JPH0456053B2 - - Google Patents

Description

[Detailed description of the invention]

<Industrial Application Field> The present invention relates to a liquid composition for impregnating glass fibers and a glass fiber cord having a coating derived from the composition. More specifically, a liquid composition suitable as an impregnating agent for glass fiber cord used as a reinforcing material in products that are subjected to both heat and external force during running, such as timing belts, and a glass fiber cord having a coating derived therefrom. Regarding. <Prior art> Conventionally, glass fiber cords used as core wires (reinforcing materials) for timing belts are treated with resorcinol-formalin latex (RFL) before being embedded in the base rubber of the timing belt. is normal. JP-A-50-3184 discloses 2 to 10 parts by weight of resorcinol aldehyde resin, 20 to 60 parts by weight of butadiene-styrene-vinylpyridine terpolymer,
An impregnating agent for glass fibers is disclosed in which the impregnating agent is 15 to 40 parts by weight of a carboxylated butadiene styrene resin and 3 to 30 parts by weight of an incompatible wax (e.g., paraffin wax). JP-A-59-53780 discloses a surface treatment agent for fibers containing an aqueous resorcinol-formaldehyde resin liquid, an aqueous sulfohalogenated polymer dispersion, and a zinc compound or a magnesium compound. Japanese Unexamined Patent Application Publication No. 59-73453 contains the above-mentioned
No. 53780 discloses a reinforcing glass fiber treated with the above-mentioned surface treatment agent. JP-A-61-207442 discloses a process in which fibers treated with a mixture of a halogen-containing polymer latex such as chlorosulfonated polyethylene and a resorcinol-formaldehyde mixture are combined with a highly saturated hydrocarbon rubber compound containing nitrile groups. A method of sulfur bonding is disclosed. Japanese Patent Publication No. 47-37513 discloses an impregnating latex containing an elastomer in an attempt to improve adhesion to a base rubber, flexibility, heat resistance, water resistance, etc. JP-A-53-70196 discloses a glass fiber impregnating agent containing a butadiene-half ester-methacrylic acid terpolymer, emulsifying mineral oils, silica derivatives, and esters as an impregnating agent for tire cords. Disclosed. Furthermore, JP-A-54-69192 discloses a glass fiber impregnating agent comprising a vinyl pyridine terpolymer, a polybutadiene latex, a wax emulsion, and a resorcinol-formaldehyde resin as a tire cord impregnating agent. <Problems to be Solved by the Invention> An object of the present invention is to provide a composition for impregnating glass fibers with a novel composition. Another object of the present invention is to provide a novel composition for impregnating glass fibers containing chlorosulfonated polyethylene as one of the rubber components as an impregnating agent. Still another object of the present invention is a composition for impregnating a glass fiber cord, which can impart excellent heat resistance, resistance to bending fatigue, and flexibility to products using the glass fiber cord, and a composition treated with the composition. Our objective is to provide glass fiber cords with high quality. Still another object of the present invention is to provide a composition for impregnating glass fibers, which can be used in products that are subjected to both heat and external forces, such as belts, to maintain the integrity of the products for a long period of time. An object of the present invention is to provide a glass fiber cord treated with a composition. Further objects and advantages of the invention will become apparent from the description below. <Means for Solving the Problems and Advantages> According to the present invention, the above objects and advantages of the present invention are as follows: (A) (1) resorcinol-formaldehyde resin (2) butadiene-styrene-vinylpyridine-terpolymer; and (3) contains chlorosulfonated polyethylene, and (B) based on the total solid content of the components (1), (2), and (3), the component (1) contains 2 to 15% by weight, the above component (2) is 15 to 80% by weight, and the above component (3) is 15 to 70% by weight. be done. The liquid composition for impregnating glass fibers of the present invention is characterized by containing the above three components (1), (2) and (3) as essential components. In a preferred embodiment of the liquid composition of the present invention, dicarboxylated butadiene-styrene resin 4 or chloroprene rubber 5 is used in place of a part of the terpolymer of component (2). As the resorcinol-formalin resin of component (1), one produced by a condensation reaction of resorcinol and formalin with a molar ratio of resorcinol to formalin of 1:1 to 3 is preferably used. For example, what is known as a resol type resin or a novolak type resin can be used, and is suitably used as an aqueous solution having a solid content of 5 to 10% by weight, for example, a solid content of 8% by weight. Component (2), the butadiene-styrene-vinylpyridine terpolymer, can be any of a number of such terpolymers well known to those skilled in the art. For example, 20-85% by weight of butadiene, 5-70% by weight of styrene and 5-30% by weight of vinylpyridine.
A terpolymer consisting of, for example, about 70% butadiene, about 15% styrene, and about 15% by weight
Examples include terpolymers made of vinylpyridine. Representative suitable butadiene-styrene-vinylpyridine terpolymers include the terpolymer available from Nippon Zeon Co. under the trade name "Nipol 2518FS" and the terpolymer available from Nippon Gosei Rubber Co. under the trade name "JSR 0650." and “Pyratex
Examples include terpolymers available from Sumitomo Naugatatsu Co., Ltd. under the trade name "J-1904". The terpolymer of component (2) is suitably used, for example, as a latex with a solid content of about 40% by weight. Component (3) ) Chlorosulfonated polyethylene is produced by chlorinating polyethylene in the presence of sulfur dioxide, and some of the hydrogen atoms in the main chain of polyethylene are chlorsulfonyl groups (ClSO ₂ −) and chlorine. The chlorosulfonated polyethylene used in the present invention preferably has a chlorine content of 25 to 43% by weight and a sulfur content of 1.0 to 1.5% by weight.Chlorsulfonated polyethylene of component (3) For example, the solid content is 30 to 60% by weight, for example, the solid content is 40% by weight.
It is suitably used as a latex. A representative suitable chlorosulfonated polyethylene is available from Sumitomo Chemical Co., Ltd. under the trademark "Esprene." Component (4) contained in the preferred composition of the present invention
