JPS63116837A - Fiber material for reinforcing hose - Google Patents

Abstract

PURPOSE:To obtain a fiber material for reinforcing a hose not corroded by the transport fluid flowing through the hose and rich in heat resistance and flexibility, by coating the fiber material with a vulcanized rubber-containing ceramic layer based on an org. fiber. CONSTITUTION:When a fiber material for reinforcing a hose is coated with a ceramic layer, the fiber material for reinforcing the hose is subjected to impregnation coating treatment using a treatment solution consisting of resorcin/ formalin/rubber latex (A), a ceramic powder (B), vulcanized rubber (C), an ethyleneurea compound (D) and an epoxy modified phenol/formaldehyde condensate (E). In the above mentioned treatment solution, the components (A)-(C) are essential ones and the components (D), (E) are arbitrary ones and either one or both of them used if are necessary.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to hose reinforcement for forming fiber reinforced layers in fuel oil hoses, lubricating oil hoses, refrigerant gas hoses for air conditioners, and hoses for transporting fluids such as chemicals and solvents. The present invention relates to textile materials for use.

[Conventional technology]

-a, for the above-mentioned various types of fluid transport hoses, a fiber reinforcing layer is closely formed on the outer periphery of the inner tube rubber layer using a hose reinforcing fiber material made of organic fiber yarn or cloth, and this fiber A material obtained by closely forming an outer tube rubber layer around the outer periphery of a reinforcing layer is used. In the above hose, synthetic fibers such as polyester fibers, nylon fibers, polyvinyl alcohol fibers, and polypropylene fibers, and natural fibers such as cotton are used as the organic fibers constituting the fiber reinforcing layer, and these yarns are braided (spiral or A fiber reinforcing layer is formed by taping a fabric (woven fabric or nonwoven fabric) obtained using the above-mentioned organic fibers.

In this case, resorcinol, formalin, rubber latex (
In order to improve the adhesion to the inner and outer tubes, an adhesive is applied to the fiber reinforcement layer made of the hose reinforcing fiber material treated with the above RFL solution. is being carried out. 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, it has been desired to provide a hose with performance characteristics that far 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, in conventional hoses, the main focus is on selecting the shape, material, etc. of the inner and outer tubes that meet the required characteristics, and the fiber reinforced layer only functions as a pressure-resistant layer. Since no consideration has been given to the fiber reinforced layer, under the recent severe usage conditions mentioned above, the fluid that has permeated through the inner tube etc. erodes the fiber reinforced layer, causing
There are many cases where the fiber reinforcing layer deteriorates before the outer tube deteriorates, causing breakage of the fiber reinforcing layer, resulting in a fatal problem of reduced pressure resistance and loss of hose function.

In order to solve these problems, it is necessary to improve the performance of the hose reinforcing fiber material constituting the fiber reinforcing layer so that it will not be eroded by the transportation fluid flowing inside the hose and will have good properties such as heat resistance. There is a strong need to improve.

As a result of repeated research to solve these problems, the inventor of the present invention found that it is suitable to cover the yarn or cloth mainly made of organic fibers constituting the fiber reinforcing layer with a ceramic layer, and has already obtained a patent. Application (October 1, 1986)
3 days)). This makes it possible to obtain a hose-reinforcing fiber material that is not eroded by the transportation fluid flowing inside the hose and has a wealth of properties such as heat resistance. however,
If the flexibility of the reinforcing fiber material is not reduced by the above treatment, a further advantageous effect can be obtained.

This invention was made in view of these circumstances, and provides a fiber material for reinforcing hoses that is not corroded by the transport fluid flowing inside the hose, has high heat resistance, and is also highly flexible. Its purpose is to provide.

[Means for solving problems]

In order to achieve the above object, the gist of the present invention is a fiber material for reinforcing a hose, which is made of thread or cloth mainly composed of organic fibers and covered with a ceramic layer containing vulcanizable rubber.

That is, the inventor of the present invention found that when covering a hose reinforcing fiber material with a ceramic layer, in order to maintain the flexibility of the hose reinforcing fiber material itself, it is necessary to include vulcanizable rubber in the ceramic layer. It was discovered that good results could be obtained and the present invention was developed.

