JP2008137882A - Glass fiber for reinforcing rubber and transmission belt using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a glass fiber for reinforcing rubber, which can impart excellent durability to water and heat resistance to a transmission belt when it is buried in heat-resistant rubber and used as the transmission belt; and to provide the transmission belt using the same. <P>SOLUTION: When the transmission belt is manufactured, the glass fiber for reinforcing rubber is buried in a base rubber and used. In the glass fiber for reinforcing rubber, a primary coating layer containing a chlorophenol-formaldehyde condensate, a vinylpyridine-styrene-butadiene copolymer, and a chlorosulfonated polyethylene is formed on a glass fiber cord obtained by bundling a plurality of glass fiber filaments and a secondary coating layer containing a chlorosulfonated polyethylene and a maleimide is formed on the primary coating layer. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a glass fiber for reinforcing rubber for embedding in a rubber which is a base material for reinforcement when producing a transmission belt. Furthermore, the present invention relates to a transmission belt using the rubber reinforcing fiber. The glass fiber for reinforcing rubber of the present invention is particularly useful for reinforcing a timing belt for automobiles.

  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 adhesion is weak and the interface peels off, so that it does not serve as a reinforcing material.

  Therefore, the glass fiber cord is coated with a coating material for improving the adhesion to the base rubber for the glass fiber for rubber reinforcement that is embedded in the base rubber when using the transmission belt. Is used. Specifically, for example, in order to improve the adhesion between the base rubber and the glass fiber and prevent the separation of the interface, a resorcinol is usually applied to a glass fiber cord formed by applying a sizing agent to a large number of glass fiber filaments and converging them. -Glass fiber for rubber reinforcement used as a coating layer after applying a coating solution for coating glass fiber in which formaldehyde condensate and various latexes are dispersed in water is used. 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. That's not always 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.

  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.

  Glass fiber as a rubber-reinforced glass fiber for providing a transmission belt that maintains long-term reliability even when running in a high-temperature environment without causing separation of the interface and maintaining the adhesive strength between HNBR and rubber-reinforced glass fiber A rubber reinforcing glass having a coating obtained after the above-described coating treatment applied to a cord as a primary coating layer, a second liquid having a different composition applied to the primary coating layer and dried to form a secondary coating layer The fiber is disclosed by patent documents 1-4.

  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 treatment agent for the second coating layer is a halogen-containing polymer, a vulcanizing agent, and a maleimide vulcanizing aid A cord for reinforcing rubber is disclosed which is characterized by having a main component.

  Further, Patent Document 3 relating to the applicant's patent application discloses a glass fiber cord 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 coating the coating solution for fiber coating, a coating layer formed by drying is provided, and the halogen-containing polymer and the weight percentage based on the weight of the halogen-containing polymer are 0.3 wt% to 10.0 wt%. A glass fiber for reinforcing rubber characterized by coating a coating solution for coating glass fiber in which bisallylnadiimide is dispersed in an organic solvent and providing a further coating layer is disclosed. The rubber reinforcing glass fiber showed a preferable adhesive strength in bonding with 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. Disclosed is a glass fiber for reinforcing rubber, characterized in that the second liquid for glass fiber coating is obtained by dispersing bisallyldiimide, rubber elastomer, vulcanizing agent and inorganic filler in an organic solvent. ing. The glass fiber for rubber reinforcement exhibits a preferable adhesive strength in bonding with HNBR, and has excellent heat resistance as a transmission belt embedded in HNBR without any decrease in tensile strength even after running for a long time at high temperatures. I had it.

  In the conventional rubber reinforcing glass fiber, for example, the rubber reinforcing glass fiber described in Patent Documents 1 to 4, the initial adhesive strength between the rubber reinforcing glass fiber and the base rubber was obtained. When used, there is nothing to give a transmission belt that has excellent water resistance and heat resistance that maintains the tensile strength before running and does not change in dimensions after running for a long time under high temperature and humidity, especially inferior in water resistance There was a problem of being.

  Compared to conventional transmission belts in which glass fibers for rubber reinforcement are embedded in heat-resistant rubber, they have the same or higher adhesion strength between glass fibers for rubber reinforcement and heat-resistant rubber, and run for a long time at high temperatures. In addition to the heat resistance that keeps the initial adhesive strength even if the coating layer is applied, even if it is run for a long time while water is applied to the transmission belt, the coating layer prevents the penetration of water into the glass fiber cord. Development of a rubber reinforcing glass fiber that gives the transmission belt water resistance that maintains adhesive strength and a transmission belt that has both excellent heat resistance and water resistance by using the rubber reinforcing glass fiber is awaited.

  In Patent Document 5 relating to the applicant's patent application, monohydroxybenzene-formaldehyde resin, vinylpyridine-styrene-butadiene copolymer and chlorosulfonated polyethylene are dispersed in water and coated on a glass fiber cord as an emulsion. A glass fiber coating coating solution is disclosed.

  In Patent Document 6 related to the applicant's patent application, a glass fiber coating coating solution described in Patent Document 5 is applied to a glass fiber cord to form a primary coating layer, and a halogen-containing polymer and bisallyldiimide are formed thereon. A glass fiber for reinforcing rubber comprising a secondary coating layer containing a rubber, and a glass for reinforcing rubber comprising a secondary coating layer containing a halogen-containing polymer and maleimide as an upper layer of the primary coating layer Fiber, glass fiber for reinforcing rubber comprising a secondary coating layer containing a halogen-containing polymer, organic diisocyanate and zinc methacrylate on the upper layer of the primary coating layer, and a halogen-containing polymer on the upper layer of the primary coating layer And a glass fiber for reinforcing rubber comprising a secondary coating layer containing a triazine compound.

Further, Patent Document 7 discloses a glass fiber impregnating agent comprising a resorcin-chlorophenol-formaldehyde resin as a composition. The resorcin-chlorophenol-formaldehyde resin reacts with resorcin, chlorophenol and formaldehyde as an aqueous solution. It is said that it is a water-soluble addition condensate obtained in the form of an aqueous solution having a solid content of about 20% by weight and can be obtained from ICI under the trade name of VALQUABOND E, using a water-soluble resorcin-chlorophenol-formaldehyde resin. Yes.
Japanese Examined Patent Publication No. 2-4715 Japanese Patent No. 3201330 JP 2004-203730 A JP 2004-244785 A JP 2006-104595 A WO / 2006/038490 brochure Japanese Patent Laid-Open No. 3-65536

  Conventionally, a chlorophenol-formaldehyde condensate obtained by reacting formaldehyde with chlorophenol has a low solubility in water as compared with a resorcin-formaldehyde condensate that has been used in a coating solution for coating glass fibers. Once dissolved in water, the liquid stability is poor and the chlorophenol-formaldehyde condensate is likely to precipitate. Therefore, the chlorophenol-formaldehyde condensate is not used as a composition for a rubber-reinforced glass fiber coating material.

  Thus, the chlorophenol-formaldehyde condensate obtained by reacting chlorophenol with formaldehyde has low solubility in water, and alkali or the like is added to the reaction solution in a state where the chlorophenol-formaldehyde condensate is precipitated. Even if the precipitate of the formaldehyde condensate is dissolved in water, a vinylpyridine-styrene-butadiene copolymer (B) emulsion and / or chlorosulfonated polyethylene (C) is then prepared for preparing a coating solution for coating glass fibers. When mixed with the emulsion, there was a problem that the chlorophenol-formaldehyde condensate (A) was precipitated again.

  Therefore, an alkali such as sodium hydroxide is added to the reaction solution in which the chlorophenol-formaldehyde condensate (A) is precipitated to dissolve the precipitate of the chlorophenol-formaldehyde condensate (A), and then vinylpyridine-styrene-butadiene copolymer is used. When a coating solution for coating glass fibers is prepared by mixing with the combined (B) emulsion and / or chlorosulfonated polyethylene (C) emulsion, the chlorophenol-formaldehyde condensate (A) does not precipitate. However, since sodium hydroxide is a strong alkali, the glass fiber cord coated and coated with the glass fiber coating coating solution is eroded and the glass fiber cord is coated with the glass fiber coating coating solution. There was a problem that the tensile strength of the reinforcing glass fiber was lowered.

  The present invention is a rubber reinforcing glass fiber that gives excellent water resistance and heat resistance to a transmission belt when embedded in a heat resistant rubber, and compared to a conventional transmission belt using the same. Water resistance that keeps the initial adhesive strength even when running for a long time with water on the belt, and heat resistance that keeps the initial adhesive strength even if the coating layer runs for a long time at high temperatures It aims at providing the power transmission belt which it has together.

  As a result of intensive studies by the present inventors, a vinylpyridine-styrene-butadiene copolymer (B) is added to an aqueous solution of a chlorophenol-formaldehyde condensate (A) obtained by reacting formaldehyde (F) with chlorophenol (E). A coating solution for primary coating in which an emulsion of chlorosulfonated polyethylene (C) is mixed is applied to a glass fiber cord and then dried to form a primary coating layer. The upper layer is coated with chlorosulfonated polyethylene (C) and After applying a coating solution for secondary coating in which maleimide (D) is dispersed in an organic solvent, a rubber reinforcing glass fiber provided with a dried secondary coating layer is embedded in HNBR to form a power transmission belt. A desirable initial bond strength is obtained for the reinforcing glass fiber and HNBR, and the transmission belt is also provided with excellent water resistance. Maintaining under and long travel also tensile strength after the test under irrigation, rubber-reinforcing glass fiber to provide a good dimensional stability to the transmission belt is found to be provided.

  That is, the present invention provides a chlorophenol-formaldehyde condensate (A), a vinylpyridine-styrene-butadiene copolymer (B), and a chlorosulfonated polyethylene (C) on a glass fiber cord obtained by bundling a plurality of glass fiber filaments. A glass fiber for reinforcing rubber, characterized in that a secondary coating layer containing chlorosulfonated polyethylene (C) and maleimide (D) is provided thereon as a primary coating layer containing . Usually, a glass fiber cord is made by bundling a large number of glass fiber filaments after applying a bundling agent.

  As a result of intensive studies by the present inventors, the precipitation of a chlorophenol-formaldehyde condensate (A) obtained by condensation reaction of chlorophenol (E) and formaldehyde (F) in water was added to the alcohol compound (G). When dissolved, when preparing a coating solution for coating glass fiber, an aqueous solution of chlorophenol-formaldehyde condensate (A) is dissolved in a vinylpyridine-styrene-butadiene copolymer (B) emulsion, chlorosulfonated polyethylene (C) emulsion. It was found that the chlorophenol-formaldehyde condensate (A) did not precipitate even after mixing. As a result, the above-mentioned coating solution for primary coating was obtained.

  That is, in the present invention, the precipitation of chlorophenol-formaldehyde condensate (A) in which the primary coating layer is a condensation reaction of chlorophenol (E) and formaldehyde (F) in water is dissolved by adding alcohol compound (G). A coating solution for primary coating obtained by mixing a vinylpyridine-styrene-butadiene copolymer (B) emulsion and a chlorosulfonated polyethylene (C) emulsion in an aqueous solution of the chlorophenol-formaldehyde condensate (A) is made of glass. The glass fiber for reinforcing rubber described above, which is applied to a fiber cord and dried.

  Further, in the present invention, the amount of the alcohol compound (G) added is expressed as a percentage by weight based on the weight of the chlorophenol-formaldehyde condensate (A) as 100%, and G / A = 50% by weight or more and 500% by weight. % Of the above-mentioned rubber reinforcing glass fiber. In other words, the amount of the alcohol compound (G) added is expressed as a weight ratio with respect to the chlorophenol-formaldehyde condensate (A) and is G / A = 0.5 or more and 5.0 or less. It is a glass fiber for rubber reinforcement.

