JPS6392888A - Hose and manufacture thereof - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a hose used for transporting fluids such as fuel oil, lubricating oil, refrigerant gas for air conditioners, chemicals, and solvents, and a method for manufacturing the same.

[Conventional technology]

In general, for hoses for transporting various fluids as described above, a fiber reinforced layer made of organic fiber yarn or cloth is closely formed around the outer periphery of an inner tube rubber layer, and an outer tube rubber layer is further formed around the outer periphery of this fiber reinforced layer. The material obtained by closely forming the is used. In the above hose, polyester fibers and nylon fibers are used as organic fibers constituting the fiber reinforcing layer.

Fabrics (woven fabrics or non-woven fabrics) obtained by using synthetic fibers such as polyvinyl alcohol fibers and polypropylene fibers and natural fibers such as cotton, by braiding these threads (spiral or braid), or by using the above organic fibers. is taped to form a fiber reinforcement layer. In this case, in order to improve the adhesion of the organic fiber thread or cloth to the inner tube and outer tube, resorcinol, formalin, etc.
An organic fiber yarn impregnated with a rubber latex (rRFLJ) solution and further treated with the RFL solution,
An adhesive is applied to a fiber reinforced layer made of cloth to improve its adhesion to the inner and outer tubes. In the thus obtained hose, the fiber reinforcing layer adheres well to the inner and outer tubes, and exhibits good performance in transporting various fluids.

[Problem that the invention seeks to solve]

However, recently, there has been a desire to provide a hose with performance characteristics that warmly exceed those of the conventional fluid transport hoses. For example, with fuel hoses for automobiles, excessive heat is applied to the hoses as the temperature inside the engine room increases due to the miniaturization and higher performance of cars.
Gasoline is oxidized at high temperatures to produce peroxide-containing products, and it is desirable to have resistance to these heat and highly corrosive gasolines. Furthermore, based on future changes in fuel conditions, it is desired to improve resistance to highly soluble gasoline such as alcohol-mixed gasoline. In addition, in lubricating oil hoses, the liquid temperature of lubricating oil such as engine oil and power steering increases, and the permeability of the oil increases accordingly.
Improved resistance to heat and oil is desired. Furthermore, for car air conditioner hoses, in addition to improved resistance to heat and refrigerant gases such as Freon gas, it is also desired to have improved resistance to splashing with acids, antifreeze, and the like. However, the conventional hoses cannot fully satisfy these required characteristics. In other words, conventional hoses have inner and outer tube shapes that match the required characteristics.

The main focus is on the selection of materials, etc., and the fiber-reinforced layer merely functions as a pressure-resistant layer, and no consideration has been given to the fiber-reinforced layer. Under such usage conditions, the fluid that permeates through the inner tube etc. erodes the fiber reinforced layer, and there are many cases where the fiber reinforced layer deteriorates before the inner and outer tubes deteriorate, causing breakage of the fiber reinforced layer. However, a fatal problem arises in that the pressure resistance strength decreases and the hose loses its function.

The present invention was made in view of these circumstances, and has a fiber-reinforced layer that has a high degree of resistance to erosion by the transport fluid.
The purpose of the present invention is to provide a hose which is also excellent in heat resistance and has a long life as a whole, and a manufacturing method thereof.

[Means for solving problems]

In order to achieve the above object, the present invention includes an outer tube rubber layer, an inner tube rubber layer, and a fiber reinforcement layer interposed between the two layers,
The first hose has a fiber-reinforced layer made of yarn or cloth mainly composed of organic fibers and covered with a ceramic layer.
The main idea is that a fiber reinforcing layer made of thread or cloth mainly composed of organic fibers is closely formed on the outer periphery of the inner tube rubber layer,
A method of manufacturing a hose by closely forming an outer tube rubber layer on the outer periphery of this fiber-reinforced layer and vulcanizing and adhering them in that state, the method comprising thread or cloth mainly composed of organic fibers for constituting the fiber-reinforced layer. The second gist is a method for producing a hose containing the following components (A) and (B) and further impregnated with a treatment liquid containing at least one of components (C) and (D), (A) Resorcinol/formalin/rubber latex.

(B) Ceramic powder.

(C) Ethylene urea compound.

(D) Epoxy-modified phenol formaldehyde condensate.

Furthermore, prior to impregnation treatment with the above treatment liquid, a treatment liquid (E) polyepoxide compound containing the following components (E), (F), and (G).