The hose reinforcing fiber material of the present invention is usually impregnated and coated with a treatment liquid (water-oil type) having the following composition.

(A) Resorcinol/formalin/rubber latex.

(B) Ceramic powder.

(C) Vulcanizable rubber.

(D) Ethylene urea compound.

(E) Epoxy-modified phenol formaldehyde condensate.

In the processing liquid, components (A) to (C) are essential components and are always contained in the processing liquid.

On the other hand, components (D) and (E) are optional components, and either or both of them may be used as necessary.

As mentioned above, the resorcinol/formalin/rubber latex of component (A) is generally called RFL, and the molar ratio of resorcinol and formaldehyde is 1:0.1 to 1:8. 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.

The smaller the particle size of the ceramic powder (B), the better the performance.Those having a particle size in the range of 0.01 to 10 .mu.m are usually used, and those in the range of 0.01 to 1 .mu.m are preferable.

The vulcanizable rubber of component (C) is a rubber that has the property of being vulcanized itself, and is a so-called unvulcanized rubber. Then, after passing through the vulcanization process during hose manufacturing, it is vulcanized to become vulcanized rubber. Typical examples include styrene-butadiene rubber (SBR), butadiene rubber (BR), isoprene rubber (IR), chloroprene rubber (CR), butyl rubber (IIR), nitrile rubber (NBR), ethylene-propylene rubber (EPM,
EPDM), Hypalon (C5M), acrylic rubber (A
CM, ANM), urethane rubber (U).

Examples include fluororubber (FKM). These rubbers have strong lipophilic properties, and when mixed with the RFL aqueous solution, they are usually dissolved in a battering machine solvent such as ketone, which has a strong affinity for the RFL aqueous solution, and in that state, Mixing with the RFL aqueous solution is performed. Then, the ceramic powder is usually added and mixed into this water-oil solution.

The optional ethylene urea compound (D) is represented by the following general formula (11).

Typical examples of the above ethylene urea compounds include octadecyl isocyanate, hexamethylene diisocyanate,
Isophorone diisocyanate, tolylene diisocyanate, metaxylene diisocyanate, diphenylmethane diisocyanate.

Examples include reaction products of aromatic/aliphatic isocyanates such as naphthylene diisocyanate and triphenylmethane triisocyanate and ethyleneimine. Preferred are aromatic ethylene urea compounds such as diphenylmethane diethylene urea.

The epoxy-modified phenol formaldehyde condensate of component (E), which is also an optional component, is represented by the following general formula (2).

(Left below) In the above 2 (2), the molecule ff11200-130
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 components (A) to (E), (A
The total solid content of components (D) and (C) (optional components (D) and (E) are included in the above total solid content) is 10 to 25% by weight of the entire treatment liquid (
(hereinafter abbreviated as "%") is preferable. Then, the total amount of the above components (A) and (C) [
The ratio of the optional components (D) and (B) (if any) are included in the above total amount] and the ceramic powder (B) is 1 to 1 on a weight basis. :0.5 to 1.5, preferably t:O,S to 1.2.

In addition, the above optional components (D) and (E) are as follows:
In particular, good results can be obtained when using polyester fibers among threads and cloths mainly composed of organic fibers.

Applying ceramic coating to the organic fiber yarn or cloth using the treatment liquid can be done by immersing the organic fiber yarn or cloth in the treatment liquid, spraying it from a nozzle, or applying the ceramic coating to the organic fiber yarn or cloth using the treatment liquid. Through 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 polypropylene fibers, and natural fibers such as cotton fibers. thread,
It is cloth, and 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 (F), (G), and (H). It is preferable to perform impregnation treatment and then impregnation treatment with the above treatment liquid.

(F) Polyepoxide compound.

(G) Blocked polyisocyanate compound.

(H) Rubber latex.

In this way, the hose reinforcing fiber material of the present invention includes:
For example, one is impregnated and coated with only the treatment liquid containing components (A) to (E) mentioned above, and the other is treated with (F) as mentioned above.
~ (H) After being impregnated and coated with a treatment liquid containing the component,
There are two types of products that have been impregnated and coated with a treatment solution containing the above components (A) to (E).