  Furthermore, in the present invention, n-propanol, isopropanol, propylene glycol, 2-methoxyethanol, 2-methoxymethylethoxypropanol, 1-methoxy-2-propanol, ethylene glycol, diethylene glycol, 1, 2 are added to the alcohol compound (G). -The glass fiber for rubber reinforcement described above, wherein diethoxyethane is used.

  In addition, as a result of intensive studies by the present inventors, precipitation of chlorophenol-formaldehyde condensate (A) formed by condensation reaction of chlorophenol (E) and formaldehyde (F) in water was reduced to sodium hydroxide or the like. When the amine compound (H) is added in place of the strong alkali and the precipitate of the chlorophenol-formaldehyde condensate (A) is dissolved, the chlorophenol-formaldehyde condensate ( Even if the vinylpyridine-styrene-butadiene copolymer (B) emulsion and the chlorosulfonated polyethylene (C) emulsion are added to and mixed with the aqueous solution of A), the chlorophenol-formaldehyde condensate (A) does not precipitate after mixing. all right. As a result, the above-mentioned coating solution for primary coating was obtained.

  Further, in the present invention, the primary coating solution is obtained by adding the amine compound (H) to the precipitate of the chlorophenol-formaldehyde condensate (A) obtained by condensation reaction of chlorophenol (E) and formaldehyde (F) in water. It is characterized in that an aqueous solution of a dissolved chlorophenol-formaldehyde condensate (A) is mixed with an emulsion of vinylpyridine-styrene-butadiene copolymer (B) and an emulsion of chlorosulfonated polyethylene (C). It is said glass fiber for rubber reinforcement.

Furthermore, the present invention is the above glass fiber for reinforcing rubber, wherein the amine compound (H) has a basicity constant (Kb) of 5 × 10 ⁻⁵ or more and 1 × 10 ⁻³ or less. .

  Furthermore, in the present invention, the amount of the amine compound (H) added is expressed as a weight percentage based on 100% by weight of the chlorophenol-formaldehyde condensate (A), and H / A = 50% by weight or more and 500% by weight. % Of the above-mentioned rubber reinforcing glass fiber. In other words, the amount of the amine compound (H) added is expressed as a weight ratio with respect to the chlorophenol-formaldehyde condensate (A) and is H / A = 0.5 or more and 5.0 or less. It is a glass fiber for rubber reinforcement.

  Further, the present invention provides the amine compound (H) with methylamine, ethylamine, t-butylamine, dimethylamine, diethylamine, triethylamine, tri-n-butylamine, methanolamine, dimethanolamine, monoethanolamine, and diethylamine. The reinforcing glass fiber described above, wherein

  Furthermore, the present invention is characterized in that the chlorophenol-formaldehyde condensate (A) has a molar ratio of formaldehyde (F) to chlorophenol (E) of F / E = 0.5 or more and 3.0 or less. This is a glass fiber for reinforcing rubber.

  Furthermore, the present invention is a weight percentage based on 100% of the combined weight of chlorophenol-formaldehyde condensate (A), vinylpyridine-styrene-butadiene copolymer (B) and chlorosulfonated polyethylene (C). Chlorophenol-formaldehyde condensate (A) is A / (A + B + C) = 1.0 wt% or more, 15.0 wt% or less, vinylpyridine-styrene-butadiene copolymer (B) is B / (A + B + C) = 45.0 wt% or more, 82.0 wt% or less, chlorosulfonated polyethylene (C) is included in the range of C / (A + B + C) = 3.0 wt% or more and 40.0 wt% or less The glass fiber for rubber reinforcement as described above, which has a primary coating layer.

  Further, in the present invention, the vinylpyridine-styrene-butadiene copolymer (B) is based on the styrene-butadiene copolymer (I) and the weight of the vinylpyridine-styrene-butadiene copolymer (B) is based on 100%. The above glass fiber for reinforcing rubber, characterized by being expressed in terms of weight percentage, I / B = 5.0% by weight or more and 80.0% by weight or less.

  Furthermore, the present invention represents 10.0% by weight or more and 70.0% by weight or less of chlorosulfonated polyethylene (C), expressed as a percentage by weight based on the total weight of the secondary coating layer, and the chlorosulfonated Expressing a weight percentage of polyethylene (C), a secondary coating layer comprising maleimide (D) of D / C = 20.0 wt% or more and 90.0 wt% or less is provided. It is the glass fiber for rubber reinforcement described above.

  The balance of chlorosulfonated polyethylene (C) and maleimide (D) is carbon as an inorganic filler, magnesium oxide and a nitroso compound as a vulcanizing agent, such as p-nitrosobenzene.

Furthermore, in the present invention, maleimide (D) is N, N-m-phenylene dimaleimide, 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, 4-methyl-1,3- Selected from phenylene bismaleimide, 4,4′-diphenyl ether bismaleimide, 4,4′-diphenylsulfone bismaleimide, chlorophenyl maleimide, methylphenyl maleimide, hydroxyphenyl maleimide, carboxyphenyl maleimide, dodecyl maleimide, and / or cyclohexyl maleimide The glass fiber for rubber reinforcement as described above.

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

  Furthermore, the present invention is an automotive timing belt, wherein the rubber reinforcing glass fiber is embedded in hydrogenated nitrile rubber.

  The precipitation of chlorophenol-formaldehyde condensate (A) obtained by condensation reaction of chlorophenol (E) and formaldehyde (F) in water was dissolved by adding alcohol compound (G), so that the chlorophenol-formaldehyde condensate was dissolved. (A) When the aqueous solution, the vinylpyridine-styrene-butadiene copolymer (B) emulsion, and the chlorosulfonated polyethylene (C) emulsion are mixed, the chlorophenol-formaldehyde condensate (A) does not precipitate, A primary coating solution for coating a glass fiber cord was obtained.

  A precipitate of chlorophenol-formaldehyde condensate (A) formed by condensation reaction of chlorophenol (E) and formaldehyde (F) in water was dissolved by adding amine compound (H). (A) When the aqueous solution, the vinylpyridine-styrene-butadiene copolymer (B) emulsion, and the chlorosulfonated polyethylene (C) emulsion are mixed, the chlorophenol-formaldehyde condensate (A) does not precipitate, A primary coating solution for coating a glass fiber cord was obtained.

  Secondary coating containing chlorosulfonated polyethylene (C) and maleimide (D) on the upper layer of the primary coating layer formed by applying the primary coating solution to a glass fiber cord in which a plurality of glass fiber filaments are bundled. The glass fiber for reinforcing rubber of the present invention provided with a layer gives excellent adhesion strength to the glass fiber and HNBR when embedded in a heat-resistant rubber, for example, HNBR.

  Furthermore, the glass fiber for rubber reinforcement of the present invention is provided with heat resistance when embedded in HNBR to form a transmission belt, thereby having both water resistance and heat resistance, and as a transmission belt under high temperature and high humidity. After use for a long time, in other words, after running, there is no concern that the interface between the glass fiber and the heat-resistant rubber will peel off, and the transmission belt maintains the tensile strength and has excellent dimensional stability.

  The glass fiber for reinforcing rubber of the present invention is a heat resistant rubber, such as HNBR, when embedded in a conventional resorcin-formaldehyde condensate, vinylpyridine-styrene-butadiene copolymer and chlorosulfonated polyethylene in water. It has excellent adhesion strength between HNBR and glass fiber for rubber reinforcement equivalent to the case of using a coating solution for coating glass fiber dispersed and emulsion.

  The present invention relates to a glass fiber for reinforcing rubber that is used by embedding in a base rubber when producing a transmission belt, and a chlorophenol-formaldehyde condensate (A ), A vinylpyridine-styrene-butadiene copolymer (B) and a chlorosulfonated polyethylene (C), and a chlorosulfonated polyethylene (C) and maleimide (D) as an upper layer. It is a glass fiber for rubber reinforcement provided with a secondary coating layer to be contained.

  The production is performed by mixing an aqueous solution of chlorophenol-formaldehyde condensate (A) with an emulsion of vinylpyridine-styrene-butadiene copolymer (B) and an emulsion of chlorosulfonated polyethylene (C). After the coating liquid for coating is applied and dried, a primary coating layer having a function of preventing the penetration of water into the glass fiber cord is provided, and then chlorosulfonated polyethylene (C) and maleimide (D) are formed on the upper layer. After applying a coating solution for secondary coating in which is dispersed in an organic solvent, the coating solution is dried, and a further secondary coating layer for adhesion to the base rubber is provided and dried to form rubber reinforcing glass fibers. For example, xylene is used as the organic solvent.

  The chlorophenol-formaldehyde condensate (A) obtained by reacting chlorophenol (E) with formaldehyde (F) has low solubility in water, and chlorophenol (E) and formaldehyde (F) are subjected to a condensation reaction in water. The phenol-formaldehyde condensate (A) is formed as a precipitate.

  In order to use the chlorophenol-formaldehyde condensate (A) as the composition of the coating liquid for primary coating of the glass fiber for reinforcing rubber of the present invention, the precipitate of the produced chlorophenol-formaldehyde condensate (A) is dissolved. It is necessary to let

  As a result of intensive studies by the inventors, the alcohol compound (G) was added to the reaction solution in which the chlorophenol-formaldehyde condensate (A) was precipitated, and the precipitate of the chlorophenol-formaldehyde condensate (A) was dissolved, and then vinyl It was found that when the pyridine-styrene-butadiene copolymer (B) emulsion and the chlorosulfonated polyethylene (C) emulsion were mixed, precipitation of the chlorophenol-formaldehyde condensate (A) hardly occurred.

  Specifically, the precipitation of chlorophenol-formaldehyde condensate (A) obtained by condensation reaction of chlorophenol (D) and formaldehyde (E) in water is at least selected from water-soluble monoalcohol compounds, glycol compounds, and triol compounds. When one water-soluble alcohol compound (G) is added to dissolve the precipitate of the chlorophenol-formaldehyde condensate (A), the chlorophenol-formaldehyde condensate (A) is prepared in preparing the coating solution for primary coating. ), The vinyl pyridine-styrene-butadiene copolymer (B) emulsion and chlorosulfonated polyethylene (C) emulsion were mixed and mixed, and it was found that the chlorophenol-formaldehyde condensate (A) did not precipitate after mixing. It was.

  In other words, sodium hydroxide is added to the mixed aqueous solution of chlorophenol (D) and formaldehyde (E) only in an amount necessary for the condensation reaction, and it is heated to 30 ° C. or higher and 95 ° C. or lower for 4 hours without adding extra. As described above, the water-soluble alcohol compound (G) is added to the reaction solution in which the precipitation of the chlorophenol-formaldehyde condensate (A) obtained by the condensation reaction while stirring is generated, and the precipitate is dissolved by further stirring. Thus, an aqueous solution of the chlorophenol-formaldehyde condensate (A) is obtained.

  Thus, in order to dissolve the precipitate of the chlorophenol-formaldehyde condensate (A) formed by the condensation reaction in water, at least one water-soluble substance selected from water-soluble monoalcohol compounds, glycol compounds, and triol compounds is used. It is necessary to add the alcohol compound (G). In the present invention, the alcohol compound (G) refers to a compound in which a hydrocarbon hydrogen atom is substituted with an OH group, a monoalcohol compound having one OH group, a glycol (diol) compound having two OH groups, Triol compounds having 3 OH groups are included.

