JPH10132154A - Manufacture for hose - Google Patents

Abstract

PROBLEM TO BE SOLVED: To strengthen bonding of an inner pipe and a reinforcing layer consisting of fiber for improvement of durability by heating the outer surface of the inner pipe to obtain a melting condition before forming an outer pipe consisting of a thermoplastic material, in a hose formed by braiding the reinforcing layer between the inner pipe and the outer pipe. SOLUTION: In a manufacturing method for hose, thermoplastic material is extruded in a tubular shape by an extruder to form an inner pipe 1, and the inner pipe 1 is passed through the middle of an annular heater to heat the outer surface of the inner pipe 1 at a melting temperature of thermoplastic material or higher to obtain a melting condition. Reinforcing material such as polyester fiber is braided to form a reinforcing layer 3 with a braiding machine. A cold setting adhesives such as urethane adhesives is applied to the outer surface of the reinforcing layer 3 with an applicator to form a bonded layer 6 between the outer pipe and the reinforcing layer 3. The thermoplastic material is extruded into a tubular shape onto the outer surface of the bonded layer 6 by the extruder to form the outer pipe 2. As a result, strong interlayer bonding can be obtained, thus it is possible to manufacture a flexible hose with high durability.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a hose comprising at least an inner tube made of a thermoplastic material or a flexible material and an outer tube made of a thermoplastic material, and a reinforcing layer. The present invention relates to a method for manufacturing a hose in which an adhesive layer made of a thermoplastic material is provided between layers, and the adhesive layer and the reinforcing layer are integrally formed by heating and melting the adhesive layer to improve the durability of the hose. is there.

[0002]

2. Description of the Related Art Conventionally, in a hose composed of an inner tube, a reinforcing layer, and an outer tube, a hose in which the inner tube and the outer tube are formed of a thermoplastic material such as a thermoplastic resin composition, a thermoplastic elastomer composition, etc. Since no vulcanization step is required, production costs are reduced. For this reason, these hoses are generally widely used.

In this conventional hose, a cold-setting adhesive such as a moisture-curable urethane-based adhesive or a copolyester is used for bonding the inner tube to the reinforcing layer and bonding between the reinforcing layers. Attempts have been made to use a melt-type adhesive resin such as a resin or an olefin resin to form an inner tube, a reinforcing layer, and an outer tube, and then heat the resin to melt and bond the adhesive resin.

[0004] Further, there is also used a hose in which the use of a highly rigid thermoplastic resin for at least one of the inner tube and the outer tube eliminates the need for bonding between the inner tube and the reinforcing layer or bonding between the reinforcing layers.

[0005]

However, in a hose using a cold-setting adhesive, since this adhesive is a reactive type, the thermosetting proceeds during use and the adhesive layer becomes hard.
If the hose repeatedly undergoes bending and pressure changes, there is a problem that the fibers of the reinforcing layer are broken due to the curing of the adhesive layer, and the durability of the hose is reduced.

Further, when a melt-type adhesive resin is used, the adhesion between the adhesive layer and the layer above the adhesive layer cannot be obtained by a normal manufacturing method due to restrictions on the order of forming each layer. Must be heated and adhered to the layer above it, but after forming the outer tube, it is heated from the outside of the hose until the adhesive resin melts, giving excessive heat to the hose, thereby causing the hose to Dimensional changes and non-uniformity of the tension of the fibers of the reinforcing layer occurred, and the homogeneity of the hose was impaired, resulting in a problem that sufficient durability could not be obtained.

In recent years, there has been a strong demand for hoses to be flexible from the viewpoint of hose mounting properties. However, there is a problem in durability of hoses that use a low-rigidity (soft) thermoplastic material for the inner tube and do not bond between layers. There was a major problem in use. Further, in the case of the cold-setting adhesive, an organic solvent is used, so that there is an environmental problem. In the case of the fusion adhesive, there is a problem in productivity due to the heat treatment step after the outer tube is formed.

The present invention has been made in order to solve these problems of the conventional hose, and provides a method of manufacturing a hose which is excellent in durability, is flexible, has low production cost, and has no environmental problems. It is intended for.

[0009]

According to the present invention, there is provided an inner tube and an outer tube made of a thermoplastic material.
In the manufacture of a hose formed by braiding and forming one or more reinforcing layers of a blade structure or a spiral structure made of fibers formed therebetween, before forming the outer tube, the outer surface of the inner tube is heated by heating means. The inner surface of the inner tube is heated to a temperature higher than the softening temperature of the thermoplastic material to make the outer surface of the inner tube in a molten state, thereby strengthening the adhesion between the inner tube and the reinforcing layer.

As described above, the step of bringing the outer surface of the inner tube into a molten state can be carried out before the formation of the outer tube so that the adhesion between the two can be strengthened. If this step is installed immediately before the step of performing the bonding, the bonding can be performed more reliably. Even if this heating step is performed immediately after the formation of the first reinforcing layer and before the extrusion of the reinforcing interlayer adhesive layer, a sufficient adhesive effect can be obtained.

