JP3030999B2 - Processing method of polyester fiber for rubber reinforcement - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for treating polyester fibers for reinforcing rubber with an adhesive, and more particularly to a reinforcing cord and fabric for rubber products such as tires, conveyor belts, V-belts and hoses. The present invention relates to a method for treating a polyester fiber material used for such purposes.

[0002]

2. Description of the Related Art Polyester fibers represented by polyethylene phthalate fibers have excellent strength, modulus and dimensional stability and are widely used as rubber reinforcing fibers.

[0003] However, since polyester fiber has poor adhesion to rubber as compared with nylon, rayon, etc., various methods for improving the adhesion between polyester fiber and rubber have been conventionally proposed.

[0004] Formulations using a oxy compound, an isocyanate compound, a halogenated phenol compound and the like have been developed as an adhesive for improving the adhesiveness between the polyester fiber and the rubber, and have been treated with these adhesives. Polyester fibers have come to be widely used as reinforcing materials for rubber products such as automobile tires, hoses and belts.

[0005] One example of a conventionally known representative adhesive treatment agent is a halogenated phenol such as 2,6-bis (2 ', 4'-dihydroxyphenylmethyl) -4-chlorophenol. A reaction product of a resorcinol-formalin initial condensate and a rubber latex (RFL solution) with a reaction product of urea, resorcinol and formaldehyde, and using a mixed adhesive treatment agent (Japanese Patent Publication No. 46-1125).
No. 1 publication). However, according to this method, the initial adhesive force (pulling force) under normal temperature conditions is excellent by increasing the amount of the adhesive attached and performing high-temperature heat treatment, but the rubber with the ply peeling off There was a problem that there was little.

On the other hand, as disclosed in Japanese Patent Publication No. 60-24226, a mixture of an epoxy compound, a block isocyanate and a rubber latex is applied to a first treatment liquid, and RFL is applied to a second treatment liquid. In the method of applying (liquid), the initial adhesive force (pulling force) is relatively high, and the amount of rubber between the plies is increased, but the treated cord becomes hard,
There has been a problem that molding processing becomes difficult and fatigue resistance is reduced. Further, with the first processing liquid, it is difficult to carry out the method industrially because the dirt of the processing machine cannot be completely removed.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to significantly improve the initial adhesive force (pulling force) with rubber and the adhesion of rubber between the plies, as well as to improve the heat-resistant adhesive force and to provide a high-quality product. It is an object of the present invention to provide a method for treating a polyester fiber for rubber reinforcement which can provide the following.

[0008]

To achieve the above object, according to the Invention The method of processing a rubber-reinforcing polyester fiber of the present invention, the cord-shaped rubber reinforcing polyester fiber, the first processing
Applying a treatment liquid, heat-treating, and then applying a second treatment liquid
Of polyester fiber for rubber reinforcement to be heat treated
In the first treatment liquid, bi Nirupirijin - styrene - butadiene copolymer latex (100 parts by weight) and Les zone <br/> arsine - I and a formaldehyde precondensate 2-10 parts by weight
That mixed compound (A) 100 parts by weight of, Po Riepokishido compound (B) 10 to 20 parts by weight, the triazine compound (C). 5 to
15 parts by weight, and, block polyisocyanate compound (D) and / or d Chiren'imin compound of (E) 20
~ 40 parts by weight of the treatment liquid, and
Second processing liquid, 100 parts by weight of rubber latex and Le Zorushi <br/> emissions - consisting of formaldehyde precondensate 12 to 25 parts by weight
Mixing compound (F) 100 parts by weight, preparative triazine compound (C) 5
15 parts by weight, and, block polyisocyanate compound (D) and / or d Chiren'imin compound of (E) 5
Characterized in that it is a treatment liquid obtained by mixing up to 20 parts by weight.
I do. Further, following the application of the first treatment liquid, 70 to 15
Drying at 0 ° C. and heat treating at 200-255 ° C .;
And drying at 70 to 150 ° C. following the application of the second treatment liquid
Preferably, the heat treatment is performed at 200 to 255 ° C.

The polyester fiber used in the present invention is in the form of polyethylene terephthalate or filament yarns, cords, woven fabrics and woven fabrics of high molecular weight linear polyester mainly composed of ethylene terephthalate units. Including.

[0010] The vinylpyridine-styrene-butadiene copolymer latex contained in the first treatment liquid of the present invention is obtained by copolymerizing butadiene with styrene and further copolymerizing vinylpyridine. It is a terpolymer latex.