  The primary coating layer of the glass fiber for rubber reinforcement of the present invention is a monolithic solution in a reaction solution in which a chlorophenol-formaldehyde condensate (A) obtained by condensation reaction of chlorophenol (E) and formaldehyde (F) in water is precipitated. Aqueous solution of chlorophenol-formaldehyde condensate (A) obtained by adding alcohol compound (G) compatible with water from alcohol compound, glycol compound, triol compound and dissolving precipitate of chlorophenol-formaldehyde condensate (A) A coating solution for primary coating in which a vinylpyridine-styrene-butadiene copolymer (B) emulsion and a chlorosulfonated polyethylene (C) emulsion were mixed with each other was applied to a glass fiber cord and then dried.

  The aqueous solution of the chlorophenol-formaldehyde condensate (A) is stabilized by adding a water-soluble alcohol compound, and the chlorophenol-formaldehyde condensate (A) does not precipitate. It seems that the OH group and the OH group of the alcohol compound (G) form a three-dimensionally strong hydrogen bond. In addition, since the alcohol compound (G) has a high dipole moment and dielectric constant, the long-range interaction such as dispersion force acts strongly, and the effect of stabilizing the chlorophenol-formaldehyde condensate (A) in an aqueous solution, Because of the large coordination bond (charge transfer) interaction energy, not only the solvent-solute, but also the solvent-solvent association occurs, resulting in strong solvation and precipitation of the chlorophenol-formaldehyde condensate (A). It seems that there is an effect to stabilize in an aqueous solution without doing. The stabilizing effect is that the glycol compound and triol compound having a large number of OH groups are larger than the monoalcohol compound, and the glycol compound is particularly excellent in stabilizing effect.

  If an alcohol compound (G) having a boiling point lower than 50 ° C. is used for the glass fiber coating solution, the alcohol compound (G) is likely to volatilize and difficult to handle. When the alcohol compound (G) volatilizes, a chlorophenol-formaldehyde condensate (A) is deposited. When an alcohol compound (G) having a boiling point higher than 250 ° C. is used for the glass fiber coating solution, the alcohol compound (G) is volatilized from the coating layer when the glass fiber coating solution is applied to the glass fiber cord and coated. Hard to do. If the alcohol compound (G) is not removed from the coating layer, the heat resistance and water resistance of the transmission belt will be reduced when the glass fiber cord is embedded in heat resistant rubber to form a transmission belt. Therefore, the alcohol compound (G) used in the coating solution for coating glass fibers of the present invention has at least one water-soluble monoalcohol compound, glycol compound or triol compound having a boiling point of 50 ° C. or higher and 250 ° C. or lower. It is preferable to select and use the alcohol compound (G).

  The amount of the alcohol compound (G) added is expressed as a weight percentage based on the weight of the chlorophenol-formaldehyde condensate (A) as 100%, and is G / A = 50 wt% or more and 500 wt% or less. In other words, the weight of the alcohol compound (G) to be added is G / A = 1/2 or more and 5 or less with respect to the weight of the chlorophenol-formaldehyde condensate (A).

  When the weight of the chlorophenol-formaldehyde condensate (A) is expressed as a percentage by weight based on 100% and the amount of the alcohol compound (G) added is less than 50% by weight, the chlorophenol-formaldehyde condensate The effect of dissolving the precipitate (A) is small, and it is not necessary to contain more than G / A = 500% by weight. When the amount of the alcohol compound (G) added exceeds G / A = 500% by weight, the chlorophenol-formaldehyde condensate (A) and vinylpyridine-styrene-butadiene copolymer in the glass fiber cord primary coating solution The density | concentration of a coalescence (B) and chlorosulfonated polyethylene (C) falls, and the glass fiber for rubber reinforcement formed by apply | coating the glass fiber coating coating liquid to a glass fiber cord becomes inflexible.

  The weight of the chlorophenol-formaldehyde condensate (A) is the same as that of the reaction liquid containing the precipitation of the chlorophenol-formaldehyde condensate (A) produced by the condensation reaction between chlorophenol (E) and formaldehyde (F) in water. It is determined from the weight of the residue heated and evaporated. At this time, unreacted chlorophenol (E) and formaldehyde (F) are volatilized and removed.

The alcohol compound (G) used for dissolving the precipitate of the chlorophenol-formaldehyde condensate (A) includes a methanol (CH ₃ OH) boiling point of 65 ° C., an ethanol (C ₂ H ₅ OH) boiling point of 78 ° C., n − Propyl alcohol (C ₃ H ₈ O) boiling point 97 ° C., Isopropyl alcohol (C ₃ H ₈ O) boiling point 82 ° C., 2-methoxyethanol (ethylene glycol monomethyl ether: C ₃ H ₈ O ₂ ) boiling point 124 ° C., propylene glycol ( C ₃ H ₈ O ₂ ) boiling point 188 ° C., 2-methoxymethylethoxypropanol (C ₇ H ₁₆ O ₃ ) boiling point 190 ° C., 1-methoxy-2-propanol (C ₄ H ₁₀ O ₂ ) boiling point 120 ° C., ethylene glycol _{(1,2-ethanediol:} C ₂ H 6 _{O 2)} boiling point 196 ° C., diethylene glycol Le _{(C 4 H} 10 _{O 3)} having a boiling point 244 ° C., 1,2-diethoxyethane _{(C 6 H} 14 _{O 2)} boiling point 123 ° C., glycerin _{(C 3} H 8 _{O 3)} having a boiling point 171 ° C. and the like, preferably , N-propyl alcohol (C ₃ H ₈ O), isopropyl alcohol (C ₃ H ₈ O), 2-methoxyethanol (ethylene glycol monomethyl ether: C ₃ H ₈ O ₂ ), propylene glycol (C ₃ H ₈ O ₂₎ ), 2-methoxymethylethoxypropanol (C ₇ H ₁₆ O ₃ ), 1-methoxy-2-propanol (C ₄ H ₁₀ O ₂ ), ethylene glycol (1,2-ethanediol: C ₂ H ₆ O ₂ ) , Diethylene glycol (C ₄ H ₁₀ O ₃ ), 1,2-diethoxyethane (C ₆ H ₁₄ O ₂ ). In particular, 2-methoxyethanol and propylene glycol are not diffused and remain in the coating layer when the coating solution for primary coating is applied and then dried to form the primary coating layer on the glass fiber cord. Since the effect of stabilizing the aqueous solution of the phenol-formaldehyde condensate (A) is also high, it is a particularly preferred alcohol compound (G) for use in the coating solution for primary coating of the glass fiber for rubber reinforcement of the present invention.

  Among the two OH group glycol (diol) compounds, the concentration of the coating solution is adjusted when used in the coating solution for primary coating of the present invention for the purpose of dissolving the precipitate of the chlorophenol-formaldehyde condensate (A). However, when water is added for some purposes, a gelled product is formed. However, in adjusting the concentration in the necessary region, 2-methoxyethanol and propylene glycol are not concerned, and in addition, they are safe against fire. Yes, low toxicity, low boiling point, no concern for workers to suck, excellent environmental safety, low commercial price, high practicality, especially for use in the coating solution for glass fiber coating of the present invention Preferred alcohol compound (G).

  Methanol and ethanol contained in one OH group monoalcohol compound and glycerin contained in a triol compound having three OH groups were applied for primary coating for the purpose of dissolving the precipitate of the chlorophenol-formaldehyde condensate (A). When used in a liquid, the glass fiber cord can be coated and coated when the coating liquid for primary coating is in a high concentration state. However, if water is added to adjust the concentration of the coating solution at the time of coating, a gelled product tends to form and precipitate, making it difficult to adjust the concentration and handling.

  In addition, as a result of intensive studies by the inventors, the primary coating solution used for the primary coating layer of the glass fiber for rubber reinforcement of the present invention contains chlorophenol (E) and formaldehyde (F) in water. Of the chlorophenol-formaldehyde condensate (A) formed by adding the amine compound (H) to the reaction liquid in which the chlorophenol-formaldehyde condensate (A) precipitated by It was found that the aqueous solution can also be obtained by mixing an emulsion of vinylpyridine-styrene-butadiene copolymer (B) and an emulsion of chlorosulfonated polyethylene (C).

As the amine compound (H), an amine compound (H) having a basicity constant (Kb) of 5 × 10 ⁻⁵ or more and 1 × 10 ⁻³ or less was used.

That is, the coating solution for primary coating has a basicity constant (Kb) of 5 × 10 ⁻⁵ or more and 1 × 10 ⁻³ or less in the reaction solution in which the chlorophenol-formaldehyde condensate (A) is precipitated. The amine compound (H) is added to dissolve the precipitate of the chlorophenol-formaldehyde condensate (A), and then the vinylpyridine-styrene-butadiene copolymer (B) emulsion and the chlorosulfonated polyethylene (C) emulsion are mixed. Prepared.

  The basicity constant (Kb) is a measure of the degree of alkali's acceptance of hydrogen ions from a solution and is expressed as basicity, and is the equilibrium constant of the formula 1.

  Usually, when the chlorophenol-formaldehyde condensate (A) is dissolved in water, an alkali such as ammonia or sodium hydroxide is added to the reaction solution in which the chlorophenol-formaldehyde condensate (A) is precipitated.

  However, in order to dissolve the precipitate of the chlorophenol-formaldehyde condensate (A), an alkali having a small basicity constant (Kb) such as ammonia is added to dissolve the precipitate of the chlorophenol-formaldehyde condensate (A). Then, when the emulsion of vinylpyridine-styrene-butadiene copolymer (B) and the emulsion of chlorosulfonated polyethylene (C) are mixed, the chlorophenol-formaldehyde condensate (A) precipitates and is applied for primary coating. Do not use as a liquid.

  Further, in order to dissolve the chlorophenol-formaldehyde condensate (A) in water, an alkali having a large basicity constant (Kb) such as sodium hydroxide is added to precipitate the chlorophenol-formaldehyde condensate (A). After the dissolution, when the vinylpyridine-styrene-butadiene copolymer (B) emulsion and the chlorosulfonated polyethylene (C) emulsion are mixed, precipitation of the chlorophenol-formaldehyde condensate (A) is suppressed after mixing. However, since sodium hydroxide is a strong alkali, it degrades the glass fiber and weakens the tensile strength, making it difficult to use.

  However, an amine compound is added to the reaction solution in which the chlorophenol-formaldehyde condensate (A) is precipitated, and the precipitate of the chlorophenol-formaldehyde condensate (A) is dissolved, and then the vinylpyridine-styrene-butadiene copolymer (B) is dissolved. When the emulsion and the emulsion of chlorosulfonated polyethylene (C) are mixed, precipitation of the chlorophenol-formaldehyde condensate (A) hardly occurs and the glass fiber is not deteriorated and the tensile strength is not reduced. all right.

  In other words, sodium hydroxide is added to the mixed aqueous solution of chlorophenol (E) and formaldehyde (F) only in an amount necessary for the condensation reaction, and it is heated to 30 ° C. or higher and 95 ° C. or lower for 4 hours without adding extra. As described above, the amine compound (H) is added to the reaction solution in which the precipitation of the chlorophenol-formaldehyde condensate (A) obtained by the condensation reaction while stirring is generated, and the precipitate is dissolved by further stirring, An aqueous solution of chlorophenol-formaldehyde condensate (A) is obtained.

The basicity constant (Kb) of the amine compound (H) added in order to dissolve the precipitate in the reaction solution in which the precipitation of the chlorophenol-formaldehyde condensate (A) has been generated and to stabilize the precipitate without dissolution is 5 ^{X10 −5} or more and 1 × 10 ⁻³ or less.

