JP2001146686A - Fiber for reinforcing rubber, the production thereof and hose therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production process for rubber-reinforcing fiber that shows good adhesion to halogenated butyl rubber and causes reduced troubles in the hose production process. SOLUTION: Polyester fiber or aramide fiber is previously treated with a treatment agent including polyepoxy compound and then treated with an adhesion treatment agent including (A) initial condensate of resorcin and formaldehyde, (B) vinyl pyridine-styrene-butadiene terpolymer inclu45ding 13-20 wt.% of vinyl pyridine, 25-45 wt.% of styrene, and 40-60 wt.% of butadiene, (C) p- chlorophenol-resorcin-formaldehyde cocondensate and finally heat-treated to produce the objective fiber for reinforcing rubber.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a fiber for reinforcing rubber, a method for producing the same, and a hose.
More specifically, a method for producing a hose reinforcing synthetic fiber having good adhesion to halogenated butyl rubber and less process trouble in the production of a hose product, a rubber reinforcing fiber obtained by the production method, and a halogenated butyl rubber A hose consisting of:

[0002]

2. Description of the Related Art Conventionally, polyester fibers represented by polyethylene terephthalate fibers and aramid fibers represented by polyparaphenylene terephthalamide fibers have physical properties such as high strength, high modulus, low elongation and low creep. And is conventionally used as a reinforcing fiber for rubber hoses. However, polyester fibers and aramid fibers have a problem of poor adhesion to rubber.

For example, in recent years, hoses used in car air conditioners have a structure in which the innermost layer in contact with the refrigerant gas is made of a polyamide resin, and the outer periphery thereof is halogenated typified by chlorinated butyl rubber having excellent gas impermeability. Butyl rubber, wherein the outer layer of the halogenated butyl rubber is made of a reinforcing fiber made of polyester fiber or aramid fiber on which the adhesive composition coating is formed, and the outer layer is made of halogenated butyl rubber or EPDM rubber. Is generally used, and various techniques have been developed under such a configuration in order to improve the adhesion between polyester fiber or aramid fiber and halogenated butyl rubber or EPDM rubber.

On the other hand, when a plurality of fibers subjected to an adhesive treatment are drawn and braided or braided in a spiral shape, the frictional resistance between the fibers subjected to the adhesion treatment and the friction between the fibers and guides cause the fibers to be bonded. Problems have also been raised that the drawability deteriorates, the shape of the hose deteriorates, and scum adheres or scatters due to the fiber treatment agent, thereby impairing productivity and the working environment.

For example, JP-A-7-238473 and JP-A-7-258975 disclose a first treating agent comprising a polyepoxide compound and a vinylpyridine / styrene / butadiene terpolymer latex after twisting a polyester fiber. A method for bonding polyester fibers for high pressure hoses, which is treated with a second treating agent consisting of resorcinol-formaldehyde rubber latex (RFL), parachlorophenol-resorcinol-formaldehyde cocondensate and blocked polyisocyanate, is disclosed. ing. However, in this method, although a certain degree of adhesion between the polyester fiber and the ethylene-propylene-non-conjugated diene rubber can be ensured, it is difficult to obtain adhesion with the halogenated butyl rubber, and the technology described in the publication is difficult. In the case of only the hose, a large amount of dust caused by the treatment agent flutters in the hose manufacturing process, and there is a problem that the working environment is poor.

Further, Japanese Patent Application Laid-Open No. Hei 7-331584 discloses a polyester fiber cord to which a polyepoxide compound is preliminarily applied, comprising a precondensate of resorcinol / formaldehyde, a paracondensate of parachlorophenol / resorcinol / formaldehyde, and a blocked polyisocyanate. A polyester fiber treated with a mixture of a styrene / butadiene / vinylpyridine terpolymer latex having a compound and a composition ratio of styrene / butadiene / vinylpyridine in the range of 5: 90: 5 to 10:80:10 is described. . However, even with these methods, adhesion to the halogenated butyl rubber was not obtained, and it was difficult to suppress generation of scum due to the treating agent.

[0007]

SUMMARY OF THE INVENTION The present invention has been achieved as a result of studying to solve the problems in the prior art described above. Therefore, the object of the present invention is to
In particular, it is an object of the present invention to provide an adhesive treatment method for obtaining a polyester fiber and an aramid fiber having improved adhesion to a rubber matrix as a reinforcing fiber of a hose made of a halogenated butyl rubber matrix.

