JPH06341061A - Method and agent for treating polyester fiber material for reinforcing rubber - Google Patents

Abstract

PURPOSE:To provide a method for treating a polyester fiber material for reinforcing rubbers, giving a polyester fiber material for reinforcing the rubbers, excellent in the adhesive force of the polyester fibers to the rubber, especially in the heat-resistant adhesive force, improved in heat resistance in the rubbers (in a rubber test) and fatigue resistance, and having a high quality, and a treating agent thereof. CONSTITUTION:A method for treating a polyester fiber material for reinforcing rubbers comprises treating the polyester fiber material with a treating agent comprising A: an early condensate (RF) produced by reacting resorcinol (R) with formaldehyde (F) in a molar ratio of 1.00:0.50 to 1.00:2.00, B: a rubber latex (L), C: an ammonia aqueous solution-soluble resin obtained by reacting a substituted phenolic compound and a formaldehyde resin with a dihydroxybenzene sulfide compound produced by combining two dihydroxybenzene compounds with each other through a sulfur atom, and D: a triazine compound in an A/B compounding ratio (weight ratio) of 100/(200-1000), a (A+B)/C of 100/(10-50), and a (A+B+C)/D of 100/(1-5), and subsequently subjecting the treated polyester material to a thermal treatment.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an adhesive for treating a polyester fiber material for rubber reinforcement, and more specifically, for reinforcing 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 cords and textiles for use, and a treating agent used for this treatment.

[0002]

2. Description of the Related Art Fibers made of polyester typified by polyethylene terephthalate fibers are widely used as rubber-reinforcing fibers because of their excellent strength, modulus and dimensional stability.

However, since polyester fibers have poor adhesion to rubber as compared with other fibers such as nylon and rayon, various methods for improving the adhesion between polyester fibers and rubber have heretofore been proposed. Has been done.

As a conventional method for improving the adhesion of polyester fibers, various adhesive formulations using an epoxy compound, an isocyanate compound, a halogenated phenol compound, etc. have been developed.
Epoxy compound and block isocyanate in the first treatment liquid
A method of applying a mixed solution of rubber and latex and applying a solution (RFL solution) consisting of an initial condensate of resorcinol and formaldehyde and rubber latex as the second processing solution after the heat treatment and then heat treating (Japanese Patent Publication No. 60-24226). Gazette), a liquid (RFL liquid) consisting of an initial condensate of resorcin and formaldehyde and a rubber latex,
-Bis (2 ', 4'-dihydroxyphenylmethyl)-
A method for treating with an adhesive solution containing 4-chlorophenol (Japanese Patent Publication No. 46-11251) and a method for treating with an adhesive solution containing resulfin, formaldehyde and latex (RFL) containing a sulfide compound by sulfur crosslinking with resorcin. (JP-A-48-8733) and the like have been proposed.

However, the above Japanese Patent Publication No. 60-2422.
The polyester cord treated by the method described in JP-A No. 6-90 is adhesive as compared with those obtained by the method described in JP-B-46-11251 and JP-A-48-8733. However, the cord is hard, molding process becomes difficult, and fatigue resistance is lowered.

The methods described in JP-B-46-11251 and JP-A-48-8733 can provide a treated cord having a certain degree of adhesive strength, but the adhesive strength is still sufficient. However, the polyester fiber treated by these methods has a large adhesive force between the rubber and the polyester fiber when exposed to a high temperature for a long time in a rubber product, aiming at the development of new applications. There is a problem that the heat resistant adhesive strength is inferior because the adhesive strength is lowered.

[0007]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems in the prior art, and is excellent in the adhesive force between polyester fiber and rubber, especially in heat resistant adhesive force, and in rubber. Heat resistance (in rubber test)
Another object of the present invention is to establish a method for treating a rubber-reinforcing polyester fiber material that improves fatigue resistance and provides a high-quality rubber-reinforcing polyester fiber, and to provide a treating agent used for this treatment.