(F) Blocked polyisocyanate compound.

(G) Rubber latex.

The third gist is a method for manufacturing a hose impregnated with.

The hose of the present invention is mainly made of organic fibers and is obtained by using thread or cloth coated with a ceramic layer, an inner tube rubber layer, an outer tube rubber layer, and other raw materials as necessary.

The threads or cloths mainly composed of the above organic fibers and covered with a ceramic layer include synthetic fibers such as polyester fibers, nylon fibers, rayon fibers, polyvinyl alcohol fibers, and polypropylene fibers, or threads or cloths made of natural fibers such as cotton fibers. It is obtained by using cloth and coating it with a ceramic layer. In this case, the ceramic material that is the raw material for the ceramic layer is:
Ceramic materials containing ceramic powders such as silica powder, alumina powder, and zirconia powder alone or in combination as aggregates are used. In this case, the ceramic powder exhibits better performance as the particle size is smaller, and those having a particle size in the range of 0.001 to 10 μm are usually used, preferably in the range of 0.01 to 1 μm.

Ceramic materials such as those described above do not have adhesion properties to organic fiber threads and cloth as they are, and therefore are usually used after being formed into a treatment liquid (aqueous) having the composition shown below.

(A) Resorcinol/formalin/rubber latex.

(B) Ceramic powder.

(C) Ethylene urea compound.

(D) Epoxy-modified phenol formaldehyde condensate.

In the above treatment liquid, components (A) and (B) are essential components, and either one or both of components (C) and (D) are used.

As mentioned above, the resorcinol/formalin/rubber latex of component (A) is called RFL in -C, and the molar ratio of resorcinol and formaldehyde is 1:0.1-tea. It is set. Preferred is 1:0.5 to 1:5, most preferred is 1:1.
~1:4. Examples of the rubber latex used together with the resorcinol and formalin include natural rubber latex, styrene-butadiene copolymer latex, vinylpyridine-styrene-butadiene terpolymer latex, nitrile rubber latex,
Examples include chloroprene rubber latex, which can be used alone or in combination. Among the above-mentioned rubber latexes, it is particularly preferable to use vinylpyridine-styrene-butadiene terpolymer latex alone or in an amount of 1/2 or more of the total amount. The blending ratio of resorcinol and the rubber latex is set at 1:1 to 1:15 based on the solid content, and preferably within the range of 1:3 to 1:12.

As the ceramic powder of component (B), those described above are preferably used.

The ethylene urea compound of component (C) has the following general formula (1
).

Typical examples of the above ethylene urea compounds include octadecyl isocyanate, hexamethylene diisocyanate,
Examples include reaction products of aromatic/aliphatic isocyanates such as isophorone diisocyanate, tolylene diisocyanate, metaxylene diisocyanate, diphenylmethane diisocyanate, naphthylene diisocyanate, and triphenylmethane triisocyanate with ethyleneimine. Preferred are aromatic ethylene urea compounds such as diphenylmethane diethylene urea.

The epoxy-modified phenol formaldehyde condensate of component (D) is represented by the following general formula (2).

(Margin) In the above formula (2), molecules ff11200 to 130
Using compounds with an epoxy value of 4.0 to 4.5 eq/kg at 0 gives good results.

In the treatment liquid consisting of the above component (A) or D),
The total solid content of component (A) and at least one of components (C) and (D) is preferably set to 10 to 25% by weight (hereinafter abbreviated as "%"). The ratio of the total amount of component (A) and at least one of components (C) and (D) to the ceramic powder is 1:0.5 to 1.5 on a heavy N basis. , preferably set to 1:0.8 to 1.2.

Applying a ceramic coating to the organic fiber yarn or cloth using the above treatment liquid can be done by dipping the machine fiber yarn or cloth in the treatment liquid, spraying it from a nozzle, or using a roller. By this contact, the yarn or cloth is impregnated with the treatment liquid and dried. In this case, the amount of the above-mentioned treatment liquid deposited is 0.000% of the total amount based on the solid content.
It is suitable to set it to 5 to 10%, and more preferably about 1 to 5%.

