KR100995601B1 - Adhesive composition for supporting rubber and polyester textile coating the same - Google Patents

Abstract

The present invention relates to a rubber reinforcing adhesive composition and a polyester fiber coated thereon, in particular by coating a rubber reinforcing adhesive composition comprising a dispersion dye on the polyester fiber in a small amount of resorcinol-formaldehyde rubber latex ( The present invention relates to a rubber reinforcing adhesive composition having excellent workability as well as excellent adhesion to rubber by improving the adsorptivity of RFL) and a polyester fiber coated with the same.

Polyester fiber, adhesive, disperse dye, polyepoxide, aromatic urethane compound, aqueous solvent, resorcinol-formaldehyde rubber latex, rubber reinforcement, adhesive strength

Description

Adhesive composition for reinforcing rubber and polyester fiber coated thereon {ADHESIVE COMPOSITION FOR SUPPORTING RUBBER AND POLYESTER TEXTILE COATING THE SAME}

The present invention relates to an adhesive composition for rubber reinforcement and a polyester fiber coated with the same, and more particularly, to improve the adsorptivity of resorcinol-formaldehyde rubber latex (RFL) even at a small amount, thereby providing excellent adhesion to rubber. In addition, the present invention relates to a rubber reinforcing adhesive composition having excellent workability and a polyester fiber coated with the same.

As a reinforcing agent for rubber structures such as tires, belts, hoses, and the like, polyester fibers (for example, polyethylene terephthalate fibers, etc.), polyamide fibers (for example, nylons, etc.), aromatic polyamide fibers, or polyvinyl alcohols Synthetic fibers such as fibers are mainly used. However, the synthetic fibers have a problem of poor adhesion with rubber. Accordingly, a method of improving the adhesive strength of the synthetic fibers to rubber by covering the surface of the synthetic fibers with an adhesive comprising an epoxy compound, an isocyanate compound, a halogenated phenol compound, or the like as an adhesive matrix component has been continuously studied.                         

As a method of improving the adhesion of rubber to the rubber of conventional synthetic fibers, Japanese Patent Laid-Open No. 46-11251 discloses 2,6-bis (2) in a liquid (RFL) consisting of an initial condensate of resorcinol-formaldehyde and rubber latex. Disclosed is an adhesive treatment agent comprising a reaction product of a halogenated phenol such as', 4'-dihydroxyphenylmethyl) -4-chlorophenyl and resorcinol-formaldehyde. However, the adhesive agent has a problem in that it is required to adhere to the polyester fiber in a large amount in order to obtain sufficient adhesive force (pulling force), as well as 2,6-bis (2 ', 4'-dihydroxyphenylmethyl) -4 Halogenated phenols, such as -chlorophenyl (abbreviated as general capsules), have a problem in that workability is poor due to a bad smell by using ammonia water to enhance an adhesive effect.

In addition, U.S. Patent No. 3,234,067 discloses treating a polyester fiber with a first treatment solution consisting of a mixture of diisocyanate and epoxy compound blocked with epoxy compound and carrolactam or phenol, followed by a second treatment consisting of RFL. A method of treating with a treatment liquid is disclosed. However, when the first treatment liquid is immersed in the first treatment liquid polyester fiber with a thermosetting resin, the surface of the heat treated fiber becomes hydrophobic due to the thermosetting of the curable resin, the free space between the fiber filaments is significantly lowered There is a problem in that the rubber adhesion of the final treated fiber is lowered by significantly reducing the adsorptivity of the second treatment liquid, RFL.

Therefore, there is a need for further research on a method of improving the adhesive strength of the synthetic fibers to the rubber.

 In order to solve the problems of the prior art as described above, the present invention improves the adsorptivity of the resorcinol-formaldehyde rubber latex (RFL) in a small amount as well as excellent adhesion to rubber, significantly improving workability An object of the present invention is to provide an adhesive composition for rubber reinforcement.

Another object of the present invention is to provide a polyester fiber having excellent adhesion to rubber.

In order to achieve the above object, the present invention provides a rubber reinforcing adhesive composition comprising a dispersion dye in a rubber reinforcing adhesive composition comprising a polyepoxide, an aromatic urethane compound, and an aqueous solvent.

In another aspect, the present invention provides a polyester fiber coated with the rubber reinforcing adhesive composition.