[0008]

In order to achieve the above object, a method of treating a polyester fiber material for rubber reinforcement according to the present invention comprises: Resorcin (R) and formaldehyde (F) molar ratio 1.0
Initial condensate (RF) obtained by reacting within the range of 0: 0.50 to 1.00: 2.00, B.I. Rubber latex (L), C.I. Ammonia aqueous solution soluble resin obtained by reacting a sulfide compound of dihydroxybenzene in which two or more molecules of dihydroxybenzene are bonded via sulfur, a substituted phenol compound and a formaldehyde resin, and D.I. It is composed of a triazine compound, and their compounding ratio (weight ratio) is A / B = 100/200 to 100.
0, A + B / C = 100 / 10-50, A + B + C / D
= 100/1 to 5 is applied, and then heat treatment is performed.

The treatment agent for the rubber-reinforcing polyester fiber material of the present invention is A. The molar ratio of resorcin (R) and formaldehyde (F) is 1.00: 0.50-1.00:
The initial condensate (R
F), B. Rubber latex (L), C.I. Ammonia aqueous solution soluble resin obtained by reacting a sulfide compound of dihydroxybenzene in which two or more molecules of dihydroxybenzene are bonded via sulfur, a substituted phenol compound and a formaldehyde resin, and D.I. It is composed of a triazine compound, and their compounding ratio (weight ratio) is A / B =
100/200 to 1000, A + B / C = 100/10
.About.50, A + B + C / D = 100 / 1-5.

The polyester fiber used in the present invention is made of polyethylene terephthalate or a high molecular weight linear polyester mainly composed of ethylene terephthalate units, and as the polyester fiber material, filament yarn, cord, woven fabric, And woven fabrics and the like.

On the other hand, A. which is a constituent component of the treating agent of the present invention. As the initial condensate of resorcin and formaldehyde, resorcin and formaldehyde are mixed in a molar ratio of 1.
00: 0.50-1.00: 2.00, preferably 1.
An initial condensate obtained by condensation with an alkali or acidic catalyst in a ratio of 00: 0.75 to 1.00 to 1.50 is suitable.

Further, B. As the rubber latex, vinyl pyridine-styrene-butadiene copolymer latex, styrene-butadiene latex, polybutadiene rubber latex, acrylonitrile-butadiene latex, chloroprene latex, natural rubber latex, etc., which are suitable for the adherend rubber, are appropriately used. To be done.

C. which is a constituent of the treating agent of the present invention. As the sulfide compound of dihydroxybenzene which is a starting material of the aqueous ammonia-soluble resin, dihydroxybenzene such as resorcin, hydroquinone, catechol or an alkyl-substituted product thereof, preferably a sulfide compound of resorcin is used. Here, when dihydroxybenzene has an alkyl group, the alkyl group preferably has 1 to 4 carbon atoms, and particularly preferably a methyl group. By reacting such dihydroxybenzene with sulfur or sulfur dichloride having reactivity with the aromatic ring, a sulfide compound in which two or more molecules of dihydroxybenzene are bound via sulfur can be obtained.

Similarly, C.I. Examples of the substituted phenol compound which is a starting material of the aqueous ammonia solution resin include:
Parachlorophenol, orthochlorophenol, parabromophenol, paraiodophenol, orthobromophenol, orthoiodophenol, orthocresol, paracresol, para-tertiary butylphenol.
And 2,5-dimethylphenol and the like,
Among them, parachlorophenol and parabromophenol
, Paracresol, and para-tert-butylphenol, particularly parachlorophenol, are preferably used.

It was possible to obtain such a substituted phenol compound by condensing with formaldehyde in the presence of an alkali catalyst (sodium hydroxide), or by reacting the substituted phenol compound in advance in the presence of an acid catalyst. The substituted phenol compound and the formaldehyde-soluble resin can be obtained by reacting the condensate with formaldehyde in the presence of an alkali catalyst.

