JPH046663B2 - - Google Patents

Description

[Detailed description of the invention]

It is well known that glass fiber is used as a reinforcing material for rubber products and resin products.
In order to fully demonstrate the reinforcing properties of glass fibers, the adhesive strength between the glass fibers and rubber or resin must be high. Methods for increasing this adhesive strength include a method of surface-treating the glass fiber itself, and a method of adding additives such as compounding agents and kneaded adhesives that have the effect of improving adhesive strength to the rubber or resin side. The present invention was achieved by studying methods for improving adhesive strength from the perspective of surface treatment of glass fibers themselves. The most common method for surface treatment of glass fibers is the use of various silane coupling agents, which is generally referred to as silane treatment, and glass fibers with various surface treatments are commercially available from glass fiber manufacturers. This is well known. Furthermore, the silane-treated glass fibers are treated with an aqueous resorcinol-formaldehyde resin liquid (hereinafter referred to as RF liquid) and an aqueous dispersion of styrene-butadiene-vinylpyridine terpolymer (hereinafter, the polymer and water dispersion are referred to as latex). A surface treatment method has been reported (45th Spring Annual Meeting of the Chemical Society of Japan, Lecture No. 4VO3, 1982; Japan Rubber Association 49th Ordinary General Meeting Research Presentation Lecture Abstract 51)
(1982) However, these methods did not provide sufficient adhesive strength for practical use, and significant improvements were desired. The present inventors have obtained the present invention as a result of intensive studies regarding this period. The present invention uses a liquid mixture consisting of an RF liquid and a sulfohalogenated polymer latex as a reinforcing glass fiber (hereinafter, the sulfohalogenated polymer latex is referred to as SHP latex, and the liquid mixture consisting of RF liquid and polymer latex is referred to as RFL liquid). write down
Further, an RFL liquid when the polymer latex is a sulfohalogenated polymer latex is referred to as a SHP-based RFL liquid. ) has been discovered for reinforcing glass fibers that have been surface-treated. As mentioned above, surface treatment of glass fibers with an RFL liquid using a styrene-butadiene-vinylpyridine terpolymer latex is known. However, the glass fiber whose surface was treated with the SHP-based RFL liquid is completely new, and its remarkable adhesion effect will be shown in the examples below. The RF liquid referred to in the present invention is a substance that easily generates formaldehyde such as formaldehyde or paraformaldehyde, and a phenolic compound such as dihydroxybenzenes typified by resorcinol. This is an aqueous solution that is reacted in the presence of a compound, and is widely known as an RF liquid.
Generally, the amount of formaldehyde is adjusted to 0.5 to 4 mol per mol of the phenolic compound, and the phenol formaldehyde resin concentration is adjusted to 5 to 40% by weight. On the other hand, it is an aqueous dispersion that generally contains about 5 to 70% by weight of the SHP latex or sulfohalogenated polymer of the present invention. Examples of sulfohalogenated polymers include ethylene, propylene,
Homopolymers such as n-butylene, isobutylene, butadiene, isoprene, mutual copolymers of any two or more of these, non-conjugated dienes such as ethylidenenorbornene and dicyclopentadiene,
Those with a structure thought to be produced by treating a copolymer of styrene, vinyl chloride, acrylic acid, methacrylic acid, methacrylic acid ester, etc. with a halogen and sulfur dioxide or sulfuryl halide are listed. It will be done. Examples of the halogen include chlorine and bromine. Generally, the halogen content in these polymers is between 5 and 70% by weight, and the sulfur content is between 0.1 and 10% by weight. The RFL liquid is generally adjusted so that the sulfohalogenated polymer is 10 to 5000% by weight per 1 solid content in the RF liquid. A viscosity modifier, antioxidant, etc. are added as necessary. After the surface of the glass fiber is coated with SHP-based RFL liquid by a method such as dipping in the above-mentioned SHP-based RFL liquid or spraying the SHP-based RFL liquid,
Surface treatment is generally performed by heat treatment at a high temperature of 150°C or higher. In the case of heat treatment at a high temperature of 200° C. or higher, zinc or magnesium compounds such as oxides, organic acid salts, carbonates, etc. of these metals may be added to the SHP-based RFL liquid. The most typical one is zinc oxide. These compounds are present in an amount of 0.1 to 50 parts per 100 parts by weight of the sulfohalogenated polymer.
Excellent adhesive strength can be obtained by using 2 to 20 parts by weight, preferably 2 to 20 parts by weight. Glass fibers as used in the present invention include glass fiber canvas and short glass fibers, and also include glass fibers that have been previously silane-treated with vinyl silane, amino silane, epoxy silane, acrylic silane, etc. . When glass fibers that have been previously subjected to silane treatment are used, the effect of surface treatment with the SHP-based RFL liquid is greater than that of untreated glass fibers, and is therefore preferable. The reinforcing glass fibers surface-treated using the SHP-based RFL liquid of the present invention include natural rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber,
It is used as a reinforcing material in rubber products using chloroprene rubber, ethylene propylene rubber, etc., and resin products using resins and engineering plastics, mainly made of polyethylene, polypropylene, ethylene vinyl acetate copolymers, polyvinyl chloride, etc. Examples are shown below, but the present invention is not limited thereto. Example 1 242g of water, 0.7g of caustic soda, 11 resorcinol
g and 16.2 g of 37% formalin were mixed and aged at room temperature for 5 hours to prepare an RF solution. Next, an RFL liquid was obtained by mixing 256.4 g of chlorosulfonated polyethylene latex with a solid content of 40%, 269.9 g of RE liquid, and 135 g of water. Add 1 glass fiber canvas (plain weave) to the above RFL solution.
After dipping twice, heat treatment (baking) was performed in an oven at 150°C for 3 minutes. The following EPDM formulation was used for the adherend. Espren 501A 100 (parts by weight) FEF Black 50 Paraffin oil 10 Zinc white 5 Stearic acid 1 Soccinol BZ 1 TT 1 M 0.5 Sulfur 1 Glass fiber as an intermediate layer, with the above EPDM on both sides
Using the mixture, a bonded body of glass fiber and ethylene propylene rubber was obtained by press vulcanization at 150°C for 30 minutes. A 180° peel test was performed at a tensile speed of 50 mm/min to measure the adhesive strength between the glass fiber and ethylene propylene rubber. The results are shown below.