[0008]

In order to solve the above problems, the rubber reinforcing fiber of the present invention mainly has the following constitution. That is, an initial condensate (A) of polyalcohol and / or polyepoxide with resorcinol-formaldehyde, vinylpyridine styrene-butadiene triene which is 13 to 20% by weight of vinylpyridine, 25 to 45% by weight of styrene and 40 to 60% by weight of butadiene. A polyester fiber or an aramid fiber coated with an adhesive treatment agent containing an original copolymer latex (B) and a parachlorophenol-resorcin-formaldehyde co-condensate (C).

The method for producing a rubber reinforcing fiber of the present invention mainly has the following constitution. That is, a polyester fiber or an aramid fiber previously treated with a treatment agent containing a polyepoxide compound, a resorcinol-formaldehyde initial condensate (A), vinylpyridine 13 to 20% by weight, styrene 25 to 45% by weight and butadiene 40 to 60% by weight. % Vinyl pyridine / styrene / butadiene terpolymer latex (B) and parachlorophenol
A method for producing a rubber reinforcing fiber, which comprises applying an adhesive treatment agent containing a resorcinol-formaldehyde cocondensate (C) and subjecting it to a heat treatment.

The hose of the present invention is a hose comprising the above-mentioned rubber reinforcing fiber and halogenated butyl rubber.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The polyester fiber used in the present invention is a multifilament made of a polyester made of a dicarboxylic acid and glycol having ethylene terephthalate as a main repeating unit, and 90 mol% of the dicarboxylic acid component.
Polyethylene terephthalate, which is composed of terephthalic acid as described above and at least 90 mol% of the glycol component is composed of ethylene glycol, is preferred. Further, it is preferable to use polyethylene terephthalate which does not copolymerize an isophthalic acid component or the like or polyethylene terephthalate which does not substantially contain additives such as inorganic particles. Furthermore, in securing the strength of polyester fiber and the deterioration characteristics in rubber,
When the intrinsic viscosity is 0.80 or more and the amount of carboxyl group ends is 2
What is 0 equivalent / ton or less, Furthermore, what is 18 equivalent / ton or less are preferable at the point which is excellent in heat resistance and hydrolysis resistance. The upper limit of the intrinsic viscosity is not particularly limited as long as melt spinning is possible, but is usually preferably 1.2 or less.

The aramid fiber used in the present invention means a fiber made of a polymer in which repeating units in which aromatic rings are bonded by amide bonds account for at least 80% or more. Representative examples of aramid fibers made of these polymers or copolymers include polyparaphenylene terephthalamide fibers, polymetaphenylene terephthalamide fibers, and polyparaphenylene-3,4'-diphenylether terephthalamide fibers. Can be.

The polyester fibers and aramid fibers used in the present invention are synthetic fibers to which a polyepoxide compound has been added in advance. The polyepoxide compound provided to the fiber includes a polyepoxide compound having two or more epoxy groups in one molecule. Examples of the polyepoxide compound preferably used as the polyepoxide compound (A) include compounds containing at least two epoxy groups per molecule in an amount of 0.1 g equivalent or more per 100 g of the compound. Specifically, a reaction product of a polyhydric alcohol such as pentaerythritol, ethylene glycol, polyethylene glycol, propylene glycol, glycerol, sorbitol, and a halogen-containing epoxide such as epichlorohydrin;
Reaction products of polyhydric phenols such as resorcinol / bis (4-hydroxyphenyl) dimethylmethane, phenol / formaldehyde resin and the above-mentioned halogen-containing epoxides, obtained by oxidizing unsaturated compounds with peracetic acid or hydrogen peroxide, etc. Polyepoxide compound, ie, 3,4
-Epoxycyclohexylmethyl-3,4-epoxycyclohexenecarboxylate, bis (3,4-epoxy-6-methyl-cyclohexylmethyl) adipate,
Phenol novolak type, cresol novolak type, hydroquinone type, biphenyl type, bisphenol S type,
Aromatic polyepoxides such as brominated novolak type, xylene-modified novolak type, phenol glyoxal type, trisoxyphenylmethane type, trisphenol PA type, and bisphenol type polyepoxides are exemplified. Particularly preferred are glycidyl ether type and sorbitol glycidyl ether type polyepoxide compounds.

When the fiber is a polyester fiber,
It is preferable to apply the polyepoxide compound together with a spinning oil agent or the like in the spinning step or after the drawing step by a conventionally known method, and the adhesion amount of the polyepoxide compound in this case is 0.05 to 0.5% by weight. % Is most preferred.