The polyepoxide compound of component (F) above is a compound containing a small amount (both 2 or more) of epoxy groups in an amount of 0.2 g or more per 100 g of the compound in one molecule, such as ethylene glycol, glycerol, sorbitol, pentaerythritol, Reaction products of polyhydric alcohols such as polyethylene glycol and halogen-containing epoxides such as epichlorohydrin, resorcinol, bis(4-hydroxyphenyl) dimethylmethane, phenol-formaldehyde resin, resorcinol-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. Examples include 4-epoxycyclohexylmethyl-3,4-epoxycyclohexenecarboxylate, bis(3,4-epoxy-6-methyl-cyclohexylmethyl)adipate, etc. Particularly preferred are reaction products of polyhydric alcohols and epichlorohydrin. be.

The blocked polyisocyanate compound (G) 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.
Diphenylmethane diisocyanate hexamethylene diisocyanate, polymethylene polyphenylisocyanate, triphenylmethane triisocyanate, and other polyisocyanates and compounds having two or more active hydrogen atoms, such as trimethylolpropane, pentaerythritol, etc., are combined into isocyanate groups. Examples include terminal isocyanate group-containing polyalkylene glycol adduct polyisocyanates obtained by reacting (-N GO) 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 (H) 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 pretreatment liquid consisting of each of the above components is an aqueous liquid, and the blending weight ratio of each component is (F)/((F) + (G)) is 0.0.
5 to 0.9, and (H)/((F)+(G)) is 0.
It is preferable to use it so that it becomes 5-15. Particularly preferred is (F)/((F)+(G)) of 0.1 to 0.
．． 5, and (H)/C(F)+(G)) is in the range of 1 to 10.

It is preferable that the pretreatment aqueous liquid containing such components is impregnated into the organic fiber yarn or cloth so that the solid content is 1 to 30% by weight based on the weight of the fiber yarn or cloth. The content is more preferably 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 (E) described above. In this way,
The hose reinforcing fiber material treated with the treatment agent forms a fiber reinforcing layer between the inner tube rubber layer and the outer tube rubber layer.

Above, 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 resin), fluororubber (FKM
), chlorosulfonated polyethylene (CLSM), chlorinated polyethylene (CPE), chloroprene (CR), ethylene-propylene conjugated diene copolymer (EPDM).

It is manufactured using rubber such as isoprene-isobutylene copolymer (IIR) and thermoplastic resin such as PVC, polyamide resin, and polyolefin resin.

When manufacturing a hose using the hose reinforcing fiber material treated with a treatment agent as described above, for example, it is carried out as follows.

(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.
Ceramic-coated organic fiber threads immersed in a treatment solution consisting of components (E) and dried are 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) The three-layer structure consisting of the inner tube, fiber reinforced layer, and outer tube is integrally vulcanized and molded (150 to 60 m1n). (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 used for automobiles. It is suitable for use as a fuel oil lubricant transport hose, car air conditioner, etc.

Furthermore, a hose can also be manufactured using the treated hose reinforcing fiber material by the following method, which is different from the above method.

(11) An unvulcanized band-shaped rubber composition for forming an inner tube is spirally wound 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 components (F) to (H), and further dipped in the treatment liquid of the (A) to (E) components and dried on the 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 (150-180℃
)do. (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 due to the heat resistance of the ceramic layer itself, it also has excellent heat resistance and has an extremely long lifespan as a whole. Therefore, it can withstand use under today's harsh conditions.

Moreover, since the above-mentioned hose contains vulcanized rubber in the above-mentioned ceramic layer and has high flexibility, it can be well adapted to bent conditions and can be adapted to a wide range of uses. It becomes like this.

〔Effect of the invention〕

As described above, the hose reinforcing fiber material of the present invention includes, for example, RFL as the component (A), containing ceramic powder as the component (B), and vulcanizable rubber as the component (C), and further The inside of the hose is impregnated and coated with a treatment liquid containing one or both of the ethylene urea compound (D) and the epoxy-modified phenol formaldehyde condensate (E) as required. It is not eroded by the circulating transport fluid, has excellent properties such as heat resistance, and is highly flexible. and,
A treatment liquid containing the above components (A) to (E) and (F) to (H
) A ceramic-coated hose reinforcing fiber material treated with a treatment solution containing the component, particularly a polyester hose reinforcing fiber material, exhibits excellent properties. Therefore, hoses with a fiber-reinforced layer made of these materials, such as fuel oil hoses, have a high degree of durability against high temperatures in the engine room, sour gasoline, and the like.

