JP2006104595A - Coating fluid for covering glass fiber and glass fiber for reinforcing rubber given by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To make it possible that a glass fiber for reinforcing a rubber which has a cover layer formed by coating a glass fiber cord with a coating fluid for the glass fiber, drying the fluid, and making the dried fluid cover the cord, gives suitably excellent water resistance and heat resistance to a power transmission belt, when the glass fiber is formed into the power transmission belt by being laid in a crosslinked HNBR (hydrogenated nitrile butadiene rubber). <P>SOLUTION: The coating fluid for covering the glass fiber comprises an emulsion formed by dispersing a phenolic resin, a vinylpyridine-styrene-butadiene copolymer, and a chlorosulfonated polyethylene in water and is used for covering the glass fiber cord, wherein the phenolic resin comprises a monohydroxybenzene-formaldehyde resin formed by reacting monohydroxybenzene with formaldehyde. The fiber for reinforcing the rubber is formed by using the coating fluid. The power transmission belt is formed by laying the glass fiber for reinforcing the rubber in the heat-resistant rubber. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a glass fiber coating coating solution for providing a coating layer for enhancing the adhesion between glass fibers used for reinforcing various rubber products and a base rubber, and a rubber reinforcing glass fiber using the same.

  In order to provide tensile strength and dimensional stability to rubber products such as transmission belts and tires, it is common to embed high-strength fibers such as glass fibers, nylon fibers, and polyester fibers as a reinforcing material in the base rubber. The rubber reinforcing fiber embedded in the base rubber is required to have good adhesion to the base rubber and have a strong interface and not peel off. However, even if the glass fiber is used as it is, it does not adhere at all, or even if it adheres, the adhesiveness is weak and the interface peels off, so that it is not necessary as a reinforcing material.

  Therefore, for example, in order to improve the adhesion between the base rubber and the glass fiber and prevent the peeling of the interface, the transmission belt usually has a resorcin-formaldehyde in a glass fiber cord which is made by combining the filaments into a yarn. A glass fiber covering glass fiber in which a resin and various latexes are dispersed in water is applied and then dried to form a glass layer for rubber reinforcement. The coating layer has an effect of adhering the base rubber and the glass fiber at a high temperature when the rubber reinforcing glass fiber is embedded in the base rubber and molded into a transmission belt. Is not necessarily strong enough. For example, since a power transmission belt for an automobile is used in a high-temperature environment in an engine room, the base rubber is a heat-resistant rubber, a hydrogenated nitrile rubber cross-linked with sulfur or peroxide ( Hereinafter, it is abbreviated as HNBR). The transmission belt embedded with the glass fiber for rubber reinforcement that has been subjected only to the coating treatment does not maintain the initial adhesive strength under running conditions that continue to bend at high temperatures. The interface between the glass fiber and the base rubber may be peeled off.

  As a rubber-reinforced glass fiber for providing a transmission belt that maintains the bond strength between the cross-linked HNBR and the glass fiber for rubber reinforcement, does not cause separation of the interface, and is reliable for a long time even in a high temperature environment. The rubber obtained by applying the above-mentioned coating treatment to the glass fiber cord as a primary coating layer, applying a second liquid having a different composition on the secondary coating layer, and drying it to form a secondary coating layer Reinforcing glass fibers are disclosed in Patent Documents 1 to 4.

  For example, Patent Document 1 discloses a method of treating with a second liquid containing a halogen-containing polymer and an isocyanate.

  In Patent Document 2, a processing agent containing a resorcin-formalin condensate and a rubber latex is applied to a glass fiber for rubber reinforcement, dried and cured to form a first coating layer, and a different processing agent is further formed on the first coating layer. A glass fiber cord for reinforcing rubber having a second coating layer formed by applying and drying and curing, wherein the treating agent for the second coating layer is a rubber compound, a vulcanizing agent, and a maleimide vulcanizing aid A cord for reinforcing rubber is disclosed which is characterized by having a main component.

  In addition, Patent Document 3 relating to the applicant's patent application describes glass fiber in which an acrylic ester resin, a vinylpyridine-styrene-butadiene copolymer, and a resorcin-formaldehyde resin are dispersed in water to form an emulsion. After the coating coating solution is applied, a coating layer is provided by drying, and 0.3% by weight to 10.0% by weight of bisallylnadiimide is dispersed in an organic solvent with respect to the weight of the halogen-containing polymer. A glass fiber for reinforcing rubber is disclosed, which is obtained by applying a glass fiber coating coating solution and providing a further coating layer. The rubber reinforcing glass fiber showed a preferable adhesive strength in bonding with a cross-linked HNBR.

Further, in Patent Document 4 relating to the applicant's patent application, a glass fiber coating first liquid obtained by dispersing a resorcin-formaldehyde resin and a rubber latex in water is applied to glass fibers to form a coating film. After drying and curing to form a primary coating layer, a glass fiber coating second liquid having a different composition is applied onto the primary coating layer to form a coating film, followed by drying and curing to form a secondary coating layer. A glass fiber for reinforcing rubber, characterized in that the second liquid for glass fiber coating is obtained by dispersing bisallylnadiimide, a rubber elastomer, a vulcanizing agent, and an inorganic filler in an organic solvent. ing. The glass fiber for rubber reinforcement exhibits a preferable adhesive strength in bonding with a cross-linked HNBR, and the tensile strength is lowered even after running for a long time at high temperature as a transmission belt embedded in the cross-linked HNBR. And had excellent heat resistance.
Japanese Examined Patent Publication No. 2-4715 Japanese Patent No. 3201330 JP 2004-203730 A JP 2004-244785 A

  Glass fiber cords coated with a coating material for improving adhesion to the base rubber are used for the glass fiber for rubber reinforcement that is embedded in the base rubber when using the transmission belt. It is done.

  In the conventional transmission belt, although the initial bond strength between the rubber fiber glass and the base rubber, which was coated with a coating material on a glass fiber cord, was obtained, it was run for a long time under high humidity and temperature as a transmission belt. Later, there was no problem that the tensile strength before running was maintained and there was no excellent water resistance and heat resistance without dimensional change, and the water resistance was particularly poor.

  Compared to the conventional transmission belt in which the glass fiber for rubber reinforcement described in Patent Document 1, Patent Document 2, Patent Document 3 or Patent Document 4 is embedded in heat-resistant rubber, it is equivalent to or better than rubber In addition to the heat resistance that has the adhesive strength between glass fiber and heat-resistant belt, and the coating layer maintains the initial adhesive strength even when running for a long time at high temperatures, However, the development of a transmission belt having a water resistance by preventing the penetration of water into the glass fiber cord and the glass fiber for rubber reinforcement providing the same while the coating layer maintains the initial adhesive strength is awaited.

  As a result of intensive studies by the present inventors, a monohydroxybenzene-formaldehyde resin obtained by reacting formaldehyde with monohydroxybenzene is added to a vinylpyridine-styrene-butadiene copolymer and chlorosulfonated polyethylene, thereby coating a glass fiber. When the glass fiber cord coating solution is applied to the glass fiber cord and dried to form a coating layer, a further secondary coating layer is provided on the glass fiber cord, and the rubber fiber glass fiber is embedded in the crosslinked HNBR. When a power transmission belt is used, the preferred adhesion strength between the glass fiber for rubber reinforcement and the heat-resistant rubber is obtained, and the power transmission belt is combined with excellent water resistance and heat resistance, in other words, at a high temperature and under water injection for a long time. A glass fiber for rubber reinforcement that maintains tensile strength after running and gives the transmission belt excellent dimensional stability. It was found to be subjected.

