JPS6011630B2 - Tire cord impregnating agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a tire cord impregnating agent and to a glass-filled tire cord containing an impregnating agent that is particularly suitable for glass-filled tire cord.

By using the impregnating agent of the present invention, the bond between the elastomer and the tire cord is significantly improved. It is known to use elastomeric products reinforced with fibers, especially glass fibers.

Such products are used as automobile tires, drive belts, compare belts, etc. When using glass fiber,
The fibers are typically sized and individual fibers are plied with other strands and burned to form yarns, threads or cords. The plurality of strands are then impregnated with a latex conductor, which is usually compatible with the elastomer. The strands are then dried to establish the impregnating agent on the outer surface of the glass fibers, and then cooled. A variety of tire cord impregnating agents can be used.

Generally, these are resorcinol formaldehyde resins mixed with various latexes such as neoprene latex, butadiene latex, etc. Neoprene rubber latex is the key ingredient in many such impregnating agents.
Although the impregnating agent according to the invention can be used in any reinforcing medium, such as natural fibres, synthetic fibres, glass fibres, and steel, it will be described here for use in the treatment of glass fibres.

However, it is clear that the invention is not limited thereto. The impregnating agent according to the invention can be used on various types of glass fibers.

Preferably about 0.35 x 0.0254 to about 0.5 x 0.
E fibers with a diameter of 0254 (E fi skin)
used for The glass fibers may be sized with the usual sizing agents used in elastomeric reinforcement or used unsized. As used herein, the term "glass fiber" refers to
Refers to the continuous fibers formed by rapidly attenuating multiple streams of molten glass and the strands formed when the continuous glass fiber filaments are concentrated into the desired configuration.

The term also refers to plying and/or plying a large number of strands.
or yarns and cords formed by firing, and the striped and non-green woven fibers that form these glass fiber strands, yarns or cords. Furthermore, the term "glass fiber" refers to discontinuous fibers formed by blowing high-pressure fluid or air onto multiple streams of molten glass, and to drafting these discontinuous fibers to form a sliver; It means the yān that was formed by concentrating this to form a yān.

Still further, the term refers to knitted or non-woven fabrics formed of yarns of discontinuous fibers, as well as continuous and discontinuous fibers in the form of strands, urso cords, and knitted fabrics. The term "elastomer" in this text refers to vulcanized or uncured natural rubber in a cured or uncured state, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, chloroprene, isoprene, It means synthetic organic elastomer monopolymers and copolymers such as neoprene, isobutyl rubber, etc., and their cured and uncured, elastomer monopolymers and copolymers in their vulcanized and unvulcanized states.

A preferred embodiment of the invention provides at least one coated with a residue obtained by drying an aqueous composition consisting essentially of a resorcinol-formaldehyde resin, a vinylpyridine terpolymer, a butadiene latex and a wax emulsion. glass fiber.

The composition is substantially free of neoprene latex.

Another aspect of the invention provides that a portion of the Ptagene latex is
It is substituted with a polymer such as styrene-butadiene copolymer latex.

Another aspect of the invention provides that a portion of the butadiene latex is
It is substituted with nitrile-butadiene latex.

In addition, a desired resorcinol-formaldehyde resin initial condensate is used.

Preferably, about 75%
% total solids by weight. The resorcinol-formaldehyde resin precondensate is used in an amount of about 3-4% by weight of the dried composition. In a preferred embodiment, a proportion of about 3% by weight, based on dry residue, is used. Suitable precondensates can be prepared as described below, and the desired ones are commercially available.

For example, Shenectady SRF 1524 from Shenectady Chemical Co., Penacolite R2170 and R220 from Kotspers Company, Inc.
0, Allophane (~oSasane) 779 available from Ashland Chemical Company, Columbus, Ohio. Various vinylpyridine terpolymers can be used. Preferably, a butadiene-styrene and vinylpyridine turbolimer latex comprising about 7% by weight butadiene component, about 15% by weight styrene component and about 15% by weight vinylpyridine component is used. This component is incorporated in an amount of about 10 to about 6% by weight of the dry composition. In a preferred embodiment, the turborimer is incorporated at a weight percent of about 3. One particularly preferred vinylpyridine is Firestone FRS-5997 manufactured by Firestone Synthetic Rubber & Latex Company.

This component is a butadiene, styrene and vinylpyridine turbolimer latex consisting of 7% by weight butadiene, 15% by weight styrene and 16% by weight vinylpyridine. Use the desired polybutadiene latex.

Preferably, a polybutadiene latex having a molecular weight within the range of about 10,000 to about 2,000,000 is used.
The latex has a dry composition of about 30 to about 80%
It is used in proportions of % by weight. In a preferred embodiment of the invention, the polybutadiene latex is added to the dry composition at 6%
It is added to the impregnating agent in a proportion of % by weight. Particularly preferred polybutadiene latexes are SR-5841 and S manufactured by Firestone Synthetic Laboratories & Latex Company, Akron, Ohio.
It is R-272. A desired wax emulsion may also be incorporated into the impregnating agent. Preferably, the wax emulsion contains about 75% by weight paraffin wax and about 25% by weight microcrystalline wax. This wax emulsion is
It is incorporated into the composition in an amount of about 4 to about 6% by weight based on the dry composition. In a preferred embodiment, the wax emulsion is incorporated into the composition at a rate of about 5% by weight, based on the dry composition. One of the particularly suitable wax emulsions
As a species, Valtex Wax Emulsion M. manufactured by General Latex and Chemical Corporation, Camp Ridge, Mass. 1
5 (V-mount texWax Emulsion). When a portion of the butadiene latex is replaced with a styrene-butadiene copolymer latex, the styrene-butadiene copolymer is about 5.5% of the dry composition. weight% of
It is used by blending it into an impregnating agent in the following proportions.

