modulus within the range of 0 Kgf/cm^2,
A hose in which the outer tube is made of rubber having a 100% modulus within the range of 20 to 50 Kgf/cm^2 and higher than that of the rubber forming the outer layer of the inner tube.