  That is, the present invention is a glass fiber coating application for coating glass fibers in which a phenol resin, a vinylpyridine-styrene-butadiene copolymer (B) and a chlorosulfonated polyethylene (C) are dispersed in water to form an emulsion. A coating solution for coating glass fibers, wherein the phenol resin is a monohydroxybenzene-formaldehyde resin (A) obtained by reacting monohydroxybenzene (D) and formaldehyde (E). .

  Furthermore, the present invention relates to a resol type in which a monohydroxybenzene-formaldehyde resin (A) is reacted with a basic catalyst at a molar ratio of formaldehyde (E) to monohydroxybenzene (D) of 0.5 to 3.0. It is a coating solution for glass fiber coating, which is a resin.

  Further, the present invention is expressed as a weight percentage where the combined weight of the monohydroxybenzene-formaldehyde resin (A), the vinylpyridine-styrene-butadiene copolymer (B) and the chlorosulfonated polyethylene (C) is 100%. The monohydroxybenzene-formaldehyde resin (A) is A / (A + B + C) = 1.0% to 15.0%, and the vinylpyridine-styrene-butadiene copolymer (B) is B / (A + B + C) = 45.0. % To 82.0%, and chlorosulfonated polyethylene (C) is contained in the range of C / (A + B + C) = 3.0% to 40.0%. It is.

  Furthermore, this invention represents the said vinylpyridine-styrene-butadiene copolymer (B) to a styrene-butadiene copolymer (F) by weight percentage, and F / B = 5.0%-80.0. % Of the above-mentioned coating solution for coating glass fibers.

  Furthermore, the present invention provides a glass fiber for reinforcing rubber that is coated with the above glass fiber coating coating solution and then dried, and is expressed as a halogen-containing polymer (G) and a weight percentage, and H / G = 0.3%. A coating for glass fiber secondary coating in which 10.0% of bisallylnadiimide (H) is dispersed in an organic solvent is applied, and a further secondary coating layer is provided. Glass fiber.

  Furthermore, the present invention is a transmission belt characterized in that the rubber reinforcing glass fiber is embedded in a heat-resistant rubber.

  Furthermore, the present invention is the above transmission belt, wherein the heat resistant rubber is a cross-linked HNBR.

  The glass fiber for rubber reinforcement formed by applying the coating solution for coating glass fiber according to the present invention and providing a coating layer on the glass fiber cord is a heat-resistant rubber, for example, embedded in HNBR crosslinked with sulfur or with peroxide. In this case, the glass fiber and the cross-linked HNBR have excellent adhesive strength. Furthermore, by providing water resistance when buried in a cross-linked HNBR as a power transmission belt, it has both water resistance and heat resistance, in other words after a long time use as a power transmission belt under high temperature and humidity, in other words After running, there is no concern that the interface between the glass fiber and the heat-resistant rubber is peeled off, and the transmission belt maintains the tensile strength and is excellent in dimensional stability.

  The present invention relates to a coating for glass fiber in which a monohydroxybenzene-formaldehyde resin (A) belonging to a phenol resin, a vinylpyridine-styrene-butadiene copolymer (B), and a chlorosulfonated polyethylene (C) are dispersed in water. After the coating liquid is applied to the glass fiber cord and dried to provide a coating layer considered to have a function of preventing water penetration into the glass fiber cord, another glass fiber secondary coating is provided. It is a glass fiber for rubber reinforcement formed by applying a coating solution and drying it to provide a further secondary coating layer and drying it.

  The glass fiber for rubber reinforcement of the present invention, when compared with the conventional glass fiber for rubber reinforcement, has a water penetration into the glass fiber cord when it is embedded in a heat resistant rubber, for example, a cross-linked HNBR, as a transmission belt. By preventing it, the transmission belt is given excellent water resistance and has both water resistance and heat resistance.

  In the present invention, a coating solution for coating a glass fiber that is applied to a glass fiber cord to form a coating layer includes a monohydroxybenzene-formaldehyde resin (A), a vinylpyridine-styrene-butadiene copolymer (B), and chlorosulfonated. A glass fiber coating coating solution in which polyethylene (C) is dispersed in water is used.

  In the present invention, the transmission belt refers to a belt that transmits the driving force of a driving source such as an engine or a motor in order to operate an engine or other machine, and a toothed belt that transmits the driving force by meshing transmission, A V-belt that transmits the driving force by frictional transmission can be mentioned. The transmission belt for automobiles is the heat-resistant transmission belt used in the engine room of automobiles. A timing belt is a pulley tooth used in an engine having a camshaft to transmit the crankshaft to the timing gear and drive the camshaft to open and close the valve in the automobile transmission belt. It is a toothed belt provided with meshing teeth. Power transmission belts for automobiles must have heat resistance against engine heat and water resistance in rainy weather, and maintain tensile strength and excellent dimensional stability after running for a long time under high temperature and high humidity. That is, heat resistance and water resistance are required.

  Conventionally, a heat-resistant transmission belt is a glass for reinforcing rubber that has been coated and dried on a glass fiber cord using a coating solution for coating glass fiber made of resorcin-formaldehyde resin, vinylpyridine-styrene-butadiene copolymer, and chlorosulfonated polyethylene. The fiber was embedded in a cross-linked HNBR as a heat-resistant rubber. Further, the glass fiber for reinforcing rubber was further provided with a secondary coating layer and embedded in a cross-linked HNBR as a heat-resistant rubber.

  Compared to conventional transmission belts, monohydroxybenzene-formaldehyde resin (A) obtained by reacting monohydroxybenzene (D) with formaldehyde (E), vinylpyridine-styrene-butadiene copolymer (B), and chlorosulfonation Using the glass fiber coating coating solution of the present invention made of polyethylene (C), the glass fiber cord is coated and dried, and then the halogen-containing polymer (G) and the halogen-containing polymer (G) are used as 100% standards. Lunadiimide (H), expressed as a percentage by weight, is added in a range of 0.3% to 10.0%, that is, H / G = 0.3% to 10.0%, and dispersed in an organic solvent. A glass fiber secondary coating coating solution is applied and a further secondary coating layer is provided, and the rubber reinforcing glass fiber of the present invention is embedded in a crosslinked HNBR rubber. Even after running for a long time under high humidity and high temperature, the transmission belt maintains the initial bond strength of the glass fiber and the cross-linked HNBR by the coating layer, maintains the tensile strength and has excellent dimensional stability. It has both water resistance and heat resistance.

  As said monohydroxybenzene-formaldehyde resin (A) used for the coating liquid for glass fiber coating of this invention, the molar ratio of formaldehyde (E) with respect to monohydroxybenzene (D) is 0.5 or more, 3.0 or less, , E / D = 0.5 to 3.0, and water-soluble or water-solvent resol type resin reacted with a basic catalyst. If the molar ratio of formaldehyde (E) is less than 0.5, the adhesive strength between the glass fiber for reinforcing rubber and the heat-resistant rubber is inferior, and if it exceeds 3.0, the glass fiber coating solution is easily gelled.