The polyepoxide compound (B) contained in the first treatment liquid in the present invention is a compound containing two or more epoxy groups in one molecule, and specifically, glycerol, pentaerythritol Reaction products of polyhydric alcohols such as alcohol, sorbitol, ethylene glycol, polyethylene glycol, propylene glycol and polypropylene glycol with halogen-containing epoxides such as epichlorohydrin, resorcinol, Bis (4-hydroxyphenyl) dimethylmethane, phenol / formaldehyde resin, resorcin / formaldehyde resin, and other reactive products of halogen-containing epoxides with polyvalent phenols, bis- (3,4-epoxy- 6-methyl-dicyclohexylmethyl) adipate and 3,
A polyepoxide compound obtained by oxidizing an unsaturated bond such as 4-epoxycyclohexene epoxide. Preferred are reaction products of polyhydric alcohols and epichlorohydrin (polyglycidyl ether compounds of polyhydric alcohols).

Next, the triazine compound (C) in the present invention includes cyanuric acid, isocyanuric acid, and 2.
It is characterized in that one or a mixture of plural kinds selected from 4.6-ethyloyl-S-triazine, triallyl isocyanurate and trihydroxyethyl isocyanurate is used.

The blocked polyisocyanate compound (D) and / or ethyleneimine compound (E) include tolylene diisocyanate, metaphenylene diisocyanate, diphenyl methane diisocyanate. −
Polyisocyanate compounds such as octanol, hexamethylene diisocyanate and triphenylmethane triisocyanate; phenols such as phenol, cresol and resorcin; ε-caprolactam, valerolactam, etc. Lactams, oximes such as acetoxime, methyl ethyl ketone oxime and cyclohexane oxime, and reaction products with blocking agents such as ethyleneimine. Among these compounds, aromatic polyisocyanate compounds blocked with ε-caprolactam and aromatic ethylene urea compounds such as diphenylmethane diethylene urea give good results.

The rubber latex used in the second treatment liquid includes vinylpyridine-styrene-butadiene copolymer latex, styrene-butadiene latex, acrylonitrile-butadiene latex, chloroprene latex, chlorosulfone Polyethylene latex, acrylate latex, natural rubber latex and the like are appropriately used.

Next, the first processing liquid used in the present invention will be described. Here, a mixture (A) in which 2 to 10 parts by weight of a resorcinol-formalin precondensate is mixed with 100 parts by weight of a vinylpyridine-styrene-butadiene copolymer latex is used. Preferably, the proportion of the resorcinol-formalin precondensate is 3 to 8 parts by weight. More preferably, the resorcinol-formalin condensate is a novolak-type condensate obtained by condensing resorcinol-formalin under an acid catalyst. Things are good. If the amount of the resorcin-formalin condensate is less than 2 parts by weight, the processing machine is stained.

The resorcinol-formalin precondensate is obtained under an alkali catalyst, and the molar ratio of resorcinol-formalin is preferably 0.75 to 2.00 mol of formalin to 1 mol of resorcinol. More preferably, it is in the range of 0.75 to 1.50 mol. When a novolak condensate of resorcinol-formalin is used, it is preferable to dissolve it in an aqueous alkali catalyst solution and then add formalin to make the same molar ratio as the resorcinol-formalin initial condensate.

In the first processing solution, the mixture (A)
100 parts by weight of polyepoxide compound (B) 10
To 20 parts by weight, 5 to 15 parts by weight of a triazine compound (C), and 20 to 40 parts by weight of a blocked polyisocyanate compound (D) and / or an ethyleneimine compound (E). Otherwise, the object of the present invention cannot be achieved.

That is, the polyepoxide compound (B),
If the amount of the blocked polyisocyanate compound (D) and / or the amount of the ethyleneimine compound (E) is less than the above-mentioned mixing range, the initial adhesive strength is low.

If the mixing range of the triazine compound (C) is less than 5 parts by weight, a high heat-resistant adhesive strength cannot be obtained,
If the amount is more than 15 parts by weight, the rubber adhesion rate of peeling between plies decreases, which is not preferable.

The first processing solution usually has a solid concentration of 5 to 20%.
The polyester is treated so that the adhesion ratio to the polyester fiber is 2.5 to 6.0% based on the polyester fiber in a dry weight ratio. The heat treatment after applying the first treatment liquid is usually performed at 70 to 150 ° C. for 0.5 to 5 minutes,
This is performed at 255 ° C. for 0.3 to 5 minutes, but can be performed without drying.

Next, as the second treatment liquid, a mixture (F) in which 12 to 25 parts by weight of a resorcinol-formalin precondensate is mixed with 100 parts by weight of rubber latex according to the rubber to be adhered is used. The rubber latex used here is suitable for the rubber to be adhered, and specifically, vinyl pyridine-styrene-butadiene copolymer latex, styrene-butadiene latex, chloroprene latex, chlorosulfonated polyethylene latex, acrylonitrile-butadiene System latex, acrylate latex, natural rubber latex and the like are used.