Then, the above-mentioned sulfide compound of dihydroxybenzene, the above-mentioned substituted phenol compound and formaldehyde-soluble resin {for example, 2,6-bis (2
′, 4′-Dihydroxyphenylmethyl) -4-chlorophenol}, and water are stirred, and then water is distilled off, whereby the chlorophenol unit and the resorcin unit are bonded via the sulfur and methylene groups. C. Aqueous solution of aqueous ammonia is obtained, which is usually 3 to
It is dissolved in 5N ammonia water and used as a 20% resin solution.

Further, D.I. which is a constituent component of the treating agent of the present invention. Examples of the triazine compound include cyanuric acid, isocyanuric acid, 2,4,6-ethyloyl-S-triazine, triallyl isocyanurate, trihydroxyethyl isocyanurate, and the like. It can also be used in the form of a mixture of plural kinds.

Next, the blending ratio of each component in the treatment liquid according to the present invention will be described.

First, A. Based on 100 parts by weight of the resorcinol-formaldehyde initial condensate, B.I. Rubber latex, for example, vinylpyridine-styrene-butadiene copolymer latex 300 to 1000 parts by weight, preferably 40.
0 to 900 parts by weight are mixed to obtain a mixed solution.

The component A may be a novolac type condensate obtained by condensing resorcin-formaldehyde under an acid catalyst.

Here, A. The resorcin-formaldehyde initial condensate was obtained under an alkaline catalyst, and the molar ratio of resorcin / formaldehyde was resorcin-1.
The formaldehyde content is preferably 0.50 to 2.00 mol, and more preferably 0.75 to 1.50 mol. When using a resorcinol-formaldehyde novolak type condensate, it is preferable to dissolve it in an alkaline catalyst aqueous solution and then add formaldehyde to obtain the same molar ratio as that of the resorcinin-formaldehyde initial condensate.

In the above-mentioned component A, if the molar ratio of formaldehyde is less than the above range, not only the treatment code becomes tacky but also the processing machine is contaminated, and if it exceeds the above range, the adhesive strength is lowered. It tends to occur, which is not preferable.

Further, in the above A component and B component, B.
If the compounding ratio of the rubber latex is less than the above range, the adhesive strength will be lowered, and if it is more than the above range, the processor will be soiled, which is not preferable.

Then, a sulfide compound of resorcin, a parachlorophenol compound and a formaldehyde resin were dissolved in ammonia water to obtain C.I. Ammonia aqueous solution soluble resin is added to 100 parts by weight of the above-mentioned A component and B component in total.
The amount is 10 to 50 parts by weight, preferably 20 to 40 parts by weight.

C. When the blending ratio of the aqueous ammonia solution-soluble resin is less than the above range, the adhesive force is low, and even when it is too large, the effect of improving the adhesive force decreases, which is not preferable.

In addition, D. The compounding ratio of the triazine compound is preferably in the range of 1 to 5 parts by weight with respect to 100 parts by weight of the total of the above components A, B and C, and if less than 1 part by weight, sufficient adhesive force cannot be obtained, On the contrary, if the amount is too large, the adhesive force tends to decrease, which is not preferable.

The treating agent used in the present invention is the above-mentioned RFL solution consisting of components A and B, usually at a temperature of 20 to 30 ° C.
After aging for 4 hours or more, a sulfide compound of resorcin, a parachlorophenol compound and a formaldehyde resin were reacted with C.I. Ammonia aqueous solution soluble resin; It is prepared by adding and mixing a triazine compound.

The solid concentration of the treating agent is 12 to 25.
It is used in a weight percentage, and the adhesion ratio to the polyester fiber is preferably in the range of 3.0 to 8.0% based on the dry weight of the polyester fiber.

The polyester fiber material to which the treating agent is applied is then usually dried at 70 to 150 ° C. for 0.5 to 5 minutes and then heat treated at 230 to 255 ° C. for 0.5 to 5 minutes. By this, a strong adhesive film is formed on the fiber surface, but in some cases, drying can be omitted.

