JP4876971B2 - Glass fiber coating solution and rubber fiber reinforcing glass fiber using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a glass fiber cord imparting excellent water resistance and heat resistance suitable for transmission belts, when a rubber-reinforcing glass fiber having a coated layer, obtained by applying a coating liquid to a glass fiber and then drying the coated material, is embedded in a heat-resistant rubber (HNBR) to form the transmission belt. <P>SOLUTION: The coating liquid for glass fiber coating contains an aqueous solution of chlorophenol-formaldehyde condensation product obtained by carrying out condensation reaction of chlorophenol with formaldehyde in water, an emulsion of a vinylpyridine-styrene-butadiene copolymer, and an emulsion of chlorosulfonated polyethylene. The rubber-reinforcing fiber is obtained by applying the coating liquid to the glass fiber cord. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to a glass fiber coating coating solution for providing a coating layer for enhancing adhesion and heat resistance to a base rubber on glass fiber cords used for reinforcing various rubber products, and rubber reinforcing glass using the same. Regarding fiber.

  In order to impart tensile strength and dimensional stability to rubber products such as transmission belts and tires, it is common to embed high-strength fiber cords such as glass fibers, nylon fibers, and polyester fibers as a reinforcing material in the base rubber. The rubber reinforcing fibers embedded in the base rubber are required to have good adhesion to the base rubber, have a strong interface and do not peel off. However, even if the glass fiber cord 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 to improve 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 cord and prevent peeling at the interface, the glass fiber cord is usually bundled with glass fiber filaments, and resorcin-formaldehyde condensate and various latexes. The glass fiber coating glass fiber coating solution is applied after being coated in water and dried to form a coating layer. The coating layer has an effect of adhering the base rubber and the glass fiber cord when embedding the rubber reinforcing glass fiber in the base rubber at a high temperature to form a transmission belt. The strength is not always enough. For example, since a power transmission belt for automobiles is used in a high temperature environment in an engine room, the base rubber is a hydrogenated nitrile rubber (hereinafter referred to as a heat resistant rubber) crosslinked with sulfur or peroxide. 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.

  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 on the secondary 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 in which a glass fiber cord is coated with a second liquid containing a halogen-containing polymer and an isocyanate to form rubber reinforcing glass fibers.

  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 for reinforcing rubber having a second coating layer formed by applying and drying and curing, wherein the treating agent for the second coating layer comprises a rubber compound, a vulcanizing agent, and a maleimide vulcanizing aid. A rubber reinforcing cord characterized by having a main component is disclosed.

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

  Further, in Patent Document 4 relating to the applicant's patent application, a glass fiber cord is coated with a first liquid for glass fiber coating in which a resorcin-formaldehyde condensate and a rubber latex are dispersed in water to form a coating film. Then, after drying and curing to form a primary coating layer, a second liquid for glass fiber coating having a different composition was applied on the primary coating layer to form a coating film, and then dried and cured to form a secondary coating layer. A glass fiber for rubber reinforcement, wherein the second liquid for glass fiber coating is obtained by dispersing bisallylnadiimide, a rubber elastomer, a vulcanizing agent, and an inorganic filler in an organic solvent. Are listed. 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.

  Conventionally, for a timing belt of an automobile as a heat-resistant transmission belt reinforced with glass fiber for reinforcing rubber, a coating solution for coating glass fiber using a resorcin-formaldehyde condensate as an essential composition is used. Coating and drying to form a coating layer, followed by coating and drying using a glass fiber coating coating solution having a composition different from this, and adding a glass fiber for rubber reinforcement provided with a secondary coating layer to HNBR as a heat-resistant rubber What has been embedded and produced has been used.

  However, in the conventional transmission belt, although the initial bond strength between the rubber fiber and the base rubber was obtained by coating the glass fiber cord with a coating material, it runs for a long time under high humidity and high temperature as the transmission belt. After this, there was a problem that none had both excellent water resistance and heat resistance that maintained the tensile strength before running and had no dimensional change.

  Compared to the conventional transmission belt in which the glass fiber for rubber reinforcement described in Patent Document 1, Patent Document 2, Patent Document 3 or Patent Document 4 is embedded in heat-resistant rubber, it is equivalent to or better than rubber It has an adhesive strength between glass fiber and heat-resistant rubber. In addition to the water resistance that allows the coating layer to maintain the initial adhesive strength even if it is run for a long time with water on the transmission belt, it can be run for a long time at high temperatures. However, the development of a transmission belt having a heat resistance that allows the coating layer to maintain the initial adhesive strength and a glass fiber for rubber reinforcement that provides the belt are awaited.

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

  In Patent Document 6 relating to the applicant's patent application, a glass fiber cord 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 JP-A-11-241275 JP 2004-203730 A JP 2004-244785 A JP 2006-104595 A Pamphlet of International Publication No. 2006/038490 Japanese Patent Laid-Open No. 3-65536

  An object of this invention is to provide the coating liquid for glass fiber coating which gives the adhesive strength of the glass fiber cord and base material rubber | gum equal to or more than before.

  Furthermore, the present invention has a water resistance that allows the coating layer to maintain the initial adhesive strength even when it is run for a long time while applying water to the power transmission belt as compared with a conventional power transmission belt, and allows it to run for a long time at a high temperature. Even if the coating layer has a heat-resistant belt that maintains the initial adhesive strength, the glass-fiber coating coating solution and the glass fiber for rubber reinforcement, and the power transmission made by embedding the glass fiber for rubber reinforcement in the heat-resistant rubber The object is to provide a belt.

  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, so the chlorophenol-formaldehyde condensate is not used in the coating solution for coating glass fibers.

  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 formaldehyde condensate dissolves the precipitate in water, it can then be mixed with a vinylpyridine-styrene-butadiene copolymer emulsion and / or a chlorosulfonated polyethylene emulsion to prepare a coating solution for glass fiber coating. There was a problem that the phenol-formaldehyde condensate was precipitated again.

  Therefore, a strong alkali such as sodium hydroxide is added to the reaction liquid in which the chlorophenol-formaldehyde condensate is precipitated to dissolve the precipitate of the chlorophenol-formaldehyde condensate, and then a vinylpyridine-styrene-butadiene copolymer emulsion and / or When a coating solution for coating glass fibers is prepared by mixing with a chlorosulfonated polyethylene emulsion, the chlorophenol-formaldehyde condensate 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 relates to a chlorophenol-formaldehyde condensate (A) obtained by condensation reaction of chlorophenol (D) and formaldehyde (E) in water, an alcohol compound, and a vinylpyridine-styrene-butadiene copolymer (B) emulsion. A glass fiber coating coating solution for coating a glass fiber cord comprising a chlorosulfonated polyethylene (C) emulsion.