Hereinafter, the present invention will be described in detail.

The inventors of the present invention while studying a method for improving the adhesion of the synthetic fibers to the rubber, as a result of coating a rubber reinforcing adhesive composition containing a dispersion dye on the polyester fiber, as a result of the resorcinol-formaldehyde rubber latex ( By improving the adsorptivity of the following 'RFL', it was confirmed that the adhesive force of the polyester fiber to the rubber is excellent and workability can be improved, and based on this, the present invention has been completed.

Rubber reinforcing adhesive composition of the present invention is characterized in that it comprises a dispersion dye in the rubber reinforcing adhesive composition comprising a polyepoxide, an aromatic urethane compound, and an aqueous solvent.

The disperse dye used in the present invention adsorbs to the inside of the fiber molecular chain by dyeing principle, and serves to improve adhesion by bonding epoxy, isocyanate and RFL to hydroxyl or amine groups of the adsorbed dye.

The dispersion dye may be used a compound represented by the following formula (1).

[Formula 1]

The disperse dye preferably contains 0.01 to 1.0% by weight based on the solids of the adhesive composition. When the content is less than 0.01% by weight, the amount of adsorption of the disperse dye is too small, the effect of improving the bonding strength is insignificant, and when the content exceeds 1.0% by weight, the color of the resulting product is not good, there is a problem of cost increase.

The polyepoxides used in the present invention contain at least two epoxy groups per molecule, preferably a compound having a molecular weight of at least 100 and an epoxy equivalent of at least 100.

When the number of epoxy groups per molecule of the polyepoxide is less than two, there is a problem in that no crosslinking is formed, and when the molecular weight of the polyepoxide is less than 100, the boiling point is close to the processing temperature at the time of coating, and thus there is a problem of volatilization during processing.

The polyepoxide may be a reaction product of polyhydric alcohols and halogen-containing epoxides or a reaction product of polyhydric phenols and halogen-containing epoxides, and particularly, a reaction product of polyhydric alcohols and halogen-containing epoxides (polyglycidyl of polyhydric alcohols). Ether compounds).

As the polyhydric alcohols, glycerol, pentaerythritol, sorbitol, ethylene glycol, polyethylene glycol, propylene glycol, or polypropylene glycol may be used.

Epichlorohydrin can be used for the said halogen containing epoxide.

As said polyhydric phenol, a resorcinol, bis (4-hydroxyphenyl) diethyl ethane, a phenol formaldehyde resin, a resorcinol-formaldehyde resin, etc. can be used.

The aromatic urethane compound used in the present invention may be a compound represented by the following formula (2).

[Formula 2]

In the formula (2),

Ar is an organic compound residue having at least one benzene nucleus,

X is an allyloxy, imioxy, lactam-N-yl radical,

n is an integer of 2 or more.

The aromatic urethane compound may be a polyisocyanate compound such as triylene diisocyanate, metaphenylene diisocyanate, diphenylmethane diisocyanate, or triphenylmethane triisocyanate, phenols such as phenol, cresol, or resorcinol, carrolactam or baltero Reaction products with a blocking agent selected from the group consisting of lactams such as lactams, oximes such as acetoxime, methyl ethyl ketone oxime, or cyclooxane oxime, and ethylene imine can be used.

The polyepoxide is preferably used in a weight ratio of 0.1 to 10 with respect to the aromatic urethane compound. When the weight ratio of the polyepoxide is less than 0.1 relative to the aromatic urethane compound, the amount of polyepoxide added is too small to have an adhesive effect, and when it exceeds 10, the amount of the aromatic urethane compound added is too small to limit the adhesion. There is this.

The aqueous solvent used in the present invention is, of course, can be applied to all the usual aqueous solvent, it is preferable to use water.

In addition, the present invention is a rubber-reinforced polyester fiber prepared by coating a polyester fiber in combination or in parallel with the rubber reinforcing adhesive composition and the resorcinol-formaldehyde rubber latex (RFL) of the present invention comprising the above components to provide.

The resorcinol-formaldehyde rubber latex acts to chemically react with the molecular end groups of the polyester fiber to impart adhesion.

The resorcinol-formaldehyde rubber latex is prepared by mixing the resorcinol-formalin initial condensate obtained by condensation of resorcinol and formalin under an alkali or acidic catalyst with rubber latex, aqueous ammonia or sodium hydroxide.