On the other hand, when the fiber is an aramid fiber, it is preferable that the fiber is treated with a treating agent containing a polyepoxide compound and heat-treated immediately before winding the wet-spun fiber by a conventionally known method. Most preferably, the adhesion amount is 0.1 to 0.7% by weight.

The heat treatment temperature after applying the polyepoxide compound to the polyester fiber and the aramid fiber is 150.
To 260 ° C. or lower, more preferably 200 to 24 ° C.
0 ° C. By the heat treatment, the adhesion between the polyester fiber or the aramid fiber and the rubber can be made stronger.

In the method for producing a rubber reinforcing fiber of the present invention,
An initial condensate of resorcin / formaldehyde (A) and vinylpyridine 13 are added to a polyester fiber or aramid fiber previously treated with a treating agent containing a polyepoxide compound.
A vinylpyridine / styrene / butadiene terpolymer latex (B) composed of -20% by weight, 25-45% by weight of styrene and 40-60% by weight of butadiene, and a co-condensate (C) of parachlorophenol / resorcin / formaldehyde. Apply adhesive treatment and heat treat.

The bonding agent is an initial condensate (A) of resorcinol / formaldehyde and a vinylpyridine monomer 13
A vinylpyridine / styrene / butadiene terpolymer latex (B) composed of -20% by weight, 25-45% by weight of styrene and 40-60% by weight of butadiene, and a co-condensate (C) of parachlorophenol / resorcin / formaldehyde. Otherwise, good adhesion between the polyester fiber or aramid fiber and the rubber cannot be obtained.

The resorcinol-formaldehyde precondensate (A) preferably has a molar ratio of resorcinol to formaldehyde of 1 / 1.0 to 1 / 3.0. When the amount of formaldehyde is within the above range, sticky residue is hardly generated in the hose manufacturing process, and the fiber cord is excellent in smoothness,
The fiber cord can have a low frictional force, and the fiber cord can be finished flexibly without excessively progressing the three-dimensional reaction. Further preferred resorcinol / formaldehyde precondensate (A) has a resorcinol / formaldehyde molar ratio of resorcinol / formaldehyde = 1/1.
From 2 to 1 / 2.0, the balance between the adhesion to rubber and the stability of the hose manufacturing process is most preferable in this range.

The precondensate (A) of resorcinol-formaldehyde is reacted in a resole form in which an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is used as a catalyst, or in an acidic catalyst such as oxalic acid or hydrochloric acid. Although there is a novolak type, any type can be used in the present invention. When a particularly high adhesiveness is required, it is preferable to use a novolak-type precondensate of resorcinol-formaldehyde.

In the adhesive treatment component of the present invention, the weight ratio of the solid content of the resorcinol-formaldehyde initial condensate (A) to the rubber latex component is preferably 34/66 to 12/88. When the ratio of the resorcinol-formaldehyde initial condensate (A) is in the above range, the fibers can be made flexible and the adhesion to rubber can be made excellent. A more preferred range is that the weight ratio of the solid content of the initial condensate of resorcinol / formaldehyde (A) to the rubber latex component is A
/ B = 20/80 to 15/85.

The parachlorophenol / resorcin / formaldehyde cocondensate (C) refers to a compound containing the following general formula (I) as a main component.

[0023]

Embedded image Here, n in the general formula (I) represents 0 or an integer of 1 to 10.

Specific examples of the compound represented by the above general formula (I) include 2,6-bis (2 ', 4'-dihydroxy-phenylmethyl) -4-chlorophenol (trade name: "VALCABOND E" ( Registered trademark), "Kasabond"
(Registered trademark) and "Denabond E" (registered trademark)). Above all, a parachlorophenol-resorcin-formaldehyde cocondensate (C) having a small content of a free parachlorophenol component represented by "Denabond E" is preferable.

The total amount of the resorcinol / formaldehyde initial condensate (A) and the rubber latex component contained in the adhesive treatment agent and the solids weight ratio of parachlorophenol / resorcinol / formaldehyde cocondensate (C) are 60 / 40-
It is preferably 30/70. By setting the solid content weight ratio in the above range, it becomes a fiber that can simultaneously satisfy the adhesiveness with halogenated butyl rubber represented by chlorinated butyl rubber, the flexibility and smoothness of the fiber, and the treatment agent residue in the hose manufacturing process. . A more preferable range is such that the total amount of the initial condensate of resorcinol / formaldehyde (A) and the rubber latex component and the solid content weight ratio of parachlorophenol / resorcinol / formaldehyde cocondensate (C) are 55/45 to 45/45.
35/65.

