JPS63120178A - Treatment agent of hose reinforcing fiber material - Google Patents

Abstract

(57) [Summary] 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 hose reinforcement for forming a fiber reinforced layer 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 a processing agent for processing textile materials.

[Conventional technology]

Generally, for the various types of fluid transport hoses as described above, a fiber reinforced layer is formed in close contact with 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 reinforced layer is A material obtained by closely forming an outer tube rubber layer around the outer circumference of the tube 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, a resorcinol-formalin-rubber latex (hereinafter abbreviated as rRFI, J) solution is applied to the above-mentioned organic fiber yarn or cloth for reinforcing the hose in order to improve its adhesion to the inner and outer tubes. For the fiber reinforcing layer made of the hose reinforcing fiber material that has been impregnated and further treated with the RFL solution,
In order to improve adhesion to the outer tube, adhesive is applied. The hose obtained in this way is
The fiber reinforced layer adheres well to the inner and outer tubes, demonstrating 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 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, we need to improve the performance of the hose-reinforcing fiber material that makes up the fiber-reinforced layer so that it will not be eroded by the transportation fluid flowing through the hose and will have good properties such as heat resistance. There is a strong need to improve.

In response to such demands, the present inventors have invented a treatment agent for hose reinforcing fiber materials containing ceramic powder, and have already filed a patent application (filed on October 13, 1986).

This makes it possible to process the hose reinforcing fiber material so that it is not eroded by the transportation fluid flowing inside the hose and has high properties such as heat resistance. However, if the flexibility of the reinforcing fiber material is not impaired during the above treatment, even better effects can be obtained.

The present invention was developed in view of the above circumstances, and is a method for reinforcing a hose so that it does not reduce the flexibility of the reinforcing fiber material, is not eroded by the transportation fluid flowing through the hose, and is rich in properties such as heat resistance. The object of the present invention is to provide a treatment agent for hose reinforcing fiber materials that can treat fiber materials for hose reinforcement.

[Means for solving problems]

In order to achieve the above object, the present invention provides a hose reinforcing solution comprising a treatment liquid containing the following components (A) to (C) as essential components and at least one of components (D> and (F) as optional components). The first summary is treatment agents for fiber materials, including (A) resorcinol, formalin, and rubber latex.

(B) Ceramic powder.

(C) Vulcanizable rubber.

(D) Ethylene urea compound.

(E) Epoxy-modified phenol formaldehyde condensate.

A treatment liquid containing the following components (F), (G) and (H), with the above components (A) to (C) as essential components and a small amount of components D) and (E) (one of which is an optional component). The second gist is a treatment agent for hose reinforcing fiber materials comprising a treatment liquid.

The treatment agent for hose reinforcing fiber materials of the present invention is usually used as 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 one or both of them may be used as necessary.

As mentioned above, the resorcinol/formalin/rubber latex of component (A) is called -IC RFL, and has a molar ratio of resorcinol and formaldehyde of 1:0.1 to 1: It is set to 8. The preferred ratio is 1:0.5 to 1:5, and the most preferred ratio is l:
It is within the range of 1 to 144. The rubber latex used with the above resorcin and formalin is:
Examples include natural rubber latex, styrene-butadiene copolymer latex, vinylpyridine-styrene-butadiene terpolymer latex, nitrile rubber latex, chloroprene rubber latex, etc., which may 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, 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 a vulcanized comb. 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), Hypertff7 (C3M)
, acrylic rubber (ACM, ANM), urethane rubber (U).

Examples include fluororubber (FKM). These rubbers have strong lipophilic properties, and when mixed with the RFL aqueous solution, a ketone or the like having a strong affinity for the RFL aqueous solution is dissolved in a solvent, 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 (1).

Typical examples of the ethylene urea compounds include octadecyl isocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, metaxylene diisocyanate, and 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 as component (E), which is also an optional component, is represented by the following -S formula (2).

(Left below) 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 E),
The total solid content of component (A) and component (C) [if the optional components (D) and (E) are included, they are also included in the total solid content above] is 10 to 25% by weight of the entire treatment liquid. % (hereinafter abbreviated as "%"). Then, the total amount of the above components (A) and (C) [if the optional components (D) and (E) components are included, they are also included in the above total amount] and the ceramic powder that is the component (B). The ratio of the former to the latter is 0.5 to 1.5, preferably 1:0.8 to 1°2 on a weight basis.
It is to set it to .