The dicarboxylated butadiene-styrene resins are prepared by copolymerizing butadiene and styrene in the presence of small amounts of ethylenically unsaturated dicarboxylic acids such as maleic acid. As dicarboxylated butadiene-styrene resins, those containing, for example, 20 to 80% by weight of butadiene, 5 to 70% by weight of styrene and 1 to 10% by weight of ethylenically unsaturated dicarboxylic acid are advantageously used. The dicarboxylated butadiene-styrene resin of component (4) is preferably used as a latex with a solid content of 30 to 60% by weight, for example, 40% by weight. A representative suitable dicarboxylated butadiene-styrene resin is available from Nippon Zeon under the trade name "Nipol 2570X5." Or “JSR
0668, JSR 0691 or JSR 0697" from Japan Synthetic Rubber Co., Ltd. Similarly, preferred compositions of the present invention contain
As the chloroprene rubber (5), a large number of such rubbers known to those skilled in the art can be used. The chloroprene rubber of component (5) is preferably used as a latex with a solid content of 30 to 60% by weight, for example, 60% by weight. A representative suitable chloroprene rubber is available from Showa Neoprene Company under the trademark "Neoprene 650". or,
It is available from Bayer under the trademark "Baypren Latex". The latexes as described above in components (2) to (5) may contain emulsifiers well known to those skilled in the art. The liquid composition for impregnating glass fibers of the present invention is as described above.
(1), (2) and (3), based on the total solid weight of these three components, component (1) is 2 to 15% by weight, component (2) is 15 to 80% by weight, and Ingredient (3) 15-70
Contained in weight%. Preferred ranges of the above weight proportions are 5 to 10% by weight for component (1), 35 to 65% by weight for component (2), and 20 to 50% by weight for component (3).
Ensuring the above weight ratios of the three components is important in achieving the above object of the present invention. A preferred composition of the present invention containing component (4) or component (5) has component (2) in the above weight range.
10 to 90% of the weight ratio of (2) can be replaced. The liquid composition for impregnating glass fibers of the present invention may contain a base, such as ammonia, to adjust the pH, if necessary, and may further contain an antioxidant, etc., if necessary. The liquid composition for impregnating glass fibers of the present invention can be suitably used as an aqueous latex having a solid content of usually 15 to 30% by weight. The glass fiber impregnating composition of the present invention is applied to a glass fiber strand by dipping the glass fiber strand therein, removing excess, and optionally drying. At that time, the glass fiber strands are
It may or may not have a sizing agent applied during spinning of glass fibers. The glass fiber strands are then assembled in the desired number and typically twisted to obtain a glass fiber cord. This glass fiber cord is embedded in an unvulcanized rubber base material by a method known per se, and heated and vulcanized under pressure. In the above method, the liquid composition of the present invention usually has a solid content of 10 to 30% based on the glass fiber cord.
% by weight to provide a coating of the liquid composition on the glass fiber cord. The coating of the liquid composition is usually heat treated to provide a solid coating before being embedded in the rubber substrate. The solid coating is 10 to 30% by weight of glass fiber in terms of solid content.
It is preferable that the The glass fiber cord coated with the liquid impregnating composition of the present invention exhibits excellent adhesion to various rubbers, particularly chloroprene rubber, hydrogenated nitrile rubber, chlorosulfonated polyethylene, and the like. As temperatures near automobile engines rise, in recent years heat-resistant rubbers such as chlorosulfonated polyethylene and hydrogenated nitrile rubber have been used as rubber for automobile timing belts, in addition to the conventionally used chloroprene. It has become like that. The impregnating liquid composition of the present invention is characterized in that it also has sufficient adhesion to such heat-resistant rubber. Before embedding the glass fiber cord coated with the impregnating agent composition of the present invention in hydrogenated nitrile rubber or chlorosulfonated polyethylene rubber,
In order to further improve the adhesion, it is preferable to further treat with a treatment liquid containing a halogen-containing polymer and an isocyanate compound. Furthermore, the obtained rubber product has excellent heat resistance, resistance to bending fatigue, and flexibility. Therefore,
The impregnating composition of the present invention can be very suitably used as an impregnating composition for glass fiber cords used in timing belts, for example, which are subjected to both heat and external force. The present invention will be explained in more detail with reference to Examples below. <Example> Example 1 (1) A filament of alkali-free glass with a diameter of 9 μm was spun, and this was bundled with a sizing agent to obtain a glass strand of 33.7 tex, and three strands of glass were spun together to form the following composition: resorcinol. Formaldehyde Resin latex (solids content 8% by weight) 30 parts by weight Butadiene-styrene-vinyl pyridine terpolymer latex (solids content 40% by weight) (JSR0650) 45 parts by weight Chlorosulfonated polyethylene latex (solids content 40% by weight) (Esprene L-450) 20 parts by weight 25% aqueous ammonia 1 part by weight The cord was passed through an impregnating agent consisting of 4 parts by weight of water, and then the excess impregnant was removed until the solid content was approximately 20% by weight based on the glass cord. 250℃.
A glass fiber bundle treated with an impregnating agent was obtained by heat treatment at a temperature of 2 minutes. Next, Z is applied to this glass fiber bundle 2.1 times per inch.
A first twist was given in the direction (S direction). (2) Thirteen of these pre-twisted glass fiber bundles were combined and given 2.1 twists per inch in the S direction (Z direction) to obtain an ECG150 3/132.1S (Z) cord. Cut this cord to a length of 120mm,
Twenty pieces were arranged in parallel (total width 25 mm) on an unvulcanized chloroprene rubber sheet having the composition shown in Table 1, and the sheets were pressed from above and below at 150°C for 25 minutes to vulcanize.