In the manufacture of the above hose, an adhesive layer is formed between the inner tube and the reinforcing layer made of a thermoplastic material between the inner tube and the reinforcing layer, and the adhesive layer is formed before the outer tube is formed. A step of heating the thermoplastic material to a temperature equal to or higher than the softening temperature of the thermoplastic material by heating means to bring the outer surface of the adhesive layer into a molten state,
This strengthens the adhesion between the inner tube and the reinforcing layer. In this case, the inner tube may not be made of a thermoplastic material, but may be made of a flexible material such as a vulcanized rubber composition.

The step of bringing the outer surface of the adhesive layer into a molten state can be carried out before forming the outer tube so that the adhesion between the two can be strengthened. If this step is provided immediately before the step of forming the reinforcing layer, the bonding can be performed more reliably. Also, immediately after forming the first reinforcing layer, and before the extrusion of the reinforcing interlayer adhesive layer, a sufficient bonding effect can be obtained. Things.

In addition, the melting of the adhesive layer between the inner tube and the reinforcing layer can be performed by extruding the thermoplastic material at a temperature equal to or higher than the softening temperature by an extruder without using a heater. Immediately after that, it can be performed sufficiently by braiding the reinforcing layer, in which case no special heating step is required,
This is advantageous in terms of productivity. The following is a means for strengthening the adhesion between the reinforcing layers.In the above-mentioned hose production, a reinforcing interlayer bonding layer made of a thermoplastic material is formed between adjacent reinforcing layers, and before the outer tube is formed. The reinforcing interlayer adhesive layer is heated by a heating means to a temperature equal to or higher than the softening temperature of the thermoplastic material to bring the outer surface of the reinforcing interlayer adhesive layer into a molten state.

The step of bringing the outer surface of the reinforcing interlayer adhesive layer into a molten state can be carried out before forming the outer tube so that the adhesion between the reinforcing layers can be strengthened. Similarly to the case of the adhesive layer between the reinforcing layer and the reinforcing layer, if this step is brought immediately before the step of forming the reinforcing layer provided in contact with the outer surface of the reinforcing interlayer adhesive layer, it is possible to more securely adhere, Even if the reinforcing layer (for example, the second reinforcing layer) provided in contact with the outer surface of the reinforcing interlayer adhesive layer is formed immediately before the extrusion of the reinforcing interlayer adhesive layer, a sufficient adhesive effect can be obtained.

As described above, the reinforcing interlayer adhesive layer is melted by extruding the thermoplastic interlayer material at a temperature equal to or higher than the softening temperature by an extruder without using a heater. Can be performed sufficiently by braiding
In this case, no special heating step is required, which is advantageous in productivity. The heating device used in the present invention is not particularly limited, and a heating device using heating means such as generally used electric heating, hot air, infrared, far infrared, near infrared, ultrasonic, high frequency, and dielectric can be used. However, a heating device that heats through the center of an annular heater that transfers heat by contacting the outer surface of the adhesive layer can be preferably exemplified in that the outer surface can be efficiently heated to a molten state.

The heater used in the present invention can be further provided with a device for performing preheating, and a heating device using a generally used heating means can be widely applied as described above. A preheating device using hot air, infrared rays, far infrared rays, near infrared rays, or the like can be suitably exemplified. The method of manufacturing the above hose includes a method of bonding the inner tube and the reinforcing layer, and
Although individually described as the bonding method between the reinforcing layers, in a hose having two or more reinforcing layers, the bonding method between the inner tube and the reinforcing layer and the bonding method between the reinforcing layers are continuously performed in one production line. By doing so, all interlayer adhesion can be strengthened.

However, depending on the conditions and environment of use of the hose, the durability is sufficient even if one of the bonding between the inner tube and the reinforcing layer or the bonding between the reinforcing layers is performed by means other than the present invention. An improved hose can be manufactured. The thermoplastic material used in the hose manufactured by the hose manufacturing method of the present invention is a generally used thermoplastic resin and thermoplastic elastomer, and their compositions and the like, but are not particularly limited, Polyolefin resin, polyamide resin, thermoplastic resin such as polyester resin and its composition, polyolefin thermoplastic elastomer, polyamide thermoplastic elastomer, polyester thermoplastic elastomer, thermoplastic elastomer such as polyurethane thermoplastic elastomer and Examples of the composition include a thermoplastic elastomer composition in which a rubber composition containing a vulcanized rubber composition is dispersed in the form of particles in these thermoplastic resin and thermoplastic elastomer.

The thermoplastic material used for the inner tube, the outer tube and each adhesive layer and the combination thereof are not limited, and may be appropriately selected according to the properties and adhesiveness required for each constituent layer. . Further, as described above, the material used for the inner tube is not limited to the thermoplastic material alone, and when the inner tube is composed of a plurality of layers, or when the adhesive layer between the inner tube and the reinforcing layer is used. In this case, if the outermost layer of the inner tube or the adhesive layer between the inner tube and the reinforcing layer is a thermoplastic material, the other parts may be a flexible material such as a vulcanized rubber composition.

The fiber material constituting the reinforcing layer of the hose manufactured by the hose manufacturing method of the present invention may be a reinforcing material manufactured from generally used vinylon fiber, rayon fiber, polyester fiber, nylon fiber, aromatic polyamide fiber or the like. It is a thread. The thermoplastic resin used for the adhesive layer of the hose manufactured by the hose manufacturing method of the present invention has adhesiveness to the inner tube and / or the reinforcing layer, and softens the adhesive layer at the temperature at the time of using the hose. Any thermoplastic resin that does not cause a significant decrease in performance due to deterioration or the like may be used, and is not particularly limited, but has a softening temperature of 110 ° C.
Preferred examples include the above modified olefin-based thermoplastic resins, thermoplastic polyester-based copolymer resins, and the like.