The resorcinol and formalin is preferably used in a molar ratio of 1: 0.3 to 1: 3.0, and the initial condensate and the rubber latex are preferably mixed in a ratio of 1: 4 to 1: 8 (solid basis weight ratio). . In addition, the ammonia water or sodium hydroxide is preferably added so that the pH of the mixed solution is 9.0 to 12.0.

As the rubber latex, natural rubber latex, styrene-butadiene rubber latex, acrylonitrile-butadiene rubber latex, chloroprene rubber latex, or vinylpyridine-styrene-butadiene rubber latex may be used.

Mixing or paralleling of the rubber reinforcing adhesive composition and RFL is performed by the following three methods.

First, a method of coating a polyester fiber by mixing the rubber reinforcing adhesive composition and the resorcinol-formaldehyde rubber latex (RFL) of the present invention. At this time, the adhesive composition and the RFL is preferably mixed at a ratio of 5 to 30: 95 to 70 (solid content weight ratio).

Second, after the primary coating of the adhesive composition for rubber reinforcement of the present invention to the polyester fiber alone, and then to the polyester fiber secondary coating REL.

Third, after mixing the rubber reinforcing adhesive composition and the REL of the present invention to the primary coating on the polyester fiber, and then the REL secondary coating on the polyester fiber. At this time, it is preferable that the adhesive composition and the RFL are mixed at a ratio of 10 to 50:90 to 50 (solid content weight ratio).

The first method comprises RFL as a main component and an adhesive composition as a subcomponent.

In the first method, the polyester fiber is specifically transferred to a dipping process and coated by dipping, applying, or spraying with a mixture of the adhesive composition and RFL. At this time, the tension is preferably from 0.1 to 2 2 g / d, it is preferable that the mixture of the adhesive composition and RFL in the polyester fiber is coated with 0.5 to 5.0% by weight in terms of solid content.

Then, the coated polyester fiber is dried at a temperature of 100 to 160 ° C. for 60 to 200 seconds, and then tension heat treated at a temperature of 210 to 250 ° C. for 30 to 120 seconds in a hot stretch zone.

In addition, the second and third methods are the first coating on the polyester fiber by mixing the adhesive composition alone or with RFL and dried at a temperature of 70 to 150 ℃, heat treatment at 200 to 255 ℃, and then the polyester The fiber is secondarily coated with RFL, dried at 70 to 150 ° C., and then heat treated at 200 to 255 ° C.

At this time, it is preferable that the adhesive composition, or the mixed solution of the adhesive composition and RFL on the polyester fiber during the first coating is coated with 1.0 to 5.0% by weight in terms of solid content.

Rubber-reinforced polyester fiber of the present invention prepared by the method as described above is excellent in adhesive strength to the rubber, and thus has the advantage that can be usefully used as a reinforcement of rubber products, such as high-quality tires, belts, hoses.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

[Example]

Example 1

(Adhesive Composition Preparation)

7.5 g of a dispersion of caprolactam additive of 40% diphenylmethane-4,4'-diaisocyanate, epoxide EX-313 (Japan Nagase Chemicals, Glycerol System, Molecular Weight 270, Weight 141 g per Epoxy Reactor) 1 g, Anthra Quinone Blue Disperse Dyes CI Disp. 0.5 g of Blue6 and 91 g of water were mixed and aged at 20 ° C. for 4 hours to prepare.

(RFL manufacturing)

8.8 g of resorcinol, 4.76 g of formalin (37%), 10 g of sodium hydroxide (10%), styrene-butadiene-1,3-vinylpyridine rubber latex (styrene: butadiene: 1,3-vinylpyridine = 15: 70 RFL was prepared by mixing 28 g of 41%), 28 g of styrene-butadiene rubber latex (39%), and 17.6 g of water at a ratio of: 15.

(Coated on polyester fiber)

In the bath containing the adhesive composition prepared above, the tire reinforcing polyester cord 1,500 denier / 2 go was passed at a speed of 15 to 30 m / min so that the adhesive was attached at 1 to 3% (based on a high component). The polyester cord was then dried at a temperature of 150 ° C. for 2 minutes and heat-treated at 220 ° C. for 2 minutes to first coat.