When the basicity constant (Kb) of the amine compound (H) added to the chlorophenol-formaldehyde condensate (A) is less than 5 × 10 ⁻⁵ , the vinylpyridine-styrene-butadiene copolymer (B) emulsion and chloro When mixed with the emulsion of sulfonated polyethylene (C), the chlorophenol-formaldehyde condensate (A) precipitates over time, and when it is larger than 1 × 10 ^−3, it is used as a glass fiber coating applicator and coated on the glass fiber cord. Poor adhesion between glass fiber cord and heat resistant rubber when embedded in heat resistant rubber.

  The amount of the amine compound (H) added is H / A = 50 wt% or more and 500 wt% or less, expressed as a weight percentage based on the weight of the chlorophenol-formaldehyde condensate (A) as 100%. In other words, the weight of the added amine compound (H) is H / A = 1/2 or more and 5.0 or less with respect to the weight of the chlorophenol-formaldehyde condensate (A), expressed as a weight ratio. .

  When the amount of the amine compound (H) added is less than H / A = 50% by weight, the effect of dissolving the precipitation of the chlorophenol-formaldehyde condensate (A) is small, and the amount added is more than H / A = 500% by weight. There is no need. When the amount of the amine compound (H) added exceeds H / A = 500% by weight, the chlorophenol-formaldehyde condensate (A) and vinylpyridine-styrene-butadiene in the coating solution for primary coating of rubber reinforcing glass fibers The content ratio of the emulsion of the copolymer (B) and the emulsion of the chlorosulfonated polyethylene (C) decreases, and the rubber reinforcing fiber formed by applying the glass fiber coating coating liquid to the glass fiber cord becomes inflexible.

  The weight of the chlorophenol-formaldehyde condensate (A) is determined by heating and evaporating the reaction liquid containing the precipitate of the chlorophenol-formaldehyde condensate (A) produced by the condensation reaction between chlorophenol and formaldehyde in water. Calculated as concentration. At this time, unreacted chlorophenol (E) and formaldehyde (F) are volatilized and removed.

  In the present invention, the amine compound (H) added to dissolve the precipitate of the chlorophenol-formaldehyde condensate (A) includes methylamine, ethylamine, t-butylamine, dimethylamine, diethylamine, triethylamine, tri-n-butylamine. , Methanolamine, dimethanolamine, monoethanolamine, and diethylamine. Among these, dimethylamine and diethylamine are inexpensive and easily available, and monoethanolamine and diethanolamine are easy to handle without smell peculiar to amines, so that the coating solution for primary coating of the glass fiber for rubber reinforcement of the present invention is used. Particularly preferred amine compound (H) for use in the present invention.

The basicity constants (Kb) of these amine compounds are shown in Organic Chemistry (Middle) 3rd Edition (Tokyo Kagaku Dojin) and Organic Chemistry Glossary (Second Printing) Asakura Shoten, pages 167-175, etc. The basicity constant (Kb) of dimethylamine is 5.4 × 10 ⁻⁴ , and the basicity constant (Kb) of diethanolamine is 1.0 × 10 ^−4.5 .

  As the chlorophenol-formaldehyde condensate (A) used for the primary coating of the glass fiber for reinforcing rubber of the present invention, the molar ratio of formaldehyde (F) to chlorophenol (E) is F / E = 0.5 or more, A water-soluble or water-solvent resol type resin reacted with a basic catalyst at 3.0 or less can be mentioned. When the molar ratio of formaldehyde (F) is less than F / E = 0.5, the adhesive strength between the glass fiber for rubber reinforcement and the heat-resistant rubber is inferior, and when F / E = 3.0 is exceeded, the coating solution for primary coating However, it is easy to gel. Preferably, it is the range of F / E = 0.5 or more and 1.2 or less.

  In the vinylpyridine-styrene-butadiene copolymer (B) which is the composition of the primary coating layer of the glass fiber for reinforcing rubber of the present invention, the ratio of vinylpyridine: styrene: butadiene is 10 to 20 by weight. It is preferable to use a vinylpyridine-styrene-butadiene copolymer (B) polymerized in the range of 10 to 20:80 to 60, commercially available from Nippon A & L Co., Ltd., trade name, Pilates, manufactured by JSR Corporation, Product name, 0650, and Nippon Zeon Co., Ltd. product name, Nipol, model number, 1218FS, and the like. A rubber provided with a primary coating using a vinylpyridine-styrene-butadiene copolymer (B) deviating from the above weight ratio and provided with a secondary coating layer of chlorosulfonated polyethylene (C) and maleimide (D). The reinforcing glass fiber is inferior in adhesive strength with the base rubber.

  The chlorosulfonated polyethylene (C) used as the composition of the primary coating layer and the secondary coating layer of the glass fiber for reinforcing rubber of the present invention is represented by weight percentage, and the chlorine content is 20.0% by weight or more, 40 0.0% by weight or less and a sulfur content in the sulfone group of 0.5% by weight or more and 2.0% by weight or less is suitably used. For example, as a latex having a solid content of about 40% by weight, Sumitomo Seika A product name, CSM-450, manufactured by Co., Ltd. is commercially available and is preferably used in the present invention. In addition, the coating solution for primary coating or the coating solution for secondary coating using the chlorosulfonated polyethylene (C) deviated from the above-mentioned chlorine content and sulfur content in the sulfone group is used, and 1 is applied to the glass fiber cord. The glass fiber for rubber reinforcement produced by applying the secondary coating or the secondary coating is inferior in adhesiveness to the base material HNBR.

  In order to obtain a desired adhesive strength between the rubber reinforcing glass fiber and the base rubber when used in the transmission belt, the chlorophenol-formaldehyde condensate contained in the primary coating layer of the rubber reinforcing glass fiber of the present invention. The chlorophenol-formaldehyde condensate (A) is expressed as a weight percentage based on 100% of the combined weight of (A), vinylpyridine-styrene-butadiene copolymer (B) and chlorosulfonated polyethylene (C). A / (A + B + C) = 1.0 wt% or more, 15.0 wt% or less, vinylpyridine-styrene-butadiene copolymer (B) is B / (A + B + C) = 45.0 wt% or more, 82.0% by weight or less, and chlorosulfonated polyethylene (C) is preferably contained in the range of C / (A + B + C) = 3.0% by weight or more and 40.0% by weight or less. Arbitrariness.

  In the glass fiber for reinforcing rubber of the present invention, when the content of the chlorophenol-formaldehyde condensate (A) in the primary coating layer is less than 1.0% by weight, when the glass fiber cord coating material is used, glass The adhesive strength between the fiber and the base rubber becomes weak, and it is difficult to obtain preferable water resistance and heat resistance when a transmission belt is used. When the content of the chlorophenol-formaldehyde condensate (A) exceeds 15.0% by weight, aggregation precipitation is likely to occur, and it becomes difficult to prepare a coating solution for primary coating. Therefore, the preferable content range of the chlorophenol-formaldehyde condensate (A) in the primary coating layer of the glass fiber for rubber reinforcement of the present invention is a vinylpyridine-styrene-butadiene copolymer (B) contained in the primary coating layer. ) And chlorosulfonated polyethylene (C) in terms of weight percentage based on 100%, and A / (A + B + C) = weight is 1.0 wt% or more and 15.0 wt% or less. Preferably, A / (A + B + C) = 2.0 wt% or more and 12.0 wt% or less.

  Moreover, in the glass fiber for rubber reinforcement of the present invention, when the content of the vinylpyridine-styrene-butadiene copolymer (B) in the primary coating layer is less than 45.0% by weight, the glass fiber and HNBR are bonded. The strength becomes weak, and it is difficult to obtain preferable heat resistance when a transmission belt is used. When the content of the vinylpyridine-styrene-butadiene copolymer (B) exceeds 82.0% by weight, when the glass fiber cord is coated, the coating becomes sticky and the coating layer is easily transferred. Problems such as soiling occur. Therefore, the suitable content range of the vinylpyridine-styrene-butadiene copolymer (B) in the glass fiber for rubber reinforcement of the present invention is a chlorophenol-formaldehyde condensate (A) and a vinylpyridine-styrene-butadiene copolymer ( B / (A + B + C) = 45.0 wt% or more and 82.0 wt% or less, expressed as a weight percentage based on the total weight of B) and chlorosulfonated polyethylene (C). . Further, B / (A + B + C) = 55.0 wt% or more and 75.0 wt% or less is preferable.

  When the chlorosulfonated polyethylene (C) in the primary coating layer is less than 3.0% by weight, it is difficult to obtain desired heat resistance when the transmission belt is formed, and the chlorosulfonated polyethylene (C) is 40.0% by weight. If it is more than%, the adhesive strength between the glass fiber and the base rubber becomes weak, and it is difficult to obtain preferable heat resistance when it is used as a transmission belt. In the coating solution for primary coating of the present invention, the preferred range of content of chlorosulfonated polyethylene (C) is that of the chlorophenol-formaldehyde condensate (A) and vinylpyridine-styrene-butadiene contained in the primary coating layer. The weight of the polymer (B) and the chlorosulfonated polyethylene (C) is expressed as a weight percentage based on 100%, and C / (A + B + C) = 3.0 wt% or more and 40.0 wt% or less. It is a range. Further, C / (A + B + C) = 20.0 wt% or more and 35.0 wt% or less is preferable.

  A part of the vinylpyridine-styrene-butadiene copolymer (B) which is one of the compositions of the primary coating layer of the glass fiber for reinforcing rubber of the present invention may be replaced with another rubber elastomer. With only the vinylpyridine-styrene-butadiene copolymer (B), the coating of the rubber reinforcing glass fiber becomes sticky and the coating layer is easily transferred, and the process becomes dirty and the workability deteriorates. Examples of other rubber elastomers include carboxyl group-modified styrene-butadiene rubber and acrylonitrile-butadiene rubber, but styrene-butadiene copolymer (I) having good compatibility with vinylpyridine-styrene-butadiene copolymer (B) is used. 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.

  Expressing the weight of the vinylpyridine-styrene-butadiene copolymer (B) as a percentage by weight based on 100%, the styrene-butadiene copolymer (I) was converted into I / B = 5.0 wt% to 80.0 wt%. In the range of% by weight, it can be used in place of the vinylpyridine-styrene-butadiene copolymer (B). When I / B is less than 5.0% by weight, there is no effect of preventing the coating of the rubber reinforcing glass fiber from being sticky and preventing the coating layer from being easily transferred. Preferably, I / B = 25.0% by weight or more. When I / B = 80.0% by weight or more, the adhesiveness with 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, I / B = 55.0% by weight or less.

  As such a styrene-butadiene copolymer (I), for example, a trade name, J-9049, is commercially available from Nippon A & L Co., Ltd., and used for the primary coating of the glass fiber for rubber reinforcement of the present invention. .

  The glass fiber for rubber reinforcement of the present invention has a heat resistant rubber as a base rubber, such as HNBR, which is used as a power transmission belt by embedding water into the glass fiber cord as compared with a conventional glass fiber for rubber reinforcement. By preventing permeation, the transmission belt is given excellent water resistance and has both water resistance and heat resistance.

  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. The timing belt refers to a pulley for transmitting the crankshaft to the timing gear to drive the camshaft and opening / closing the valve at a set timing in an engine having a camshaft in the automobile transmission belt. It is a toothed belt provided with teeth that mesh with teeth.