The yarns and cloths mainly made of organic fibers that are treated with the above treatment liquid are mainly synthetic fibers such as polyester fibers, nylon fibers, rayon fibers, polyvinyl alcohol fibers, and polyester fibers, and natural fibers such as cotton fibers. The type of fiber is not particularly important. There is no problem even if some inorganic fibers such as carbon fibers, glass fibers, metal fibers, etc. are mixed in. Here, the term "mainly" means to include cases where the thread or cloth is composed only of the main organic fiber. As described above, the main constituent fibers of the threads and cloths are organic fibers, and the type thereof is not particularly limited as long as it is an organic fiber. However, good effects come to be obtained when using polyester fibers.

In particular, when using polyester fibers, in order to obtain the best effect, before treating with the above treatment liquid, use a treatment liquid containing the following components (E), (F), and (G). It is preferable to perform impregnation treatment and then impregnation treatment with the above treatment liquid.

(E) Polyepoxide compound.

(F) Blocked polyisocyanate compound.

CG) Rubber latex.

The polyepoxide compound of component (E) above is a compound containing at least two or more epoxy groups in one molecule in an amount of 0.2 g equivalent or more per 100 g of the compound, and includes ethylene glycol, glycerol, sorbitol, pentaerythritol 1 polyethylene glycol Reaction products of polyhydric alcohols such as and halogen-containing epoxides such as epichlorohydrin, resorcin, bis(4-hydroxyphenyl) dimethylmethane, pheno-/Lz formaldehyde resin, resorcin formaldehyde resin, etc. Examples include reaction products of polyhydric phenols and halogen-containing epoxides, and polyepoxide compounds obtained by oxidizing unsaturated compounds with peracetic acid or hydrogen peroxide, such as 3.4-epoxycyclohexene epoxide, 3. .4-epoxycyclohexylmethyl-3,4-epoxycyclohexenecarboxylate, bis(3,4-epoxy-6-methyl-cyclohexylmethyl)adipate, and the like.

Particularly preferred are reaction products of polyhydric alcohols and epichlorohydrin.

The blocked polyisocyanate compound of component (F) is
It is an addition compound of a polyisocyanate compound and a blocking agent, and the blocking component is liberated by heating to generate an active polyisocyanate compound. Examples of the polyisocyanate compounds include tolylene diisocyanate and metaphenylene diisocyanate.
Polyisocyanates such as diethylmethane diisocyanate, hexamethylene diisocyanate, polymethylene polyphenylisocyanate, triphenylmethane triisocyanate, and compounds having two or more active hydrogen atoms such as trimethylolpropane, pentaerythritol, etc., are used as isocyanates. Examples include terminal isocyanate group-containing polyalkylene glycol adduct polyisocyanates obtained by reacting groups (-N G O) and hydroxyl groups (-OH) in a molar ratio of more than 1. In particular, aromatic polyisocyanates such as tolylene diisocyanate, diethylmethane diisocyanate, and polymethylene polyphenylisocyanate are preferred. Examples of blocking agents include phenols such as phenol, thiophenol, cresol, and resorcinol, aromatic secondary amines such as diphenylamine and xylidine, phthalic acid imides,
Examples include lactams such as caprolactam, other oximes, and acidic sodium sulfite.

Representative examples of the rubber latex of component (G) include natural rubber latex, styrene-butadiene copolymer latex, and nitrile rubber latex.

Examples include chloroprene rubber latex, vinylpyridine/styrene/butadiene terpolymer latex, etc. Among these rubber latexes, vinylpyridine and
Good results can be obtained when the styrene-butadiene terpolymer latex is used alone or in an amount of 1/2 or more of the total amount.

The treatment liquid consisting of the above components is an aqueous liquid, and the blending weight ratio of each component is (E)/((E) + (F)) from 0.05 to
0.9, (G)/((E)+(F)) is 0.5~
It is preferable to use it so that it becomes 15. Particularly preferred is (E)/((E)+(F)) of 0
．． 1 to 0.5, (G)/C(E)+(F)] is 1 to 0.5
The range is 10.

The aqueous liquid containing such components contains the organic fiber yarn,
The solid content weight of the above fiber yarn, based on the weight of the fabric, is 1 to 1.
It is preferable to impregnate the resin at a concentration of 30%, more preferably from 3 to 20%. This method of impregnating with the treatment liquid can be carried out in the same manner as the impregnation with the treatment liquid containing the components (A) to D).

The inner tube rubber layer and outer tube rubber layer are made of acrylonitrile.
Butadiene copolymer (NBR), hydrogenated NBR, NB in which part or all of its conjugated diene units are hydrogenated
R/PVC (vinyl chloride JIi7), fluororubber (
FKM), chlorosulfonated polyethylene (CLSM)
), chlorinated polyethylene (CPE), chloroprene (C
R), ethylene propylene conjugated diene copolymer (EP
DM).