[0020]

Embodiments of the present invention will be described below with reference to the accompanying drawings. 1, 2, 3 and 4
FIGS. 1 and 2 are embodiments of a hose having one reinforcing layer, and FIGS. 3 and 4 are embodiments of a hose having one reinforcing layer. FIGS. 3 shows an embodiment of a hose.

In the method of manufacturing the hose shown in FIG. 1, a thermoplastic material such as copolyester resin is extruded into a tube by an extruder to form an inner tube 1, and the inner tube 1 is brought into contact with the outer surface of the inner tube 1. The outer surface of the inner tube 1 is heated to a temperature higher than the melting temperature of the thermoplastic material through the center of the ring-shaped heater for heat transfer to a molten state. Next, a reinforcing material such as polyester fiber is braided with a braiding machine to form the reinforcing layer 3, and then a room temperature-curable adhesive such as a urethane-based adhesive is applied to the outer surface of the reinforcing layer 3 by a coating machine. An adhesive layer 6 is formed between the tube and the reinforcing layer.

Thereafter, the thermoplastic material is extruded by an extruder into a tubular shape on the outer surface of the adhesive layer 6 between the outer tube and the reinforcing layer, and the outer tube 2 is extruded.
To form Next, in the method of manufacturing the hose of FIG. 2, a thermoplastic material such as a thermoplastic elastomer composition is extruded into a tube to form the inner tube 1, and the thermoplastic material is extruded on the outer surface of the inner tube 1 into a tube. It extrudes with a machine to form an adhesive layer 4 between the inner tube and the reinforcing layer.

Next, the inner tube and the reinforcing layer are connected to each other continuously or discontinuously through the center of a ring-shaped heater which contacts the outer surface of the adhesive layer 4 between the inner tube and the reinforcing layer and transfers heat. Is heated above the melting temperature of the thermoplastic material to bring it into a molten state. Next, a reinforcing material such as polyester fiber is braided with a braiding machine to form the reinforcing layer 3, and then a room temperature-curable adhesive such as a urethane-based adhesive is applied to the outer surface of the reinforcing layer 3 by a coating machine. An adhesive layer 6 is formed between the tube and the reinforcing layer.

Thereafter, the thermoplastic material is extruded by an extruder into a tubular shape on the outer surface of the adhesive layer 6 between the outer tube and the reinforcing layer, and the outer tube 2 is extruded.
To form In the case of the hose shown in FIG. 2, even if the inner tube is made of a flexible material such as vulcanized rubber, the inner tube 1 and the reinforcing layer 4 are bonded by the adhesive layer 4 between the inner tube 1 and the reinforcing layer. Adheres firmly. Next, in the method of manufacturing the hose shown in FIG. 3, a thermoplastic material such as a copolyester resin is extruded into a tube by an extruder to form the inner tube 1, and then the inner tube 1 is brought into contact with the outer surface of the inner tube. The outer surface of the inner tube 1 is heated to a temperature higher than the melting temperature of the thermoplastic material through the center of an annular heater that transmits heat and is brought into a molten state.

Next, a reinforcing material such as a polyester fiber is braided by a braiding machine to form a first reinforcing layer 31, and then a thermoplastic material is extruded into a tubular shape on the outer surface of the first reinforcing layer 31 by an extruder and reinforced. An interlayer adhesive layer 5 is formed. Then successively,
Alternatively, the reinforcing interlayer adhesive layer 5 is heated to a melting temperature of the thermoplastic material or higher through the center of an annular heater that contacts the outer surface of the reinforcing interlayer adhesive layer 5 and conducts heat in a discontinuous manner to be in a molten state.

Next, the reinforcing material is braided on the outer surface of the molten reinforcing interlayer adhesive layer 5 by a braiding machine to form a second reinforcing layer 3.
Then, a cold-setting adhesive such as a urethane-based adhesive is applied to the outer surface of the second reinforcing layer 32 with an applicator to form an adhesive layer 6 between the outer tube and the reinforcing layer. Thereafter, the outer tube 2 is formed by extruding the thermoplastic material into a tube on the outer surface of the adhesive layer 6 between the outer tube and the reinforcing layer using an extruder.

Next, in the method of manufacturing the hose shown in FIG. 4, the thermoplastic material of the thermoplastic elastomer composition is extruded into a tube to form the inner tube 1, and the thermoplastic material is formed on the outer surface of the inner tube 1. To form an inner tube and a reinforcing interlayer adhesive layer 4. Then the bond between the inner tube and the reinforcing layer through the center of an annular heater that transfers the heat continuously and discontinuously in contact with the outer surface of the adhesive layer between the inner tube and the reinforcing layer Layer 4 is heated above the melting temperature of the thermoplastic material to a molten state.