  Conventionally, heat-resistant transmission belts are for reinforcing rubber that has been coated on glass fiber cords and dried using a glass fiber coating coating solution consisting of resorcin-formaldehyde resin, vinylpyridine-styrene-butadiene copolymer, and chlorosulfonated polyethylene. It was produced by embedding glass fibers in HNBR as heat resistant rubber. The rubber reinforcing glass fiber was further provided with a secondary coating layer and embedded in HNBR as a heat-resistant rubber.

  Compared to a conventional transmission belt, a primary coating layer containing a chlorophenol-formaldehyde condensate (A), a vinylpyridine-styrene-butadiene copolymer (B), and a chlorosulfonated polyethylene (C). A transmission belt formed by embedding a rubber reinforcing glass fiber of the present invention, which is formed and provided with a secondary coating layer composed of chlorosulfonated polyethylene (C) and maleimide (D), in HNBR rubber, has high humidity and high temperature. Even after running for a long time, the initial adhesion strength between the glass fiber and HNBR by the secondary coating layer is maintained, the tensile strength is maintained and the dimensional stability is excellent, and both the water resistance and the heat resistance are maintained.

  At that time, the content of the chlorosulfonated polyethylene (C) is 10.0% by weight or more and 70.0% by weight or less, expressed as a percentage by weight based on the weight of the secondary coating layer as 100%. Expressing the weight of C) as a percentage by weight based on 100%, the coating solution for secondary coating is adjusted so that the content of maleimide (D) is D / C = 20 wt% or more and 90 wt% or less. It is preferable to adjust, and the remainder to be an inorganic filler and a vulcanizing material. Examples of the inorganic filler include carbon and magnesium oxide, and examples of the vulcanizing agent include zinc methacrylate.

  When the content of the chlorosulfonated polyethylene (C) in the secondary coating layer is less than 10.0% by weight, it is difficult to obtain the excellent heat resistance described above. If it exceeds 70.0% by weight, the adhesive strength between the glass fiber cord and the base rubber becomes weak, and the produced transmission belt is inferior in durability. Preferably, they are 25.0 weight% or more and 60.0 weight% or less.

  The content of maleimide (D) in the secondary coating layer is expressed as a percentage by weight based on 100% by weight of chlorosulfonated polyethylene (C), and D / C = 20.0% by weight or more, 90.0% by weight. % Or less. When the content of maleimide (D) is less than 20.0% by weight, it is difficult to obtain the excellent heat resistance described above. If it exceeds 90.0% by weight, the adhesive strength between the glass fiber cord and the base rubber becomes weak, and the produced transmission belt is inferior in durability. Preferably, D / C = 50.0 wt% or more and 90.0 wt% or less.

  Further, adding zinc methacrylate as a vulcanizing agent, inorganic filler such as carbon black or magnesium oxide to the coating solution for secondary coating and adding it as a composition to the secondary coating layer There is a further effect of increasing the heat resistance of a transmission belt produced by embedding glass fibers in rubber. In the secondary coating layer, the weight percentage of chlorosulfonated polyethylene (C) in the coating solution for secondary coating is expressed as a percentage by weight based on 100%, and zinc methacrylate is 5.0% by weight or less, and an inorganic filler is added. When added in a range of 10.0% by weight or more and 70.0% by weight or less, the produced transmission belt exhibits further heat resistance. When zinc methacrylate exceeds 5.0% by weight and an inorganic filler exceeds 70.0% by weight, the adhesive strength between the glass fiber cord and the base rubber is weakened. Inferior in durability.

As maleimide (D) preferably used in the present invention, N, N-m-phenylene dimaleimide, 4,4′-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, 4-methyl-1 , 3-phenylene bismaleimide, 4,4′-diphenyl ether bismaleimide, 4,4′-diphenylsulfone bismaleimide, chlorophenyl maleimide, methylphenyl maleimide, hydroxyphenyl maleimide, carboxyphenyl maleimide, dodecyl maleimide, cyclohexyl maleimide, and the like. In particular, N, Nm-phenylene dimaleimide is preferably used.

  In addition to the coating solution for primary coating and the coating solution for secondary coating in forming the primary coating layer and the secondary coating layer of the glass fiber for rubber reinforcement of the present invention, an anti-aging agent, a pH adjuster, and a stabilizer Etc. may be included. Examples of the anti-aging agent include diphenylamine compounds, and examples of the pH adjusting agent include ammonia.

  Chlorophenol (E) and formaldehyde (F) are subjected to a condensation reaction in water, and 2-methoxyalcohol as an alcohol compound (G) is added to the reaction solution in which a precipitate of chlorophenol-formaldehyde condensate (A) is formed. Coating for primary coating in which vinyl pyridine-styrene-butadiene copolymer (B) emulsion and chlorosulfonated polyethylene (C) emulsion are mixed in an aqueous solution of chlorophenol-formaldehyde condensate (A) obtained by dissolving the precipitate. The solution is applied to a glass fiber cord and then dried, and a coating solution for secondary coating in which chlorosulfonated polyethylene (C) and maleimide (D) are dispersed in an organic solvent is applied to the upper layer and then dried. In the secondary coating layer as the coating layer, the content of maleimide is in a suitable range. To produce a reinforcing glass fiber. (Examples 1-4).

  Next, dimethylamine as an amine compound (H) is added to the reaction liquid in which chlorophenol (E) and formaldehyde (F) are subjected to a condensation reaction in water to form a precipitate of chlorophenol-formaldehyde condensate (A), Coating for primary coating in which vinyl pyridine-styrene-butadiene copolymer (B) emulsion and chlorosulfonated polyethylene (C) emulsion are mixed in an aqueous solution of chlorophenol-formaldehyde condensate (A) obtained by dissolving the precipitate. The solution is applied to a glass fiber cord and then dried, and a coating solution for secondary coating in which chlorosulfonated polyethylene (C) and maleimide (D) are dispersed in an organic solvent is applied to the upper layer and then dried. Rubber of the present invention in which the content of maleimide is in a suitable range in the secondary coating layer as a coating layer To prepare a glass fiber for strength. (Examples 5-8).

  Next, glass fibers for rubber reinforcement having a maleimide content different from the preferred range in the secondary coating layer were produced. (Comparative Examples 1-3). The adhesion strength evaluation test with respect to the heat-resistant rubber of these glass fibers for rubber reinforcement (Examples 1 to 8, Comparative Examples 1 to 3) was performed, and the evaluation results were compared.

  Further, a power transmission belt in which the glass fiber for reinforcing rubber of the present invention was embedded in 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 allowed to run for a long time while being sprinkled with water. A rubber of the present invention in which the tensile strength does not change even after running and a water-resistant running fatigue performance evaluation test for evaluating excellent dimensional stability is performed, and the content of maleimide in the secondary coating layer is in a suitable range Transmission belt in which reinforcing glass fibers (Examples 1 to 8) are embedded In the transmission belt in which rubber reinforcing glass fibers (Comparative Examples 1 to 3) different from the preferred range in the content of maleimide in the secondary coating layer are embedded The evaluation results 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. For rubber reinforcement of the present invention in which the content of maleimide in the secondary coating layer is within a suitable range by performing a heat resistance and bending running fatigue performance evaluation test for evaluating that the strength does not change and the dimensional stability is excellent Transmission belt in which glass fibers (Examples 2, 4, 6, 8) are embedded, and transmission in which glass fibers for rubber reinforcement (Comparative Examples 1 and 2) having a maleimide content different from the preferred range in the secondary coating layer are embedded. The evaluation results in the belt were compared.

Details will be described below.
Example 1
(Preparation of coating solution for primary coating using alcohol compound)
The synthesis of the chlorophenol-formaldehyde condensate (A) and the dissolution of the produced chlorophenol-formaldehyde condensate (A) by the alcohol compound (G) will be described.

  In a three-necked separable flask equipped with a reflux condenser, a thermometer, and a stirrer, chlorophenol (E), 128 parts by weight, 37.0% by weight formaldehyde (F) aqueous solution, 80 parts by weight (in molar ratio) F / E = 1.0), concentration, 1 wt% sodium hydroxide aqueous solution, 20 parts by weight, diluted with water to 1000 parts by weight, and then heated to 80 ° C. For 5 hours. In this reaction solution, the chlorophenol-formaldehyde condensate (A) was polymerized as a precipitate.

  To 100 parts by weight of the reaction solution, 2-methoxyethanol belonging to the alcohol compound (G) is added to dissolve the precipitate of the chlorophenol-formaldehyde condensate (A), and the chlorophenol-formaldehyde condensate (A ) Was prepared. In this case, the weight of the chlorophenol-formaldehyde condensate (A) is expressed as a percentage by weight based on 100%, and the amount of 2-methoxyethanol added to the chlorophenol-formaldehyde condensate (A) is 200% by weight. That is, G / A = 2.0 in terms of weight ratio.

  The addition of an aqueous sodium hydroxide solution having a concentration of 1.0% by weight is condensed as a catalyst for the condensation reaction of chlorophenol (E) and formaldehyde (F) to form a chlorophenol-formaldehyde condensate (A). Do not add more than necessary for the reaction.

  In addition, P-chlorophenol was used for chlorophenol.

  Next, using an aqueous solution of the chlorophenol-formaldehyde condensate (A) synthesized by the above procedure, an emulsion of a commercially available vinylpyridine-styrene-butadiene copolymer (B), an emulsion of chlorosulfonated polyethylene (C), Ammonia water and water were added thereto to prepare a coating solution for primary coating.

  Specifically, the aqueous solution of chlorophenol-formaldehyde condensate (A) obtained by adding 2-methoxyethanol to dissolve the precipitate of chlorophenol-formaldehyde condensate (A), 42 parts by weight of vinyl pyridine, styrene, Product name, pilatex (solid content) manufactured by Nippon A & L Co., Ltd., as an emulsion of vinylpyridine-styrene-butadiene polymer obtained by polymerizing butadiene in a weight ratio of vinylpyridine: styrene: butadiene = 15: 15: 70 (Concentration 41.0% by weight) 476 parts by weight, and Sumitomo Seika Co., Ltd., trade name, CSM450 (solid content concentration, 40.0% by weight) 206 parts by weight as an emulsion of chlorosulfonated polyethylene (C) , Ammonia water (concentration: 25.0% by weight) 22 wt. DOO, the water was added so as a whole to 1000 parts by weight, to prepare a primary coating coating liquid.

  The content ratio of each component in the coating solution for primary coating is the combined weight of chlorophenol-formaldehyde condensate (A), vinylpyridine-styrene-butadiene copolymer (B) and chlorosulfonated polyethylene (C). Expressed as a weight percentage based on 100%, the chlorophenol-formaldehyde condensate (A) is A / (A + B + C) = 3.6% by weight, the vinylpyridine-styrene-butadiene copolymer (B) is B / (A + B + C) = 67.8 wt%, chlorosulfonated polyethylene (C) is C / (A + B + C) = 28.6 wt%. When it is applied to glass fiber cords and dried, the primary coating is obtained at almost the same weight ratio.

The weight of the vinylpyridine-styrene-butadiene copolymer (B) and the chlorosulfonated polyethylene (C) in the coating solution for primary coating is converted into the solid content from the solid content concentration of the pilatex and CSM450. Asked.
(Preparation of secondary coating solution)
Next, a coating solution for secondary coating, in which carbon black is added to chlorosulfonated polyethylene (C), p-dinitrosolobenzene, and N, Nmmphenylenedimaleimide belonging to maleimide (D) and dispersed in xylene. Was prepared.