When the temperature of the heat treatment is less than 230 ° C., the formation of the adhesive film on the fiber and the reaction with the rubber are insufficient, so that a satisfactory adhesive force may not be obtained.
When the temperature is higher than 5 ° C., the treatment agent film formed on the fiber is deteriorated to lower the adhesive strength, or the polyester forming the fiber material is thermally decomposed, and the strength of the fiber is lowered, which is not preferable.

It should be noted that the treatment with the treating agent in the present invention usually requires one-step treatment, but in some cases,
After the first-stage treatment with the treatment agent of the present invention, the second-stage treatment with a normal RFL solution, or the second-stage treatment with the treatment agent of the present invention having a different concentration (usually lowering the second-stage concentration) You may.

The polyester fiber material thus treated with the treating agent and heat-treated is embedded in a rubber composition mainly composed of natural rubber or synthetic rubber,
It is heated under pressure to be vulcanized and bonded to rubber.

[0033]

EXAMPLES Next, the present invention will be explained concretely by way of examples.

In the following examples, as the rubber composition, the rubber used for ordinary tire carcass was used.

Each measured value is obtained by the following method.

T-initial adhesive strength and T-heat resistant adhesive strength Adhesive strength of JIS L-1017 (1983) -Under the unvulcanized rubber, the treated cord was embedded under the following conditions according to the A method.
The initial adhesive strength under pressure is 150 ° C, and the heat-resistant adhesive strength for 30 minutes is 1
After press vulcanization at 70 ° C. for 70 minutes and allowing to cool, the cord was pulled out from the rubber block at a speed of 30 cm / min, and the withdrawal load was expressed in Kg / cm.

Code peeling adhesive strength treatment This shows the adhesive strength between the cord and the rubber. Embed 7 cords near the surface of the rubber sheet at 20 ℃ at 20 ℃
It was vulcanized under a pressure of 30 kg / cm for 3 minutes. From the obtained vulcanizate, 5 cords (with both ends removed) were removed from the rubber sheet by 3
The force required for peeling at a speed of 00 mm / min is displayed in Kg / 5 lines.

[0038] In rubber The strength retention after vulcanization in heat resistant rubber is shown. The cord was taken out of the rubber after vulcanization at 170 ° C./3 hrs under constant length in the rubber, and the tensile strength remaining rate at a rate of 200 mm / min was shown as a percentage.

Fatigue resistance (Goodrich disc fatigue)
JIS L-1017 (1983) A rubber block filled with a polyester fiber material has an elongation rate of 5% and a compression rate of 15
% Is a percentage of the remaining strength after being attached around two disks tilted so as to be 100% and repeatedly fatigued at 1705 rpm for 48 hours.

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

The co - JISl using the de powerful Tensilon L-1017 (198
3 years).

Cord hardness The cord was straightened and cut into 2 cm, and the bridge of the Tensilon tensile tester (1 cm interval, φ: 0.6 m) was used.
m)), and hook bar (φ: 0.
6 mm) was applied to the center of the cord and lowered (2 cm / min) to find the maximum stress, which was defined as the cord hardness.

Examples 1 to 8 Formalin (F) was added to 1 mol of resorcin (R) in the presence of caustic soda.
The initial condensate (RF) obtained by reacting with the ratio shown in Table 1 (0.75 to 1.50 mol) and the vinylpyridine-styrene-butadiene copolymer latex (L) are prescribed in Table 1. The mixture was mixed in the following ratio and aged at 25 ° C. for 24 hours.

In the RFL solution thus obtained, a soluble resin (C) prepared by dissolving a reaction product of a resorcin sulfide compound, a parachlorophenol compound and a formaldehyde resin in an aqueous ammonia solution and trihydroxyethyl isocyanurate ( What melt | dissolved D) in water was mixed at the predetermined ratio shown in Table 1, and the processing agent of solid content concentration 20% was obtained.

On the other hand, two polyethylene terephthalates having a yarn viscosity of 0.95 were melt-spun and drawn, and two 1500 denier multifilaments were twisted with a lower twist of 40 times / 10 cm and an upper twist of 40 times / 10 cm. The fibrous material twisted into a cord by means of a cord was dipped in each of the above treating agent solutions using a computer treating machine (manufactured by Ritzler Co., Ltd.) (solid content: 5.0% by weight). And then dried at 130 ° C for 120 seconds,
Table 1 also shows the characteristic evaluation results of the obtained treated cords which were subsequently heat treated at 250 ° C. for 60 seconds.