  As monohydroxybenzene-formaldehyde resin (A) used for the coating liquid for glass fiber coating of the present invention, for example, Gunei Chemical Industry Co., Ltd. marketed as industrial phenol resin, trade name, cash register top, model number PL-4667 is mentioned.

  Examples of the basic catalyst include lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, and barium hydroxide.

  In the vinylpyridine-styrene-butadiene copolymer (B) used as the composition for the coating solution for coating glass fibers of the present invention, the ratio of vinylpyridine: styrene: butadiene is 10-20: 10-20: It is preferable to use a vinylpyridine-styrene-butadiene copolymer (B) polymerized in the range of 80 to 60, and commercially available Nippon A & L Co., Ltd., trade name, Pilatex, JSR Corporation, trade name, 0650. And Nippon Zeon Co., Ltd., trade name, Nipol, model number, 1218FS, and the like. In addition, after using the coating solution for glass fiber coating using the vinylpyridine-styrene-butadiene copolymer (B) deviating from the above weight ratio, it was dried after coating, and the rubber reinforcement produced by coating the glass fiber cord. Glass fiber for use is inferior in adhesive strength with the base rubber.

  The chlorosulfonated polyethylene (C) used as a composition for the coating solution for coating glass fibers of the present invention is expressed in terms of weight percentage, the chlorine content is 20.0% to 40.0%, and the sulfur content in the sulfone group Of 0.5% to 2.0% is preferably used. For example, as a latex having a solid content of about 40% by weight, a product name, CSM-450, manufactured by Sumitomo Seika Co., Ltd. is commercially available. It is used for the coating liquid for glass fiber coating of the invention. In addition, for the reinforcement of rubber produced by coating the glass fiber cord using the coating liquid for coating the glass fiber using the chlorosulfonated polyethylene (C) deviating from the chlorine content and the sulfur content in the sulfone group. Glass fiber is inferior in adhesiveness with the cross-linked HNBR which is a base material.

  Monohydroxybenzene-formaldehyde resin (A) and vinylpyridine contained in the coating solution for glass fiber coating are used to obtain the desired adhesion strength to the glass fiber and the base rubber for rubber reinforcement when used in the transmission belt. Expressed as a percentage by weight based on the combined weight of the styrene-butadiene copolymer (B) and the chlorosulfonated polyethylene (C), the monohydroxybenzene-formaldehyde resin (A) is 1.0% or more, 15.0% or less, that is, A / (A + B + C) = 1.0% to 15.0%, and vinylpyridine-styrene-butadiene copolymer (B) is 45.0% or more and 82.0% or less, , B / (A + B + C) = 45.0% -82.0%, chlorosulfonated polyethylene (C) is 3.0% or more and 40.0% or less, that is, C / (A + B + ) = It is preferably contained in the range of 3.0% 40.0%.

  When the content of the monohydroxybenzene-formaldehyde resin (A) in the coating solution for glass fiber coating is less than 1.0%, the adhesive strength between the glass fiber and the base rubber when the glass fiber cord coating material is used. However, it is difficult to obtain preferable water resistance and heat resistance when a transmission belt is used. If the content of the monohydroxybenzene-formaldehyde resin (A) exceeds 15.0%, the glass fiber coating solution tends to cause aggregation and precipitation and cannot be used. Therefore, the preferable content range of the monohydroxybenzene-formaldehyde resin (A) in the coating solution for glass fiber coating of the present invention is that of the vinylpyridine-styrene-butadiene copolymer (B) contained in the coating solution for glass fiber coating. A / (A + B + C) = 1.0% to 15.0% on the basis of the combined weight of the chlorosulfonated polyethylene (C) as 100%.

  Further, when the content of the vinylpyridine-styrene-butadiene copolymer (B) in the coating solution for coating glass fiber is less than 45.0%, the adhesive strength between the glass fiber and the crosslinked HNBR is weakened, It is difficult to obtain preferable heat resistance when using a transmission belt. When the content of the vinylpyridine-styrene-butadiene copolymer (B) exceeds 82.0%, when the glass fiber cord is coated, the coating becomes sticky and the coating layer is easily transferred, and the process becomes dirty. Such problems occur. Therefore, the preferable content range of the vinylpyridine-styrene-butadiene copolymer (B) in the coating solution for glass fiber coating of the present invention is the monohydroxybenzene-formaldehyde resin (A) contained in the coating solution for glass fiber coating. B / (A + B + C) = 45.0% to 82.0%, based on 100% of the total weight of the vinylpyridine-styrene-butadiene copolymer (B) and the chlorosulfonated polyethylene (C).

  When the chlorosulfonated polyethylene (C) in the coating layer is less than 3.0%, it is difficult to obtain desired heat resistance when the transmission belt is formed, and the chlorosulfonated polyethylene (C) is more than 40.0%. In addition, the adhesive strength between the glass fiber and the base rubber becomes weak, and it is difficult to obtain preferable heat resistance when a transmission belt is used. In the coating solution for glass fiber coating of the present invention, the preferred range of chlorosulfonated polyethylene (C) is monohydroxybenzene-formaldehyde resin (A) and vinylpyridine-styrene-butadiene contained in the coating solution for glass fiber coating. A / (A + B + C) = 3.0% to 40.0% on the basis of the combined weight of the copolymer (B) and the chlorosulfonated polyethylene (C) as 100%.

  A part of the vinylpyridine-styrene-butadiene copolymer (B), which is one of the compositions of the glass fiber coating liquid used for the rubber reinforcing glass fiber of the present invention, may be replaced with another rubber elastomer. . With only the vinylpyridine-styrene-butadiene copolymer, the coating of the glass fiber for rubber reinforcement becomes sticky, the coating layer is easily transferred, the process becomes dirty, and the workability deteriorates. Other rubber elastomers include carboxyl group-modified styrene-butadiene rubber, acrylonitrile-butadiene rubber, etc., but styrene-butadiene copolymer (F) having good compatibility with vinylpyridine-styrene-butadiene copolymer (B). It is particularly preferably used and does not impair the adhesiveness with the base rubber, which is a feature of the glass fiber for reinforcing rubber of the present invention, and the heat resistance when embedded in a heat-resistant rubber as the base rubber to form a transmission belt.

  Based on the weight of the vinylpyridine-styrene-butadiene copolymer (B) as 100%, expressed in weight%, the styrene-butadiene copolymer (F) is F / B = 5.0% to 80.0%. In this range, it can be used instead of the vinylpyridine-styrene-butadiene copolymer (B). If it is less than 5.0%, the coating of the glass fiber for reinforcing rubber has an adhesive effect, and there is no effect of suppressing the coating layer from being easily transferred. Preferably, it is 25.0% or more. If it exceeds 80.0%, the adhesiveness to the base rubber and the heat resistance when embedded in the heat-resistant rubber as the base rubber to form a transmission belt are lost. Preferably, it is 55.0% or less.

  As such a styrene-butadiene copolymer (F), for example, a trade name, J-9049, is commercially available from Nippon A & L Co., Ltd., for forming the coating layer of the glass fiber for rubber reinforcement of the present invention. Used in glass fiber coating solution.