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.

As described above, the treatment agent for the hose reinforcing fiber material of the present invention includes one consisting only of the treatment liquid containing the above-mentioned component (A) or E), and the treatment agent containing the above-mentioned component (A) or E). E
There are two types of processing agents, one consisting of a processing liquid containing the component (F) and the other containing the component (F) or H).

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

The blocked polyisocyanate-1 compound as component (G) 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 compound include polyisocyanates such as tolylene diisocyanate, metaphenylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, polymethylene polyphenylisocyanate, and triphenylmethane triisocyanate, and those polyisocyanates with two active hydrogen atoms. A metal compound having the above, such as trimethylolpropane, pentaerythritol, etc., is combined with an isocyanate group (-NGO) and a hydroxyl! Examples include terminal incyanate group-containing polyalkylene glycol adduct polyisocyanates obtained by reacting with (-OH) at a molar ratio of more than 1. In particular, aromatic polyisocyanates such as tolylene diisocyanate, diethylmethane diisocyanate, and polymethylene polyphenylisocyanate are preferred. As a blocking agent,
Examples include phenols such as phenol, thiophenol, cresol, and resorcinol, aromatic secondary amines such as diphenylamine and xylidine, lactams such as phthalic acid imides, 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 (F) / C (F) + (G)] is 0.0.
5 to 0.9, and (H)/((F)+(c)) 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, (H)/l: (F) + (G)1 is 1 to 1
The range is 0.

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).

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.

The inner tube rubber layer and the outer tube rubber layer are made of acrylonitrile-butadiene copolymer (NBR), hydrogenated NBR in which part or all of its conjugated diene unit portion is hydrogenated,
NBR/PVC (vinyl chloride resin JIR), fluororubber (FKM), chlorosulfonated polyethylene (CL)
SM), chlorinated polyethylene (CPE), chloroprene (CR), ethylene-propylene conjugated diene i1 (
EP DM), isoprene-isobutylene copolymer (
It is manufactured using rubber such as IIR), PVC, thermoplastic resin such as polyamide resin, polyolefin resin, etc.

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

(1) 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 that have been immersed in a treatment solution consisting of component or E) and dried are braided to form a fiber reinforcing 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.

Further, a hose using the reinforcing fiber material treated with the processing agent 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 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 (F) or H) component, and further dipped in the treatment liquid of the (A) or E) 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. Then, on top of this steel wire winding layer,
A second intermediate rubber layer is formed by spirally winding the same band-shaped rubber composition as used in the first intermediate layer.

(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 processing agent of the present invention has the RFL of component (A).
contains a ceramic powder as a component (B), a vulcanizable rubber as a component (C), and one of an ethylene urea compound as a component (D) and an epoxy-modified phenol formaldehyde condensate as a component (E). Alternatively, since both are contained as necessary, the fiber material for reinforcing the hose can be treated so that it is not corroded by the transportation fluid flowing inside the hose, has rich properties such as heat resistance, and has high flexibility. .