Specifically, Tosoh Corporation product name, TS-430, 100 parts by weight as chlorosulfonated polyethylene (C), p-dinitosobenzene, 40 parts by weight, and weight of chlorosulfonated polyethylene (C) Is expressed as a percentage by weight based on 100%, and N, N-m-phenylenedimaleimide belonging to maleimide (D) is added to 30% by weight, carbon black and 30 parts by weight are further added, and xylene, 1315% by weight A coating solution for secondary coating was prepared by dispersing in a part. That is, with respect to the weight of chlorosulfonated polyethylene (C), 30% by weight of N, N-m-phenylenedimaleimide belonging to maleimide (D), 40% by weight of p-dinitrosolobenzene as a vulcanizing agent, inorganic A coating solution for secondary coating was prepared so that carbon black as a filler was 30% by weight. When it is applied to glass fiber cords and dried, a secondary coating is obtained with the weight ratio almost unchanged.
(Production of glass fiber for rubber reinforcement)
A glass fiber filament having a diameter of 9 μm is coated with a sizing agent with an applicator, and after three glass fiber cords formed by bundling 200 are aligned, the coating solution for primary coating produced by the above-described procedure is applied, A primary coating layer was provided by drying at a temperature of 280 ° C. for 22 seconds. At this time, the solid content adhesion rate, that is, the weight ratio of the primary coating layer was 19.0% by weight with respect to the total weight of the glass fiber bundle provided with the primary coating layer.

  The glass fiber cord provided with the coating layer is given a twist of 2.0 times per 2.54 cm, and further 13 wires are aligned and twisted 2.0 times per 2.54 cm in the opposite direction to the twist. Worked. Then, after apply | coating the coating liquid for secondary coating produced in the above-mentioned procedure, it dried for 1 minute at 110 degreeC, provided the secondary coating layer, and provided the glass fiber for rubber reinforcement (Example 1) of this invention. Produced.

  In this way, two types of glass fibers for rubber reinforcement were produced in which the directions of the lower twist and the upper twist were reversed. These are called S twist and Z twist, 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 cord for rubber reinforcement provided with the primary coating layer and the secondary coating layer. It was.
Example 2
A coating solution for primary coating similar to that in Example 1 was prepared by the procedure shown in Example 1, and the same procedure as in Example 5 was performed to provide a primary coating layer on the glass fiber cord.

Next, Tosoh Corporation's product name, TS-430, 100 parts by weight as chlorosulfonated polyethylene (C), p-dinitosobenzene, 40 parts by weight, and the weight of chlorosulfonated polyethylene (C) Expressed as a percentage by weight based on 100%, N, N-m phenylene dimaleimide belonging to maleimide (D) is added to 50.0% by weight, carbon black and 30 parts by weight are added, xylene, 1315% by weight A coating solution for secondary coating was prepared by dispersing in a part. That is, the weight percentage of the chlorosulfonated polyethylene (C) is expressed as a percentage by weight based on 100%, 50% by weight of N, Nmmylene dimaleimide belonging to maleimide (D), and p-dinini which is a vulcanizing agent. A coating solution for secondary coating was prepared so that 40% by weight of tosolobenzene and 30.0% by weight of carbon black, which is an inorganic filler, were prepared, and the same procedure as in Example 5 was performed. An additional secondary coating layer was provided on the rubber reinforcing glass fiber (Example 2) of the present invention.
Example 3
A coating solution for primary coating similar to that in Example 1 was prepared according to the procedure shown in Example 1, and a procedure similar to that in Example 1 was performed to provide a primary coating layer on the glass fiber cord.

  Next, Tosoh Corporation's product name, TS-430, 100 parts by weight as chlorosulfonated polyethylene (C), p-dinitosobenzene, 40 parts by weight, and the weight of chlorosulfonated polyethylene (C) Expressed as a percentage by weight based on 100%, N, N-m-phenylenedimaleimide belonging to maleimide (D) is added to 85% by weight, carbon black and 30 parts by weight are added, and xylene is added to 1315 parts by weight. A coating solution for secondary coating was prepared by dispersing.

That is, the weight of chlorosulfonated polyethylene (C) is expressed as a percentage by weight based on 100%, 85% by weight of N, Nmmylene dimaleimide belonging to maleimide (D), and p-dinitosolo which is a vulcanizing agent. A coating solution for secondary coating was prepared so that benzene was 40% by weight and carbon black as an inorganic filler was 30% by weight, and the same procedure as in Example 1 was performed. Next, a glass fiber for reinforcing rubber of the present invention (Example 3) was prepared by providing a coating layer.
Example 4
83 parts by weight of the chlorophenol-formaldehyde condensate (A) is added to the coating solution for primary coating of Example 1, and vinyl pyridine, styrene and butadiene are added 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 coating solution for primary coating was prepared in the same manner as in Example 1 except for changing. That is, the total weight of the chlorophenol-formaldehyde condensate (A), vinylpyridine-styrene-butadiene copolymer (B) and chlorosulfonated polyethylene (C) in the coating solution for primary coating is based on 100%. Expressed in weight percentage, chlorophenol-formaldehyde condensate (A) is A / (A + B + C) = 7.2% by weight, vinylpyridine-styrene-butadiene copolymer (B) is B / (A + B + C) = 64.2. % By weight, chlorosulfonated polyethylene (C) was adjusted so that C / (A + B + C) = 28.6% by weight. When applied to glass fiber cords and dried, primary coating was obtained at almost the same weight ratio. .

Next, a coating solution for secondary coating similar to that in Example 2 is prepared by the procedure shown in Example 1, and the procedure is performed in the same manner as in Example 5 to provide a further secondary coating layer on the glass fiber cord. A glass fiber for reinforcing rubber of the present invention (Example 4) was produced.
Example 5
(Preparation of coating solution for primary coating using amine compound)
The synthesis of the chlorophenol-formaldehyde condensate (A) and the dissolution of the produced chlorophenol-formaldehyde condensate (A) by the amine compound (H) will be described.

  In a three-necked separable flask equipped with a reflux condenser, a thermometer, and a stirrer, chlorophenol (E), 128 parts by weight, 37.0% by weight formaldehyde (F) aqueous solution, 80 parts by weight (in molar ratio) F / E = 1.0), concentration, 1 wt% sodium hydroxide aqueous solution, 20 parts by weight, diluted with water to 1000 parts by weight, and then heated to 80 ° C. For 5 hours. In this reaction solution, the chlorophenol-formaldehyde condensate (A) was polymerized as a precipitate.

To 100 parts by weight of the reaction solution, dimethylamine belonging to the amine compound (H) is added to dissolve the precipitate of the chlorophenol-formaldehyde condensate (A), and the chlorophenol-formaldehyde condensate (A) An aqueous solution was prepared. The basicity constant (Kb) of dimethylamine is 5.4 × 10 ⁻⁴ . In this case, the weight of the chlorophenol-formaldehyde condensate (A) is expressed as a percentage by weight based on 100%, and the amount of dimethylamine added to the chlorophenol-formaldehyde condensate (A) is 200% by weight, The weight ratio was H / A = 2.0.

  In addition, the addition of the sodium hydroxide aqueous solution having a concentration of 1.0% by weight is more than the amount necessary for the condensation reaction as a catalyst for the condensation reaction of chlorophenol and formaldehyde to form a chlorophenol-formaldehyde condensate (A). Is not in addition.

  In addition, P-chlorophenol was used for chlorophenol.

  Next, using an aqueous solution of the chlorophenol-formaldehyde condensate (A) synthesized by the above procedure, an emulsion of a commercially available vinylpyridine-styrene-butadiene copolymer (B), an emulsion of chlorosulfonated polyethylene (C), Ammonia water and water were added to to prepare a coating solution for primary fiber coating.

  Specifically, vinyl pyridine, styrene, butadiene were added to 42 parts by weight of an aqueous solution of chlorophenol-formaldehyde condensate (A) dissolved by adding dimethylamine, and vinyl pyridine: styrene: butadiene = 15: 15: 70. Made by Nippon A & L Co., Ltd. as an emulsion of vinylpyridine-styrene-butadiene polymer polymerized to a weight ratio, 476 parts by weight of pilatex (solid content concentration, 41.0% by weight), and chlorosulfonated Product name, CSM450 (solid content concentration, 40.0% by weight) 206 parts by weight as an emulsion of polyethylene (C), and ammonia water (concentration 25.0% by weight) as a pH adjuster Water is added to 22 parts by weight so that the total amount becomes 1000 parts by weight. The coating solution was prepared.

  The content ratio of each component in the coating solution for primary coating is the combined weight of chlorophenol-formaldehyde condensate (A), vinylpyridine-styrene-butadiene copolymer (B) and chlorosulfonated polyethylene (C). Expressed as a weight percentage based on 100%, the chlorophenol-formaldehyde condensate (A) is A / (A + B + C) = 3.6% by weight, the vinylpyridine-styrene-butadiene copolymer (B) is B / (A + B + C) = 67.8 wt%, chlorosulfonated polyethylene (C) is C / (A + B + C) = 28.6 wt%. When it is applied to glass fiber cords and dried, the primary coating layer is formed with the weight ratio almost unchanged.

The weight of the vinylpyridine-styrene-butadiene copolymer (B) and the chlorosulfonated polyethylene (C) in the coating solution for primary coating is converted to the solid content from the solid content concentration of the pilatex and CSM450. Asked.
(Preparation of secondary coating solution)
Next, a coating solution for secondary coating in which carbon black is added to chlorosulfonated polyethylene (C), p-dinitrosolobenzene, and N, Nmmylene dimaleimide belonging to maleimide (D) and dispersed in xylene. Was prepared.

Specifically, Tosoh Corporation product name, TS-430, 100 parts by weight as chlorosulfonated polyethylene (C), p-dinitosobenzene, 40 parts by weight, and weight of chlorosulfonated polyethylene (C) Is expressed as a percentage by weight based on 100%, and N, N-m-phenylenedimaleimide belonging to maleimide (D) is added to 30% by weight, carbon black and 30 parts by weight are further added, and xylene, 1315% by weight A coating solution for secondary coating was prepared by dispersing in a part. That is, with respect to the weight of chlorosulfonated polyethylene (C), 30% by weight of N, N-m-phenylenedimaleimide belonging to maleimide (D), 40% by weight of p-dinitrosolobenzene as a vulcanizing agent, inorganic A coating solution for secondary coating was prepared so that carbon black as a filler was 30% by weight. When it is applied to glass fiber cords and dried, a secondary coating is obtained with the weight ratio almost unchanged.
(Production of glass fiber for rubber reinforcement)
A glass fiber filament having a diameter of 9 μm is coated with a sizing agent with an applicator, and after three glass fiber cords formed by bundling 200 are aligned, the coating solution for primary coating produced by the above-described procedure is applied, A primary coating layer was provided by drying at a temperature of 280 ° C. for 22 seconds. At this time, the solid content adhesion rate, that is, the weight ratio of the primary coating layer was 19.0% by weight with respect to the total weight of the glass fiber bundle provided with the primary coating layer.

  The glass fiber cord provided with the coating layer is given a twist of 2.0 times per 2.54 cm, and further 13 wires are aligned and twisted 2.0 times per 2.54 cm in the opposite direction to the twist. Worked. Then, after applying the coating solution for secondary coating prepared in the above-described procedure, drying is 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 5) is provided. Produced.

  In this way, two types of glass fibers for rubber reinforcement were produced in which the directions of the lower twist and the upper twist were reversed. These are called S twist and Z twist, 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 cord for rubber reinforcement provided with the primary coating layer and the secondary coating layer. It was.
Example 6
A coating solution for primary coating similar to that in Example 5 was prepared by the procedure shown in Example 5, and the same procedure as in Example 5 was performed to provide a primary coating layer on the glass fiber cord.