The resorcinol-formalin precondensate is obtained in the presence of an alkali catalyst. The molar ratio of resorcinol-formalin is preferably 0.75 to 2.00 mol, more preferably 0.75 to 2.00 mol, for 1 mol of resorcinol. ,
It is in the range of 0.75 to 1.50 mol. The resorcin-formalin condensate is more preferably a novolak-type condensate obtained by condensing resorcin-formalin under an acid catalyst. When a novolak-type condensate is used, it is preferable to dissolve it in an aqueous alkali catalyst solution and then add formalin to obtain a molar ratio similar to that of the resorcinol-formalin initial condensate.

In the second treatment liquid, the mixture (F) 10
High adhesion by adding 5 to 15 parts by weight of triazine compound (C) and 5 to 20 parts by weight of blocked polyisocyanate compound (D) and / or ethyleneimine compound (E) to 0 parts by weight. Power is gained.

[0024] The second processing solution usually has a solid content of 5 to 15%.
And is treated so that the adhesion ratio to the polyester fiber is 0.2 to 3.0% with respect to the polyester fiber in a dry weight ratio. The heat treatment after the application of the second treatment liquid is usually performed at 70 to 150 ° C. for 0.5 to 5 minutes,
This is performed at 255 ° C. for 0.3 to 5 minutes, but can be performed without drying.

The polyester fiber thus treated and heat-treated with the adhesive treatment liquid is embedded in a rubber composition mainly composed of natural rubber or synthetic rubber, vulcanized under pressure, and Strongly adhered.

[0026]

Next, the present invention will be specifically described with reference to examples. Each measurement value was obtained by the following method.

T-initial adhesive strength and T-heat resistant adhesive strength: J
According to the adhesive force-A method of IS L-1017 (1983), the treated code was embedded in unvulcanized rubber under the following conditions.
Press vulcanization is performed under pressure at an initial adhesive strength of 150 ° C. for 30 minutes and at a heat resistant adhesive strength of 170 ° C. for 70 minutes. After cooling, the cord is pulled out of the rubber block at a speed of 30 cm / min. It is expressed in Kg / cm.

Peeling between plies (rubber adhesion rate, peeling force): A 2-ply processing code is embedded in rubber as a cross ply (code driving density 28 / inch) forming an angle of 90 degrees. Press vulcanization is performed at 150 ° C. for 30 minutes under pressure, and after cooling, both plies are peeled off at a pulling speed of 10 cm / min. The rubber adhesion rate is a percentage of the cord surface peeled from the rubber, which is visually observed, and the portion of the cord surface where the rubber is adhered is expressed as a percentage. Expressed in 2 cm.

In the above-mentioned evaluation of adhesion, an unvulcanized rubber containing carcass containing natural rubber as a main component was used as the rubber compound.

Fatigue resistance (Good-rich method disk fatigue): According to JIS L-1017 (1983).
In other words, a rubber block filled with polyester fibers
The strength retention rate after 100 hours of fatigue after repeated mounting at 1705 rpm for 48 hours is shown by attaching to the periphery of two disks tilted so that the elongation rate is 5% and the compression rate is 15%. The rubber compound used was the same as that used for the bonding.

Code strength: JIS using Tensilon
1 Measured according to L-1017 (1983).

Code hardness: The code is straightened,
Cut to 2cm and use a tensilon tensile tester bridge (1
cm interval, φ: 0.6 mm), hook the hook bar (φ: 0.6 mm) perpendicular to the code on the center of the code, and lower it (2
cm / min), the maximum stress was determined, and the value was defined as the code hardness.

Examples 1 to 7 As the mixture (A) in the first treatment liquid, formalin was used in an amount of 0.7 mol per mol of resorcinol in the presence of caustic soda.
A resorcinol-formalin precondensate obtained by reacting 5 to 1.50 mol was mixed with vinylpyridine-styrene-butadiene copolymer latex at a predetermined ratio shown in Table 1, and aged for 24 hours. Was used. Then, with respect to 100 parts by weight of this mixture (A), water (B) obtained by adding water to polyglycerol polyglycidyl ether using a homogenizer and trihydroxyethyl isocyanurate (C) were used. Aqueous dispersion of 4,4'-diphenylmethane diisocyanate (D) or diphenylmethane-bis 4,4'-N, N'-diethylamine (E) dissolved in water and blocked with ε-caprolactam Were mixed at a predetermined ratio shown in Table 1 to obtain a first bath treatment liquid having a solid content of 15%.

On the other hand, the second processing solution was obtained by reacting 0.75 to 1.50 mol of formalin with respect to 1 mol of resorcinol in the presence of caustic soda in the same manner as in the first processing solution. Resorcin-formalin precondensate and vinylpyridine-styrene-butadiene copolymer latex,
The mixture was mixed at a predetermined ratio shown in Table 1 and aged for 24 hours to prepare a mixture (F). This mixture (F)
100 parts by weight of diphenylmethane-bis 4,4 '
A solution of trihydroxyethyl isocyanurate (C) dissolved in water in an aqueous dispersion of -N, N'-diethyleimine (D) was mixed at a predetermined ratio shown in Table 1 to obtain a solid content of 9%. % Of the second treatment liquid was obtained.