Next, a reinforcing material such as a polyester fiber is braided by a braiding machine to form a first reinforcing layer 31, and then a thermoplastic material is extruded on the outer surface of the first reinforcing layer 31 into a tubular shape by an extruder to reinforce. An interlayer adhesive layer 5 is formed. And continuously,
Alternatively, the reinforcing interlayer adhesive layer 5 is heated to a melting temperature of the thermoplastic material or higher through the center of an annular heater that contacts the outer surface of the reinforcing interlayer adhesive layer and conducts heat in a discontinuous manner to bring it into a molten state.

Next, the reinforcing material is braided on the outer surface of the molten reinforcing interlayer adhesive layer 5 by a braiding machine to form a second reinforcing layer 3.
Then, a cold-setting adhesive such as a urethane-based adhesive is applied to the outer surface of the second reinforcing layer 32 with an applicator to form an adhesive layer 6 between the outer tube and the reinforcing layer. Thereafter, the outer tube 2 is formed by extruding the thermoplastic material into a tube on the outer surface of the adhesive layer 6 between the outer tube and the reinforcing layer using an extruder. In this case, as in the case of the hose of FIG. 2, a flexible material such as a vulcanized rubber composition can be used for the inner tube.

In each of the hoses shown in FIGS. 1 to 4, a thermoplastic material can be used except for the reinforcing layer.
Unlike a hose made of vulcanized rubber, it hardens when the temperature of the hose drops without a vulcanizing step. Therefore, the individual production steps of these hoses can be performed continuously on one production line. In addition, even when a flexible material such as a vulcanized rubber composition is used for the inner tube, it can be continuously performed on one production line by a production method such as so-called continuous vulcanization.

As a heating means of the heater, hot air, infrared rays, far infrared rays, near infrared rays, ultrasonic high frequency, dielectric, and the like can be used. Further, the heat melting, without using a heater, in the step of extrusion molding of a thermoplastic material,
Heat the thermoplastic material above the melting temperature in the extruder, maintain the temperature until after the thermoplastic material is extruded into a tube and formed into an inner tube or adhesive layer, and proceed to the next step while maintaining the molten state The same effect can be obtained also by the above.

In particular, increasing the temperature of the adhesive layer by contacting the heater with the thermoplastic material is a preferable method, and the temperature of the adhesive layer can be effectively increased. Furthermore, these heating means may be used in combination, and after melt extrusion,
Maintaining the molten state through a heater is a preferable method. Even if the above-mentioned heating and melting of the inner tube and each adhesive layer are performed after forming the reinforcing layer on the outer surface of the inner tube and each adhesive layer, the same effect can be obtained.

The thermoplastic material that can be used for the adhesive layer between the inner tube and the reinforcing layer, the reinforcing interlayer adhesive layer, and the inner tube when no adhesive layer is used between the inner tube and the reinforcing layer includes: There is no particular limitation, and any thermoplastic material having adhesiveness can be used. However, the softening temperature of the above material is 110
C. or higher is preferred. If the temperature is lower than 110 ° C., the hose is likely to be softened at the time of use, and the durability may be reduced. The structure of the reinforcing layer may be either a braided structure or a spiral structure.

Conventionally used cold-setting adhesives, such as urethane-based adhesives, undergo excessive thermal curing during use, and the adhesive layer becomes hard. Although the reinforcing layer was cut and the durability was impaired, the adhesive layer of the present invention is made of a thermoplastic material such as copolyester resin, which is excellent in heat aging and bending fatigue resistance and does not harden during use. Therefore, a hose having excellent durability and flexibility can be provided.

Further, the adhesive layer of the present invention is brought into a molten state by heating at a temperature higher than the softening temperature, and in this molten state, there is an opportunity to come into contact with the reinforcing layer at least once. As a result, an anchoring effect occurs and the contact area increases. As a result, the adhesion is strengthened, and the adhesion is maintained for a long time with little fatigue, so that a hose having excellent durability can be obtained.

However, a thermoplastic material having a softening temperature of less than 110 ° C. may be slightly softened due to a high-temperature environment or excessive repetitive stress, and may impair durability. Further, since the heating of the adhesive layer in the present invention is performed at least before the outer tube is formed, the amount of heat applied to each part of the hose such as the reinforcing layer is much smaller than the heating after the outer tube is formed. Therefore, thermal degradation of the reinforcing layer and the like that occurs at the time of heating after the outer tube is formed does not occur in the present invention.

In the present invention, the heating of the adhesive layer
Since it can be performed simply by passing through a heater having a simple structure such as an annular heater, it can be incorporated into a continuous production line and heated. Therefore, the manufacturing method of the present invention is a manufacturing method which requires no man-hours and is excellent in productivity, as compared with a case where a heater having a large amount of heat is used such as heating after forming the outer tube. Furthermore, in a method in which an adhesive layer is molded and heated and melted by an extruder at the same time, there is no need for a separate heating step, and the production method is more excellent in productivity. It is more preferable to use a thermoplastic resin also as an adhesive layer between the reinforcing layer and the outer tube.

[0038]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The hose of the present invention (Examples 1 to 3)
0) and a conventional hose (Comparative Examples 1 to 17)
Was manufactured and a durability test was performed. Tables 1 to 7 below show the configuration of the manufactured hose, the material of each part, the bonding method, and the results of the durability test evaluation.