The adhesive treatment agent of the present invention includes a vinylpyridine / styrene / butadiene terpolymer latex (B) comprising 13 to 20% by weight of vinylpyridine, 25 to 45% by weight of styrene and 40 to 60% by weight of butadiene. It must be included. Unless such a rubber latex is used, it is not possible to obtain high adhesiveness particularly to a hose rubber represented by a halogenated butyl rubber. Furthermore, it is not possible to provide a hose reinforcing fiber having a small dynamic friction coefficient and a smooth surface, and it is not possible to suppress yarn breakage, poor alignment and the like when manufacturing a hose. When the styrene component exceeds 45 parts by weight, high adhesiveness to a hose rubber represented by a halogenated butyl rubber is obtained, but the cord is hard and a yarn breakage is likely to occur when a finished hose is manufactured. Conversely, if the styrene component is less than 25 parts by weight, the cord is soft and finished, and troubles in the hose manufacturing process are eliminated, but good adhesion to hose rubber represented by halogenated butyl rubber is obtained. Absent. On the other hand, if the amount of vinylpyridine exceeds 20 parts by weight, the fiber becomes a highly adhesive hose reinforcing fiber having a large coefficient of dynamic friction, and the vinylpyridine component contains 1%.
When the amount is less than 3 parts by weight, the fiber becomes a hose reinforcing fiber having poor adhesion, and in any case, it is not preferable as the hose reinforcing fiber.

The above terpolymer rubber latex (B)
In the above, 1,3-butadiene is preferably used as butadiene, and 2-vinylpyridine is preferably used as vinylpyridine.

The terpolymer rubber latex is
The weight average particle diameter is preferably from 110 to 250 nm, more preferably from 120 to 180 nm, and the Mooney viscosity of the latex is preferably from 100 to 140, more preferably from 110 to 130. The weight average particle diameter is a value determined by a laser diffraction particle size distribution analyzer.

When the weight average particle size of the dispersed rubber particles in the terpolymer rubber latex is in the above range, the stability of the adhesive force at the time of heating can be excellent, and the stability of the latex itself can be excellent.

The Mooney viscosity of the terpolymer rubber latex is preferably from 100 to 140. When the Mooney viscosity is within such a range, the strength of the polyester fiber is prevented from being reduced, and the adhesion to rubber can be improved.

The adhesive agent may contain another rubber latex as long as the effects of the present invention are not impaired. In this case, of the total rubber latex, the vinyl pyridine / styrene / butadiene terpolymer latex (B) comprising 13 to 20% by weight of vinylpyridine, 25 to 45% by weight of styrene, and 40 to 60% by weight of butadiene is 50% by weight. % By weight, preferably 70% by weight or more.
As the rubber latex used other than the latex (B), vinyl pyridine / styrene / butadiene terpolymer latex and / or styrene / butadiene copolymer latex and / or polybutadiene latex are preferably used.

Further, a blocked isocyanate may be added to the adhesive treatment agent. By adding the blocked isocyanate, when the hose is braided or spirally knitted, the residue caused by the adhesive agent is reduced.

The blocked polyisocyanate compound referred to in the present invention is a compound in which a blocking agent is released by heat to produce an active isocyanate compound. Specifically, tolylene diisocyanate, metaphenylene diisocyanate, diphenyl methane diisocyanate, Hexamethylene diisocyanate, polyisocyanate compounds such as triphenylmethane triisocyanate, and phenols such as phenol, cresol, resorcinol,
lactams such as ε-caprolactam and valerolactam,
The polyisocyanate compound itself also functions as a blocking agent, such as an oxime such as acetoxime, methylketyl ketone oxime, or cyclohexane oxime, a reaction product with a blocking agent such as ethyleneimine, or a dimer of 2,4 toluene diisocyanate. And the like. Among them, 2,4 toluene diisocyanate dimer is most preferred.

The released blocking agent is considered to be volatilized in the heat treatment step after the treatment agent is applied. However, a residue which does not contribute to the crosslinking of the treatment agent is generated, which may adversely affect the adhesiveness. Further, when the fiber to which the aqueous dispersion of the treating agent is applied is heat-treated, the surface layer of the treating agent attached to the fiber is first solidified to form a film of the treating agent. After this film is formed, the gas derived from the blocking agent volatilizes, causing local adhesion unevenness of the treatment agent (hereinafter referred to as blister).