The symbol contents in Table 1 are as follows. X: Formalin (F) / resorcinol (R) molar ratio A: RF amount (parts by weight) B: Vinyl pyridine-styrene-butadiene copolymer latex (parts by weight) C: Resorcinol sulfide compound and parachlorophenol Soluble resin [A, B (RFL) obtained by dissolving a reaction product of a compound and a formaldehyde resin in an aqueous ammonia solution
Of the mixture liquid to 100 parts by weight of the mixed solution] D: Triazine compound (indicates the weight ratio of 100 parts by weight of the mixed solution of A, B, and C) The unit of each characteristic is as follows. T-adhesion: Kg / cm Code peeling adhesion: Kg / 5 pieces Heat resistance in rubber:% Fatigue resistance:% Code strength: Kg Code hardness: g / piece

[0047]

[Table 1]

[Comparative Examples 1 and 2] R / F in Example 2
A treatment code was obtained in the same manner as in the above example except that the molar ratio of was changed as shown in Table 2 and the addition of trihydroxyethyl isocyanurate was omitted.

Table 2 also shows the evaluation results of the characteristics of these processing codes.

[Comparative Examples 3 to 4] R / F in Example 2
While changing the molar ratio of the compound as shown in Table 2 and replacing the trihydroxyethyl isocyanurate with VALCABOND E {2,6-bis (2 ', 4'-dihydroxyphenylmethyl) -4-chlorophenol}. Or Sumikano
A treatment code was obtained in the same manner as in the above example except that 28 parts by weight of each of 750 (resorcin sulfide compound) was used.

Table 2 also shows the characteristic evaluation results of these processing codes.

In Table 2, CE means VALCABOND E and CF means SUMICANOL 750.

[0053]

[Table 2]

[0054]

EFFECT OF THE INVENTION The polyester fiber material treated by the method of the present invention is superior in adhesive strength to rubber, particularly heat resistant adhesive strength, and heat resistance in rubber (in rubber test) as compared with conventional methods. Further, fatigue resistance is improved, durability is improved, and a high quality rubber-reinforced fiber product can be provided.

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Claims (2)

[Claims] 1. A method of treating a polyester fiber material for rubber reinforcement, wherein the polyester fiber material for rubber reinforcement comprises:
A. An initial condensate (RF) obtained by reacting resorcin (R) and formaldehyde (F) in a molar ratio of 1.00: 0.50 to 1.00: 2.00; Rubber latex (L), C.I. Ammonia aqueous solution soluble resin obtained by reacting a sulfide compound of dihydroxybenzene in which two or more molecules of dihydroxybenzene are bonded via sulfur, a substituted phenol compound and a formaldehyde resin, and D.I. It is composed of a triazine compound, and their compounding ratio (weight ratio) is A / B = 100/200 to 100.
0, A + B / C = 100 / 10-50, A + B + C / D
A method of treating a polyester fiber material for rubber reinforcement, which comprises applying a treating agent of 100/1 to 5 and then performing heat treatment. 2. A. The molar ratio of resorcin (R) and formaldehyde (F) is 1.00: 0.50 to 1.00: 2.
Initial condensate (RF) obtained by reacting within the range of 00,
B. Rubber latex (L), C.I. Ammonia aqueous solution soluble resin obtained by reacting a sulfide compound of dihydroxybenzene in which two or more molecules of dihydroxybenzene are bonded via sulfur, a substituted phenol compound and a formaldehyde resin, and D.I. It is composed of a triazine compound and their compounding ratio (weight ratio) is A / B = 100.
/ 200-1000, A + B / C = 100 / 10-5
0, A + B + C / D = 100 / 1-5, The processing agent of the polyester fiber material for rubber reinforcement characterized by the above-mentioned.