Then, the prepared RFL bath was passed, dried, and heat treated in the same manner as the primary coating to obtain a secondary coated polyester reinforcing polyester cord.

Example 2

(Adhesive Composition Preparation)

Anthraquinone-based blue dispersion dye C.I. Disp. Anthraquinone Red Disperse Dyes C.I. Disp. The same procedure as in Example 1 was carried out except that 0.5 g of Red4 was used.

(RFL manufacturing)

It carried out in the same manner as in Example 1.

(Coated on polyester fiber)

In the bath containing the adhesive composition prepared above, the tire reinforcing polyester cord 1,500 denier / 2 go was passed at a speed of 15 to 30 m / min so that the adhesive was attached at 1 to 3% (based on a high component). The polyester cord was then dried at a temperature of 150 ° C. for 2 minutes and heat-treated at 220 ° C. for 2 minutes to first coat.

Thereafter, the tub containing the RFL prepared in Example 1 was passed, dried, and heat treated in the same manner as the primary coating to obtain a secondary coated polyester reinforcing polyester cord.

Example 3

(Adhesive Composition Preparation)                     

Anthraquinone-based blue dispersion dye C.I. Disp. Anthraquinone-based yellow disperse dye C.I. Disp. The same procedure as in Example 1 was carried out except that 0.5 g of Yellow1 was used.

(RFL manufacturing)

It carried out in the same manner as in Example 1.

(Coated on polyester fiber)

In the bath containing the adhesive composition prepared above, the tire reinforcing polyester cord 1,500 denier / 2 go was passed at a speed of 15 to 30 m / min so that the adhesive was attached at 1 to 3% (based on a high component). The polyester cord was then dried at a temperature of 150 ° C. for 2 minutes and heat-treated at 220 ° C. for 2 minutes to first coat.

Thereafter, the tub containing the RFL prepared in Example 1 was passed, dried, and heat treated in the same manner as the primary coating to obtain a secondary coated polyester reinforcing polyester cord.

Example 4

(Adhesive Composition Preparation)

Anthraquinone-based blue dispersion dye C.I. Disp. Anthraquinone-based yellow disperse dye C.I. Disp. The same procedure as in Example 1 was carried out except that 0.5 g of Yellow1 was used.

(RFL manufacturing)                     

It carried out in the same manner as in Example 1.

(Coated on polyester fiber)

In the bath containing the adhesive composition prepared above, the tire reinforcing polyester cord 1,500 denier / 2 go was passed at a speed of 15 to 30 m / min so that the adhesive was attached at 1 to 3% (based on a high component). The polyester cord was then dried at a temperature of 150 ° C. for 2 minutes and heat-treated at 220 ° C. for 2 minutes to first coat.

Thereafter, the tub containing the RFL prepared in Example 1 was passed, dried, and heat treated in the same manner as the primary coating to obtain a secondary coated polyester reinforcing polyester cord.

Example 5

(Adhesive Composition Preparation)

Anthraquinone-based blue dispersion dye C.I. Disp. Anthraquinone Red Disperse Dyes C.I. Disp. The same procedure as in Example 1 was conducted except that 0.9 g of Red4 was used.

(RFL manufacturing)

It carried out in the same manner as in Example 1.

(Coated on polyester fiber)

In the bath containing the adhesive composition prepared above, the tire reinforcing polyester cord 1,500 denier / 2 go was passed at a speed of 15 to 30 m / min so that the adhesive was attached at 1 to 3% (based on solid content). The polyester cord was then dried at a temperature of 150 ° C. for 2 minutes and heat-treated at 220 ° C. for 2 minutes to first coat.

Thereafter, the bath containing the RFL prepared in Example 1 was passed, dried, and heat treated in the same manner as the primary coating to obtain a secondary coated polyester reinforcing polyester cord.

Comparative Example 1

(Adhesive Composition Preparation)

Anthraquinone-based blue dispersion dye C.I. Disp. Except that Blue6 was not used, it was carried out in the same manner as in Example 1.

(RFL manufacturing)

It carried out in the same manner as in Example 1.

(Coated on polyester fiber)

In the bath containing the adhesive composition prepared above, the tire reinforcing polyester cord 1,500 denier / 2 go was passed at a speed of 15 to 30 m / min so that the adhesive was attached at 1 to 3% (based on a high component). The polyester cord was then dried at a temperature of 150 ° C. for 2 minutes and heat-treated at 220 ° C. for 2 minutes to first coat.