The hoses of Examples 1 to 12 and Comparative Examples 1 and 2 shown in Tables 1 and 2 each have one reinforcing layer, and evaluated the adhesion between the inner tube and the reinforcing layer. Further, the hoses of Examples 13 to 30 and Comparative Examples 3 to 17 shown in Tables 3 to 7 have two reinforcing layers, and evaluated the adhesion between the reinforcing layers. In Examples 27 to 30, the adhesion between the inner tube and the reinforcing layer and the adhesion between the reinforcing layers were simultaneously evaluated. The method for producing the hoses of the examples and comparative examples is as follows.

The inner tube was 9.5 mm in inner diameter by an extruder.
It is formed into a tube having a thickness of 1.0 mm. The adhesive layer between the inner tube and the reinforcing layer is applied to the outer surface of the inner tube in the case of a room-temperature-curable urethane-based adhesive and air-dried. And extruded into a tube having a wall thickness of 0.1 mm. The reinforcing layer is braided by a braiding machine. In the case of a room-temperature-curable urethane-based adhesive, the reinforcing interlayer adhesive layer is applied to the surface of the reinforcing layer and air-dried. In the case of a thermoplastic material, the thickness of the reinforcing layer is 0.1 mm on the reinforcing layer using a crosshead extruder.
Extruded into a tube.

In the case of a room-temperature-curable urethane-based adhesive, the adhesive layer between the outer tube and the reinforcing layer is applied to the surface of the reinforcing layer, air-dried, and further dried at 60 ° C. for one hour. In the case of a thermoplastic material, a crosshead resin extruder is used to extrude a 0.1 mm-thick tube on the inner tube. The outer tube is extruded by a crosshead resin extruder into a tube having an outer diameter of 17.5 mm on the adhesive layer between the outer tube and the reinforcing layer.

The method of heating the adhesive layer described in the table is as follows. Heating in the oven after forming the outer tube,
In order to heat the adhesive layer above the melting temperature, the hose whose outer tube has been formed is placed in an oven and heated at a predetermined temperature and time. In the direct heating of the inner tube immediately before the braid, the outer surface of the inner tube is heated and melted by a heater before forming a reinforcing layer. In the heating immediately before braiding, the adhesive layer is heated and melted by a heater before the reinforcing layer is braided on the adhesive layer. In the melt extrusion, an adhesive layer is formed by extruding a thermoplastic material at a temperature equal to or higher than a softening temperature by an extruder, and immediately after that, a reinforcing layer is braided.

The durability test was performed using SAE J188 TYPE
In a so-called impulse endurance test according to
The operation is performed at 0 ° C. and a pressure of 27.5 MPa, and is performed up to 400,000 times.
The abbreviations of the materials shown in the tables are shown below. COPE is a thermoplastic copolyester elastomer used for the inner tube material.
Hytrel 5557 was used. ACM / COPE
(1) is a thermoplastic elastomer composition in which a vulcanized rubber composition of an acrylic rubber (ACM) composition is finely dispersed in a thermoplastic copolyester elastomer used for an inner tube material. (Blending Table ACM / COPE (1)) NBR / PP (1) and NBR / PP (2) are obtained by adding an acrylonitrile-butadiene copolymer rubber (NBR) composition to the polypropylene thermoplastic resin used for the inner tube material. It is a thermoplastic elastomer composition in which a vulcanized rubber composition is finely dispersed. NBR / PP (1) used GEOLAST 703-40 manufactured by AES Japan Co., Ltd. NBR / PP (2) used was a blend of NBR / PP (1) and Admar QB-540 manufactured by Mitsui Petrochemical Co., Ltd. at 20% by weight.

COPE (1), COPE (2), COP
E (3) is a thermoplastic copolyester elastomer used for the adhesive layer, COPE (1) is Hytrel 2551 manufactured by Toray Dupont, and COPE (2) is Byron manufactured by Toyobo Co., Ltd. GM-990, COPE
For (3), Byron GM-400 manufactured by Toyobo Co., Ltd. was used.

The modified olefin is a modified polyolefin resin used for the adhesive layer, and Admer QB-540 manufactured by Mitsui Petrochemical Co., Ltd. was used. TPU is a thermoplastic urethane elastomer used for the outer tube material, and Esten 58212 manufactured by Kyowa Hakko Kogyo Co., Ltd. was used.

ACM / COPE (2) is a thermoplastic elastomer composition in which a vulcanized rubber composition of an acrylic rubber (ACM) composition is finely dispersed in a thermoplastic copolyester elastomer used for an outer tube material. (Formulation ACM
/ COPE (2)) EPDM / PP (1) and EPDM / PP (2)
This is a thermoplastic elastomer composition in which a vulcanized rubber composition of an ethylene-propylene-diene copolymer rubber (EPDM) composition is finely dispersed in a polypropylene-based thermoplastic resin used for an outer tube material.

EPDM / PP (1) is an AES
SANTOPRENE 201-6 manufactured by Japan Co., Ltd.
4 was used. EPDM / PP (2) is EPDM / P
Admer QB-54 manufactured by Mitsui Petrochemical Co., Ltd.
0 was blended at 20% by weight.