On the fiber surface having a large amount of blisters, the amount of the treatment agent is locally large and the layer is sometimes thick. In the part where the treatment agent is in a thick layer, the moisture in the treatment agent is not sufficiently evaporated, latex particles are less likely to be bonded, the adhesiveness is increased, and the cord tends to cause trouble in the hose manufacturing process.

The 2,4-toluene diisocyanate dimer has a small amount of volatile substances and residues that do not contribute to crosslinking, and can extremely reduce blister generation as compared with commonly used blocked isocyanate compounds. Therefore, 2,
4-Toluene diisocyanate dimer and parachlorophenol / resorcinol / formaldehyde cocondensate (C) and resorcinol / formaldehyde initial condensate (A)
By combining the rubber latex (B) and the rubber latex (B), a fiber treatment agent particularly useful for hose reinforcement can be obtained.

When the blocked isocyanate is added, the solid content is preferably 3 to 10% by weight of the total solid content of the resorcinol-formaldehyde initial condensate (A) and the rubber latex.

The treating agent has a total solid content concentration of the mixed solution of 5 to 2.
It is preferably used in an amount of 0% by weight, especially in the range of 7 to 15% by weight. Within such a range, the stability of the treating agent will be excellent. In order to attach the treating agent composition to the fibers, any method such as immersion, nozzle spraying, or application with a roller can be adopted.

The amount of the treatment composition adhering to the fibers is 1.0 to 7.0% by weight, especially 2.0 to 4.5% by dry weight.
The range of% by weight is preferable. By setting the content in this range, it is possible to make the adhesion to rubber excellent, and it is possible to suppress troubles in the hose manufacturing process.

The heat treatment after the adhesive agent is applied to the polyester fiber or the aramid fiber is usually from 200 to 255 ° C.
For 20 to 300 seconds. By the heat treatment, the adhesion between the fiber and the rubber can be further strengthened.

Thus, the fiber obtained by the method of bonding the synthetic fiber and the halogenated butyl rubber of the present invention has good adhesion to rubber, excellent stability in the hose production process, and especially for car air conditioners. It can be suitably used as a hose.

Next, the rubber hose of the present invention will be described. As the shape of the rubber hose of the present invention, a conventionally known shape can be used, but one in which one or two or more reinforcing fibers are wound on an inner rubber layer and an outer rubber layer is coated thereon. Is preferred.

Examples of the method of winding the reinforcing fibers include a blade method in which one fiber and the other fiber are wound alternately up and down, and a spiral method in which one fiber is wound and then the other fiber is wound. There are shapes in which the reinforcing fibers are in close contact with each other and shapes in which the reinforcing fibers are spaced from each other, but are not particularly specified.

As a method for vulcanizing a rubber hose, there are vulcanization under dry heat and vulcanization under steam.
The reaction is performed at 0 ° C. for 30 minutes to 1 hour, and conditions such as a vulcanization method, a vulcanization time and a vulcanization temperature may be appropriately selected.

In the hose of the present invention, the halogenated butyl rubber compound only needs to be placed in contact with the reinforcing fibers, and there is no problem even if the types of the inner rubber and the outer rubber are different. For example, in the case of an air conditioner hose, reinforcing fibers are braided on the inner tube of an unvulcanized halogenated butyl rubber compound, and an unvulcanized ethylene-α-olefin-non-conjugated diene rubber compound or halogen The coated butyl rubber compound is coated and then vulcanized.

The method of vulcanizing the hose includes vulcanization under dry heat and vulcanization under steam.
For 30 minutes to 1 hour, but conditions such as a vulcanization method, a vulcanization time and a vulcanization temperature may be appropriately selected.