[Table] *Reference Comparative Example This example compared the surface treatment of glass fiber with a known RFL liquid using vinylpyridine styrene butadiene copolymer to chlorosulfonated polyethylene, which is the most typical sulfohalogenated polymer. The glass fiber surface treatment method of the present invention using the above method has extremely excellent adhesive strength, indicating that it has a large reinforcing effect. Furthermore, when surface-treated glass fibers are used, superior adhesive strength can be obtained. Example 2 When glass fibers are surface treated using a SHP-based RFL liquid and heat treated at a high temperature of 200°C or higher, the effects of combined use of metal compounds will be shown below. The methods for preparing the RF liquid, RFL liquid, adherend, etc., and testing methods were the same as in Example 1. However, the metal compound should be used in an amount of 10 parts by weight per 100 parts by weight of chlorosulfonated polyethylene, and mixed with the RFL liquid.
When a metal compound was used as an emulsion, the amount of water used in preparing the RFL liquid was reduced by the amount of water used as a dispersant. The glass fiber used here is aminosilane-treated canvas (plain weave).
The heat treatment conditions after dipping the glass fibers in the SHP-based RFL liquid were 240°C x 2 minutes.

[Table] When performing heat treatment at high temperatures, it is desirable to add or use a compound containing zinc or magnesium to the SHP-based RFL liquid, and zinc oxide is particularly desirable.

Claims (1)

[Scope of Claims] 1. A reinforcing glass fiber characterized in that its surface is treated with a liquid mixture consisting of an aqueous resorcinol-formaldehyde resin solution and an aqueous dispersion of a sulfohalogenated polymer. 2. Per 100 parts by weight of sulfohalogenated polymer,
2. The reinforcing glass fiber according to claim 1, wherein the glass fiber is surface-treated at 200° C. or higher using a liquid mixture containing 0.1 to 50 parts by weight of a zinc compound or a magnesium compound. 3. The reinforcing glass fiber according to claim 1 or 2, characterized in that the reinforcing glass fiber is a glass fiber that has been previously treated with silane.