Furthermore, it has excellent flexibility, so it can be easily bent into a bent state in a narrow space such as an engine room. The performance of the fiber reinforced layer does not deteriorate. In other words, in hoses using the hose reinforcing fiber material of the present invention, the performance of the fiber reinforcement layer is significantly improved, and the fiber reinforcement layer is eroded earlier than the inner and outer tubes, resulting in a shorter hose life. It does not cause shortening and has great flexibility. 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 barrier layer, resulting in low fluid permeability and improved hose performance. These effects are
The same applies to lubricant transportation and car air conditioners.

Furthermore, since the fiber-reinforced layer has excellent chemical resistance, it can also be used as a hose for transporting chemicals, solvents, etc., and the same remarkable effects as above can be obtained. Furthermore, since the fiber reinforced layer has excellent properties, it is possible to make the inner and outer tube layers thinner.

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) 60
g was added and thoroughly stirred to disperse. On the other hand, a 40% water emulsion of vinylpyridine-styrene-butadiene terpolymer latex (manufactured by Nippon Zeon Co., Ltd., Nirapol 25)
1) 240g and 40% water emulsion of styrene-butadiene copolymer (manufactured by Nippon Zeon Co., Ltd., Nirapol LX-1
12) 100g was diluted with 200g of water. Next, the above-mentioned resorcin-formalin initial condensation dispersion was added to this diluted solution while stirring, and 20 g of a 37% formalin aqueous solution was further added thereto to uniformly mix to prepare a component A) solution. Next, 14 g of diphenylmethane diethylene urea as component (D), 5 g of a 30% aqueous solution of dioctyl sulfosuccinate sodium salt (Neocol SW-30, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and 36 g of water were added to this mixed solution in a ball mill. An aqueous dispersion obtained by mixing for 24 hours was added and mixed. On the other hand, the component (E), phenol,
7.5 g of an epoxy compound of formalin resin condensate (manufactured by Ciba Geigy, ECN1299) was dissolved in toluene in advance, and 0.1 g of dioctyl sulfosuccinate sodium salt (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., Neocol P) and methyl cellulose were dissolved in toluene. 28g of water to which 0.6g was added and dissolved
While stirring, the dispersed material was added and mixed.

In addition, as the vulcanizable rubber of component (B), a solution (concentration 15%) was prepared by dissolving NBR (manufactured by Nippon Zeon Co., Ltd., Ni-Ball 202) in a ketone solvent, and this was added to the above-mentioned mixed solution and mixed. A ceramic material (using silica powder as aggregate), which is component (B), is added and mixed in an amount equivalent to the solid content of the mixed liquid in which each component is added and mixed, and the desired products (A) to (E) are obtained. A processing solution containing the ingredients was prepared. Next, a vinylon fiber thread was impregnated with the treatment solution by continuously passing through the treatment solution, and then dried at 150° C. for 2 minutes, and then heat-treated at 250° C. for 1 minute to form a ceramic coating layer. In this case, the amount of the treatment agent deposited is 2.
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 rubber composition for forming the inner tube is extruded from an extruder to form the inner tube rubber layer l.
(see drawing), and this extruded inner tube rubber layer 1
A fiber reinforced layer 2 is formed on the outer periphery of the fiber reinforced layer 2 by braiding the ceramic-coated yarn, and a rubber composition for forming an outer tube is extruded from an extruder onto the fiber reinforced layer 2 to form an outer tube rubber layer 3. was formed.

[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] Polyester fiber yarn was used as the organic fiber yarn for configuring the fiber reinforced layer, and (A) to (
Prior to impregnation and drying with a treatment agent consisting of component E), the following impregnation treatment with a treatment agent consisting of components (F) to ('H) was carried out. That is, 4 g of a 30% aqueous solution of dioctyl sulfosuccinate sodium salt (Neocol SW-30, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) as a surfactant was added to 6 g of sorbitol polyglycidyl ether (manufactured by Nagase Sangyo Co., Ltd., Tenacol EX-611). Dissolved uniformly.