It is manufactured using rubber such as isoprene-isobutylene copolymer (IIR) and thermoplastic resin such as PVC, polyamide resin, and polyolefin resin. As described above, the inner and outer tube rubber layers in the present invention may be composed not only of rubber but also of synthetic resin, and include such embodiments.

In the present invention, a hose is manufactured using the above raw materials, for example, in the following manner.

(11) An unvulcanized rubber composition for forming an inner tube is extruded from an extruder to form an inner tube.

(2) Next, place the above (A) on the extruded inner tube in advance.
A ceramic-coated organic fiber thread that has been soaked in a treatment solution consisting of component (or D) and dried is braided to form a fiber-reinforced layer around the outer periphery of the inner tube.

(3) An unvulcanized rubber composition for forming an outer tube is extruded around the outer periphery of the fiber-reinforced layer to form an outer tube.

(4) Integrally vulcanize and mold the three-layer structure consisting of the inner tube, fiber reinforced layer, and outer tube (150-180℃ x 20-60m1n)
), (In this step, the ceramic layer covering the organic fiber thread is fired at a low temperature and hardened by heating, and is firmly bound to the organic fiber thread.) The hose obtained in this way is generally It is used for automobiles and is suitably used as a fuel oil lubricant transport hose, car air conditioner, etc.

The hose of the present invention can also be manufactured by the following method, which is different from the above method.

(1) An unvulcanized band-shaped rubber composition for forming an inner tube is wound spirally around a mandrel to form an inner tube.

(2) Ceramic-coated organic fiber fabric that has been pre-dipped and dried in the above-mentioned component (E) or G), and further dipped in the treatment solution of the (A) or D) component and dried on the above-mentioned inner tube. The cloth is wound in a spiral manner to form a first reinforcing layer.

(3) After forming a first intermediate rubber layer by spirally winding a belt-shaped rubber composition for forming an intermediate rubber layer on the first reinforcing layer, steel wires are placed on top of the first intermediate rubber layer at an appropriate pitch. A second intermediate rubber layer is formed by spirally winding the steel wire, and then spirally winding a band-shaped rubber composition similar to that used in the first intermediate layer on the wound layer of the steel wire.

(4) On the second intermediate rubber layer, a ceramic-coated organic fiber woven fabric similar to that used in (2) above is spirally wound to form a second fiber-reinforced layer.

(5) A band-shaped rubber composition for forming an outer tube is spirally wound on the second fiber reinforcing layer to form an outer tube.

(6) The laminate obtained through the steps (1) to (5) above is integrally vulcanized and molded (150 to bn). (In this step, the ceramic layer covering the organic fiber woven fabric is fired at a low temperature, heat-cured, and firmly bonded to the fabric.) The hose obtained as described above has a fiber reinforced layer made of ceramic. coated and reinforced with layers and therefore
It has a high degree of resistance to the corrosive properties of transport fluids, and also has excellent heat resistance due to the heat resistance of the ceramic layer itself, resulting in an extremely long lifespan as a whole. Therefore, it can withstand use under today's harsh conditions.

〔Effect of the invention〕

As described above, the hose of the present invention has a fiber reinforcing layer mainly composed of organic fibers and is composed of thread or cloth covered with a ceramic layer, and has a high degree of resistance to the corrosive properties of transport fluid. Therefore, for example, fuel oil hoses have a high degree of durability against high temperatures in the engine room and sour gasoline. That is, in the hose of the present invention, the performance of the fiber reinforcing layer is significantly improved, and the inner tube has a significantly improved performance.

Compared to the outer tube, the fiber reinforcing layer is not eroded earlier and the hose life is not shortened. Moreover, in the fiber reinforced layer, the elongation of the ceramic-covered yarn and cloth is smaller than that of conventional products, which suppresses the change in diameter under internal pressure load, thereby preventing loosening of the fiber reinforced layer structure. Become. As a result, the fiber-reinforced layer acts as a single barrier layer, resulting in low fluid permeability and improved hose performance. These effects are the same for lubricant transportation and car air conditioners. Furthermore, since the fiber-reinforced layer has excellent chemical resistance, it can be used as a hose for transporting chemicals, solvents, etc., and the same remarkable effects as above can be obtained. Moreover,
Since the above-mentioned fiber reinforcing layer has excellent properties, it becomes possible to realize thinning of the inner and outer tube layers. Furthermore, according to the method of the present invention, a hose having the above-mentioned excellent performance can be rationally manufactured.