and a treatment liquid containing the above-mentioned (A) or E) component;
A treatment agent comprising a treatment liquid containing component (F) or H) can particularly suitably exhibit the above-mentioned effects on polyester hose reinforcing fiber materials. Therefore, a hose having a fiber-reinforced layer made of these materials, such as a fuel oil hose, has a high degree of durability against high temperatures in the engine room, sour gasoline, and the like. Moreover, since the above-mentioned hose has high flexibility, it can be easily bent into a bent state in a narrow space such as an engine room, and at that time, the fiber reinforced layer also follows the bending state well. , the performance of the fiber reinforced layer does not deteriorate due to bending. In other words, in hoses using the hose reinforcing fiber material treated with the above-mentioned treatment agent of the present invention, the performance of the fiber reinforcing layer is significantly improved, and the fiber reinforcing layer is formed earlier than in the inner tube and outer tube. It does not cause the hose life to be shortened due to corrosion, and has excellent flexibility. Moreover, in the above-mentioned fiber-reinforced layer, the elongation of the ceramic-coated hose-reinforcing fiber material is smaller than that of conventional products, which suppresses the change in diameter under internal pressure loads and provides the effect of preventing loosening of the structure of the fiber-reinforced layer. It's going to be like that. 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 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 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., Nilaball 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. Add and mix the aqueous dispersion obtained by mixing for 24 hours. On the other hand, the component (E), phenol,
7.5 g of an epoxy compound of formalin resin condensate (manufactured by Ciba Geigy, ECNI 299) was dissolved in toluene in advance, and 0.1 g of dioctyl sulfosuccinate sodium salt (manufactured by Daiichi Kogyo Seiyaku, Neocol P) was dissolved in toluene.
and 0.6 g of methyl cellulose were added and dissolved in 28 g of water. While stirring, the resulting mixture was added and mixed. In addition, NBR (
A solution (concentration 15%) is prepared by dissolving Ni-Ball 202 (manufactured by Nippon Zeon Co., Ltd.) in a ketone solvent, and this is added to and mixed with the above mixed liquid, and the solid content of each of the above components is equivalent to the solid content of the mixed liquid. Quantity of ceramic material (B) component (silica powder used as aggregate) is added and mixed,
A treatment solution containing the desired component (A) or E) was prepared. Next, a vinylon fiber thread was impregnated with the treatment solution by continuously passing it 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 was 2.5% in terms of solid content. Using the ceramic-coated thread thus obtained, according to a conventionally known method,
A hose was manufactured by constructing an inner tube and an outer tube. That is,
The inner tube rubber layer 1 (see drawing) is formed by extruding the 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 N1 to form fibers. A reinforcing layer 2 was formed, and an outer tube rubber layer 3 was further formed on the fiber reinforcing layer 2 by extruding a rubber composition for forming an outer tube from an extruder.

[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 E) obtained in Example 1 above prior to drying. , Impregnation treatment with a treatment agent consisting of the following components (F) or H) was carried out. That is, sorbitol polyglycidyl ether (manufactured by Nagashio Sangyo Co., Ltd., Tenacol EX-611)
To 6 g, 4 g of a 30% aqueous solution of dioctyl sulfosuccinate sodium salt (Neocol SW-30, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as a surfactant 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 of 4,4-diphenylmethane diisocyanate (manufactured by DuPont, Hiren MP
) 14 g, 4 g of a 30% aqueous solution of dioctyl sulfosuccinate sodium salt as surfactant and 42 g of water
in a ball mill for 24 hours, and a 40% water emulsion of vinylpyridine-styrene-butadiene terpolymer (manufactured by Nippon Zeon Co., Ltd., Nilaball 2).
125 g of 51FS) was added and mixed uniformly to prepare a treatment liquid consisting of CF) or H) components. 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). 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) As is clear from the above table, in the hoses using the hose reinforcing fiber material treated with the treatment agent of the example, the fiber reinforcing layer is composed of 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 also noteworthy is that the hose made of the hose reinforcing fiber material treated with the treatment agent of the example has significantly reduced permeation of fluids such as Freon gas or gasoline 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 lower than that of the conventional RF
As a result of the L treatment, the elongation decreases by about 10 to 30%, which suppresses the change in the diameter of the hose under internal pressure loading, and this appears as an effect of preventing the expansion of the stitches in the braided layer. This is because it is thought to suppress fluid permeation. Furthermore, in the hose using the hose reinforcing fiber material treated with the treatment agent 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. As a result, an anchoring effect is produced between the hose reinforcing fiber material and the rubber forming the inner and outer tubes, and the chemical bonding force based on the resorcinol and formalin components of the fiber threads and the anchoring effect are Together with the physical bonding strength, the mutual adhesive strength is greatly improved. Further, since the ceramic layer contains vulcanizable rubber and the ceramic 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 treated with a treatment agent according to an embodiment of the present invention. 1... Inner tube rubber layer 2... Fiber reinforcement layer 3... Outer tube rubber layer

Claims (2)

[Claims] (1) The following components (A) to (C) are essential components,
A treatment agent for a fiber material for reinforcing hoses, comprising 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. (2) A treatment liquid containing the following components (F), (G) and (H), and (F) a polyepoxide compound. (G) Blocked polyisocyanate compound. (H) Rubber latex. The following components (A) to (C) are essential components, and (D)
and (E) A treatment agent for a fiber material for reinforcing a hose, comprising a treatment liquid containing at least one of the components 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.