【table】

[Table] After vulcanization, firmly grasp the tip of the cord and the tip of the rubber, pull them in opposite directions, peel the cord from the rubber, and check the adhesion according to the following criteria. I judged it. ◎: Rubber destroyed, ○: 3/4 or more rubber destroyed, △: 1/2 or more rubber destroyed, ×: rubber not destroyed. The adhesive strength is the highest at ◎ and decreases sequentially as ○, △, and ×. In addition, nylon canvas is wrapped around a cylindrical drum,
On top of that, the treated cord was alternately spun into S-twisted products and Z-twisted products, and further an unvulcanized sheet of the rubber compound shown in Table 1 was laminated and vulcanized under the above conditions.
Next, the cylindrical product was cut into inch width pieces to produce timing belts. The timing belt has a diameter of
After being attached between two 10cm pulleys and running for 300 hours in an atmosphere of 80℃, the belt was cut along the cord, and the condition of the cord at the cut surface was observed using an electron microscope. Therefore, the condition of the impregnating agent (RFL) was determined. ◎: Same as when not running, ○: RFL becomes hard and has started cohesive failure, △: Cohesive failure progresses and breaks into stone-like pieces, ×: Cohesive failure progresses further and becomes sand-like. The strength retention rate of the resulting belt was examined as follows. That is, this timing belt was attached to a tensile tester equipped with pulleys on the upper and lower clamps and pulled, and the strength at the time of timing belt breakage was measured.
Next, the strength retention rate after the timing belt running test was determined using the following calculation formula. Strength retention rate (%) = Tensile strength of timing belt after running/Tensile strength of timing belt before running x 100 The results are shown in Table 3. Example 2 Resorcinol-formaldehyde resin latex (solid content 8% by weight) 30 parts by weight Butadiene-styrene-vinyl pyridine terpolymer latex (solid content 40% by weight) (JSR 0650) 30 parts by weight Chlorosulfonated polyethylene latex ( (Solid content 40% by weight) (Esprene L-450) 20 parts by weight Dicarboxylated butadiene-styrene resin latex (Solid content 40% by weight) (Nipol 2570X5) 15 parts by weight 25% aqueous ammonia 1 part by weight Water 4 parts by weight The treatment was carried out in the same manner as in Example 1 using an impregnating agent consisting of: The results are shown in Table-3. Example 3 Resorcinol-formaldehyde resin latex (solid content 8% by weight) 30 parts by weight Butadiene-styrene-vinyl pyridine terpolymer latex (solid content 40% by weight) (JSR 0650) 23 parts by weight Chlorosulfonated polyethylene latex ( (Solid content: 40% by weight) (Esprene L-450) 30 parts by weight Dicarboxylated butadiene-styrene resin latex (Solid content: 40% by weight) (Nipol 2570X5) 12 parts by weight 25% aqueous ammonia 1 part by weight Water 4 parts by weight The treatment was carried out in the same manner as in Example 1 using an impregnating agent consisting of: The results are shown in Table-3. Example 4 Resorcinol-formaldehyde resin latex (solid content 8% by weight) 30 parts by weight Butadiene-styrene-vinyl pyridine terpolymer latex (solid content 40% by weight) (JSR 0650) 30 parts by weight Chlorosulfonated polyethylene latex ( (solid content 40% by weight) (Esprene L-450) 20 parts by weight Chloroprene latex (solid content 60% by weight) (Nioprene 650) 10 parts by weight 25% ammonia water 1 part by weight Water 9 parts by weight. The treatment was carried out in the same manner as in Example 1. The results are shown in Table-3. Example 5 A treatment solution with the following composition was applied to the ECG 150 3/13 2.1S (Z) cord obtained in Example 2 so that the amount of nonvolatile matter attached was 2.5 to 3.5% by weight, and an organic solvent was added. After evaporation and removal, a glass fiber cord with a secondary coating layer was obtained. Chlorosulfonated polyethylene TS-340 (manufactured by TOSO Co., Ltd.) 5.25 parts by weight Methylenebis(4-phenyl isocyanate) 4.5 parts by weight P-dinitrosobenzene 2.25 parts by weight Carbon black 3.0 parts by weight Xylene 51.0 parts by weight Trichlorethylene 34.0 parts by weight This glass Using the fiber cord, a test was conducted in the same manner as in Example 1, except that an unvulcanized hydrogenated nitrile rubber sheet was used in the rubber compound shown in Table 2. However, the ambient temperature for the timing belt running test was 120°C. The results are shown in Table-3.