  The glass fiber coating coating solution of the present invention may contain an antioxidant, a pH adjuster, a stabilizer and the like. Examples of the anti-aging agent include diphenylamine compounds, and examples of the pH adjusting agent include ammonia.

  The glass fiber coating coating solution of the present invention is applied to a glass fiber cord and then dried to form a coating layer, which is further coated with a halogen-containing polymer (G) and bisallyldiimide (H) as an organic solvent. It is preferable to apply a coating solution for secondary coating of glass fiber dispersed in to provide a secondary coating layer. When a secondary coating layer is provided and embedded in various base rubbers, particularly heat-resistant rubbers such as cross-linked HNBR, and used as a transmission belt, excellent adhesion between the glass fiber cord and the base rubber is obtained, and the rubber of the present invention The reinforcing glass fiber works effectively as a reinforcing material for the transmission belt. Further, in the power transmission belt, the coating layer maintains the initial adhesive strength and is excellent in dimensional stability, that is, excellent in heat resistance and water resistance when used for a long time in a high temperature and humidity environment. Examples of the organic solvent include xylene.

  At that time, the bisallylnadiimide (H) in the coating solution for the glass fiber secondary coating layer is expressed as a percentage by weight based on the weight of the halogen-containing polymer (G) as 100%. 0.0% or less, that is, H / G = 0.3% to 10.0% is preferable. When the content of bisallylnadiimide (H) is less than 0.3%, the above-described excellent heat resistance is difficult to obtain. If it exceeds 10.0%, the adhesive strength between the glass fiber cord and the base rubber becomes weak, and the produced transmission belt is inferior in durability.

  Bisallyl nadiimide (H) is a kind of thermosetting imide resin, and low molecular weight bisallyl nadiimide (H) is excellent in compatibility with other resins. The glass transition point is 300 ° C. or higher, and has the effect of increasing the heat resistance of the transmission belt, and is commercially available from Maruzen Petrochemical Co., Ltd. under trade names such as BANI-M, BANI-H, and BANI-X. It is suitably used for rubber reinforcing glass fibers.

  For heat resistance, it is preferable to use chlorosulfonated polyethylene (C) for the halogen-containing polymer (G). Furthermore, a nitroso compound as a vulcanizing agent such as p-nitrosobenzene, an inorganic filler such as carbon black or magnesium oxide is added to the glass fiber secondary coating solution, and the rubber reinforcing glass fiber is secondary coated. Adding to the layer has a further effect of increasing the heat resistance of the transmission belt produced by embedding the rubber reinforcing glass fiber in rubber. In the glass fiber secondary coating coating solution, the weight of the halogen-containing polymer (G) in the coating solution is expressed as a percentage by weight based on 100%, and the vulcanizing agent is 0.5% or more and 20.0% or less. When the inorganic filler is added in the range of 10.0% or more and 70.0% or less, the produced transmission belt exhibits further heat resistance. When the content of the vulcanizing agent is less than 0.5% and the content of the inorganic filler is less than 10.0%, the effect of improving the heat resistance is not exhibited, and the vulcanizing agent exceeds 20.0%, It is not necessary to add more than 70.0% inorganic filler.

A monohydroxybenzene-formaldehyde resin (A), a vinylpyridine-styrene-butadiene copolymer (B), and a chlorosulfonated polyethylene (C), which are coating solutions for coating glass fibers of the present invention, are dispersed in water to give an emulsion. The glass fiber coating solution of the present invention is applied to a glass fiber cord and then dried, and further, a glass fiber secondary coating in which a halogen-containing polymer (G) and bisallylnadiimide (H) are dispersed in an organic solvent. A glass fiber for reinforcing rubber was prepared as a coating layer by applying a coating solution. (Examples 1-4)
Subsequently, a glass fiber for rubber reinforcement not within the scope of the present invention was produced. (Comparative Examples 1-3). These rubber reinforcing glass fibers of the present invention (Examples 1 to 4) and rubber reinforcing glass fibers not in the category of the present invention (Comparative Examples 1 to 3) were subjected to an adhesive strength evaluation test for heat-resistant rubber, and the evaluation results were obtained. Compared.

  In addition, a power transmission belt in which the rubber reinforcing glass fiber of the present invention or the conventional rubber reinforcing glass fiber was embedded in a heat resistant rubber was produced. Next, these transmission belts are set on pulleys, and in order to evaluate the water resistance, the transmission belts are run for a long time while water is applied, and the coating layers maintain the initial adhesive strength for a long time. The transmission in which the tensile strength does not change and the water resistance fatigue resistance evaluation test for evaluating that the dimensional stability is excellent is performed, and the glass fiber for rubber reinforcement (Examples 1 to 4) of the present invention is embedded. The evaluation results of the belt and the transmission belt in which the glass fibers for rubber reinforcement (Comparative Examples 1 to 3) not within the scope of the present invention were embedded were compared. In order to evaluate the heat resistance, a plurality of pulleys were used at high temperature on the transmission belt, and the belt was allowed to run for a long time. A power transmission belt in which the heat-resistant and bending-resistant running fatigue performance evaluation test for evaluating that the strength does not change and the dimensional stability is excellent is performed, and the glass fibers for rubber reinforcement of the present invention (Examples 2 and 4) are embedded. The evaluation results of the transmission belts in which the glass fibers for rubber reinforcement (Comparative Examples 1 and 2) not within the scope of the present invention were embedded were compared.

Details will be described below.
Example 1
(Preparation of coating solution for coating glass fiber of the present invention)
First, synthesis of the monohydroxybenzene-formaldehyde resin (A) will be described. In a three-necked separable flask equipped with a reflux condenser, a thermometer, and a stirrer, monohydroxybenzene (D), 100 parts by weight, 37.0% by weight formaldehyde (E) aqueous solution, 157 parts by weight (molar ratio) E / D = 1.8), 5 parts by weight of a 10% strength by weight aqueous sodium hydroxide solution was charged, and the mixture was stirred at 80 ° C. for 3 hours. After stirring was stopped and the mixture was cooled, 370 parts by weight of a 1 wt% aqueous sodium hydroxide solution was added to polymerize the monohydroxybenzene-formaldehyde resin (A).

  Next, using the monohydroxybenzene-formaldehyde resin (A) synthesized by the above procedure, aqueous vinylpyridine-styrene-butadiene copolymer (B) emulsion, chlorosulfonated polyethylene (C) emulsion, Water was added to prepare a glass fiber coating coating solution of the present invention.

  Specifically, vinylpyridine-styrene obtained by polymerizing monohydroxybenzene-formaldehyde resin (A), 42 parts by weight, vinylpyridine, styrene, and butadiene so that a ratio of vinylpyridine: styrene: butadiene = 15: 15: 70 is obtained. -Nippon A & L Co., Ltd., trade name as butadiene polymer (B) emulsion, 476 parts by weight of pilatex (solid content concentration, 41.0% by weight), and Sumitomo Seika as chlorosulfonated polyethylene (C) emulsion Product name, CSM450 (solid content concentration, 40.0% by weight) 206 parts by weight and ammonia water (concentration, 25.0% by weight) 22 parts by weight as a PH regulator, 1000 parts by weight as a whole Water was added so that the coating solution for coating glass fiber of the present invention was prepared.