[0047]

The present invention will be described more specifically with reference to the following examples. In addition, each measurement value in an Example is calculated | required by the following method. [Treatment agent composition adhesion amount] JIS L 1017 (199)
It was determined by the dip pickup-mass method of 5). [Peeling adhesive strength] Unvulcanized rubber having the following rubber composition is adhered as an inner rubber to an aluminum pipe having a diameter of 10 cm and a length of 6 cm, and a treatment cord is wound thereon so that there is no gap. An unvulcanized rubber having the following composition was adhered as an outer rubber to form a cord / rubber composite, and a wrapping cloth (manufactured by Toray Industries, Inc.) was wound thereon and vulcanized at 160 ° C. for 30 minutes in an autoclave. After cooling, the wrapping cloth was removed, the cord / rubber composite was peeled off from the aluminum pipe, and the cord and the horizontal direction were cut to a width of 1 inch to form a tangled test piece.
According to IS K6301 (1995), the interface between the treated cord and the outer rubber was peeled off at a speed of 50 cm / min.
The peel force per inch was measured. Rubber compounding composition: (compound) (parts by weight) Chlorinated butyl rubber 100.0 Zinc white 5.0 Stearic acid 1.0 Carbon black 55.0 Processing oil 6.5 Sulfur 1.5 2-Mercaptobenzothiazole 0.7 Tetra Methylthiuram disulfide 1.5 [with hose adhesive rubber] JIS K 6330-6 (19
1998), the vulcanized hose was cut into a ring having a width of 1 inch to obtain a test piece, and the interface between the treated cord and the outer rubber was peeled off at a speed of 50 cm / min. The peeled surface was visually observed, and ◎ indicates that the rubber adhered to the fiber was fairly good, ○ indicates that the rubber adhered to the fiber, and x indicates that the rubber was bad. [Fiber Smoothness (Dynamic Friction Coefficient)] Using a friction tester manufactured by Toray Engineering, the dynamic friction coefficient between the fiber and the matte chrome-plated pipe is calculated by measuring the tension T1 on the side where the fiber enters the matte chrome-plated pipe and the side where the fiber exits. Is calculated according to the following equation from the tension T2. The lower the coefficient of kinetic friction, the better the smoothness of the fiber, and the less likely it is for trouble in the hose manufacturing process. Dynamic friction coefficient = (T2−T1) / (T1 + T2) At this time, the measurement was performed under the following conditions. Friction body: matte chrome-plated pipe with a diameter of 40 mm and surface roughness of 0.1 S Friction body temperature: 25 ° C Temperature and humidity of the measurement chamber: 25 ° C, 65% Contact angle: 180 ° Tension T1 on the friction body side: 1000 gf Yarn speed: 20 m / min [Adhesion of scum to the process] The adhesion of scum to guides at the time of measuring the dynamic friction coefficient between the fiber and the matte chrome-plated pipe used as an index of the smoothness was used as an index. ◎: extremely low generation of scum, ○: low
Those with a large amount of scum are indicated by x, and those that are hard to judge are indicated by △.

(Example 1) An initial condensate of resorcinol-formaldehyde obtained by reacting 2.0 mol of formaldehyde with 1.0 mol of resorcinol, 55% by weight of butadiene / 2% by weight of 2-vinylpyridine / An RFL liquid obtained by mixing a vinylpyridine / styrene / butadiene terpolymer latex (mooney viscosity: 110, weight average particle diameter: 170 nm) composed of 30% by weight of styrene at a ratio of 1/3 by weight of the solid content was added to the total solids. 10w
It was adjusted to t% and aged for 24 hours. At this time, a novolak-type precondensate ("Sumikanol 700S" manufactured by Sumitomo Chemical Co., Ltd.), which was obtained by precondensing resorcinol and formaldehyde in a molar ratio of resorcinol / formaldehyde = 1 / 0.65 in the presence of an acidic catalyst, was used. After dissolving in water in which sodium hydroxide is dissolved, formaldehyde is additionally added. Nagase Kasei Co., Ltd., which is a compound (C) obtained by co-condensing parachlorophenol and resorcinol from Nagase Kasei Co., Ltd. with formaldehyde to the RFL.
"Denabond" was mixed at a solid concentration of RFL: parachlorophenol / formaldehyde / resorcinol derivative = 3: 1 to obtain a treating agent having a solid concentration of 15% by weight. To a polyepoxide compound ("Denacole EX3" manufactured by Nagase Kasei Kogyo Co., Ltd.)
13 ") and applied to the fiber, roller temperature 230 ° C
1650 decitex, 360 filament polyethylene terephthalate fiber (heat-treated at 25 ° C., intrinsic viscosity measured in o-chlorophenol at 25 ° C. is 0.95, carboxyl group terminal amount is 17 equivalent / ton, adhesion amount of polyepoxide compound is 0.08) (% By weight)
The cord was twisted 0 times to obtain a cord. Next, the approximate fibers were immersed in an adhesive treatment agent using a Ritzler computer treater, and heat-treated at 240 ° C. for 2 minutes. Table 1 shows the evaluation results of the properties of the fibers thus obtained.