  The coating solution for coating glass fibers of the present invention comprises a monoalcohol compound and glycol in a reaction solution in which a chlorophenol-formaldehyde condensate (A) formed by condensation reaction of chlorophenol (D) and formaldehyde (E) in water is precipitated. A water-soluble alcohol compound containing a compound and a triol compound, that is, a water-compatible alcohol compound, is added to an aqueous solution of a chlorophenol-formaldehyde condensate (A) obtained by dissolving a precipitate of the chlorophenol-formaldehyde condensate (A). It was obtained by mixing a pyridine-styrene-butadiene copolymer (B) emulsion and a chlorosulfonated polyethylene (C) emulsion. In the present invention, an alcohol compound 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, and three OH groups. Having triol compounds.

  That is, as a result of intensive studies by the inventors, a water-soluble monoalcohol compound was precipitated in the precipitation of a chlorophenol-formaldehyde condensate (A) obtained by condensation reaction of chlorophenol (D) and formaldehyde (E) in water. When at least one water-soluble alcohol compound among glycol compounds and triol compounds is added to dissolve the precipitate of the chlorophenol-formaldehyde condensate (A), a chlorophenol-formaldehyde coating solution is prepared. Even if the vinylpyridine-styrene-butadiene copolymer (B) emulsion and the chlorosulfonated polyethylene (C) emulsion are added to the aqueous solution of the phenol-formaldehyde condensate (A) and mixed, the chlorophenol-formaldehyde condensate (A ) Was not precipitated.

  Thus, in order to dissolve the precipitate of the chlorophenol-formaldehyde condensate (A) formed by the condensation reaction in water, at least one of the water-soluble monoalcohol compound, glycol compound, and triol compound is soluble in water. It is necessary to add an alcohol compound.

  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. This is probably because the OH group and the OH group of the alcohol compound form a three-dimensionally strong hydrogen bond. In addition, since alcohol compounds have high values of dipole moment and dielectric constant, long-range interactions such as dispersion force work strongly, and the effect of stabilizing the chlorophenol-formaldehyde condensate (A) in an aqueous solution, as well as coordination Since the binding (charge transfer) interaction energy is large, association not only between the solvent and solute but also between the solvent and solvent causes strong solvation, and the chlorophenol-formaldehyde condensate (A) does not precipitate. It seems to have an effect of stabilizing in an aqueous solution. 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.

  Further, when an alcohol compound having a boiling point lower than 50 ° C. is used for the glass fiber coating liquid, the alcohol compound is likely to volatilize and is difficult to handle. When the alcohol compound volatilizes, a chlorophenol-formaldehyde condensate (A) is deposited. When an alcohol compound having a boiling point higher than 250 ° C. is used for the glass fiber coating liquid, the alcohol compound is less likely to volatilize than the coating layer when the glass fiber coating liquid is applied to the glass fiber cord and coated. If the alcohol compound is not removed from the coating layer, the heat resistance and water resistance of the power transmission belt when the fiberglass cord is embedded in the heat resistant rubber to form a power transmission belt are lowered. Therefore, the alcohol compound used in the coating solution for coating glass fibers of the present invention contains at least one water-soluble alcohol compound from a 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.

  Furthermore, the present invention relates to a chlorophenol-formaldehyde condensate (A) obtained by condensation reaction of chlorophenol (D) and formaldehyde (E) in water, an alcohol compound and a vinylpyridine-styrene-butadiene copolymer (B). The glass fiber coating coating liquid for coating a glass fiber cord, wherein the emulsion is mixed with a chlorosulfonated polyethylene (C) emulsion.

  Specifically, the precipitation of the chlorophenol-formaldehyde condensate (A) obtained by condensation reaction of chlorophenol (D) and formaldehyde (E) in water is at least one water-soluble substance selected from monoalcohol compounds, glycol compounds, and triol compounds. An aqueous solution of a chlorophenol-formaldehyde condensate (A) and then mixing a vinylpyridine-styrene-butadiene copolymer (B) emulsion and a chlorosulfonated polyethylene (C) emulsion. The glass fiber coating coating solution for coating a glass fiber cord characterized by comprising:

  In the present invention, the alcohol compound is selected from water-soluble monoalcohol compounds, glycol compounds, or triol compounds.

  Furthermore, the present invention is characterized in that the amount of the alcohol compound added is 50% by weight or more and 500% by weight or less, expressed as a weight percentage based on 100% by weight of the chlorophenol-formaldehyde condensate (A). It is said coating liquid for glass fiber coating. In other words, in the above glass fiber coating coating solution, the weight of the alcohol compound to be added is 1/2 or more and 5 times or less of the weight of the chlorophenol-formaldehyde condensate (A). .

  Furthermore, the present invention provides an alcohol compound containing n-propanol, isopropanol, 2-methoxyethanol, propylene glycol, 2-methoxymethylethoxypropanol, 1-methoxy-2-propanol, ethylene glycol, diethylene glycol, 1,2-diethoxy. It is the above-mentioned coating liquid for glass fiber coating, characterized by using ethane.

  Furthermore, the present invention is characterized in that the chlorophenol-formaldehyde condensate (A) has a molar ratio of formaldehyde (E) to chlorophenol (D) of E / D = 0.5 or more and 3.0 or less. It is said coating liquid for glass fiber coating.

  Furthermore, the present invention is expressed by weight percentage, and the chlorophenol-formaldehyde condensate (A) is A / (A + B + C) = 1.0% or more, 15.0% or less, vinylpyridine-styrene-butadiene copolymer ( B) is included in the range of B / (A + B + C) = 45.0% or more and 82.0% or less, and chlorosulfonated polyethylene (C) is included in the range of C / (A + B + C) = 3.0% or more and 40.0% or less. It is said glass fiber coating coating liquid characterized by being formed.

  Furthermore, this invention represents the said vinylpyridine-styrene-butadiene copolymer (B) to a styrene-butadiene copolymer (G) by weight percentage, G / B = 5.0% or more, 80. The glass fiber coating coating liquid described above, wherein the coating liquid is changed within a range of 0% or less.

  Further, in the present invention, after precipitation of a chlorophenol-formaldehyde condensate (A) obtained by condensation reaction of chlorophenol (D) and formaldehyde (E) in water by adding an alcohol compound, vinylpyridine- A method for producing a glass fiber-coated coating basket as described above, wherein a styrene-butadiene copolymer (B) emulsion and a chlorosulfonated polyethylene (C) emulsion are mixed.

  In the present invention, the glass fiber for reinforcing rubber coated with the above glass fiber coating solution is dried, and then chlorosulfonated polyethylene (C) and F / C = 0.3% in weight percentage. A rubber reinforcement characterized by applying a coating solution for glass fiber secondary coating in which 10.0% or less of bisallylnadiimide (F) is dispersed in an organic solvent and providing a further secondary coating layer Glass fiber.

  The present invention also provides a power transmission belt comprising the rubber reinforcing glass fiber embedded in a heat resistant rubber.