The content ratio of each component in the coating solution for glass fiber coating is the total weight of monohydroxybenzene-formaldehyde resin (A), vinylpyridine-styrene-butadiene copolymer (B) and chlorosulfonated polyethylene (C). Expressed as a percentage by weight based on 100%, monohydroxybenzene-formaldehyde resin (A) is 3.6%, vinylpyridine-styrene-butadiene copolymer (B) is 67.8%, chlorosulfonated polyethylene (C ) Is 28.6%. The weights of vinylpyridine-styrene-butadiene copolymer (B) and chlorosulfonated polyethylene (C) in the coating solution for glass fiber coating are converted into solid content from the solid content concentration of the above-mentioned pyrexate and CSM450. Asked.
(Preparation of glass fiber for rubber reinforcement of the present invention)
Next, the rubber reinforcement of the present invention, in which carbon black was added to chlorosulfonated polyethylene (C), p-dinitrobenzene, and hexamethylene diallyl nadiimide belonging to bisallyl nadiimide (G) and dispersed in xylene. A glass fiber secondary coating coating solution for providing a secondary coating layer on the glass fiber was prepared.

  Specifically, as Tosoh Co., Ltd. as chlorosulfonated polyethylene (C), trade name, TS-430, 100 parts by weight, p-dinitrobenzene, 40 parts by weight, and NN′-hexamethylene diallyl nadiimide Made by Maruzen Petrochemical Co., Ltd., trade name, BANI-H, 0.3 parts by weight, carbon black, 30 parts by weight, and xylene, 1315 parts by weight, are dispersed in glass fiber secondary coating solution. Prepared. That is, NN′-hexamethylenediallylnadiimide belonging to bisallylnadiimide (G) is H / G = 0.3% by weight and a vulcanizing agent with respect to the weight of chlorosulfonated polyethylene (C). A glass fiber secondary coating coating solution was prepared such that p-dinitrobenzene was 40 wt% and carbon black as an inorganic filler was 30.0 wt%.

  After aligning three glass fiber cords of 200 glass fiber filaments having a diameter of 9 μm, the glass fiber coating coating solution prepared in the above procedure is applied, and then dried at a temperature of 280 ° C. for 22 seconds. To provide a coating layer.

  The solid content adhesion rate at this time, that is, the weight ratio of the coating layer was 19.0% by weight with respect to the total weight of the glass fiber bundle provided with the coating layer.

  The glass fiber cord provided with the coating layer is given a twist of 2.0 times per 2.54 cm, and is further drawn 13 times to twist 2.0 times per 2.54 cm in the opposite direction to the twist. Worked. Then, after applying the glass fiber secondary coating coating solution prepared in the above-described procedure, drying was performed at 110 ° C. for 1 minute to provide a secondary coating layer, and the glass fiber for rubber reinforcement of the present invention (Example 1) ) Was produced. In this way, two types of glass fibers for reinforcing rubber were prepared in which the directions of lower kneading and upper kneading were reversed. These are called S-kneading and Z-kneading, respectively.

At this time, the solid content adhesion rate, that is, the weight ratio of the secondary coating layer was 3.5% by weight with respect to the weight of the glass fiber bundle provided with the primary and secondary coating layers.
Example 2
83 parts by weight of the monohydroxybenzene-formaldehyde resin (A) is added to the coating solution for coating glass fibers of Example 1, vinyl pyridine, styrene, and butadiene at a weight ratio of 15:15:70. The added amount of vinylpyridine-styrene-butadiene copolymer (B) emulsion (trade name, pilatex, solid content, 41.0% by weight, manufactured by Nippon A & L Co., Ltd.) is 451 parts by weight. A glass fiber coating coating solution of the present invention was prepared in the same manner as in Example 1 except that this was changed. That is, based on the total weight of monohydroxybenzene-formaldehyde resin (A), vinylpyridine-styrene-butadiene copolymer (B) and chlorosulfonated polyethylene (C) in the coating solution for glass fiber coating as 100%, Expressed in weight percentage, the monohydroxybenzene-formaldehyde resin (A) is 7.2%, the vinylpyridine-styrene-butadiene copolymer (B) is 64.2%, and the chlorosulfonated polyethylene (C) is 28.6. %.

Next, a secondary solution for glass fiber coating similar to that in Example 1 is prepared by the procedure shown in Example 1, and the operation is performed in the same procedure as in Example 1 to further add a secondary coating layer to the glass fiber cord. A glass fiber for reinforcing rubber of the present invention (Example 2) was produced.
Example 3
124 parts by weight of the monohydroxybenzene-formaldehyde resin (A) is added to the coating solution for coating glass fibers of Example 1, vinyl pyridine, styrene, and butadiene at a weight ratio of 15:15:70. The added amount of vinylpyridine-styrene-butadiene copolymer (B) emulsion (trade name, pilatex, solid content, 41.0% by weight, manufactured by Nippon A & L Co., Ltd.) is 426 parts by weight. A glass fiber coating coating solution of the present invention was prepared in the same manner as in Example 1 except that the amount was changed. That is, in terms of weight percentage, the total weight of monohydroxybenzene-formaldehyde resin (A), vinylpyridine-styrene-butadiene copolymer (C) and chlorosulfonated polyethylene in the coating solution for glass fiber coating is 100%. In other words, the monohydroxybenzene-formaldehyde resin (A) is 10.8%, the vinylpyridine-styrene-butadiene copolymer (B) is 60.6%, and the chlorosulfonated polyethylene (C) is 28.6%. Adjusted as follows.

Next, a secondary solution for glass fiber coating similar to that in Example 1 is prepared by the procedure shown in Example 1, and the operation is performed in the same procedure as in Example 1 to further add a secondary coating layer to the glass fiber cord. A glass fiber for reinforcing rubber of the present invention (Example 3) was prepared.
Example 4
1 weight of commercially available monohydroxybenzene-formaldehyde resin (A) (manufactured by Gunei Chemical Industry Co., Ltd., trade name, cash register top, model number PL-4667, solid content, 50% by weight) to monohydroxybenzene-formaldehyde resin (A) What was diluted with a sodium hydroxide aqueous solution with a concentration of 2% at a weight ratio of 2% was used.

  83 parts by weight of the registration top, model number PL-4667 as the monohydroxybenzene-formaldehyde resin (A), 83 parts by weight of vinyl pyridine, styrene, and butadiene are added to the glass fiber coating coating solution of Example 1; : Addition amount of vinylpyridine-styrene-butadiene copolymer (B) emulsion polymerized to a weight ratio of 15:70 (trade name, pilatex, solid content, 41% by weight, manufactured by Nippon A & L Co., Ltd.) A glass fiber coating coating solution of the present invention was prepared in the same manner as in Example 1 except that the amount was changed to 451 parts by weight. That is, based on the total weight of monohydroxybenzene-formaldehyde resin (A), vinylpyridine-styrene-butadiene copolymer (B) and chlorosulfonated polyethylene (C) in the coating solution for glass fiber coating as 100% standard The monohydroxybenzene-formaldehyde resin was adjusted to 7.2%, the vinylpyridine-styrene-butadiene copolymer was 64.2%, and the chlorosulfonated polyethylene was adjusted to 28.6%. .