As the urethane-based adhesive, Tylite 7411 manufactured by Lord Far East was used. (Blending Table) ACM / COPE (1) (parts by weight) COPE Hytrel 5556 Toray DuPont 334.40 ACM1 100.00 EA (ethyl acrylate) = 40% by weight BA (butyl acrylate) = 32% by weight MEA ( Methoxyethyl acrylate) = 19% by weight GMA (glycidyl methacrylate) = 9% by weight FEF grade carbon black Seast SO Tokai Carbon Co., Ltd. 40.00 Anti-aging agent Irganox 1010 Ciba-Geigy 3.00 Cross-linking agent Butanetetracarboxylic acid Mitsui Higashi Katsu Fine Co., Ltd. 1.60 EMA-GMA 33.44 E (ethylene) = 67% by weight MA (methyl acrylate) = 30% by weight GMA (glycidyl methacrylate) = 3% by weight ACM / COPE (2) (parts by weight) COPE C Itrel 5556 Toray Dupont Co., Ltd. 144.30 ACM1 100.00 FEF grade carbon black Seast SO Tokai Carbon Co., Ltd. 40.00 Anti-aging agent Irganox 1010 Ciba Geigy Corporation 3.00 Crosslinking agent Butanetetracarboxylic acid Mitsui Toatsu Fine 1.60 EMA-GMA 14.43

[0049]

[Table 1]

[0050]

[Table 2]

[0051]

[Table 3]

[0052]

[Table 4]

[0053]

[Table 5]

[0054]

[Table 6]

[0055]

[Table 7]

[Explanation of Effects of Examples] (Adhesion manufacturing method between inner tube and reinforcing layer; Examples 1 to 12, ratio
Comparative Examples 1 and 2 illustrate the effect of the production method of the present invention on the adhesion between the inner tube and the reinforcing layer. Comparative Example 1
Because the room temperature curing type urethane-based adhesive is used for the adhesive layer between the inner tube and the reinforcing layer, the adhesive layer hardens during use and cuts the fibers of the reinforcing layer, resulting in poor durability. I have. In Comparative Example 2, although a thermoplastic material was used for the adhesive layer between the inner tube and the reinforcing layer, an excessive amount of heat was applied to the fibers of the reinforcing layer because the oven was heated after the outer tube was formed. Due to thermal deterioration of the fiber, durability is poor.

In Examples 1 to 4, the adhesive layer between the inner tube made of a thermoplastic material extruded on the inner tube and the reinforcing layer was heated to a temperature higher than the melting temperature, and the surface in contact with the fiber to be braided. Is a braided reinforcing layer when is in a molten state.
In Examples 5 to 8, the inner tube was directly heated to a melting temperature or higher immediately before braiding the reinforcing layer, and the reinforcing layer was braided when the surface in contact with the fiber to be braided was in a molten state.
Examples 9 to 12 show that the adhesive layer between the inner tube made of thermoplastic material and the reinforcing layer is melt-extruded on the inner tube, and the reinforcing layer is in contact with the fiber to be braided when the surface is in a molten state. Is braided. Regardless of the hose configuration (inner tube, outer tube material, and reinforcing fiber material), the hoses of these embodiments can provide strong adhesion between the inner tube and the reinforcing layer, do not have thermosetting of the adhesive layer, and have the reinforcing layer. Since an excessive amount of heat is not applied to the substrate, it has excellent durability. (Reinforcing interlayer bonding method; Examples 13 to 30, Comparative Examples 3-1)
7) Explain the effect of the manufacturing method of the present invention on the adhesion between reinforcing layers.

In Comparative Examples 3 to 6, no adhesive layer was provided between the reinforcing layers, and no heat treatment was performed. Since there was no adhesion between the reinforcing layers, the main body was destroyed early and the durability was poor. Comparative Examples 7 to 10 used a room-temperature-curable urethane-based adhesive for the reinforcing interlayer adhesive layer and were not subjected to heat treatment. The adhesive layer was cured during use, and the fibers of the reinforcing layer were cut. The results were poor.

In Comparative Examples 11 to 17, the thermoplastic material was used for the reinforcing interlayer adhesive layer and the oven was heated after the outer tube was formed. Excessive heat was applied to the fibers of the reinforcing layer, and the fibers deteriorated. The result was inferior. Examples 13 and 2
2 is to heat the reinforcing interlayer adhesive layer made of a thermoplastic material extruded on the first reinforcing layer to a temperature higher than the melting temperature, and when the surface in contact with the fiber to be braided is in a molten state, Is braided.

In Examples 23 to 26, the reinforcing interlayer adhesive layer made of a thermoplastic material was melt-extruded on the first reinforcing layer, and when the surface in contact with the fiber to be braided was in a molten state, the second reinforcing layer was formed. Is braided. Regardless of the hose configuration (inner tube, outer tube material, and reinforcing fiber material), the hoses of these examples have strong adhesion between the reinforcing layers, do not have thermosetting of the adhesive layer, and have an excessive amount of Since no heat is applied, it has excellent durability. (Inner tube and joint production method between reinforcement layer and reinforcement layer; Example
27-30) The effects of the combined use of the manufacturing method of the present invention on the adhesion between the inner tube and the reinforcing layer and the bonding between the reinforcing layers will be described.