Next, the present invention will be explained in detail based on examples.

[Example 1] Add 10% caustic soda aqueous solution Log and 30 g of 28% ammonia aqueous solution to 250 g of water, stir well, and in the resulting aqueous solution, react under an acidic catalyst to obtain a resorcin-formalin initial condensate. (40% acetone solution)
60g was added and sufficiently stirred to disperse. On the other hand, 240 g of a 40% water emulsion of vinylpyridine-styrene-butadiene terpolymer latex (manufactured by Nippon Zeon Co., Ltd., Nilaball 251) and a 40% water emulsion of styrene-butadiene copolymer (manufactured by Nippon Zeon Co., Ltd., Nilaball LX)
-112) 100g was diluted with 200g of water. next,
The above resorcin-formalin initial condensation dispersion was added to this diluted solution while stirring, and 20 g of a 37% formalin aqueous solution was added and mixed uniformly. Then,
In this mixture, diphenylmethane diethylene urea 14
g.

5 g of 30% aqueous solution of dioctyl sulfosuccinate sodium salt (Neocol SW-30, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
, an aqueous dispersion obtained by mixing 36 g of water in a ball mill for 24 hours is added and mixed. Then, an amount of ceramic material (using silica powder as aggregate) equivalent to the solid content of this mixed solution is added and mixed, and an epoxy compound of phenol/formalin resin condensate (manufactured by Ciba Geigy,
ECN1299) 7.5g was previously dissolved in toluene, 0.1g of dioctyl sulfosuccinate sodium salt (Neocol P, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 0.6g of methyl cellulose were added and 28g of water was dissolved. The added and dispersed components were added and mixed with stirring to prepare a treatment solution containing the desired component (A) or D). Next, vinylon fiber threads were continuously passed through this treatment liquid to be impregnated with the treatment liquid, and then dried at 150°C for 2 minutes.
Subsequently, heat treatment was performed at 250° C. for 1 minute to form a ceramic coating layer. In this case, the amount of treatment agent attached is 2 in terms of solid content.
．． It was 5%. Using the thus obtained ceramic-coated yarn, an inner tube and an outer tube were constructed to manufacture a hose according to a conventionally known method.

That is, the inner tube rubber layer 1 (see drawing) is formed by extruding a rubber composition for forming the inner tube from an extruder, and the ceramic-covered yarn is braided around the outer periphery of the extruded inner tube rubber layer 1. A fiber-reinforced layer 2 was formed, and a rubber composition for forming an outer tube was extruded from an extruder to form an outer tube rubber layer 3 on the fiber-reinforced layer 2.

[Example 2] Polyester fiber yarn was used as the organic fiber yarn constituting the fiber reinforcing layer. A hose was made in substantially the same manner as in Example 1 except for this.

[Example 3] A polyester fiber thread was used as the organic fiber thread for configuring the fiber reinforcing layer, and was impregnated with a treatment agent consisting of component (A) or D) obtained in Example 1 above prior to drying. , Impregnation treatment with a treatment agent consisting of the following components (E) to G) was performed. That is, sorbitol polyglycidyl ether (manufactured by Nagashio Sangyo Co., Ltd., Tenacol EX-611)
6 g, a 30% aqueous solution of dioctyl sulfosuccinate sodium salt (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.,
4 g of Neocol SW-30) was added and uniformly dissolved. Next, this was added to 805 g of water with stirring to uniformly dissolve the sorbitol polyglycidyl ether in the water. Next, a phenol block compound of 4,4-diphenylmethane diisocyanate was added to Hiren M, manufactured by DuPont.
P) 14 g, 4 g of a 30% aqueous solution of dioctyl sulfosuccinate sodium salt as surfactant and 42 g of water
A dispersion obtained by mixing g in a ball mill for 24 hours,
Then, 125 g of a 40% water emulsion of vinylpyridine-styrene-butadiene terpolymer (Nilaball 251FS, manufactured by Nippon Zeon Co., Ltd.) was added and mixed uniformly to prepare a treatment liquid consisting of components (E) to G). Next, a polyester fiber thread was passed through this treatment solution and dried at 150° C. for 2 minutes, followed by heat treatment at 250° C. for 1 minute so that a solid content of 2.2% was deposited. Next, to this,
As in Example 1, the impregnation treatment with a treatment liquid consisting of components (A) to D) was carried out in the same manner. A hose was obtained in the same manner as in Example 1 except for the above.