  Furthermore, the present invention is the above transmission belt characterized in that the heat resistant rubber is HNBR.

  According to the present invention, an alcohol compound is added to and dissolved in a precipitate of a chlorophenol-formaldehyde condensate (A) obtained by condensation reaction of chlorophenol (D) and formaldehyde (E) in water. When the product (A) 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 glass fiber coating coating solution for coating a glass fiber cord was obtained.

  Further, a chlorophenol-formaldehyde condensate (A) obtained by condensation reaction of chlorophenol (D) and formaldehyde (E) in water, a vinylpyridine-styrene-butadiene copolymer (B) emulsion and chlorosulfonated polyethylene ( C) A glass fiber for reinforcing rubber comprising a glass fiber cord coated with a coating solution for coating glass fiber according to the present invention for coating a glass fiber cord characterized by containing an emulsion. Gives excellent adhesion strength to the glass fiber cord and HNBR when embedded in HNBR which is a heat-resistant rubber.

  Furthermore, by providing heat resistance when buried in HNBR as a power transmission belt, it has both water resistance and heat resistance, and after use for a long time as a power transmission belt under high temperature and high humidity, in other words, for a long time After the running, there is no concern that the interface between the glass fiber and the heat-resistant rubber is peeled off, and the transmission belt maintains the tensile strength and is excellent in dimensional stability.

  A chlorophenol-formaldehyde condensate (A) obtained by condensation reaction of chlorophenol (D) and formaldehyde (E) of the present invention in water, a vinylpyridine-styrene-butadiene copolymer (B) emulsion, and chlorosulfonated A glass fiber for rubber reinforcement formed by applying a glass fiber coating coating solution for coating a glass fiber cord, comprising a polyethylene (C) emulsion, and providing a coating layer on the glass fiber cord, Glass fiber coating coating that is a heat resistant rubber, for example, a conventional resorcin-formaldehyde condensate, vinylpyridine-styrene-butadiene copolymer and chlorosulfonated polyethylene dispersed in water when embedded in HNBR Glass fiber for rubber reinforcement and HNBR equivalent to the case of using liquid It has excellent adhesion strength of.

  The present invention relates to a chlorophenol-formaldehyde condensate (A) obtained by condensation reaction of chlorophenol (D) and formaldehyde (E) in water, a vinylpyridine-styrene-butadiene copolymer (B) emulsion, and chlorosulfone. It is a glass fiber coating coating solution for coating a glass fiber cord characterized by comprising a modified polyethylene (C) emulsion.

  Specifically, the present invention relates to an aqueous solution of a chlorophenol-formaldehyde condensate (A) obtained by condensation reaction of chlorophenol (D) and formaldehyde (E) in water, and a vinylpyridine-styrene-butadiene copolymer (B). A glass fiber coating coating solution for coating a glass fiber cord comprising an emulsion and a chlorosulfonated polyethylene (C) emulsion.

  Furthermore, the present invention relates to a chlorophenol-formaldehyde condensate (A) obtained by condensation reaction of chlorophenol (D) and formaldehyde (E) in water, an alcohol compound and a vinylpyridine-styrene-butadiene copolymer (B). A glass fiber coating coating solution for coating a glass fiber cord by mixing an emulsion and a chlorosulfonated polyethylene (C) emulsion.

  Specifically, the precipitation of chlorophenol-formaldehyde condensate (A) obtained by condensation reaction of chlorophenol (D) and formaldehyde (E) in water, an alcohol compound and a vinylpyridine-styrene-butadiene copolymer (B) emulsion And the above glass fiber coating coating solution for coating a glass fiber cord, which is obtained by mixing chlorosulfonated polyethylene (C) emulsion.

  The coating solution for glass fiber coating of the present invention is obtained by adding an alcohol compound to a reaction solution in which a chlorophenol-formaldehyde condensate (A) obtained by condensation reaction of chlorophenol (D) and formaldehyde (E) in water is added. An aqueous solution of chlorophenol-formaldehyde condensate (A) obtained by dissolving a precipitate of phenol-formaldehyde condensate (A), vinylpyridine-styrene-butadiene copolymer (B) emulsion, chlorosulfonated polyethylene (C) emulsion, Obtained by mixing.

  For example, when the chlorophenol-formaldehyde condensate (A) is dissolved in water, an alkali such as ammonia or sodium hydroxide is usually 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). Thereafter, when the vinylpyridine-styrene-butadiene copolymer (B) emulsion and the chlorosulfonated polyethylene (C) emulsion are mixed, the chlorophenol-formaldehyde condensate (A) is precipitated.

  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). When dissolved, the vinylpyridine-styrene-butadiene copolymer (B) emulsion and the chlorosulfonated polyethylene (C) emulsion are mixed to suppress the precipitation of the chlorophenol-formaldehyde condensate (A) after mixing. The 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 alcohol 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 a vinylpyridine-styrene-butadiene copolymer (B) emulsion. It was found that when chlorosulfonated polyethylene (C) emulsion was mixed with chlorosulfonated formaldehyde condensate (A), precipitation of chlorophenol-formaldehyde condensate (A) hardly occurred and the glass fiber was not deteriorated to lower the tensile strength. In the present invention, an alcohol compound 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, and three OH groups. Having triol compounds.

  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, a water-soluble alcohol compound 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 to obtain a chlorophenol. An aqueous solution of the phenol-formaldehyde condensate (A) is obtained.

  If an alcohol compound having a boiling point lower than 50 ° C. is used for the glass fiber coating coating solution, the alcohol compound is easily volatilized and difficult to handle. If an alcohol compound having a boiling point higher than 250 ° C. is used, the glass fiber coating coating solution is made of When the fiber cord is applied and coated, the alcohol compound is less likely to volatilize than the coating layer. Therefore, the alcohol compound used in the coating solution for glass fiber coating of the present invention has a boiling point, a monoalcohol compound having a boiling point of 50 ° C. or higher and 250 ° C. or lower, It is preferable to select and use at least one water-soluble alcohol compound from a glycol compound or a triol compound.

  The amount of the alcohol compound added is 50% by weight or more and 500% by weight 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 alcohol compound added is 1/2 or more and 5 or less with respect to the weight of the chlorophenol-formaldehyde condensate (A).

  Expressing the weight of the chlorophenol-formaldehyde condensate (A) as a percentage by weight based on 100%, if the amount of the alcohol compound added is less than 50% by weight, the precipitate of the chlorophenol-formaldehyde condensate (A) is dissolved. There is no effect and it is not necessary to contain more than 500 weight%. When the amount of the glycol compound added exceeds 500% by weight, the chlorophenol-formaldehyde condensate (A) and the vinylpyridine-styrene-butadiene copolymer (B) and the chlorosulfonated polyethylene (C) in the coating of the glass fiber cord Thus, the glass fiber for rubber reinforcement 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 the same as that of the reaction liquid containing the precipitation of the chlorophenol-formaldehyde condensate (A) produced by the condensation reaction between chlorophenol (D) and formaldehyde (E) in water. It is determined from the weight of the residue heated and evaporated. At this time, unreacted chlorophenol (D) and formaldehyde (E) are volatilized and removed.

