JPH10280280A - Adhesive treatment of polyester fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the adhesion to rubber, especially ethylene-propylene-based rubber by treating a polyester fiber with a treating agent containing a polyepoxide compound and thereafter treating the treated fiber with a treating agent containing polyallylamine compound. SOLUTION: This adhesive treating method of a polyester fiber comprises a step for treating the polyester fiber with a treating agent containing a polyepoxide compound, and a step for treating the treated fiber with a treating agent containing a polyallylamine of the formula (having 2,000-100,000 number average molecular weight, preferably 2,500-50,000 number average molecular weight). The adhesive treating method is useful for production of a rubber hose, a diaphragm, a V-belt, a conveyer belt, etc., having a fiber reinforcing layer or a fiber substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for bonding polyester fiber and rubber, and more particularly, to a method for bonding polyester fiber and ethylene propylene rubber (EPDM). Rubber hoses, diaphragms, with reinforcement layers and fiber base fabrics
V-belts, conveyor belts and the like can be mentioned.

[0002]

2. Description of the Related Art Polyester fibers represented by polyethylene terephthalate fibers have high strength and high Young's modulus, and are utilized widely as rubber reinforcing fibers for tires, hoses, belts and the like.

[0003] However, since the surface of the polyester fiber is relatively inert, it has low adhesion to rubber,
In order to improve the adhesiveness, a method of treating a polyester fiber with an epoxy compound, an isocyanate compound or the like (JP-A-54-77794, JP-A-60-99076)
And Japanese Patent Application Laid-Open No. Sho 60-21924).

Further, in the field of hoses and belts, since the temperature of the engine room of an automobile becomes high, rubbers having excellent high-temperature characteristics are being developed in terms of rubber material.
One of them is an ethylene propylene rubber. However, the rubber has a problem that bonding is very difficult because the rubber has few double bonds in chemical structure and poor reactivity.

For this reason, when bonding with the rubber, a method of increasing reactivity with the rubber by using a highly polar chlorosulfonated polyethylene latex or a special chlorophenol compound instead of the above compound (Japanese Patent Publication No. −201
No. 36, Japanese Unexamined Patent Publication No. Hei 7-138880) and the like have been proposed, but in reality, no satisfactory adhesive force is obtained in any of the methods.

On the other hand, Japanese Patent Application Laid-Open No. Hei 5-125671 discloses that a polyallylamine compound is imparted to polyester fibers to improve the adhesiveness with general-purpose resins such as polyurethane resins, halogen-containing vinyl resins and ethylene vinyl acetate. Although a bath bonding treatment method is disclosed, when the method is applied as it is to the above-mentioned bonding with rubber, the bonding level is not sufficiently satisfactory for rubber reinforcing applications.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a polyester fiber having improved adhesion to an ethylene propylene rubber matrix. An object of the present invention is to provide a bonding method.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object. As a result, when bonding polyester fibers to ethylene propylene rubber, an epoxy compound and a polyallylamine used for resin bonding were used. It has been clarified that when used in combination with a compound, the adhesiveness to an ethylene propylene rubber polyester fiber can be remarkably improved.

Thus, according to the present invention, a polyester fiber is treated with a treating agent containing a polyepoxide compound and then treated with a treating agent containing a polyallylamine compound represented by the following general formula. An adhesive treatment method is provided.

[0010]

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[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The polyester fibers used in the present invention are polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate and the like.

It goes without saying that the denier, the number of filaments, the cross-sectional shape, the fiber properties, the fine structure, the presence or absence of additives, and the properties of the polymer (molecular weight, terminal carboxyl group concentration, etc.) of the polyester fiber are not limited at all.

The polyepoxide compound used in the present invention is a compound containing at least two epoxy groups per molecule in an amount of 0.2 g equivalent or more per 100 g of the compound, and ethylene glycol, glycerol,
Reaction products of polyhydric alcohols such as sorbitol, pentaerythritol and polyethylene glycol with halogen-containing epoxides such as epichlorohydrin, resorcinol bis (4-hydroxyphenyl) dimethylmethane, phenol formaldehyde resin, resorcinol
Examples include a reaction product of a polyhydric phenol such as a formaldehyde resin and an epoxide containing a halogen, or a polyepoxide compound obtained by oxidizing an unsaturated compound with peracetic acid or hydrogen peroxide.