[Comparative Examples 1 to 4] As reinforcing fiber yarns, vinylon fiber yarns and polyester fiber yarns were used, and the fiber yarns were either untreated or subjected to RFL treatment. A hose was obtained in the same manner as in Example 1 except for the above.

The performance of the hoses obtained in the above Examples and Comparative Examples was tested and shown in Table 1 below.

(Left below) − to dimension: force: tl 2ka: s±
1.As is clear from the above table, the fiber reinforcement layer of the hose of the example is composed of ceramic-coated fiber yarn, so it does not deteriorate due to heat or antifreeze, and has excellent heat resistance and antifreeze resistance. It is equipped with What is also noteworthy is that the hose of the example has a high resistance to permeation of fluids such as Freon gas or gasoline.
This is a considerable decrease compared to the comparative example. 4. In hoses having a braided fiber reinforcement layer made of ceramic-coated yarn, as mentioned above, the fiber yarn elongation is lower than that of the conventional RFL treatment (the elongation reduction rate is 10 to 10%).
30%), the change in diameter of the hose under internal pressure load conditions is suppressed, and this appears as an effect of preventing the meshes of the braided layer from expanding, which is thought to suppress fluid permeation. Furthermore, in the hose of the example, the surface of the fiber threads constituting the fiber reinforcing layer is coated with ceramics and is formed into a rough surface by ceramic particles.
Anchor hardening occurs between the fiber threads and the rubber forming the inner and outer tubes, and the chemical bonding force and the physical bonding force based on the anchoring hardening occur based on the resorcin and formalin components of the fiber threads. Together, the mutual adhesion strength is greatly improved.As a result, the interlayer adhesion strength of the hose is improved, and even if the hose is used in a bent position, it will not peel off between the eyebrows and the hose will have a long service life. will be realized.

Note that in the above examples, antifreeze resistance is shown as resistance to fluids, but due to the characteristics of ceramic itself, it has chemical resistance and lubricant resistance.

It has been confirmed that excellent effects are also exhibited in properties such as solvent resistance.

[Brief explanation of the drawing]

The drawing shows a cross section of a hose according to an embodiment of the invention. 1... Inner tube rubber layer 2... Fiber reinforcement layer 3... Outer tube rubber layer

Claims (3)

[Claims] (1) It comprises an outer tube rubber layer, an inner tube rubber layer, and a fiber reinforcing layer interposed between the two layers, and the fiber reinforcing layer is composed of thread or cloth mainly composed of organic fibers and covered with a ceramic layer. A hose characterized by: (2) A fiber-reinforced layer made of thread or cloth mainly composed of organic fibers is closely formed on the outer periphery of the inner tube rubber layer, and an outer tube rubber layer is closely formed on the outer periphery of this fiber-reinforced layer. A method of manufacturing a hose by vulcanizing and adhering these,
Impregnated with a treatment liquid containing the following components (A) and (B) and further containing at least one of the components (C) and (D) as a yarn or cloth mainly composed of organic fibers for forming a fiber reinforcement layer. A method for manufacturing a hose characterized by using a treated material. (A) Resorcinol/formalin/rubber latex. (B) Ceramics powder. (C) Ethylene urea compound. (D) Epoxy-modified phenol formaldehyde condensate. (3) A fiber reinforcing layer made of thread or cloth mainly composed of organic fibers is closely formed on the outer periphery of the inner tube rubber layer, and an outer tube rubber layer is closely formed on the outer periphery of this fiber reinforcing layer. A method of manufacturing a hose by vulcanizing and adhering these,
A yarn or cloth mainly composed of organic fibers for forming a fiber reinforcing layer is impregnated with a treatment solution containing the following components (E), (F), and (G), and (E) a polyepoxide compound. (F) Blocked polyisocyanate compound. (G) Rubber latex. A method for producing a hose, which is then impregnated with a treatment liquid containing the following components (A) and (B) and further containing at least one of components (C) and (D). (A) Resorcinol/formalin/rubber latex. (B) Ceramic powder. (C) Ethylene urea compound. (D) Epoxy-modified phenol formaldehyde condensate.