Next, a secondary solution for glass fiber coating similar to that in Example 1 is prepared by the procedure shown in Example 1, and the operation is performed in the same procedure as in Example 1 to further add a secondary coating layer to the glass fiber cord. A glass fiber for reinforcing rubber of the present invention (Example 4) was prepared.
Comparative Example 1
A glass fiber coating solution for rubber reinforcement comprising a conventional resorcin-formaldehyde resin, vinylpyridine-styrene-butadiene copolymer emulsion and chlorosulfonated polyethylene was prepared.

  Unlike Example 1, instead of monohydroxybenzene-formaldehyde resin (A), resorcin-formaldehyde resin (molar ratio of resorcin to formaldehyde, reacted at 1.0: 1.0, solid content, 8.7 239 parts by weight of vinyl pyridine, styrene, and butadiene in a weight ratio of 15:15:70 (made by Nippon A & L Co., Ltd., trade name, pilatex, A glass fiber coating coating solution was prepared in the same manner as in Example 1 except that the addition amount of the solid content (41.0% by weight) was changed to 451 parts by weight. A coating solution for fiber coating was prepared. That is, the resorcin-formaldehyde resin is expressed as a percentage by weight based on the total weight of the resorcin-formaldehyde resin, vinylpyridine-styrene-butadiene copolymer and chlorosulfonated polyethylene in the coating solution for glass fiber coating. 0.2%, vinylpyridine-styrene-butadiene copolymer 64.2%, and chlorosulfonated polyethylene 28.6%.

Next, a secondary solution for glass fiber coating similar to that in Example 1 is prepared by the procedure shown in Example 1, and the operation is performed in the same procedure as in Example 1 to further add a secondary coating layer to the glass fiber cord. A glass fiber for rubber reinforcement (Comparative Example 1) was prepared.
Comparative Example 2
Using the same glass fiber coating coating solution as in Example 1, then chlorosulfonated polyethylene (trade name, TS-430, manufactured by Tosoh Corporation), 100 parts by weight, 4,4′-diphenylmethane diisocyanate, 40 parts by weight Then, using a glass fiber secondary coating coating solution composed of 30 parts by weight of carbon black, 1315 parts by weight of xylene, and 1315 parts by weight, the procedure was performed in accordance with the procedure shown in Example 1 to provide a coating layer and a secondary coating layer. A glass fiber for rubber reinforcement (Comparative Example 2) was produced. That is, 40% by weight of 4,4′-diphenylmethane diisocyanate and 30% by weight of carbon black were used with respect to the weight of chlorosulfonated polyethylene in the glass fiber secondary coating solution.
Comparative Example 3
The same glass fiber coating coating solution as in Example 2 was used, then the same glass fiber secondary coating coating solution as in Comparative Example 2 was prepared, and the primary coating layer and the secondary coating were prepared according to the procedure shown in Example 1. A glass fiber for rubber reinforcement (Comparative Example 3) provided with a layer was produced.
(Adhesion strength evaluation test)
Before describing the adhesive strength evaluation test, the heat resistant rubber used in the test will be described.

  HNBR (made by Nippon Zeon Co., Ltd., model number, 2020) as a base rubber, 100 parts by weight, carbon black, 40 parts by weight, zinc white, 5 parts by weight, stearic acid, 0.5 parts by weight , Sulfur, 0.4 parts by weight, vulcanization accelerator, 2.5 parts by weight, antiaging agent, 1.5 parts by weight of HNBR cross-linked heat resistant rubber (hereinafter referred to as heat resistant rubber A) And HNBR (manufactured by Nippon Zeon Co., Ltd., model number, 2010), 100 parts by weight, carbon black, 40 parts by weight, zinc white, 5 parts by weight, stearic acid, 0.5 parts by weight, Heat-resistant rubber obtained by crosslinking HNBR containing 5 parts by weight of 1,3-di (t-butylperoxyisopropyl) benzene, an antioxidant and 1.5 parts by weight (hereinafter referred to as heat-resistant rubber B) Was used for the adhesive strength evaluation test.

The test pieces are arranged on a 3 mm thick and 25 mm wide rubber sheet made of heat resistant rubber A or heat resistant rubber B, and 20 glass fiber cords for rubber reinforcement (Examples 1 to 4 and Comparative Examples 1 to 3) are arranged from above. Cover with cloth, heat resistant rubber A, temperature, 150 ° C., 196 Newton / cm ² (hereinafter Newton is abbreviated as N), and heat resistant rubber B, temperature, 170 ° C., 196 N / cm ² The test piece for pressing the adhesive strength evaluation, in other words, a rubber sheet was obtained. For the measurement of the adhesive strength of the test piece, each rubber sheet and rubber reinforcing glass fiber are individually clamped at the end, the peeling speed is 50 mm / min, and the rubber reinforcing glass fiber is peeled off from the rubber sheet. The maximum resistance value at the time was measured to determine the peel strength. The greater the peel strength, the better the adhesive strength.
(Adhesion strength evaluation results)
Table 1 shows the evaluation results of the adhesive strength.

  In Table 1, the destruction state in which the glass fiber and the rubber were not separated from the interface was defined as rubber failure, and the destruction state in which only a part was separated from the interface was defined as interface separation. Rubber destruction is superior in adhesion strength to interfacial peeling.

  As shown in Table 1, the glass fiber for reinforcing rubber of the present invention of Example 1 was measured for peel strength. As a result, the heat resistant rubber A was 314N and the heat resistant rubber B was 284N. On the other hand, the adhesiveness was good and the adhesive strength was excellent.

  As shown in Table 1, the glass fiber for reinforcing rubber of the present invention of Example 2 was measured for peel strength. As a result, the heat resistant rubber A was 333 N, the heat resistant rubber B was 304 N, both rubbers On the other hand, the adhesiveness was good and the adhesive strength was excellent.

  As shown in Table 1, the glass fiber for rubber reinforcement of Example 3 of the present invention was measured for peel strength. As a result, the heat resistant rubber A was 323N and the heat resistant rubber B was 309N. On the other hand, the adhesiveness was good and the adhesive strength was excellent.

  As shown in Example 4 of Table 1, the glass fiber for reinforcing rubber of the present invention of Example 4 is 343N for the heat-resistant rubber A and 345N for the heat-resistant rubber B, and is bonded to both rubbers. The properties were good and the adhesive strength was excellent.

  Moreover, when the heat-resistant rubber A is used for the glass fiber for rubber reinforcement of Examples 1-4 of this invention as shown in Examples 1-4 of Table 1, when the destruction state uses heat-resistant rubber B Both were rubber breaks and had excellent adhesive strength.

  A glass fiber for rubber reinforcement that does not belong to the category of the present invention in Comparative Example 1 was prepared in the same manner as in Example 1 and a test piece was prepared and evaluated for adhesive strength. Thus, the heat resistant rubber A was 323N and the heat resistant rubber B was 314N, and the adhesive properties were good for both rubbers and the adhesive strength was excellent. When the heat-resistant rubber A was used and the heat-resistant rubber B was used, the broken state was rubber breakage and the adhesive strength was excellent.