Specific examples of the above compounds include 3,4-epoxycyclohexene epoxide, 3,4-epoxycyclohexenemethyl 3,4-epoxycyclohexenecarboxylate, bis (3,4-epoxy-6-methyl-
(Cyclohexylmethyl) adipate and the like.

Among them, a reaction product of a polyhydric alcohol and epichlorohydrin, that is, a polyglycidyl ether compound of a polyhydric alcohol is preferable because it exhibits excellent performance. The compound is usually used as an emulsion. In order to prepare an emulsion or a solution, the compound is dissolved as it is or in a small amount of a solvent as required, and a known emulsifier such as sodium alkylbenzene sulfonate, sodium dioctyl sulfosuccinate, nonylphenol ethylene oxide adduct and the like are used. And emulsify or dissolve.

The amount of the polyepoxide compound is preferably 0.1 to 10% by weight based on the weight of the fiber. More preferably, it is in the range of 0.5 to 5% by weight.

If the amount is less than 0.1% by weight, the effect of the polyepoxide compound is not sufficiently exhibited, and satisfactory adhesive performance between the polyester fiber and the ethylene propylene rubber cannot be obtained. On the other hand, if the adhesion amount of the polyepoxide compound exceeds 10% by weight, the fiber becomes very hard, and the impregnating property of the treatment agent to be applied later is reduced, and as a result, the adhesive performance is reduced.

This polyepoxide compound can be added in advance together with a spinning oil or the like in the spinning process. At this time, the adhesion amount of the polyepoxide compound was 0.1.
Most preferred is 1-0.5% by weight.

The resorcinol-formalin rubber latex (RFL) used in the present invention is an initial condensate, a special chlorophenol compound, a rubber latex, a block obtained by reacting resorcinol-formalin (RF) under an alkali or acidic catalyst. It is a mixture of polyisocyanate compounds.

Regarding the mixing ratio of resorcinol, formalin and rubber latex, effects can be obtained by applying any of the known techniques.

The mixing ratio of the special chlorophenol compound and the resorcinol-formalin rubber latex varies slightly depending on the mixing ratio of the rubber to be adhered. Generally, the mixing ratio of the RF and the special chlorophenol compound is 50 /.
50-80 / 20 (weight ratio) is preferred.

The special chlorophenol compound used here is a compound obtained by co-condensing parachlorophenol and resorcinol with formaldehyde, and comprises a trinuclear (I), a pentanuclear (II), and a seven-nuclear compound represented by the following structural formulas. Compounds containing the compound (III) as a main component are preferred.

[0023]

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The rubber latex used in the RFL is preferably a mixture of a vinylpyridine / styrene / butadiene terpolymer latex and a polybutadiene latex. It is necessary to change the compounding ratio of these rubber latexes according to the characteristics of the rubber to be adhered, and vinyl pyridine / styrene / butadiene terpolymer latex / polybutadiene latex is usually 70%.
It is generally used at a ratio of / 30 to 30/70 (weight ratio). However, the composition is not particularly limited.

Regarding the mixing ratio of resorcinol-formalin and rubber latex, an effect can be obtained by applying any of the known techniques.

It is preferable that a blocked polyisocyanate compound is added to the RFL for use. The blocked polyisocyanate compound is an addition compound of the polyisocyanate compound and the blocking agent, and releases a blocking component upon heating to generate an active polyisocyanate compound.

As the above polyisocyanate compound,
For example, polyisocyanates such as tolylene diisocyanate, metaphenylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, polymethylene polyphenyl polyisocyanate, and triphenylmethane triisocyanate, or compounds having these polyisocyanates and two or more active hydrogen atoms such as trimethylol Polyalkylene glycol adduct polyisocyanate having a terminal isocyanate group obtained by reacting propane, pentaerythritol, or the like with a molar ratio of the isocyanate group (—NCO) to the hydroxyl group (—OH) exceeding 1 is exemplified.

Among them, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and polymethylene polyphenyl isocyanate are preferred because they exhibit excellent performance.

Examples of the blocking agent include phenols such as phenol, thiophenol, cresol and resorcinol; aromatic secondary amines such as diphenylamine and xylidine; phthalic imides; caprolactam and valerolactam. Oximes such as lactams, acetoxime, methyl ethyl ketone oxime and cyclohexane oxime, and sodium acid sulfite are included. These additives are usually used in an aqueous dispersion using a dispersant, and are added alone or in combination. The above-mentioned RFL is usually adjusted to contain 10 to 25 wt% of the total solid content.