In the present invention, the alcohol compound used to dissolve 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) a boiling point 97 ° C., isopropyl alcohol _{(C 3 H} 8 O) a 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., diethyl Glycol _{(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-methoxymethyl-ethoxy propanol _{(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 a coating layer is formed on the glass fiber cord by applying a glass fiber coating coating solution and then drying, and chlorophenol- Since the effect of stabilizing the aqueous solution of the formaldehyde condensate (A) is also high, it is a particularly preferred alcohol compound for use in the glass fiber coating coating solution of the present invention.

  Among the two OH group glycol (diol) compounds, for use in the coating solution for glass fiber coating for the purpose of dissolving the precipitate of the chlorophenol-formaldehyde condensate (A), for adjusting the concentration of the coating solution. In some cases, gelation is formed when water is added. However, 2-methoxyethanol and propylene glycol are not concerned in the concentration adjustment in the necessary area. In addition, they are safe against fire and toxic. The alcohol compound is particularly preferable for use in the coating solution for coating a glass fiber of the present invention because it has a low boiling point and no concern about the operator's suction, is excellent in environmental safety, has a low commercial price, and is highly practical. It is.

  Methanol and ethanol contained in one OH group monoalcohol compound and glycerin contained in a triol compound having three OH groups were coated for coating glass fiber 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 glass fiber coating liquid 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 the glass fiber coating coating solution of the invention, the chlorophenol-formaldehyde resin (A) used has a molar ratio of formaldehyde (E) to chlorophenol (D) of 0.5 or more and 3.0 or less, It is preferable to use a resol type resin reacted with a basic catalyst at E / D = 0.5 or more and 3.0 or less.

  When the molar ratio of formaldehyde (E) is less than 0.5 in the glass fiber coating coating solution of the present invention, the adhesive strength between the glass fiber for rubber reinforcement and the heat-resistant rubber is inferior. The coating liquid for use is easily gelled. Thus, it is preferable that the molar ratio of formaldehyde (E) to chlorophenol (D) in the chlorophenol-formaldehyde condensate (A) is E / D = 0.5 or more and 3.0 or less.

  In the coating solution for coating glass fibers of the present invention, the chlorophenol-formaldehyde condensate (A) is expressed as a percentage by weight, and A / (A + B + C) = 1.0% or more, 15.0% or less, vinylpyridine-styrene- Butadiene copolymer (B) is B / (A + B + C) = 45.0% or more and 82.0% or less, and chlorosulfonated polyethylene (C) is C / (A + B + C) = 3.0% or more, 40.0%. It is preferable to be included in the following ranges.

  Specifically, in a transmission belt produced by embedding a rubber reinforcing glass fiber in which the glass fiber coating coating solution of the present invention is applied and coated on a glass fiber cord in a heat resistant rubber, desired adhesion to the rubber reinforcing glass fiber and the heat resistant rubber is achieved. In order to obtain strength, the chlorophenol-formaldehyde condensate (A), vinylpyridine-styrene-butadiene copolymer (B) and chlorosulfonated polyethylene (C) contained in the glass fiber coating solution were combined. The chlorophenol-formaldehyde condensate (A) is expressed as a percentage by weight based on 100%, and A / (A + B + C) = 1.0% or more, 15.0% or less, vinylpyridine-styrene-butadiene copolymer The coalescence (B) is B / (A + B + C) = 45.0% or more and 82.0% or less, and the chlorosulfonated polyethylene (C) is C (A + B + C) = 3.0% or more is preferably contained in the range of less than 40.0%. Further, a part of the chlorophenol-formaldehyde condensate (A) may be replaced with a monohydroxybenzene-formaldehyde condensate and / or a resorcin-formaldehyde condensate, and there is an effect such as imparting flexibility to the rubber reinforcing fiber. . In addition, the coating layer of the glass fiber for rubber reinforcement is formed with the content ratio of each component in the coating solution for glass fiber coating.

  A part of the vinylpyridine-styrene-butadiene copolymer (B), which is one of the compositions of the glass fiber coating liquid used for the rubber reinforcing glass fiber of the present invention, may be replaced with another rubber elastomer. . With only the vinylpyridine-styrene-butadiene copolymer (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. Other rubber elastomers include carboxyl group-modified styrene-butadiene copolymers, acrylonitrile-butadiene copolymers, etc., but styrene having good compatibility with vinylpyridine-styrene-butadiene copolymer (B), in other words, good compatibility. -Butadiene copolymer (G) is particularly preferably used, and is a power transmission belt embedded in a heat-resistant rubber as a base rubber and adhesiveness to the base rubber, which is a characteristic of the glass fiber for rubber reinforcement of the present invention. Does not impair the heat resistance.

  A preferred range for replacing the vinylpyridine-styrene-butadiene copolymer (B) with the styrene-butadiene copolymer (G) is based on the weight of the vinylpyridine-styrene-butadiene copolymer (B) as 100%. Expressed as a percentage by weight, G / B is in the range of 5.0% to 80.0%. When the styrene-butadiene copolymer (G) is less than 5.0%, the coating layer of the glass fiber for reinforcing rubber is tacky, and there is no effect of suppressing the coating layer from being easily transferred. Preferably, it is 25.0% or more. If the styrene-butadiene copolymer (G) exceeds 80.0%, the adhesion to the base rubber and the heat resistance when embedded in the heat-resistant rubber as the base rubber to form a transmission belt are lost. Preferably, it is 55.0% or less.

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

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

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

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

  Conventionally, a heat-resistant transmission belt is a rubber coated and dried on a glass fiber cord using a coating solution for glass fiber coating comprising resorcin-formaldehyde condensate, vinylpyridine-styrene-butadiene copolymer, and chlorosulfonated polyethylene. The reinforcing glass fiber was embedded 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.

  After the glass fiber coating coating solution of the present invention is applied to a glass fiber cord, the glass fiber for rubber reinforcement used as a coating layer is dried and further coated with chlorosulfonated polyethylene (C) and bisallyl nadiimide (F). It is preferable to apply a glass fiber secondary coating coating solution dispersed in a solvent to provide a secondary coating layer. When a secondary coating layer is provided and embedded in various base rubbers, particularly heat resistant rubbers such as HNBR, and used as a transmission belt, excellent adhesion between the glass fiber cord and the base rubber is obtained, and the rubber reinforcing glass of the present invention The fiber works effectively as a reinforcement for the transmission belt. Further, in the transmission belt, the coating layer maintains the initial adhesive strength and is excellent in dimensional stability, that is, excellent in heat resistance and water resistance, when used for a long time in a hot and humid environment. Examples of the organic solvent include xylene.