  The glass fiber for rubber reinforcement that does not belong to the category of the present invention in Comparative Example 2 was prepared in the same procedure as in Example 1 and a test piece was prepared and the adhesion strength was evaluated. As described above, the heat resistant rubber A had a good adhesive strength of 294N, whereas the heat resistant rubber B had a good adhesive strength of 127N, and the adhesive strength was weak and the adhesive strength was poor.

A glass fiber for reinforcing rubber that does not belong to the category of the present invention in Comparative Example 3 was prepared in the same procedure as in Example 1 and a test piece was evaluated. As described above, the heat resistant rubber A had a good adhesive strength of 319N, but the heat resistant rubber B had a good adhesive strength of 118N, and the adhesive strength was weak and the adhesive strength was poor.
(Water resistance evaluation)
Using the glass fiber for rubber reinforcement produced in Examples 1, 2, and 4 and Comparative Examples 1 to 3 as a reinforcing material, the heat-resistant rubber B was used as a base rubber, and a transmission belt having a width of 19 mm and a length of 876 mm was produced. A water resistance running fatigue test for evaluating water resistance was conducted. The water resistance is evaluated based on the tensile strength retention rate after a certain period of time, that is, the water resistance running fatigue performance, by running the transmission belt using gears, that is, pulleys, under water injection.

  FIG. 1 is a perspective view when a transmission belt produced by embedding rubber reinforcing glass fibers in heat-resistant rubber is cut.

  The transmission belt 1 has many protrusions 1A having a height of 3.2 mm for meshing with pulleys, and the thickness of the back part 1B excluding the protrusions is 2.0 mm. So that the twisting directions of the upper twist and the lower twist are different, S twist, 6 Z twist, 6 and 12 glass fibers for rubber reinforcement 2 in total, S twist and Z twist alternately Buried.

  FIG. 2 is a schematic side view of a water resistance running fatigue tester for a transmission belt.

  As shown in FIG. 2, each transmission belt 1 is attached to a water resistance running fatigue tester equipped with a drive motor and a generator (not shown) to measure water resistance.

  The transmission belt 1 travels while the driven pulleys 4 and 5 are rotated by the driving force of the driving pulley 3 that is rotationally driven by the driving motor. The driven pulley 5 is connected to a generator (not shown), and drives the generator to generate 1 kW of power. The idler 6 has a role of tensioning the transmission belt 1 while rotating during traveling in the water resistance traveling fatigue test, and applies 500 N to the transmission belt 1 as a load for tensioning the transmission belt 1. The driven pulleys 4 and 5 have a diameter, 60 mm, the number of teeth, and 20T, and the driving pulley 3 has a diameter of 120 mm, and the number of teeth, 40T. The rotational speed per minute of the driving pulley 3 during the water-resistant running fatigue test is 3000 rpm, and the rotational speed per minute of the driven pulleys 4 and 5 is 6000 rpm. The direction of rotation is indicated by an arrow parallel to the transmission belt 1.

At room temperature, as shown in FIG. 2, 6000 ml of water 7 per hour is uniformly dropped on the transmission belt 1 between the drive pulley 3 and the driven pulley 4 while rotating the drive pulley 3 at 3000 rpm. The transmission belt 1 was run using driven pulleys 4 and 5 and an idler 6. Thus, the water-resistant running fatigue test which runs the transmission belt 1 for 36 hours was implemented. The tensile strength of the transmission belt 1 before the water-resistant running fatigue test and the tensile strength after the water-resistant running fatigue test are measured, and the tensile strength retention rate of the transmission belt 1 after the test with respect to the test before the test is obtained by the equation (1). The water resistance of the transmission belt 1 manufactured using the rubber reinforcing glass 2 of Examples 1, 2, 4 and Comparative Examples 1 to 3 was comparatively evaluated.
(Tensile strength measurement)
The length of the test piece used for measuring the tensile strength is 257 mm, and three pieces can be cut out from one transmission belt. Each end of these test pieces was clamped with a clamp having a distance of 145 mm between the clamps, the tensile speed was 50 mm / min, and the maximum resistance value until the belt was broken was the tensile strength. The resistance value was measured three times from one belt, and the average value was taken as the tensile strength of the transmission belt.

Tensile strength retention rate (%) = Tensile strength after test ÷ Tensile strength before test × 100
Table 2 shows the tensile strength retention ratio of each transmission belt after the water-resistant running fatigue test.

  As shown in Table 2, for glass fiber coating comprising the compositions of Examples 1, 2, 4 and Comparative Example 3 monohydroxybenzene-formaldehyde resin, vinylpyridine-styrene-butadiene copolymer and chlorosulfonated polyethylene. The tensile strength retention after the running test of the transmission belt 1 using the glass fiber 2 for rubber reinforcement having a coating layer obtained by coating and drying the coating liquid on the glass fiber cord and a further secondary coating layer is shown in Example 1. When the rubber reinforcing glass fiber 2 was used, it was 56%, and when the rubber reinforcing glass fiber 2 of Example 2 was used, it was 61%, and the rubber reinforcing glass fiber 2 of Example 4 was used. The ratio was 63%, and 51% when the glass fiber 2 for rubber reinforcement of Comparative Example 3 was used.

  On the other hand, as shown in Comparative Example 1 and Comparative Example 2, resorcin-formaldehyde resin, vinylpyridine-styrene-butadiene copolymer prepared using resorcin-formaldehyde resin instead of not using monohydroxybenzene-formaldehyde resin Tensile strength retention of rubber-reinforced glass fiber 2 having a coating layer obtained by coating a glass fiber cord with a coating solution for coating glass fiber comprising merging and chlorosulfonated polyethylene on a glass fiber cord and a further secondary coating layer When the rubber reinforcing glass fiber 2 of Comparative Example 1 was used, it was 47%, and when the rubber reinforcing glass fiber 2 of Comparative Example 2 was used, it was 39%, which was inferior in water resistance. When the rubber reinforcing glass fiber 2 of Example 2 was used, the tensile strength retention was 61%, compared with 51% when using the rubber reinforcing glass fiber 2 of Comparative Example 3. Big.

From the results of this water resistance running fatigue test, compared with the conventional glass fiber 2 for rubber reinforcement, monohydroxybenzene-formaldehyde resin (A), vinylpyridine-styrene-butadiene copolymer (B), and chlorosulfonation. NN′-hexamethylene diallyl belonging to bisallylnadiimide (H), which has a coating coating layer formed by applying and drying the glass fiber coating coating solution of the present invention comprising polyethylene (C) as a composition Transmission belt using the glass fiber 2 for reinforcing rubber of the present invention having a further secondary coating layer composed of nadiimide, chlorosulfonated polyethylene as the halogen-containing polymer (G), and p-dinitrobenzene. 1 was found to have excellent water resistance.
(Heat resistance evaluation)
Then, using the heat-resistant rubber B as a base rubber, using the glass fiber cord for reinforcing rubber produced in Examples 2 and 4 and Comparative Examples 1 and 2 as a reinforcing material, a width of 19 mm, A transmission belt having a length of 876 mm was produced, respectively, and a heat-resistant, bending-resistant running fatigue test for evaluating heat resistance was performed. The heat resistance is evaluated by using a plurality of gears, that is, pulleys, while the power transmission belt is bent while being bent at a high temperature, and the tensile strength retention rate after a certain period of time, that is, the heat resistance bending resistance fatigue resistance performance.