The polyallylamine (hereinafter sometimes referred to as PAA) compound used in the present invention is a polymer of allylamine having an amino group in a side chain and having a pendant group in a basic skeleton represented by the following general formula. Polymer.

[0031]

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The above PAA compound is disclosed in JP-A-58-2018.
No. 11, the number average molecular weight Mn is 2000 to 100,000, preferably 2500 to 500
00.

Since this compound is produced by a radical polymerization method, it is difficult to obtain a stable product in the region where Mn is less than 2,000. On the other hand, when Mn exceeds 100,000, the viscosity of the treating agent increases and the handleability decreases. .

The above PAA compound is usually used as an aqueous solution. At this time, a surfactant, a blocked isocyanate compound, or the like may be added as long as the adhesiveness is not impaired.

However, mixing with RFL is not preferred because the polyallylamine compound exhibits cationicity, which causes aggregation and precipitation of latex components.

The treating agent containing the PAA compound is adjusted so that the total solid content is usually 1 to 20% by weight, preferably 3 to 10% by weight.

The treatment with a treating agent and a RFL containing a polyepoxide compound and a treating agent containing a PAA compound means that the above compound is applied to polyester fiber by any method such as contact with a roller or application or dipping by spraying from a nozzle. Means to adhere.

At this time, with respect to the polyepoxide compound, a so-called pre-treated yarn to which the compound has been previously applied in the spinning process may be used.

The amount of the solid content adhered to the polyester fiber is 0.1 to 10% for the treating agent containing the polyepoxide compound.
wt%, preferably 0.5 to 5 wt%, and RFL of 0.5
10 to 10 wt%, preferably 1 to 5 wt%, and 0.1 to 5.0 wt% of the treating agent containing the PAA compound, preferably 1.
0-2.0 wt% is suitable.

In order to control the amount of adhered solids, means such as squeezing with a pressing roller, scraping with a scraper, blowing off with air blowing, suctioning, and beating with a beater may be used.

When the present invention is used for rubber hose applications, the treating agent containing the RFL and PAA compounds can be applied to a hose molded through a blade process.

In the present invention, after the polyester fiber is treated with a treating agent containing a polyepoxide compound,
At 180 to 180 ° C for 0.5 to 5 minutes, preferably 1 to 3 minutes, and then at a temperature of 180 ° C to 10 ° C lower than the melting point of the polyester fiber, preferably at a temperature of 220 to 250 ° C for 0.5 to 5. Heat treatment is performed for 0 minutes, preferably 1 to 3 minutes.

After the treatment with the treating agent containing RFL, the treatment is carried out at 80 to 180 ° C. for 0.5 to 5 minutes, preferably 1 to 50 minutes.
Dry for 3 minutes, then 150-260 ° C, preferably 2
Heat treatment is performed at a temperature of 20 to 250 ° C. for 0.5 to 5.0 minutes, preferably 1 to 3 minutes.

Further, the treating agent containing the PAA compound is applied at the final stage of the treatment, and heat-treated at a temperature lower than 110 ° C. for 1 minute or more, preferably for 1 to 2 minutes.

Treatment Agent Containing Polyepoxide Compound and RF
Regarding L, if the heat treatment temperature is too low, adhesion to rubbers becomes insufficient. On the other hand, if the heat treatment temperature is too high, PAA
Becomes extremely hard, and furthermore, the polyester fiber melts and fuses, becomes extremely hard, or undergoes strong deterioration, and cannot be put to practical use.

[0046]

The polyester fiber obtained by the present invention has a surface coated with a treating agent containing an epoxy group.
On the other hand, since a PAA compound having an affinity for the ethylene-propylene rubber as the adhered rubber covers the fiber surface near the surface of the fiber, the adhesiveness is excellent.

The cohesive force of the adhesive layer can be increased by using RFL together with this, which contributes to the improvement of heat resistance and the like, and the adhesiveness can be further enhanced. As a result, the excellent properties inherent to polyester fibers as rubber reinforcing fibers can be sufficiently exhibited.

[0048]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited thereto. In addition, the evaluation method in an Example is as follows.