[0049]

[Table 1] Next, the chlorinated butyl rubber compound is extruded with an extruder to form an inner tube, and the above treatment cords are braided thereon, and the same chlorinated butyl rubber compound as the inner tube rubber is extruded and coated on the outside as an outer tube. did. It is formed into a long roll,
Steam can vulcanization was performed at 0 ° C. for 30 minutes to produce a reinforced rubber hose having an inner diameter of 16 mm and an outer diameter of 24 mm. The evaluation results of the properties of the rubber hose thus obtained are also shown in Table 1.

Comparative Example 1 As a rubber latex, vinylpyridine / styrene / 55% by weight of butadiene / 2% by weight of 2-vinylpyridine / 30% by weight of styrene was used.
Instead of the butadiene terpolymer latex, a vinylpyridine / styrene / butadiene terpolymer latex composed of 70% by weight of butadiene / 2 15% by weight of 2-vinylpyridine / 15% by weight of styrene (Mooney viscosity 40, sodium alginate method) All tests were carried out in the same manner as in Example 1 except that the average particle size in the particle size distribution measurement was 35 nm. The results are shown in Table 1.

Example 2 An initial condensate of resorcinol-formaldehyde obtained by reacting 2.0 mol of formaldehyde with 1.0 mol of formalin, and 55% by weight of butadiene / 2% by weight of 2-vinylpyridine / An RFL liquid obtained by mixing a vinylpyridine / styrene / butadiene terpolymer latex (mooney viscosity: 110, weight average particle diameter: 170 nm) composed of 30% by weight of styrene at a ratio of 1/3 by weight of the solid content was added to the total solids. 10w
It was adjusted to t% and aged for 24 hours. At this time, a novolak-type precondensate ("Sumikanol 700S" manufactured by Sumitomo Chemical Co., Ltd.), which was obtained by precondensing resorcinol and formaldehyde in a molar ratio of resorcinol / formaldehyde = 1 / 0.65 in the presence of an acidic catalyst, was used. After dissolving in water in which sodium hydroxide is dissolved, formaldehyde is additionally added. Nagase Kasei Co., Ltd., which is a compound (C) obtained by co-condensing parachlorophenol and resorcinol from Nagase Kasei Co., Ltd. with formaldehyde to the RFL.
"Denabond" was mixed at a solid content concentration of RFL: parachlorophenol / formaldehyde / resorcin derivative = 3: 1 to obtain a treating agent having a solid content concentration of 15% by weight. Liquid (D) dispersed in dioctyl sulfosuccinate sodium salt (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., "Neocol SW-3") in terms of solids weight ratio of RFL: 2,4 toluene diisocyanate dimer = 1: 0.1 to obtain a treating agent having a solid content of 15% by weight, and all tests were carried out in the same manner as in Example 1 except for using the adhesive treating agent.
The results are shown in Table 1.

Example 3 Instead of 2,4 toluene diisocyanate dimer, diphenylmethane diisocyanate methyl ethyl ketoxime blocked isocyanate (“Elastron BN-69” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
It was used. Other conditions were tested as in Example 1. The results are shown in Table 1.

Example 4 An initial condensate of resorcinol-formaldehyde obtained by reacting 2.0 mol of formaldehyde with 1.0 mol of formalin, and 55% by weight of butadiene / 2% by weight of 2-vinylpyridine / An RFL liquid obtained by mixing a vinylpyridine / styrene / butadiene terpolymer latex (mooney viscosity: 110, weight average particle diameter: 170 nm) composed of 30% by weight of styrene at a ratio of 1/3 by weight of the solid content was added to the total solids. 10w
It was adjusted to t% and aged for 24 hours. At this time, a novolak-type precondensate ("Sumikanol 700S" manufactured by Sumitomo Chemical Co., Ltd.), which was obtained by precondensing resorcinol and formaldehyde in a molar ratio of resorcinol / formaldehyde = 1 / 0.65 in the presence of an acidic catalyst, was used. After dissolving in water in which sodium hydroxide is dissolved, formaldehyde is additionally added. Nagase Kasei Co., Ltd., which is a compound (C) obtained by co-condensing parachlorophenol and resorcinol from Nagase Kasei Co., Ltd. with formaldehyde to the RFL.
"Denabond" was mixed at a solid content concentration of RFL: parachlorophenol / formaldehyde / resorcin derivative = 3: 1 to obtain a treating agent having a solid content concentration of 15% by weight. Liquid (D) dispersed in dioctyl sulfosuccinate sodium salt (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., "Neocol SW-3") in terms of solids weight ratio of RFL: 2,4 toluene diisocyanate dimer = 1: 0.1 to obtain a treating agent having a solid content of 15% by weight, and a polyepoxide compound (“Denacole EX313” manufactured by Nagase Kasei Kogyo Co., Ltd.) immediately before winding in the spinning process. ) As an aqueous solution and heat-treated at 240 ° C., 1650 decitex, 1000 filament polyparaphenylene terephthalamide fiber 1 (Attached amount of polyepoxide compound: 0.13% by weight) was twisted 80 times per meter to obtain a cord, and then the fibers were immersed in an adhesive using a Ritzler computer treater. ,
Heat treatment was performed at 240 ° C. for 2 minutes. Table 2 shows the property evaluation results of the fibers obtained in this manner.