  The glass fiber coating coating solution of the present invention is applied to a glass fiber cord and dried to obtain a glass fiber for rubber reinforcement. Compared to a conventional transmission belt, a glycol compound and a chlorophenol-formaldehyde condensate (A) Using the glass fiber coating coating liquid of the present invention in which an emulsion of vinylpyridine-styrene-butadiene copolymer (B) and an emulsion of chlorosulfonated polyethylene (C) are mixed, the glass fiber cord is coated and dried, and then primary. After providing the coating layer, expressed as a percentage by weight based on 100% of chlorosulfonated polyethylene (C), bisallylnadiimide (F) is F / C = 0.3% or more and 10.0% or less. In addition to the above range, the glass fiber secondary coating coating solution dispersed in an organic solvent is applied, and a further secondary coating layer is provided for reinforcing the rubber of the present invention The transmission belt made by embedding the lath fiber in HNBR maintains the initial bond strength between the glass fiber and HNBR by the coating layer even after running for a long time under high humidity and high temperature, and maintains the tensile strength. It has excellent stability and has both water resistance and heat resistance.

  When the content of bisallylnadiimide (F) is less than F / C = 0.3%, the above-described excellent heat resistance is difficult to obtain. When F / C = 10.0% is exceeded, the adhesive strength between the glass fiber cord and the base rubber becomes weak and the produced transmission belt is inferior in durability.

  Bisallyl nadiimide (F) is a kind of thermosetting imide resin, and low molecular weight bisallyl nadiimide (F) is excellent in compatibility with other resins. The glass transition point is 300 ° C. or higher, and the heat resistance of the transmission belt is enhanced.

The bisallyl nadiimide (F) is represented by the structural formula of Chemical Formula 1 before curing, and the alkyl group of the structural formula of Chemical Formula 1 is represented by the structural formula of Chemical Formula 2 or Chemical Formula 3, and in particular, N—N '-Hexamethylene diallyl nadiimide is preferably used.

  Bisallyl nadiimide (F) is commercially available from Maruzen Petrochemical Co., Ltd. under trade names such as BANI-M, BANI-H, and BANI-X, and is suitably used for the glass fiber for rubber reinforcement of the present invention.

  The glass fiber cord contains a chlorophenol-formaldehyde condensate (A), a vinylpyridine-styrene-butadiene copolymer (B) emulsion, and a chlorosulfonated polyethylene (C) emulsion for coating glass fibers. When a further secondary coating is provided on the glass fiber for rubber reinforcement of the present invention, which is dried and then provided with a coating layer after applying the coating solution, instead of bisallylnadiimide (F) Also, a rubber reinforcing glass fiber provided with a secondary coating layer containing maleimide, provided with a secondary coating layer containing organic diisocyanate and zinc methacrylate, or provided with a secondary coating layer containing a triazine-based compound is also conceivable. However, in the heat resistance of the transmission belt for the reasons described above, that is, when the transmission belt requires heat resistance, it is embedded in rubber. The chlorosulfonated polyethylene (C) and bisallylnadiimide (F) and a glass fiber coated coating liquid dispersed in an organic solvent was applied before that, it is particularly preferable to provide a further coating layer.

  In order to give heat resistance to the glass fiber for rubber reinforcement of the present invention, it is preferable to use chlorosulfonated polyethylene (C) as the composition of the secondary coating, and further, a nitroso compound as a vulcanizing agent, for example, It is possible to add p-nitrosobenzene, carbon black or magnesium oxide as an inorganic filler to the glass fiber secondary coating solution, and add the rubber reinforcing glass fiber to the secondary coating layer. There is a further effect of increasing the heat resistance of a transmission belt produced by embedding fibers in rubber. The glass fiber secondary coating coating solution is expressed as a weight percentage based on 100% of the weight of chlorosulfonated polyethylene (C) in the coating solution, and the vulcanizing agent is 0.5% or more and 20.0% or less. When the inorganic filler is added in the range of 10.0% or more and 70.0% or less, the produced transmission belt exhibits further heat resistance. When the content of the vulcanizing agent is less than 0.5% and the content of the inorganic filler is less than 10.0%, the effect of improving the heat resistance is not exhibited, and the vulcanizing agent exceeds 20.0%, It is not necessary to add more than 70.0% inorganic filler.

  As described above, the glass fiber for rubber reinforcement of the present invention has a heat resistance to the glass fiber cord when it is embedded in a heat resistant rubber, for example, HNBR, as a transmission belt, as compared with the conventional glass fiber for rubber reinforcement. By improving it, the transmission belt is given heat resistance, and it has excellent 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.

  Further, the power transmission belt for automobiles refers to the heat resistant power transmission belt used in the engine room of the automobile.

  Timing belt is a tooth of a pulley for performing rotation of a crankshaft to a timing gear and driving the camshaft to open and close a valve in an engine having a camshaft in the above-mentioned automobile transmission belt. It is a toothed belt provided with meshing teeth. Power transmission belts for automobiles must have heat resistance against engine heat and water resistance in rainy weather, and maintain tensile strength and excellent dimensional stability after running for a long time under high temperature and high humidity. That is, it is required to have excellent heat resistance and water resistance. Glass fiber coating coating solution of the present invention, glass fiber for rubber reinforcement formed by coating the glass fiber coating coating solution on a glass fiber cord, a transmission belt formed by embedding the rubber reinforcing glass fiber in heat-resistant rubber, for example, A timing belt formed by embedding the rubber reinforcing glass fiber in HNBR is excellent in heat resistance and durability.

  Chlorophenol-, which is obtained by adding an alcohol compound to a reaction solution in which a precipitation of chlorophenol-formaldehyde condensate (A) is produced by condensation reaction of chlorophenol (D) and formaldehyde (E) in water. The glass fiber coating coating solution of the present invention obtained by mixing a vinylpyridine-styrene-butadiene copolymer (B) emulsion and a chlorosulfonated polyethylene (C) emulsion in an aqueous solution of formaldehyde condensate (A) is applied to a glass fiber cord. A glass fiber for reinforcing rubber which is post-dried and further coated with a coating solution for secondary coating of glass fiber in which chlorosulfonated polyethylene (C) and bisallylnadiimide (F) are dispersed in an organic solvent is used as a coating layer. It produced (Examples 1-4).

  Subsequently, a glass fiber for rubber reinforcement not within the scope of the present invention was produced. (Comparative Examples 1 and 2). The rubber reinforcing glass fibers of the present invention (Examples 1 to 4) and rubber reinforcing glass fibers not in the category of the present invention (Comparative Examples 1 and 2) were subjected to an adhesive strength evaluation test for heat-resistant rubber, and the evaluation results were obtained. Compared.