(1) Cord peeling adhesive strength A value indicating the magnitude of the adhesive strength between the treated cord and the rubber, 25 of the resulting treated cords are arranged in one inch and embedded in an ethylene-propylene unvulcanized rubber. , Surface pressure 5kg / c
After pre-pressing at m ² and a temperature of 80 ° C., it is covered with a polyester sheet and rubber so as not to be affected by moisture, and steam-vulcanized at 150 ° C. for 30 minutes.

The force required to peel the cord from the rubber at a speed of 200 mm / min using the test piece is shown in kg / inch.

Example 1 As an RFL treatment agent, resorcinol-formalin initial condensate Sumikanol 700S (Sumitomo Chemical Co., Ltd., 65% aqueous solution) was added to water containing an aqueous solution of caustic soda and aqueous ammonia with an acidic catalyst. And stir well to disperse.

Next, Nippol 2518FS (a water emulsion of vinyl pyridine / styrene / butadiene terpolymer manufactured by Zeon Corporation) and Nippol LX-111NF
(Polybutadiene rubber latex 55% aqueous emulsion manufactured by Zeon Corporation) was mixed with the above resorcinol-formalin initial condensation dispersion at a solid content ratio of 1: 4 (vinyl pyridine / styrene / butadiene terpolymer / polybutadiene rubber latex = 3). : 7 (weight ratio))
/ F ratio is 1: 2 (molar ratio) and uniformly mixed.

Next, Elastron B was added to the RFL mixture.
N-69 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., diphenylmethane diisocyanate methyl ethyl ketoxime block 33)
% Aqueous dispersion) was added to and mixed with RFL at a solid content ratio of 6: 1 and aged at 20 ° C. for 24 hours.

Further, immediately before use, Denabond E (a 20% solution of a special chlorophenol compound manufactured by Nagase Kasei Kogyo Co., Ltd.) was added to RFL at a solid content ratio of 2.5: 1, and the mixture was sufficiently stirred. used.

As a treating agent containing a PAA compound, PA
A-10C (10% aqueous solution, manufactured by Nitto Bo Co., Ltd.) was used.

The control of the viscosity and the amount of adhesion of the treating agent was adjusted by adding and diluting water to the treating agent.

Next, a polyethylene terephthalate pretreated yarn (manufactured by Teijin Limited, [η] = 0.89, 150) to which a polyepoxide compound has been previously applied in the yarn making process.
A single filament (0 denier / 250 filaments) was twisted at 10 T / 10 cm to obtain a cord.

This code was used for resorcinol-formalin rubber latex (RF) using a computer treater (tire code processor manufactured by CA Ritzler Co., Ltd.).
After immersion in the treating agent containing L) and the treating agent containing the polyallylamine compound, respectively, they were heat-treated to obtain a treated code.

At this time, the RFL heat treatment was dried at 170 ° C. for 2 minutes, then at 235 ° C. for 1 minute, and further at 240 ° C. for 1 minute.
The heat treatment of the PAA compound was performed at 105 ° C. for 1 minute.

The polyester treatment cord had a solid content of RFL of 2.5 wt% and PAA of 1.0 wt%.

The treated cord thus obtained was vulcanized by the method described above, and the adhesive strength was measured.

The rubber composition used in the evaluation is as follows. EPDM 100 parts HAF-carbon black 120 parts Process oil (paraffin type) 90 parts Zinc flower 5 parts Stearic acid 3 parts Dicumyl peroxide 3 parts Vulcanization accelerator 2.5 parts

Table 1 shows the results.

[Examples 2 to 5, Comparative Examples 1 and 2] Example 1
In the same manner as in Example 1, except that the amounts of RFL and PAA compound attached were changed as shown in Table 1.

In Comparative Examples 1 and 2, the treatment with the PAA compound was not performed. The results are shown in Table 1.

[0066]

[Table 1]

Claims (3)

[Claims] 1. A method for bonding polyester fibers, comprising treating a polyester fiber with a treating agent containing a polyepoxide compound and then treating it with a treating agent containing a polyallylamine compound represented by the following general formula. Embedded image 2. The method according to claim 1, wherein after treating with a treating agent containing a polyepoxide compound, prior to treating with a treating agent containing a polyallylamine compound, treating with a treating agent containing resorcinol-formalin rubber latex (RFL). Bonding method for polyester fiber. 3. The method for bonding polyester fibers according to claim 1, wherein after the treatment agent containing the polyallylamine compound is applied, heat treatment is performed at a temperature lower than 110 ° C. for 1 minute or more.