【table】

[Table] Comparative example 1 Resorcinol-formaldehyde resin latex (solid content 8% by weight) 30 parts by weight Butadiene-styrene-vinyl pyridine terpolymer latex (solid content 40% by weight) (JSR 0650) 30 parts by weight Dicarboxylation Butadiene-styrene resin latex (solid content 40% by weight) (Nipol 2570X5) 35 parts by weight 25% aqueous ammonia 1 part by weight Water 4 parts by weight The treatment was carried out in the same manner as in Example 1. Ta. The results are shown in Table-3. Comparative Example 2 Resorcinol-formaldehyde resin latex (solid content 8% by weight) 30 parts by weight Chlorosulfonated polyethylene latex (solid content 40% by weight) (Esprene L-450) 65 parts by weight 25% aqueous ammonia 1 part by weight Water 4 The treatment was carried out in the same manner as in Example 1 using an impregnating agent consisting of parts by weight. The results are shown in Table-3. Comparative Example 3 The same procedure as in Example 5 was carried out except that the glass fiber cord obtained in Comparative Example 1 was used. The results are shown in Table-3.

【table】

【table】

Claims (1)

[Scope of Claims] 1(A) (1) contains a resorcinol-formaldehyde resin, (2) a butadiene-styrene-vinylpyridine terpolymer, and (3) a chlorosulfonated polyethylene, and (B) the above-mentioned The above component (1) is 2 to 15% by weight based on the total solid content of components (1), (2), and (3),
A liquid composition for impregnating glass fibers, wherein the component (2) is 15 to 80% by weight, and the component (3) is 15 to 70% by weight. 2. The composition according to claim 1, wherein dicarboxylated butadiene-styrene resin 4 is used in place of a part of the terpolymer of component (2). 3. The composition according to claim 1, wherein 10 to 90% of the amount of component (2) used is used in place of dicarboxylated butadiene-styrene resin 4. 4. The composition according to claim 1, wherein chloroprene rubber 5 is used in place of a part of the terpolymer of component (2). 5. The composition according to claim 1, wherein 10 to 90% of the amount of component (2) used is used in place of chloroprene rubber 5. 6. The composition according to claim 1, which is an aqueous latex having a solids content of 15 to 30% by weight. 7 A glass fiber cord having a film of the following liquid composition for impregnating glass fibers. (A) contains (1) a resorcinol-formaldehyde resin, (2) a butadiene-styrene-vinylpyridine terpolymer, and (3) a chlorosulfonated polyethylene, and (B) the above (1) and (2). , and the above component (1) is 2 to 15% by weight based on the total solid content of components (3),
A liquid composition for impregnating glass fibers, wherein the component (2) is 15 to 80% by weight, and the component (3) is 15 to 70% by weight. 8. The glass fiber cord according to claim 7, having a solid film derived from the liquid composition. 9. The glass fiber cord according to claim 8, wherein the solid coating is present in an amount of 10 to 30% by weight based on the glass fibers in terms of solid content.