The styrene-butadiene copolymer is preferably prepared using about 25 parts by weight of styrene and about 35 parts by weight of butadiene. Suitable styrene-butadiene copolymer latexes are commercially available. When a portion of the butadiene latex is replaced with nitrile-butadiene latex, the nitrile-butadiene latex is used by blending it into the impregnating agent in a proportion of not more than about 5% by weight based on the dry composition. .

Preferably, the nitrile-butadiene is prepared using about 65 parts by weight of acrylonitrile and about 35 parts by weight of butadiene. A commercially available nitrilubutagene latex is used.

The impregnating agent according to the invention contains, as dry ingredients, about 1% by weight of formaldehyde, about 0.0% by weight of formaldehyde. Contains % ammonium hydroxide and approximately 0.1% potassium hydroxide by weight.

If desired, a portion of the butadiene latex may be replaced with other latexes. For example, either a styrene-butadiene copolymer latex or a nitrile-butadiene copolymer latex can be used to replace a portion of the polybutadiene latex in an amount up to about 5% by weight. . The following example illustrates a process for making the impregnating agent of the present invention. Each example represents a 100 x 3.78 quantity to make the impregnating agent. Example 1 A resorcinol-formaldehyde resin premix solution was prepared by placing 25.7 x 0.45 k9 of deionized water in a premix tank and adding 257 x 0.45 kg of a commercially available resorcinol-formaldehyde premix. .

This mixture was stirred for 5 minutes. Then 5.2×0.4
25.7 x 0.45 containing 5k9 potassium hydroxide
K9 deionized water was added and the worship continued for 20 minutes.
A commercially available butadiene-styrene-vinylpyridine latex measuring 463.2 x 0.45 x 9 was charged into the main tank.

Next, 231.6 x 0.45k9 of commercially available polyptadiene latex was poured into the mixing tank with a frame.
The pre-made resorcinol-formaldehyde resin premix was charged into the main reaction tank over a period of 4-6 minutes. This was followed by mixing for 10 minutes. After aging for 2 hours, the impregnating agent was ready for use.

．． The pH was about 9, the viscosity was about 2 ps, and the total solids was about 4% by weight. The impregnating agent of the present invention can be used, for example, in A. It can be attached to glass fibers in a conventional manner using the method and apparatus disclosed in Marzotsuchi et al., US Pat. No. 3,424,608.

After applying the impregnating agent to the glass fiber strands, the coated surface is air dried and cured in a conventional manner, e.g., at a temperature of 260-34° (500-65°) for about 5-10 seconds. The glass fibers having at least part of their surface coated with an impregnating agent can be in the form of yarns, rovings or knitted fabrics in the form of packages and the like. Example
2. In addition to the following data, various levels of vinylpyridine terpolymer content and ptadiene content for impregnation agents according to the invention when the invention is used in various embodiments and applied to substantially the same glass strands. Shows the effect of ingredient amounts.

The above data show that the amounts of turborimer and butadiene latex components can be varied within a wide range and the resulting glass strands have sufficient properties for use as tire cord.

Example 3 The following data shows the effect of partially replacing styrene-butadiene latex with polybutadiene latex while keeping the amount of vinylpyridine latex constant.

The above properties were measured after one day of aging.

The above data shows that styrene-butadiene latex
It can replace polybutadiene latex within a wide range, and has satisfactory characteristics for use as tire cord.
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The data below shows a comparison of the impregnating agent according to the present invention and the impregnating agent of Marzocchi et al., US Pat. No. 3,424,608. The impregnating agent of the latter patent uses neoprene as one of its main components, along with butadiene latex. on the other hand,
The impregnating agent according to the invention uses butadiene latex as the main component and is substantially free of neoprene.

The following compositional components of the impregnating agent represent preferred embodiments of the impregnating agent according to the invention. From the above data, it can be seen that the impregnating agent of the present invention, which is substantially free of neoprene latex and contains wax, is superior to conventional ones.

Claims (1)

Claims: 1. A composition consisting essentially of a vinylpyridine-butadiene-styrene terpolymer, a polybutadiene homopolymer latex, a wax emulsion, and a resorcinol-formaldehyde resin, wherein the amount of said polybutadiene homopolymer latex is Glass fibers with a residue obtained by removing water from a composition that is about 30-80% by weight. 2 The vinyl pyridine terpolymer is about 70% by weight
of butadiene, about 15% by weight styrene, and about 15% by weight of styrene.
The glass fiber of claim 1 which is a butadiene-styrene and vinylpyridine terpolymer latex comprising % by weight of vinylpyridine. 3. The glass fiber of claim 1, wherein the wax emulsion contains about 75% by weight paraffin wax and about 25% by weight microcrystalline wax. 4 The vinyl pyridine terpolymer has a molecular weight of about 10 to 60
The polybutadiene latex is present in an amount within the range of about 30-80% by weight; the wax emulsion is present in an amount within the range of about 4-6% by weight. and wherein the resorcinol-formaldehyde resin is present in an amount within the range of about 3-4% by weight.