Next, this was added to 805 g of water with stirring to uniformly dissolve the sorbitol polyglycidyl ether in the water. Next, 14 g of a phenol block of 4,4-diphenylmethane diisocyanate (manufactured by DuPont, Hiren MP), 4 g of a 30% aqueous solution of dioctyl sulfosuccinate sodium salt as a surfactant, and 4 g of water were added.
A dispersion obtained by mixing 2 g of 2 g in a ball mill for 24 hours, and 125 g of a 40% water emulsion of vinyl and lysine-styrene-butadiene terpolymer (Nilaball 251FS, manufactured by Nippon Zeon Co., Ltd.) were added and mixed uniformly. F)～
A processing solution consisting of component (H) was prepared. Next, a polyester fiber thread was passed through this treatment solution and heated at 150°C for 2 hours.
It was dried for 1 minute and then heat treated at 250° C. for 1 minute to achieve a solid content of 2.2%. Next, in the same manner as in Example 1, this was impregnated with a treatment liquid consisting of components (A) to (E) 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.

(Leaving space below) ・÷・H State State State State As is clear from the above table, in the hose using the hose reinforcing fiber material of the example, the fiber reinforcing layer is constituted by the ceramic-coated hose reinforcing fiber material. Therefore, it does not deteriorate due to heat or antifreeze, and has excellent heat resistance and antifreeze resistance. What is further noteworthy is that the hose using the hose reinforcing fiber material of the example
The permeation of fluids such as Freon gas or gasoline is considerably reduced compared to the comparative example. This is because, as mentioned earlier, in a hose with a braided fiber reinforced layer of ceramic-coated yarn, the elongation of the fiber yarn is reduced compared to the conventional RFL treatment system (the elongation reduction rate is 10 to 30%).
This is because, as a result, changes in the diameter of the hose under internal pressure load conditions are suppressed, and this appears as an effect of preventing the stitches of the braided layer from expanding, thereby suppressing fluid permeation. Furthermore, in the hose using the hose reinforcing fiber material of the example, the surface of the hose reinforcing fiber material constituting the fiber reinforcing layer is coated with ceramics and is formed into a rough surface by ceramic particles. An anchoring effect is developed between the reinforcing fiber material and the rubber forming the inner and outer tubes, and the chemical bonding force based on the resorcin and formalin components of the fiber yarn and the physical bonding force based on the anchoring effect are combined. Together, the mutual adhesion strength is greatly improved. Further, since the ceramic layer contains vulcanizable rubber and maintains flexibility, the hose can be easily bent and used while maintaining the above characteristics.

Therefore, the effect of expanding the range of use can be obtained.

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 is a sectional view of a hose using a hose reinforcing fiber material according to an embodiment of the present invention. 1... Inner tube rubber layer 2... Fiber reinforcement layer 3... Outer tube rubber layer

Claims (3)

[Claims] (1) A fibrous material for reinforcing hoses consisting of thread or cloth mainly composed of organic fibers and covered with a ceramic layer containing vulcanizable rubber. (2) Covering with a ceramic layer containing vulcanizable rubber
The following (A) ~
The hose according to claim 1, wherein the hose is impregnated and coated with a treatment liquid containing component (C) as an essential component and at least one of components (D) and (E) as an optional component. Reinforcing fiber material. (A) Resorcinol/formalin/rubber latex. (B) Ceramic powder. (C) Vulcanizable rubber. (D) Ethylene urea compound. (E) Epoxy-modified phenol formaldehyde condensate. (3) Covering with a ceramic layer containing vulcanizable rubber
Threads or cloths mainly composed of organic fibers are the following (F),
Impregnated and coated with a treatment solution containing components (G) and (H), and (F) a polyepoxide compound. (G) Blocked polyisocyanate compound. (H) Rubber latex. Next, the following components (A) to (C) are considered essential components, and (
The fibrous material for reinforcing a hose according to claim 1, which is impregnated and coated with a treatment liquid containing at least one of components D) and (E) as an optional component. (A) Resorcinol/formalin/rubber latex. (B) Ceramic powder. (C) Vulcanizable rubber. (D) Ethylene urea compound. (E) Epoxy-modified phenol formaldehyde condensate.