  FIG. 3 is a schematic side view of a heat-resistant bending-resistant running fatigue tester for a transmission belt.

As shown in FIG. 3, each transmission belt 1 is mounted on a heat-resistant and bending-resistant running fatigue tester equipped with a drive motor (not shown) to measure heat resistance. Transmission belt 1 by the driving force of the driving pulley 8, which is rotated by a driving motor, three driven pulleys 9, 9 ', travels while rotating the 9 ^〃. The idler 10 is for tensioning the transmission belt 1 during traveling in the heat resistance and bending resistance fatigue test, has a role of tensioning the transmission belt 1, and gives 500 N to the transmission belt 1 as a load for tensioning the transmission belt 1. . Driving pulley 8, the diameter, 120 mm, number of teeth, a 40T, driven pulley 9 and 9 ', 9 ^〃 is diameter 60 mm, number of teeth, it is 20T. Revolutions per minute of the driving pulley 8 in the heat bending running fatigue test, 3000 rpm, driven pulley 9 and 9 ', 9 revolutions per minute ^〃 is 6000 rpm. The direction of rotation is indicated by an arrow parallel to the transmission belt 1.

Temperature, under 130 ° C. of environment, as shown in FIG. 3, the drive pulley 8, is rotated at 3000 rpm, the transmission belt 1 driven pulley 9 and 9 ', 9 ^〃, was run while bending with the idler 10 It was. In this manner, the transmission belt 1 was run for 500 hours, and a heat-resistant and bending-resistant running fatigue test was performed. The tensile strength of the transmission belt 1 before the heat-resistant bending resistance running fatigue test and the tensile strength after the heat-resistant bending resistance fatigue test are measured. The retention rate was determined, and the heat resistance, bending resistance, and fatigue resistance of the transmission belt 1 produced using the glass fibers 2 for rubber reinforcement of Examples 1 and 2 and Comparative Example 2 were compared and evaluated.
Table 2 shows the tensile strength retention ratio of each transmission belt after the heat-resistant and bending-resistant running fatigue test.

  As shown in Table 3, the tensile strength retention ratios of the transmission belt 1 manufactured using the glass fibers 2 for rubber reinforcement of Examples 2 and 4 after the heat and bending resistance fatigue test are 91% and 93%, respectively. The transmission belts 1 using the rubber fibers 2 for reinforcing rubber of Comparative Examples 1 and 2 are superior to the tensile strength retention after the heat and bending resistance running fatigue test, respectively 90% and 80%, and have excellent heat resistance. Have

  Based on the results of this heat resistance and bending resistance fatigue test, a composition comprising a monohydroxybenzene-formaldehyde resin (A), a vinylpyridine-styrene-butadiene copolymer (B), and a chlorosulfonated polyethylene (C). It has a coating coating layer formed by applying and drying the coating solution for coating glass fibers of the invention, and belongs to NN'-hexamethylenediallylnadiimide belonging to bisallylnadiimide (H) and halogen-containing polymer (G) The power transmission belt 1 using the glass fiber 2 for rubber reinforcement of the present invention having a further secondary coating layer composed of chlorosulfonated polyethylene and p-dinitrobenzene has excellent heat resistance. understood.

  The rubber reinforcing glass fibers 2 of Examples 1 to 4 have excellent adhesive strength with the cross-linked HNBR, and the power transmission belts produced using the rubber reinforcing glass fibers 2 of Examples 1 to 4 were excellent. Since it has water resistance and heat resistance, it is suitable for use as a core wire of a transmission belt for automobiles such as a timing belt used for a long time under high temperature and high humidity.

  According to the present invention, there is obtained a glass fiber coating coating solution for providing a glass fiber cord coating layer that gives a preferable adhesion strength to the glass fiber cord and the crosslinked HNBR as the base rubber. When the glass fiber cord is applied to the glass fiber cord and then dried and covered to form a coating layer, the rubber reinforcing glass fiber is embedded in a cross-linked HNBR to give excellent water resistance and transmission. The belt has excellent water resistance and heat resistance. Therefore, it is embedded as a reinforcement in a transmission belt for transmitting the driving force of a drive source such as an engine or a motor, and is embedded in HNBR for use in an automobile transmission belt such as a timing belt. Used as a rubber reinforcing glass fiber that provides tensile strength maintenance and dimensional stability under high humidity and high temperatures.

It is a perspective view at the time of cut | disconnecting the power transmission belt produced by embedding the rubber fiber for rubber reinforcement in heat-resistant rubber. It is a schematic side view of the water-resistant running fatigue performance tester of a transmission belt. It is a schematic side view of the heat-resistant bending-proof running fatigue performance testing machine of a transmission belt.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Transmission belt 1A Protrusion part 1B Back part 2 Glass fiber cord for rubber reinforcement 3 Drive pulley (connected to drive motor)
4 Driven pulley 5 Driven pulley (connected to generator)
6 Idler
7 Water 8 Drive pulley 9, 9 ', 9 ^〃 Follow pulley 10 Idler

Claims (7)

A glass fiber coating coating solution for coating a glass fiber cord in which a phenol resin, a vinylpyridine-styrene-butadiene copolymer (B) and a chlorosulfonated polyethylene (C) are dispersed in water to form an emulsion, A glass fiber coating coating solution, wherein the phenol resin is a monohydroxybenzene-formaldehyde resin (A) obtained by reacting monohydroxybenzene (D) and formaldehyde (E). Resole type resin in which monohydroxybenzene-formaldehyde resin (A) is reacted with a basic catalyst at a molar ratio of formaldehyde (E) to monohydroxybenzene (D) of E / D = 0.5 to 3.0 The coating solution for coating glass fibers according to claim 1, wherein Expressed by weight of 100%, monohydroxybenzene-formaldehyde resin (A) is A / (A + B + C) = 1.0% to 15.0%, vinylpyridine-styrene-butadiene copolymer (B) is B / (A + B + C) ) = 45.0% to 82.0%, and chlorosulfonated polyethylene (C) is contained in the range of C / (A + B + C) = 3.0% to 40.0%. Or the coating liquid for glass fiber coating of Claim 2. The vinylpyridine-styrene-butadiene copolymer (B) is expressed as a percentage by weight with respect to the styrene-butadiene copolymer (F), and F / B = 5.0% to 80.0%. The coating liquid for glass fiber coating according to any one of claims 1 to 3, wherein: After applying the glass fiber coating coating solution according to any one of claims 1 to 4, the glass fiber for rubber reinforcement dried and applied to the halogen-containing polymer (G) and expressed in weight percentage as H / G = 0.3% to 10.0% of bisallylnadiimide (H) dispersed in an organic solvent is applied to a glass fiber secondary coating solution, and a further secondary coating layer is provided. Characteristic glass fiber for rubber reinforcement. A power transmission belt comprising the rubber reinforcing fiber according to claim 5 embedded in a heat resistant rubber. The power transmission belt according to claim 6, wherein the heat-resistant rubber is a crosslinked hydrogenated nitrile rubber.

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