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

Details will be described below.
Example 1
(Preparation of coating solution for coating glass fiber of the present invention)
First, the synthesis of the chlorophenol-formaldehyde condensate (A) will be described. To a three-necked separable flask equipped with a reflux condenser, a thermometer, and a stirrer, chlorophenol (D), 128 parts by weight, 37.0% by weight aqueous formaldehyde (E) solution, 80 parts by weight (in molar ratio) E / D = 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 glycol compound is added to dissolve the precipitate of the chlorophenol-formaldehyde condensate (A), and an aqueous solution of the chlorophenol-formaldehyde condensate (A). Was made.

  At this time, the weight of the chlorophenol-formaldehyde condensate (A) was expressed as a percentage by weight based on 100%, and the amount of 2-methoxyethanol added was 200.0% by weight. That is, 2-methoxyethanol was added to the chlorophenol-formaldehyde condensate (A) in a weight ratio so as to be doubled.

  In addition, the said addition of 1.0 weight% of sodium hydroxide aqueous solution is condensed as a catalyst for carrying out the condensation reaction of chlorophenol (D) and formaldehyde (E) to make a chlorophenol-formaldehyde condensate (A). Do not add more than necessary for the reaction. In addition, P-chlorophenol was used for chlorophenol (D).

  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 the glass fiber coating solution of the present invention.

  Specifically, vinyl pyridine, styrene and butadiene were added to 42 parts by weight of an aqueous solution of chlorophenol-formaldehyde condensate (A) dissolved by adding 2-methoxyethanol, and vinyl pyridine: styrene: butadiene = 15: 15: Made by Nippon A & L Co., Ltd. as an emulsion of vinylpyridine-styrene-butadiene polymer (B) polymerized so as to have a weight ratio of 70, 476 parts by weight, tradename (solid content concentration, 41.0% by weight) Manufactured by Sumitomo Seika Chemicals Co., Ltd. as an emulsion of chlorosulfonated polyethylene (C), trade name, 206 parts by weight of CSM450 (solid content concentration, 40.0% by weight), and aqueous ammonia (concentration, 25) 0.0% by weight) and 22 parts by weight of water to add 1000 parts by weight as a whole. It was prepared fiberglass coating the coating solution of the present invention.

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

Specifically, Tosoh Corporation product name, TS-430, 100 parts by weight as chlorosulfonated polyethylene (C), p-dinitrobenzene, 40 parts by weight, and Maruzen as NN'-hexamethylene diallyl nadiimide Made by Petrochemical Co., Ltd., trade name, BANI-H, 0.3 parts by weight, carbon black and 30 parts by weight were added, and xylene was dispersed in 1315 parts by weight to prepare a coating solution for glass fiber secondary coating. . That is, NN′-hexamethylene diallyl nadiimide belonging to bisallyl nadiimide (F) is F / C = 0.5% by weight and a vulcanizing agent based on the weight of chlorosulfonated polyethylene (C). A glass fiber secondary coating coating solution was prepared such that p-dinitrobenzene was 40 wt% and carbon black as an inorganic filler was 30.0 wt%.

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

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

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

At this time, the solid content adhesion rate, that is, the weight ratio of the secondary coating layer was 3.5% by weight based on the weight of the glass fiber for rubber reinforcement provided with the primary and secondary coating layers.
Example 2
83 parts by weight of the chlorophenol-formaldehyde condensate (A) is added to the coating solution for coating glass fibers of Example 1, and vinylpyridine, styrene and butadiene are added at a weight ratio of 15:15:70. 451 parts by weight of an added amount of a vinylpyridine-styrene-butadiene copolymer (B) emulsion (trade name, pilatex, solid content, 41.0% by weight, manufactured by Nippon A & L Co., Ltd.) A glass fiber coating coating solution of the present invention was prepared in the same manner as in Example 1 except that it was changed to. That is, based on the total weight of the chlorophenol-formaldehyde condensate (A), the vinylpyridine-styrene-butadiene copolymer (B), and the chlorosulfonated polyethylene (C) in the glass fiber coating solution, Expressed in weight percentage, chlorophenol-formaldehyde condensate (A) is A / (A + B + C) = 7.2%, vinylpyridine-styrene-butadiene copolymer (B) is B / (A + B + C) = 64. 2%, chlorosulfonated polyethylene (C) was C / (A + B + C) = 28.6%. In addition, the coating layer of the glass fiber for rubber reinforcement is formed with the content ratio of each component in the coating solution for glass fiber coating.

Next, a secondary liquid for glass fiber coating similar to that in Example 1 is prepared by the procedure shown in Example 1, and the operation is performed in the same procedure as in Example 1. A further secondary coating layer is applied to the glass fiber cord. A glass fiber for reinforcing rubber of the present invention (Example 2) was produced.
Example 3
124 parts by weight of the chlorophenol-formaldehyde condensate (A) is added to the coating solution for coating glass fibers of Example 1, vinyl pyridine, styrene, and butadiene at a weight ratio of 15:15:70. The added amount of vinylpyridine-styrene-butadiene copolymer (B) emulsion (trade name, pilatex, solid content, 41.0% by weight, manufactured by Nippon A & L Co., Ltd.) is 426 parts by weight. A glass fiber coating coating solution of the present invention was prepared in the same manner as in Example 1 except that the amount was changed. That is, based on the total weight of the chlorophenol-formaldehyde condensate (A), the vinylpyridine-styrene-butadiene copolymer (B), and the chlorosulfonated polyethylene (C) in the glass fiber coating solution, Expressed in weight percentage, chlorophenol-formaldehyde condensate (A) is A / (A + B + C) = 10.8%, vinylpyridine-styrene-butadiene copolymer (B) is B / (A + B + C) = 60. 6%, chlorosulfonated polyethylene (C) was adjusted to C / (A + B + C) = 28.6%.

Next, a secondary liquid for glass fiber coating similar to that in Example 1 is prepared by the procedure shown in Example 1, and the operation is performed in the same procedure as in Example 1. A further secondary coating layer is applied to the glass fiber cord. A glass fiber for reinforcing rubber of the present invention (Example 3) was produced.
Example 4
To a three-necked separable flask equipped with a reflux condenser, a thermometer, and a stirrer, chlorophenol (D), 128 parts by weight, 37.0% by weight aqueous formaldehyde (E) solution, 80 parts by weight (in molar ratio) E / D = 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. Propylene glycol belonging to the glycol compound is added to 100 parts by weight of the reaction solution, and the precipitate of the chlorophenol-formaldehyde condensate (A) is dissolved to prepare an aqueous solution of the chlorophenol-formaldehyde condensate (A). did. At this time, the amount of propylene glycol added to the weight of the chlorophenol-formaldehyde condensate (A) was 200.0% by weight. That is, propylene glycol was added to the chlorophenol-formaldehyde condensate (A) in a weight ratio so as to be doubled.