Next, Tosoh Corporation's product name, TS-430, 100 parts by weight as chlorosulfonated polyethylene (C), p-dinitosobenzene, 40 parts by weight, and the weight of chlorosulfonated polyethylene (C) N, N-m phenylene dimaleimide belonging to maleimide (D), expressed as a percentage by weight based on 100%, is added to 50% by weight, carbon black and 30 parts by weight are added, and xylene is added to 1315 parts by weight. A coating solution for secondary coating was prepared by dispersing. That is, the weight percentage of the chlorosulfonated polyethylene (C) is expressed as a percentage by weight based on 100%, 50% by weight of N, Nmmylene dimaleimide belonging to maleimide (D), and p-dinini which is a vulcanizing agent. A coating solution for secondary coating was prepared so that 40% by weight of tosolobenzene and 30% by weight of carbon black, which is an inorganic filler, were prepared, and the same procedure as in Example 5 was performed. A secondary coating layer was provided to produce a glass fiber for rubber reinforcement (Example 6) of the present invention.
Example 7
A coating solution for primary coating similar to that in Example 5 was prepared by the procedure shown in Example 5, and the same procedure as in Example 5 was performed to provide a primary coating layer on the glass fiber cord.

  Next, Tosoh Corporation's product name, TS-430, 100 parts by weight as chlorosulfonated polyethylene (C), p-dinitosobenzene, 40 parts by weight, and the weight of chlorosulfonated polyethylene (C) Expressed as a percentage by weight based on 100%, N, N-m-phenylenedimaleimide belonging to maleimide (D) is added to 85% by weight, carbon black and 30 parts by weight are added, and xylene is added to 1315 parts by weight. A coating solution for secondary coating was prepared by dispersing.

That is, the weight of chlorosulfonated polyethylene (C) is expressed as a percentage by weight based on 100%, 85% by weight of N, Nmmylene dimaleimide belonging to maleimide (D), and p-dinitosolo which is a vulcanizing agent. A coating solution for secondary coating was prepared so that benzene was 40 wt% and carbon black as an inorganic filler was 30 wt%, and the same procedure as in Example 5 was performed. Next, a glass fiber for reinforcing rubber of the present invention (Example 7) was prepared by providing a coating layer.
Example 8
83 parts by weight of the chlorophenol-formaldehyde condensate (A) is added to the coating solution for primary coating in Example 5, and vinyl pyridine, styrene and butadiene are added 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 coating solution for primary coating was prepared in the same manner as in Example 5 except for changing. That is, the total weight of the chlorophenol-formaldehyde condensate (A), vinylpyridine-styrene-butadiene copolymer (B) and chlorosulfonated polyethylene (C) in the coating solution for primary coating is based on 100%. Expressed in weight percentage, chlorophenol-formaldehyde condensate (A) is A / (A + B + C) = 7.2% by weight, vinylpyridine-styrene-butadiene copolymer (B) is B / (A + B + C) = 64.2. % By weight, chlorosulfonated polyethylene (C) was adjusted so that C / (A + B + C) = 28.6% by weight. When applied to glass fiber cords and dried, primary coating was obtained at almost the same weight ratio. .

Next, a coating solution for secondary coating similar to that in Example 7 is prepared according to the procedure shown in Example 5, and the same procedure as in Example 5 is performed to provide a further secondary coating layer on the glass fiber cord. A glass fiber for rubber reinforcement (Example 8) according to the present invention was prepared.
Comparative Example 1
A coating solution for primary coating similar to that in Example 1 was prepared according to the procedure shown in Example 1, and a procedure similar to that in Example 1 was performed to provide a primary coating layer on the glass fiber cord.

Unlike Example 1, then, chlorosulfonated polyethylene (C) manufactured by Tosoh Corporation, trade name, TS-430, 100 parts by weight, p-dinitosolobenzene, 40 parts by weight Expressing the weight of (C) as a percentage by weight based on 100%, N, N-m-phenylenedimaleimide belonging to maleimide (D) is added so as to be 5.0% by weight, and 30 parts by weight of carbon black is further added. In addition, a coating solution for secondary coating was prepared by dispersing in 1315 parts by weight of xylene. That is, 5.0% by weight of N, N-mphenylene dimaleimide belonging to maleimide (D) and 40% by weight of p-dinitrosolobenzene as a vulcanizing agent based on the weight of chlorosulfonated polyethylene (C). Then, a coating solution for secondary coating was prepared so that carbon black as an inorganic filler would be 30% by weight, and the same procedure as in Example 5 was performed to provide a further secondary coating layer on the glass fiber cord. Rubber reinforcing glass fibers (Comparative Example 1) having a maleimide content different from the preferred range in the secondary coating layer were produced.
Comparative Example 2
Using the same coating solution for primary coating as in Example 1, then, Tosoh Corporation, trade name, TS-430, 100 parts by weight as chlorosulfonated polyethylene (C), p-dinitosolobenzene, 40% by weight N, N-m phenylene dimaleimide belonging to maleimide (D) expressed as a percentage by weight based on 100% of the weight of chlorosulfonated polyethylene (C) is added to 120 parts by weight, and carbon. Black and 30 parts by weight were added and dispersed in xylene and 1315 parts by weight to prepare a coating solution for secondary coating. That is, 120% by weight of N, Nmmylene dimaleimide (D) belonging to maleimide (D) and 40% by weight of p-dinitrosolobenzene as a vulcanizing agent based on the weight of chlorosulfonated polyethylene (C). %, A coating solution for secondary coating was prepared so that carbon black as an inorganic filler would be 30% by weight, and the procedure was performed in the same manner as in Example 5 to provide a further secondary coating layer on the glass fiber cord. Rubber reinforcing glass fibers (Comparative Example 2) having a maleimide content different from the preferred range in the provided secondary coating layer were 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 part by weight, vulcanization accelerator, 2.5 part by weight, anti-aging agent, 1.5 part by weight heat-resistant rubber for HNBR (hereinafter referred to as heat-resistant rubber A) In addition, HNBR (manufactured by Zeon Corporation, 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, 1, Adhesive strength of heat resistant rubber for HNBR (hereinafter referred to as heat resistant rubber B), comprising 5 parts by weight of 3-di (t-butylperoxyisopropyl) benzene, anti-aging agent and 1.5 parts by weight It was used for the evaluation test.

A test piece is a 3 mm thick and 25 mm wide rubber sheet made of heat-resistant rubber A or heat-resistant rubber B, and 20 glass fibers for reinforcing rubber (Examples 1 to 8 and Comparative Examples 1 and 2) are arranged on top of each other and a cloth is formed thereon. The heat-resistant rubber A is 196 Newton / cm ^{2 at} a temperature of 150 ° C. (hereinafter Newton is abbreviated as N), and the heat-resistant rubber B is 196 N / cm ^{2 at} a temperature of 170 ° C. and 196 N / cm ² . A test piece for evaluating adhesive strength, in other words, a rubber sheet, was obtained by pressing except for the edge and molding while vulcanizing for 30 minutes. 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. Also, the greater the peel strength, the better the adhesive strength.

  In the preparation of the primary coating liquid, the rubber reinforcing glass fiber of the present invention of Example 1 using 2-methoxyethanol as the alcohol compound (G) for dissolving the precipitate of the chlorophenol-formaldehyde condensate (A) As shown in FIG. 1, when peel strength was measured, heat-resistant rubber A was 329N, heat-resistant rubber B was 318N, good adhesion to both rubbers, and excellent adhesive strength. It was.

  Similarly, when the peel strength of the glass fiber for reinforcing rubber of the present invention of Example 2 using 2-methoxyethanol was measured as shown in Table 1, the heat resistant rubber A was 318 N, and the heat resistant rubber About B, it was 309N, adhesiveness with both rubber | gum was favorable, and it was excellent in adhesive strength.

  Similarly, when the peel strength of the glass fiber for reinforcing rubber of the present invention of Example 3 using 2-methoxyethanol was measured as shown in Table 1, the heat resistant rubber A was 320 N, and the heat resistant rubber About B, it was 310N, adhesiveness with both rubber | gum was favorable, and it was excellent in adhesive strength.

  Similarly, the glass fiber for rubber reinforcement of Example 4 of the present invention using 2-methoxyethanol as shown in Table 1 is 311N for heat resistant rubber A and 302N for heat resistant rubber B, both Adhesiveness was good with respect to the rubber, and the adhesive strength was excellent.

  In the preparation of the primary coating solution, the rubber reinforcing glass fiber of the present invention of Example 5 using dimethylamine as the amine compound (H) for dissolving the precipitate of the chlorophenol-formaldehyde condensate (A) is shown in Table 1. As shown, when the peel strength was measured, it was 302 for heat-resistant rubber A and 298 N for heat-resistant rubber B. The adhesiveness to both rubbers was good and the adhesive strength was excellent. .

  Similarly, the rubber reinforcing glass fiber of the present invention of Example 6 using dimethylamine was measured for peel strength as shown in Table 1. As a result, the heat resistant rubber A was 332N, and the heat resistant rubber B was Of 316N, good adhesion to both rubbers, and excellent adhesion strength.

  Similarly, as for the glass fiber for rubber reinforcement of the present invention of Example 7 using dimethylamine, as shown in Table 1, when the peel strength was measured, the heat resistant rubber A was 321N, and the heat resistant rubber B Was 310 N, good adhesion to both rubbers, and excellent adhesion strength.

  Similarly, the rubber reinforcing glass fiber of the present invention of Example 8 using dimethylamine was 318N for heat resistant rubber A and 306N for heat resistant rubber B, as shown in Table 1, and both rubbers. On the other hand, the adhesiveness was 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 1-8 of the present invention as shown in Examples 1-8 of Table 1, the fracture state is when the heat-resistant rubber B is used. Both were rubber breaks and had excellent adhesive strength.

  As for the glass fiber for rubber reinforcement of Comparative Example 1, when a test piece was prepared and the adhesive strength was evaluated by the above-described procedure, as shown in Comparative Example 1 of Table 1, heat resistant rubber A was 178 N, heat resistant. About rubber B, it is 196N, and adhesive strength is weak, and when heat-resistant rubber A is used, when both heat-resistant rubber B is used, interface peeling is inferior, and it is inferior to adhesive strength compared with Examples 1-8 It was.

  The glass fiber for rubber reinforcement of Comparative Example 2 was produced by the test procedure described above and evaluated for adhesive strength. As shown in Comparative Example 2 of Table 1, heat resistant rubber A was 197N, The heat-resistant rubber B was 203 N, and when the heat-resistant rubber A was used, both the cases where the heat-resistant rubber B was used were peeled off at the interface, and the adhesive strength was inferior to those of Examples 1-8.

(Water resistance evaluation)
Using the heat-resistant rubber B as a base rubber, the glass fiber for rubber reinforcement produced in Examples 1, 2, 4, 5, 6, 8 and Comparative Examples 1 and 2 as a reinforcing material, and having a width of 19 mm and a length of 876 mm Each of the transmission belts was produced, and a water resistance running fatigue test for evaluating water resistance was performed. 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 a total of 12 rubber reinforcing glass fibers 2 are alternately S twist and Z twist. 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 normal temperature, as shown in FIG. 2, 6000 ml of water 7 per hour is dropped evenly on the transmission belt 1 between the driving pulley 3 and the driven pulley 4 while rotating the driving pulley 3 at 3000 rpm to transmit power. The 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 produced using the rubber reinforcing glass 2 of Examples 5, 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. As for the tensile strength before the test, the resistance value was measured three times from ten similarly produced belts, and the average value was used as the initial value.