Examples 27 to 30 show that the adhesive layer between the inner tube made of thermoplastic material extruded on the inner tube and the reinforcing layer is heated above the melting temperature and the surface in contact with the fibers to be braided. Is in a molten state, the first reinforcing layer is braided, and a reinforcing interlayer adhesive layer formed by extrusion on the first reinforcing layer,
The second reinforcing layer is braided when heated above the melting temperature and the surface in contact with the fiber to be braided is in a molten state.

In these examples, a thermoplastic resin is used for the adhesive layer between the reinforcing layer and the outer tube, which is more preferable. Regardless of the hose configuration (inner tube, outer tube material and reinforcing fiber material), the hoses of these embodiments can provide strong adhesion between the inner tube and the reinforcing layer and between the reinforcing layers, Since there is no curing and no excessive amount of heat is applied to the reinforcing layer, the durability is excellent.

[0063]

Since the present invention is configured as described above, it has the following excellent effects. In the production method of the present invention, the adhesive layer is brought into a molten state by heating at a temperature higher than the softening temperature, and comes into contact with the adhesive layer or the inner tube in the molten state, so that a strong interlayer adhesion is obtained, and
Since the thermoplastic material constituting the adhesive layer does not cure even after long-term use and is excellent in heat aging and fatigue resistance, a flexible hose having excellent durability can be manufactured.

Since the heating of the adhesive layer and the inner tube is performed before the formation of the outer tube, the amount of heat applied to each part such as the reinforcing layer is small. Does not occur. Further, in the manufacturing method of the present invention,
Heating the adhesive layer and the inner tube is a simple heater, or
Since it is performed simultaneously with molding by an extruder that molds the adhesive layer and inner tube, it can be heated continuously in the production line,
A production method with high productivity can be provided.

Further, since an adhesive containing a solvent is not used, environmental problems due to the solvent do not occur.

[Brief description of the drawings]

FIG. 1 is a partially cut-away side view of a hose of a first embodiment manufactured by a manufacturing method of the present invention.

FIG. 2 is a partially cut-away side view of a hose according to a second embodiment of the present invention.

FIG. 3 is a partially cut-away side view of a hose according to a third embodiment of the present invention.

FIG. 4 is a partially cut-away side view of a hose according to a fourth embodiment of the present invention.

[Explanation of symbols]

Reference Signs List 1 inner pipe 32 second reinforcing layer 2 outer pipe 4 adhesive layer between inner pipe and reinforcing layer 3 reinforcing layer 5 reinforcing interlayer adhesive layer 31 first reinforcing layer 6 adhesive layer between outer pipe and reinforcing layer

Continued on the front page (72) Inventor Yoshihiro Soeda 2-1 Oiwake, Hiratsuka-shi, Kanagawa Yokohama Rubber Co., Ltd. Hiratsuka Works (72) Inventor Osamu 2-1 Oiwake, Hiratsuka-shi, Kanagawa Yokohama Rubber Hiratsuka, Ltd. In the factory

Claims (16)