  In addition, the said addition of the sodium hydroxide aqueous solution of a density | concentration and 1.0 weight% is required for a condensation reaction as a catalyst for carrying out the condensation reaction of chlorophenol (D) and formaldehyde (E) to make a chlorophenol-formaldehyde condensate. I don't add more than the right amount. In addition, P-chlorophenol was used for chlorophenol (D).

  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 the glass fiber coating solution of the present invention.

  83 parts by weight of the chlorophenol-formaldehyde condensate (A) prepared above with respect to the glass fiber coating solution, and 15:15:70 by weight of vinylpyridine, styrene and butadiene. Except that the addition amount of the vinylpyridine-styrene-butadiene copolymer (B) emulsion (manufactured by Nippon A & L Co., Ltd., trade name, pilatex, solid content, 41% by weight) was changed to 451 parts by weight. A glass fiber coating coating solution of the present invention was prepared in the same manner as in Example 1.

  That is, based on the total weight of the chlorophenol-formaldehyde condensate (A), the vinylpyridine-styrene-butadiene copolymer (B), and the chlorosulfonated polyethylene (C) in the glass fiber coating solution, Expressed in weight percentage, chlorophenol-formaldehyde condensate (A) is A / (A + B + C) = 7.2%, vinylpyridine-styrene-butadiene copolymer (B) is B / (A + B + C) = 64. 2%, chlorosulfonated polyethylene (C) was adjusted to C / (A + B + C) = 28.6%.

  Next, a secondary liquid for glass fiber coating similar to that in Example 1 is prepared by the procedure shown in Example 1, and the operation is performed in the same procedure as in Example 1. A further secondary coating layer is applied to the glass fiber cord. A glass fiber for reinforcing rubber of the present invention (Example 4) was produced.

Comparative Example 1
A glass fiber coating solution for reinforcing rubber comprising a conventional resorcin-formaldehyde condensate, vinylpyridine-styrene-butadiene copolymer emulsion (B) and chlorosulfonated polyethylene (C) was prepared.

  Unlike Example 1, in place of the chlorophenol-formaldehyde condensate (A), resorcin-formaldehyde condensate (resorcin-formaldehyde molar ratio, 1.0: 1.0 reacted, solid content, 8. 7 wt%) and a vinylpyridine-styrene-butadiene copolymer emulsion containing 239 parts by weight of vinylpyridine, styrene, and butadiene in a weight ratio of 15:15:70 (manufactured by Nippon A & L Co., Ltd., product) The coating solution for glass fiber coating was prepared in the same manner as in Example 1 except that the amount added was 451 parts by weight, and the procedure shown in Example 1 was followed. Thus, a conventional glass fiber coating coating solution was prepared. That is, resorcin-formaldehyde condensation expressed in weight percentage based on 100% of the total weight of resorcin-formaldehyde condensate, vinylpyridine-styrene-butadiene copolymer and chlorosulfonated polyethylene in the coating solution for glass fiber coating The product was adjusted to 7.2%, vinylpyridine-styrene-butadiene copolymer 64.2%, and chlorosulfonated polyethylene 28.6%.

Next, a secondary liquid for glass fiber coating similar to that in Example 1 is prepared by the procedure shown in Example 1, and the operation is performed in the same procedure as in Example 1. A further secondary coating layer is applied to the glass fiber cord. A provided glass fiber for reinforcing rubber (Comparative Example 1) was produced.
Comparative Example 2
A primary coating layer was prepared using the same glass fiber coating coating solution as in Example 1 except that the precipitate of the chlorophenol-formaldehyde condensate (A) was dissolved in sodium hydroxide. Next, a secondary solution for glass fiber coating similar to that of Example 1 was prepared, and the procedure was performed in the same manner as in Example 1. A further secondary coating layer was provided on the glass fiber cord, and glass fibers for rubber reinforcement (Comparative Example) 2) was produced.
Comparative Example 3
The same coating solution for glass fiber coating as in Example 1 was prepared except that the precipitate of the chlorophenol-formaldehyde condensate (A) was dissolved with ammonia, but the chlorophenol-formaldehyde condensate (A) was deposited and applied. (Comparative Example 3).
(Adhesion strength evaluation test)
Before describing the adhesive strength evaluation test, the heat resistant rubber used in the test will be described.

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

The test pieces were arranged on a 3 mm thick and 25 mm wide rubber sheet made of heat resistant rubber A or heat resistant rubber B and 20 glass fiber cords for rubber reinforcement (Examples 1 to 4 and Comparative Examples 1 and 2) were arranged from above. Cover the fabric and heat-resistant rubber A at a temperature of 150 ° C. and 196 Newton / cm ²
(Hereinafter, Newton is abbreviated as N), and heat-resistant rubber B is pressed under the condition of 196 N / cm ^{2 at} a temperature of 170 ° C. and vulcanized for 30 minutes. A test piece for evaluation, in other words, a rubber sheet was obtained. For the measurement of the adhesive strength of the test piece, each rubber sheet and rubber reinforcing glass fiber are individually clamped at the end, the peeling speed is 50 mm / min, and the rubber reinforcing glass fiber is peeled off from the rubber sheet. The maximum resistance value at the time was measured to determine the peel strength. The greater the peel strength, the better the adhesive strength.
(Adhesion strength evaluation results)
Table 1 shows the evaluation results of the adhesive strength.

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

As shown in Table 1, the glass fiber for rubber reinforcement of Example 1 of the present invention, when measured for peel strength, was 340 N for heat resistant rubber A and 295 N for heat resistant rubber B. Both rubbers On the other hand, the adhesiveness was good and the adhesive strength was excellent.

As shown in Table 1, the glass fiber for rubber reinforcement of Example 2 of the present invention was measured for peel strength. As a result, the heat resistant rubber A was 352N and the heat resistant rubber B was 337N. On the other hand, the adhesiveness was good and the adhesive strength was excellent.

  As shown in Table 1, the glass fiber for rubber reinforcement of Example 3 of the present invention was measured for peel strength. As a result, the heat resistant rubber A was 345N and the heat resistant rubber B was 322N. On the other hand, the adhesiveness was good and the adhesive strength was excellent.

  As shown in Example 4 in Table 1, the glass fiber for rubber reinforcement of Example 4 of the present invention is 318 N for heat-resistant rubber A and 305 N for heat-resistant rubber B, and is bonded to both rubbers. The properties were good and the adhesive strength was excellent.

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

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

  The glass fiber for rubber reinforcement that does not belong to the category of the present invention in Comparative Example 2 was prepared in the same procedure as in Example 1 and a test piece was prepared and the adhesion strength was evaluated. As described above, the heat resistant rubber A was 315N and the heat resistant rubber B was 312N. The adhesive properties were good for both rubbers, and the adhesive strength was excellent. When the heat-resistant rubber A was used and the heat-resistant rubber B was used, the broken state was rubber breakage and the adhesive strength was excellent.