  The tensile strength retention after the water-resistant running fatigue test was calculated using the formula (1).

  Table 2 shows the tensile strength retention ratio of each transmission belt after the water-resistant running fatigue test.

  As shown in Table 2, the chlorophenol-formaldehyde condensate (A), vinylpyridine-styrene-butadiene copolymer (B) of Examples 1, 2, 4, 5, 6, and 8 and chlorosulfonated polyethylene (C And a secondary coating layer that is dried after being applied to a glass fiber cord, and the composition of the secondary coating layer is chlorosulfonated polyethylene ( C), p-dinitrosolobenzene, N, N-m phenylene dimaleimide belonging to maleimide (D), and a running test of the transmission belt 1 using a coating solution for glass fiber secondary coating for rubber reinforcement. The subsequent tensile strength retention rate was obtained when the alcohol compound (G) was used to dissolve the precipitate of the chlorophenol-formaldehyde condensate (A) in the preparation of the primary coating solution. When the rubber reinforcing glass fiber 2 of Example 1 is used, it is 67%, and when the rubber reinforcing glass fiber 2 of Example 2 is used, it is 63%, and the rubber reinforcing glass fiber 2 of Example 4 is used. Was 65%. In the preparation of the primary coating solution, 58% when the glass fiber 2 for rubber reinforcement of Example 5 using the amine compound (H) was used to dissolve the precipitate of the chlorophenol-formaldehyde condensate (A). Yes, it is 65% when the rubber reinforcing glass fiber 2 of Example 6 is used, and 62% when the rubber reinforcing glass fiber 2 of Example 7 is used, and the rubber reinforcing glass of Example 8 is used. When fiber 2 was used, it was 65%.

  On the other hand, as shown in Comparative Example 1 and Comparative Example 2, when the amount of maleimide (D) added is as small as 5.0% by weight, when it is as large as 120.0% by weight, the tensile strength retention is compared. When the rubber reinforcing glass fiber cord of Example 1 was used, it was 46%, and when the rubber reinforcing glass fiber cord of Comparative Example 2 was used, it was 43%, which was inferior in water resistance. When the rubber reinforcing glass fiber 2 of Example 5 was used, the tensile strength retention was 58%, compared with 46% when the rubber reinforcing glass fiber 2 of Comparative Example 1 was used. Big.

From the results of this water resistance running fatigue test, a primary composition comprising chlorophenol-formaldehyde condensate (A), vinylpyridine-styrene-butadiene copolymer (B), and chlorosulfonated polyethylene (C) as a composition. A book having a secondary coating layer on which a secondary liquid using chlorosulfonated polyethylene (C) to which maleimide (D) is added in an amount of 20.0 wt% to 90.0 wt% is applied and then dried. It was found that the transmission belt 1 using the rubber-reinforced glass fiber cord of the invention has excellent water resistance.
(Heat resistance evaluation)
Next, the glass fiber cord for reinforcing rubber produced in Examples 2, 4, 6, and 8 and Comparative Examples 1 and 2 was used as a reinforcing material, and the heat-resistant rubber B was used as a base rubber, similarly to the water resistance evaluation described above. Each of the transmission belts having a width of 19 mm and a length of 876 mm was produced, and a heat resistance bending resistance 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.

As shown in FIG. 3, the drive pulley 8 is rotated at 3000 rpm and the transmission belt 1 is run while being bent using the driven pulleys 9, 9 ′, 9 ^〃 and the idler 10 in an environment of temperature of 130 ° C. 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 and bending resistance running fatigue test and the tensile strength after the heat resistance and bending resistance fatigue test are measured. The retention rate was determined, and the heat resistance and bending resistance of the transmission belt 1 produced using the glass fibers 2 for reinforcing rubber of Examples 1 to 8 and Comparative Examples 1 and 2, that is, heat resistance, were comparatively evaluated.

  Table 3 shows the tensile strength retention rate of each transmission belt after the heat-resistant and bending-resistant running fatigue test.

  As shown in Table 3, the tensile strength retention rates of the transmission belt 1 manufactured using the glass fibers 2 for rubber reinforcement of Examples 1 to 8 after the heat resistance and bending resistance fatigue test are 95%, 94%, and 92, respectively. %, 95%, 94%, 96%, 88%, and 92%, and the tensile strength of the power transmission belt 1 using the glass fiber 2 for rubber reinforcement of Comparative Examples 1 and 2 after the heat and bending resistance running fatigue test Retention ratios are better than 60% and 68%, respectively, and have excellent heat resistance.

  From the results of this heat and bending resistance running fatigue test, a composition comprising chlorophenol-formaldehyde condensate (A), vinylpyridine-styrene-butadiene copolymer (B), and chlorosulfonated polyethylene (C) 1 The present invention has a secondary coating layer in which a coating solution for secondary coating using chlorosulfonated polyethylene (C) added with 20% to 90% by weight of maleimide (D) is applied on the secondary coating layer and then dried. It was found that the transmission belt 1 using the glass fiber cord for rubber reinforcement had excellent heat resistance.

  The glass fibers for rubber reinforcement of Examples 1 to 8 have excellent adhesive strength with HNBR, and the power transmission belt produced using the glass fibers 2 for rubber reinforcement of Examples 1 to 8 has excellent water resistance and heat resistance. Therefore, it is suitable for use as a core wire of a transmission belt for automobiles such as a timing belt that is used for a long time under high temperature and high humidity.

  According to the present invention, a glass fiber for rubber reinforcement provided with a coating layer of a glass fiber cord that gives a preferable adhesive strength to the adhesion between a glass fiber cord and a heat-resistant rubber, for example, HNBR, is obtained, and the glass fiber for rubber reinforcement is obtained. When the transmission belt was embedded in HNBR, the transmission belt was provided with excellent water resistance and heat resistance. Therefore, it is embedded as a reinforcement in a transmission belt for transmitting the driving force of a driving source such as an engine or a motor, and is embedded in a HNBR for use in an automotive transmission belt such as a timing belt, and a high temperature is applied to the automotive transmission belt. Used as glass fiber for rubber reinforcement that provides tensile strength maintenance and dimensional stability under high humidity.

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 (15)

A primary containing a chlorophenol-formaldehyde condensate (A), a vinylpyridine-styrene-butadiene copolymer (B), and a chlorosulfonated polyethylene (C) in a glass fiber cord obtained by bundling a plurality of glass fiber filaments. A glass fiber for reinforcing rubber, wherein a coating layer is formed and a secondary coating layer containing chlorosulfonated polyethylene (C) and maleimide (D) is provided thereon. Chlorophenol in which the primary coating layer is a precipitate of chlorophenol-formaldehyde condensate (A) obtained by condensation reaction of chlorophenol (E) and formaldehyde (F) in water, and alcohol compound (G) is added to dissolve the precipitate. -A coating solution for primary coating formed by mixing a vinylpyridine-styrene-butadiene copolymer (B) emulsion and a chlorosulfonated polyethylene (C) emulsion in an aqueous solution of formaldehyde condensate (A) with glass fiber cord The glass fiber for rubber reinforcement according to claim 1, wherein the glass fiber is applied and dried. The amount of the alcohol compound (G) added is expressed as a percentage by weight based on the weight of the chlorophenol-formaldehyde condensate (A) as 100%, and G / A = 50 wt% or more and 500 wt% or less. The glass fiber for rubber reinforcement according to claim 1 or 2, characterized by the above. N-propanol, isopropanol, propylene glycol, 2-methoxyethanol, 2-methoxymethylethoxypropanol, 1-methoxy-2-propanol, ethylene glycol, diethylene glycol, 1,2-diethoxyethane are used for the alcohol compound (G). The glass fiber for rubber reinforcement according to any one of claims 1 to 3, wherein the glass fiber is for rubber reinforcement. The primary coating solution is a chlorophenol-formaldehyde condensate (A) precipitate obtained by condensation reaction of chlorophenol (E) and formaldehyde (F) in water with the addition of an amine compound (H). The aqueous solution of formaldehyde condensate (A) is obtained by mixing an emulsion of vinylpyridine-styrene-butadiene copolymer (B) and an emulsion of chlorosulfonated polyethylene (C). Glass fiber for rubber reinforcement. 6. The glass fiber for rubber reinforcement according to claim 5, wherein the basicity constant (Kb) of the amine compound (H) is 5 × 10 ⁻⁵ or more and 1 × 10 ⁻³ or less. The amount of the amine compound (H) added is expressed as a percentage by weight based on the weight of the chlorophenol-formaldehyde condensate (A) as 100%, and H / A = 50 wt% or more and 500 wt% or less. The glass fiber for rubber reinforcement according to claim 5 or 6, characterized in that It is characterized by using methylamine, ethylamine, t-butylamine, dimethylamine, diethylamine, triethylamine, tri-n-butylamine, methanolamine, dimethanolamine, monoethanolamine, or diethanolamine as the amine compound (H). The glass fiber for rubber reinforcement according to any one of claims 5 to 7. The chlorophenol-formaldehyde condensate (A) is characterized in that the molar ratio of formaldehyde (F) to chlorophenol (E) is F / E = 0.5 or more and 3.0 or less. Item 9. The glass fiber for reinforcing rubber according to any one of items 8 to 9. The weight of chlorophenol-formaldehyde condensate (A), vinylpyridine-styrene-butadiene copolymer (B) and chlorosulfonated polyethylene (C) is expressed as a percentage by weight based on 100%. The formaldehyde condensate (A) is A / (A + B + C) = 1.0 wt% or more and 15.0 wt% or less, and the vinylpyridine-styrene-butadiene copolymer (B) is B / (A + B + C) = 45. 0% by weight or more and 82.0% by weight or less, and chlorosulfonated polyethylene (C) is contained in a range of C / (A + B + C) = weight 3.0% by weight or more and 40.0% by weight or less 1 The glass fiber for rubber reinforcement according to any one of claims 1 to 9, further comprising a secondary coating layer. The vinylpyridine-styrene-butadiene copolymer (B) is expressed as a percentage by weight based on the styrene-butadiene copolymer (I) and the weight of the vinylpyridine-styrene-butadiene copolymer (B) as 100%, The glass fiber for rubber reinforcement according to any one of claims 1 to 10, wherein I / B = 5.0% by weight or more and 80.0% by weight or less. Expressing the total weight of the secondary coating layer as a percentage by weight based on 100%, 10.0% by weight or more and 70.0% by weight or less of chlorosulfonated polyethylene (C), and the chlorosulfonated polyethylene (C) A secondary coating layer composed of maleimide (D) in a weight percentage of D / C = 20.0 wt% or more and 90.0 wt% or less is provided. The glass fiber for rubber reinforcement according to any one of Items 1 to 11. Maleimide (D) is N, N-m-phenylene dimaleimide, 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4, 4. 4′-diphenyl ether bismaleimide, 4,4′-diphenylsulfone bismaleimide, chlorophenyl maleimide, methylphenyl maleimide, hydroxyphenyl maleimide, carboxyphenyl maleimide, dodecyl maleimide and / or cyclohexyl maleimide The glass fiber for rubber reinforcement according to any one of claims 12 to 13. A power transmission belt comprising the rubber fiber reinforcing glass fiber according to any one of claims 1 to 13 embedded in a base rubber. 15. A timing belt for automobiles, wherein the rubber reinforcing glass fiber according to claim 1 is embedded in hydrogenated nitrile rubber.

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