[Claims] 1. An inner tube made of a thermoplastic material is formed into a tube, and one or more reinforcing layers are braided or braided on the inner tube, and a thermoplastic material is formed on the reinforcing layer. A method for manufacturing a hose in which an outer tube is laminated in a tubular form, wherein before forming the outer tube, the outer surface of the inner tube is heated to a temperature equal to or higher than a softening temperature of the thermoplastic material by a heating means. A method for producing a hose, comprising: bringing an outer surface of a hose into a molten state. 2. The method for producing a hose according to claim 1, wherein the step of heating the outer surface of the inner tube to a temperature higher than the softening temperature of the thermoplastic material to bring it into a molten state is performed immediately before the step of forming a reinforcing layer. . 3. The hose manufacturing method according to claim 1, wherein the step of heating the outer surface of the inner tube to a temperature higher than the softening temperature of the thermoplastic material to bring it into a molten state is performed after the step of forming a reinforcing layer. 4. An inner tube made of a thermoplastic material or a flexible material is formed into a tube, and an adhesive layer between the inner tube made of a thermoplastic material and a reinforcing layer is formed on the inner tube into a tube. A method for producing a hose in which one or more reinforcing layers are braided in a braided or spiral shape on the adhesive layer, and an outer tube made of a thermoplastic material is laminated on the reinforcing layer in a tubular manner,
Before forming the outer tube, the adhesive layer between the inner tube and the reinforcing layer is heated by a heating means to a temperature equal to or higher than the softening temperature of the thermoplastic material to bring the outer surface of the adhesive layer into a molten state. Hose manufacturing method. 5. A step of heating the adhesive layer between the inner tube and the reinforcing layer to a melting state by heating means at a temperature higher than a softening temperature of the thermoplastic material, and forming the adhesive layer in contact with an outer surface of the adhesive layer. The method for producing a hose according to claim 4, wherein the step is performed immediately before forming the reinforcing layer. 6. A step of heating the adhesive layer between the inner tube and the reinforcing layer to a melting state by heating at or above a softening temperature of the thermoplastic material by a heating means, wherein the step of forming the adhesive layer is in contact with an outer surface of the adhesive layer. The method for producing a hose according to claim 4, wherein the method is performed after the step of forming a reinforcing layer. 7. The step of bringing the molten state into the molten state is a step of melt-extruding the adhesive layer between the inner tube and the reinforcing layer, and extruding the thermoplastic material at a temperature equal to or higher than the softening temperature to form the adhesive layer in the molten state. The method for manufacturing a hose according to claim 5, wherein the adhesive layer is maintained in a molten state by doing. 8. The step of bringing the molten state into a molten state is a step of melting and extruding the adhesive layer between the inner tube and the reinforcing layer immediately after the inner tube is extruded, and melting the thermoplastic material at a temperature equal to or higher than the softening temperature. Extruded to form a molten adhesive layer, thereby bonding the inner tube and the adhesive layer between the inner tube and the reinforcing layer,
The method for producing a hose according to claim 7, wherein the adhesive layer is maintained in a molten state. 9. An inner tube made of a thermoplastic material or a flexible material is formed into a tube, and a plurality of reinforcing layers are directly formed on the inner tube.
Or a braided braided or spiral braid via an adhesive layer between an inner tube and a reinforcing layer, and a hose manufacturing method in which an outer tube made of a thermoplastic material is laminated on the reinforcing layer in a tubular shape and molded. The reinforcing interlayer adhesive layer made of the thermoplastic material is formed into a tubular shape between the adjacent reinforcing layers, and in a step before forming the outer tube, a thermoplastic material constituting the reinforcing interlayer adhesive layer by heating means is used. A method for producing a hose, wherein the outer surface of a reinforcing interlayer adhesive layer is brought into a molten state by heating to a softening temperature or higher. 10. The step of heating the reinforcing interlayer adhesive layer to a molten state by heating it to a temperature higher than the softening temperature of the thermoplastic material by heating means, comprising forming the reinforcing layer formed in contact with the outer surface of the reinforcing interlayer adhesive layer. The method for producing a hose according to claim 9, wherein the method is performed immediately before the step of performing a hose. 11. The step of heating the reinforcing interlayer adhesive layer to a molten state by heating it to a temperature not lower than the softening temperature of the thermoplastic material by heating means includes forming a reinforcing layer formed in contact with an outer surface of the reinforcing interlayer adhesive layer. The method for producing a hose according to claim 9, wherein the method is performed after the step of: 12. The step of bringing into a molten state is a melt extrusion, in which a thermoplastic material is melt-extruded at a temperature equal to or higher than a softening temperature, and a reinforcing interlayer adhesive layer in a molten state is formed.
The method for producing a hose according to claim 10, wherein the reinforcing interlayer adhesive layer is maintained in a molten state. 13. An inner tube made of a thermoplastic material is formed into a tube, and a plurality of reinforcing layers are braided or spirally braided on the inner tube, and an outer tube made of a thermoplastic material is formed on the reinforcing layer. A method for producing a hose that is laminated in a tubular form, wherein before forming the outer tube, the outer surface of the inner tube is heated to a temperature equal to or higher than the softening temperature of the thermoplastic material by a heating means, and the outer surface of the inner tube is formed. In a molten state, and thereafter, a reinforcing interlayer adhesive layer made of a thermoplastic material is formed into a tubular shape between adjacent reinforcing layers, and in a step prior to forming an outer tube, a heating means is used to heat the softening temperature of the thermoplastic material or more. And heating the outer surface of the reinforcing interlayer adhesive layer to a molten state. 14. The step of bringing the outer surface of the reinforcing interlayer adhesive layer into a molten state is melt extrusion, which is performed by extruding at a temperature equal to or higher than the softening temperature of the thermoplastic material to form a molten reinforcing interlayer adhesive layer. The method for producing a hose according to claim 13, wherein the reinforcing interlayer adhesive layer is maintained in a molten state. 15. An inner tube made of a thermoplastic material or a flexible material is formed into a tube, and an adhesive layer between the inner tube made of a thermoplastic material and a reinforcing layer is formed on the inner tube into a tube. A method of manufacturing a hose in which a plurality of reinforcing layers are braided in a braid or spiral shape on an adhesive layer, and an outer tube made of a thermoplastic material is laminated in a tubular shape on the reinforcing layer, wherein the outer tube is formed. Before, the adhesive layer is heated by a heating means to a temperature equal to or higher than the softening temperature of the thermoplastic material to bring the outer surface of the adhesive layer into a molten state, and thereafter, a reinforcing interlayer adhesive layer made of a thermoplastic material and an adjacent reinforcing layer In a step before forming the outer tube, the outer surface of the reinforcing interlayer adhesive layer is melted by heating to a temperature equal to or higher than the softening temperature of the thermoplastic material forming the reinforcing interlayer adhesive layer by a heating means in a step prior to forming the outer tube. Hose manufacturing method characterized by Law. 16. The step of bringing the outer surface of the adhesive layer between the inner tube and the reinforcing layer into a molten state by melt extrusion, wherein the adhesive layer is melt-extruded at a temperature equal to or higher than the softening temperature of the thermoplastic material. Is a method of manufacturing a hose that holds the adhesive layer in a molten state by molding, and the step of bringing the outer surface of the reinforcing interlayer adhesive layer into a molten state is melt extrusion, and is performed at a temperature equal to or higher than the softening temperature of the thermoplastic material. The method for producing a hose according to claim 15, which is a method for producing a hose in which the reinforcing interlayer adhesive layer is maintained in a molten state by melt-extrusion at a temperature of 3 to form a reinforcing interlayer adhesive layer in a molten state.