Thereafter, the tub containing the RFL prepared in Example 1 was passed, dried, and heat treated in the same manner as the primary coating to obtain a secondary coated polyester reinforcing polyester cord.

Comparative Example 2

(Adhesive Composition Preparation)

Anthraquinone-based blue dispersion dye C.I. Disp. Anthraquinone Red Disperse Dyes C.I. Disp. The same procedure as in Example 1 was carried out except that 0.01 g of Red4 was used.

(RFL manufacturing)

It carried out in the same manner as in Example 1.

(Coated on polyester fiber)

In the bath containing the adhesive composition prepared above, the tire reinforcing polyester cord 1,500 denier / 2 go was passed at a speed of 15 to 30 m / min so that the adhesive was attached at 1 to 3% (based on a high component). The polyester cord was then dried at a temperature of 150 ° C. for 2 minutes and heat-treated at 220 ° C. for 2 minutes to first coat.

Thereafter, the tub containing the RFL prepared in Example 1 was passed, dried, and heat treated in the same manner as the primary coating to obtain a secondary coated polyester reinforcing polyester cord.

Using the tire reinforcement polyester cords obtained in Examples 1 to 5, and Comparative Examples 1 or 2, the content and adhesion of the adhesive coated on the polyester cord were measured by the following method, and the results are shown in Table 1 below. Shown in                     

At this time, the adhesive strength of the polyester cord for tire reinforcement and natural rubber obtained in Examples 1 to 5, and Comparative Examples 1 or 2, 100 kg, zinc oxide 3 kg, carbon black 29.8 kg, stearic acid 2.0 kg, pintaar (pine tar) After mixing the rubber composition mixed with 7.0 kg, 1.25 kg of mercaptobenzothiazole, 3.0 kg of sulfur, 0.15 kg of diphenylguanidine, and 1.0 kg of phenylbetanaphthylamine for 4 minutes at a temperature of 204 ° C. The adhesive force between the rubber and the cord was evaluated with a 1/4 inch U-shaped sample which was vulcanized.

division Example Comparative example One 2 3 4 5 One 2 Adhesive content (%) 2.9 2.8 3.0 2.8 3.1 2.5 2.5 Adhesive force (Kgf) 14.1 14.5 15.1 14.1 15.2 12.5 12.6

Through Table 1, it was confirmed that the polyester cord for reinforcing the tire of Examples 1 to 5 coated with the adhesive composition according to the present invention is excellent in adhesion to rubber compared to Comparative Example 1 or 2.

The adhesive composition for rubber reinforcement according to the present invention improves the adsorptivity of resorcinol-formaldehyde rubber latex (RFL) even with a small amount, thereby significantly improving the adhesion to rubber, and excellent workability as well as excellent high-quality tires, There is an effect that can be usefully used as a reinforcement of rubber products such as belts, hoses.

Claims (8)

An adhesive composition for rubber reinforcement comprising a polyepoxide, an aromatic urethane compound, and an aqueous solvent, the adhesive composition for rubber reinforcement comprising a dispersion dye which is a compound represented by the following general formula (1). [Formula 1]

delete The method of claim 1, Rubber dispersion composition for the rubber reinforcement comprising the dispersion dye 0.01 to 1.0% by weight based on the solids of the adhesive composition. The method of claim 1, The polyepoxide contains at least two epoxy per molecule, the molecular weight is at least 100, the epoxy equivalent adhesive composition for rubber reinforcement is a compound of at least 100. The method of claim 1, Adhesive composition for rubber reinforcement wherein the aromatic urethane compound is a compound represented by the following formula (2): [Formula 2]

In the formula (2), Ar is an organic compound residue having at least one benzene nucleus, X is an allyloxy, imioxy, lactam-N-yl radical, n is an integer of 2 or more. The method of claim 1, Rubber reinforcement adhesive composition wherein the polyepoxide is contained in a weight ratio of 0.1 to 10 with respect to the aromatic urethane compound. A polyester fiber coated with the rubber reinforcing adhesive composition according to claim 1. A polyester fiber coated with a mixture of the rubber reinforcing adhesive composition according to claim 1 and a resorcinol-formaldehyde rubber latex (RFL).