[0054]

[Table 2]

(Comparative Example 2) As rubber latex, vinylpyridine / styrene / 55% by weight of butadiene / 2 15% by weight of 2-vinylpyridine / 30% by weight of styrene
Instead of the butadiene terpolymer latex, a vinylpyridine / styrene / butadiene terpolymer latex (70% by weight butadiene / 15% by weight of 2-vinylpyridine / 15% by weight of styrene) having a Mooney viscosity of 40 and a weight average particle diameter of 35 nm is used. All tests were carried out in the same manner as in Example 4 except that ()) was used. The results are shown in Table 2.

As is clear from the above results, the hose reinforcing fiber obtained by the bonding treatment method of the present invention has a better adhesion to rubber and a higher hose strength than the hose reinforcing fiber obtained by the conventional formulation. It can exhibit excellent performance in the stability of the manufacturing process.

[0057]

According to the present invention, it is possible to obtain a hose reinforcing fiber which has good adhesion to a halogenated butyl rubber, has excellent smoothness, and has little trouble in hose production such as a small amount of an adhesive treatment residue. it can.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) D06M 15/41 D06M 15/41 15/00 F16L 11/08 A F16L 11/08 D06M 101: 36 // D06M 101: 36 15/72 F-term (reference) 3H111 AA02 BA12 BA25 CC02 DA26 DB09 DB19 4J040 CA061 CA081 EB031 EB062 EF332 LA06 MB02 MB06 NA05 NA10 4L033 AA07 AA08 AB01 AC11 AC15 BA05 BA12 BA13 BA69 CA15 CA34 CA24 MA36 MA30 MA0 MA0 4L0 PA01 PA03 PA17 PA21 PA26 RA24 UA08 UA21

Claims (7)

[Claims] 1. An initial condensate (A) of polyalcohol and / or polyepoxide with resorcinol-formaldehyde, vinylpyridine 13 to 20% by weight, styrene 2
5 to 45% by weight and 40 to 60% by weight of butadiene are coated with an adhesive containing vinyl pyridine / styrene / butadiene terpolymer latex (B) and parachlorophenol / resorcin / formaldehyde cocondensate (C). A rubber reinforcing fiber comprising a polyester fiber or an aramid fiber. 2. A polyester fiber or an aramid fiber previously treated with a treating agent containing a polyepoxide compound, a resorcinol-formaldehyde initial condensate (A), vinylpyridine 13 to 20% by weight, styrene 25 to 45% by weight and butadiene 40. An adhesive treatment agent containing a vinyl pyridine / styrene / butadiene terpolymer latex (B) and parachlorophenol / resorcin / formaldehyde cocondensate (C) of up to 60% by weight; Method for producing rubber reinforcing fiber. 3. The method for producing a rubber reinforcing fiber according to claim 2, wherein the adhesion treating agent contains a blocked isocyanate (D). 4. When the blocked isocyanate (D) is 2,
The method for producing a rubber reinforcing fiber according to claim 3, which is a dimer of 4-toluene diisocyanate. 5. The rubber reinforcing fiber according to claim 2, wherein the treatment of the polyester fiber with the treating agent containing the polyepoxide compound is performed before or after the drawing in melt spinning of the polyester fiber. Manufacturing method. 6. The aramid fiber is treated with a treating agent containing a polyepoxide compound immediately before winding of the aramid fiber in wet spinning.
The method for producing a rubber reinforcing fiber according to any one of the above. 7. A hose comprising the fiber for reinforcing rubber according to claim 1 and halogenated butyl rubber.