Two 1500 filament multifilaments obtained by melt-spinning polyethylene terephthalate having a yarn viscosity of 0.95 and twisting were twisted at a twist of 40 times / 10 cm and a twist of 40 times / 10 cm. It was immersed in the first bath treatment liquid (solid content: 4.0% by weight) using a computer treating machine (manufactured by Ritzler Co.), and then heated to 130 ° C.
For 120 seconds and then heat treated at 240 ° C. for 45 seconds.

Next, it was immersed in the second treatment liquid (solid content adhesion amount: 0.8% by weight), dried at 100 ° C. for 100 seconds, and subsequently heat-treated at 240 ° C. for 60 seconds. Table 1 shows the evaluation results of the obtained polyester fibers.

The contents of the symbols in Table 1 are as follows. X: resorcinol - the molar ratio of the formaldehyde precondensate, Ho Le <br/> Marine (F) / resorcin (R) Y: vinylpyridine - styrene - butadiene copolymer La
For Tex 100 parts by weight, Les Zorushin - blending ratio (parts by weight) of formaldehyde precondensate B: proportion of Poriepoki Sid of compound (parts by weight) C: blending ratio (parts by weight) of a triazine compound D: block Kudoporii isocyanate the mixing ratio of the compound (parts by weight), E: proportion of ethylene imination compound (parts by weight) Note, B, C, D, the mixing ratio of E are mixed compound (a) or
Mixture (F) indicated by Weight ratio 100 parts by weight.

[0038]

[Table 1]

Comparative Examples 1 to 3 In the above Examples, the proportions of the resorcinol-formalin precondensate and the butadiene-styrene-vinylpyridine copolymer latex were changed as shown in Table 2. The polyester fiber was treated under the same conditions as in Example 1 (Comparative Example 1).

In the above example, polyester fibers were treated under the same conditions as in the example except that the mixing ratio of trihydroxyethyl isocyanurate (C) was changed as shown in Table 2. Examples 2 and 3).

The evaluation results of each of the obtained polyester fibers are shown in Table 2.

[0042]

[Table 2]

Example 8 The epoxy compound (B) in Examples 1 to 7 was replaced by polyglycidyl ether, glycerol polyglycidyl ether and sorbitol, instead of polyglycerol polyglycidyl ether. Even when the polyglycidyl ether was changed, the characteristics of the obtained polyester fiber were as described in Examples 1 to 7.
It was almost the same.

[0044]

The polyester fiber treated by the method of the present invention has a higher initial adhesive strength with rubber,
The heat-resistant adhesive strength is improved, and the roller is not stained in the processing step and dip scum adheres to the cord. Therefore, according to the method of the present invention, productivity is improved and a high-quality product can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI D06M 15/41 D06M 15/41 15/564 15/564 // D02G 3/48 D02G 3/48 D06M 101: 32 (58) Survey Field (Int.Cl. ⁷ , DB name) C08J 5/06 D06M 13/00-15/715 D02G 3/48

Claims (2)

(57) [Claims] 1. A cord-like polyester fiber for reinforcing rubber.
, A first treatment liquid is applied thereto, and a heat treatment is performed.
Of polyester fiber for rubber reinforcement
In the processing method, the first treatment liquid, bi Nirupirijin - styrene - butadiene copolymer latex 100 wt
Parts and Les Zorushin - formalin initial condensate 2 to 10 parts by weight
Mixing compounds consisting of (A) 100 parts by weight of, Po Riepokishido compound (B) 1 0 to 20 parts by weight, the triazine compound (C) 5 to 15 parts by weight, and, block polyisocyanate compound (D) and / or d Chiren'imin compound treatment liquid der obtained by mixing 20 to 40 parts by weight of the (E)
Ri, and the second treatment liquid, rubber latex 100 parts by weight of les Zorushin - mixing compound consisting of formalin precondensate 1 2-25 parts by weight (F) 100 parts by weight, preparative triazine compound (C) 5-15 parts by weight, and, block polyisocyanate compound (D) and / or d Chiren'imin compound treatment liquid der obtained by mixing 5 to 20 parts by weight of the (E)
A method for treating a polyester fiber for rubber reinforcement, comprising: 2. The method according to claim 1, further comprising the step of:
Drying at 0 ° C. and heat treating at 200-255 ° C .;
And drying at 70 to 150 ° C. following the application of the second treatment liquid
And heat treatment at 200 to 255 ° C.
The method for treating a polyester fiber for rubber reinforcement according to claim 1.