(Water resistance evaluation)
Using the rubber reinforcing glass fibers prepared in Examples 1, 2, and 4 and Comparative Examples 1 and 2 as a reinforcing material, the heat-resistant rubber B was used as a base rubber, and a transmission belt having a width of 19 mm and a length of 876 mm was prepared. A water resistance running fatigue test for evaluating water resistance was conducted. The water resistance is evaluated based on the tensile strength retention rate after a certain period of time, that is, the water resistance running fatigue performance, by running the transmission belt using gears, that is, pulleys, under water injection.

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

  The transmission belt 1 has many protrusions 1A having a height of 3.2 mm for meshing with pulleys, and the thickness of the back part 1B excluding the protrusions is 2.0 mm. As shown in the figure, the glass fibers 2 for rubber reinforcement 2 in which the twisting directions of the upper twist and the lower twist are different, such as S twist, 6, Z twist, 6 and 12 in total, the S twist and Z twist are alternated. It is buried in.

  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. 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 1, 2, 4, 5, 6, 8 and Comparative Examples 1 and 2 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. In addition, the tensile strength before a test measured the tensile strength 3 times each from ten similarly produced belts, and used the average value as an initial value.

  The tensile strength retention rate was calculated according to 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 and Comparative Examples 1, 2 and chlorosulfonated polyethylene (C ) And a glass fiber cord coating solution dried on a glass fiber cord, and a tension after a running test of the transmission belt 1 using a rubber fiber glass 2 for rubber reinforcement having a further secondary coating layer. The strength retention is 70% when the rubber reinforcing glass fiber 2 of Example 1 is used, and 68% when the rubber reinforcing glass fiber 2 of Example 2 is used. When the glass fiber 2 for rubber reinforcement was used, it was 65%.

  On the other hand, as shown in Comparative Example 1, resorcin-formaldehyde condensate, vinylpyridine-styrene-butadiene co-polymer prepared by using resorcin-formaldehyde condensate instead of not using chlorophenol-formaldehyde condensate (A). Tensile strength retention of rubber fiber-reinforced glass fiber 2 having a coating layer obtained by coating and drying a glass fiber coating solution containing a polymer and chlorosulfonated polyethylene on a glass fiber cord and a further secondary coating layer When the glass fiber 2 for rubber reinforcement of the comparative example 1 was used, it was 47% and was inferior in water resistance.

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

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

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

Temperature, under 130 ° C. of environment, as shown in FIG. 3, the drive pulley 8, is rotated at 3000 rpm, the transmission belt 1 driven pulley 9 and 9 ', 9 ^〃, was run while bending with the idler 10 It was. In this manner, the transmission belt 1 was run for 500 hours, and a heat-resistant and bending-resistant running fatigue test was performed. The tensile strength of the transmission belt 1 before the heat-resistant bending resistance running fatigue test and the tensile strength after the heat-resistant bending resistance fatigue test are measured. The retention rate was determined, and the heat resistance and bending resistance of the transmission belt 1 produced using the glass fibers 2 for reinforcing rubber of Examples 2 and 4 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 ratios of the transmission belt 1 manufactured using the glass fibers 2 for rubber reinforcement of Examples 2 and 4 after the heat and bending resistance fatigue test are 96% and 93%, respectively. When the transmission belt 1 using the rubber fiber 2 for reinforcing rubber of Comparative Example 1 had a tensile strength retention rate of 90% after the heat-resistant and bending-resistant running fatigue test, the Comparative Example 2 was broken during traveling.

Based on the results of the heat resistance and bending resistance fatigue test, a chlorophenol-formaldehyde condensate (A), a vinylpyridine-styrene-butadiene copolymer (B), and a chlorosulfonated polyethylene (C) as a composition It has a coating layer formed by applying and then drying the glass fiber coating coating solution of the invention, NN'-hexamethylenediallylnadiimide belonging to bisallylnadiimide (F), chlorosulfonated polyethylene (C), It was found that the power transmission belt 1 using the glass fiber 2 for rubber reinforcement of the present invention having a further secondary coating layer composed of p-dinitrobenzene has excellent heat resistance.

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

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

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

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Transmission belt 1A Protrusion part 1B Back part 2 Glass fiber 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 (10)

A chlorophenol-formaldehyde condensate (A) obtained by condensation reaction of chlorophenol (D) and formaldehyde (E) in water, an alcohol compound, a vinylpyridine-styrene-butadiene copolymer (B) emulsion, and chlorosulfonated A glass fiber coating coating solution for coating a glass fiber cord, comprising a polyethylene (C) emulsion. The amount of addition of the alcohol compound, chlorophenol - expressed in weight percentage to 100% by weight of the formaldehyde condensate (A), 50 wt% or more, in claim 1, characterized in that 500 wt% or less The coating liquid for glass fiber coating as described. N-propanol, isopropanol, propylene glycol, 2-methoxyethanol, 2-methoxymethylethoxypropanol, 1-methoxy-2-propanol, ethylene glycol, diethylene glycol, 1,2-diethoxyethane was used as the alcohol compound. The glass fiber coating coating solution according to claim 1 , wherein the coating solution is for coating glass fibers. The chlorophenol-formaldehyde condensate (A) has a molar ratio of formaldehyde (E) to chlorophenol (D) of E / D = 0.5 or more and 3.0 or less. The glass fiber coating coating solution according to claim 3 . Expressed in weight percentage, the chlorophenol-formaldehyde condensate (A) is A / (A + B + C) = 1.0% or more and 15.0% or less, and the vinylpyridine-styrene-butadiene copolymer (B) is B / ( A + B + C) = 45.0% or more, 82.0% or less, and chlorosulfonated polyethylene (C) is contained in the range of C / (A + B + C) = 3.0% or more and 40.0% or less. The coating liquid for glass fiber coating according to any one of claims 1 to 4 . When the vinylpyridine-styrene-butadiene copolymer (B) is expressed in weight percentage with respect to the styrene-butadiene copolymer (G), G / B = 5.0% or more and 80.0% or less. glass fiber coated coating liquid according to any one of claims 1 to 5, characterized by comprising in place. A precipitate of chlorophenol-formaldehyde condensate (A) formed by condensation reaction of chlorophenol (D) and formaldehyde (E) in water is dissolved by adding an alcohol compound, and then a vinylpyridine-styrene-butadiene copolymer. (B) Emulsion and chlorosulfonated polyethylene (C) emulsion are mixed, The manufacturing method of the coating liquid for glass fiber coating of any one of Claim 1 thru | or 6 characterized by the above-mentioned. After coating the glass fiber coated coating liquid according to any one of claims 1乃optimum claim 6, the rubber-reinforcing glass fiber is dried, and chlorosulfonated polyethylene (C), expressed in weight percent F / C = 0.3% or more and 10.0% or less of bisallyl nadiimide (F) is applied in a glass fiber secondary coating solution dispersed in an organic solvent, and a further secondary coating layer is provided. A glass fiber for rubber reinforcement characterized by comprising: A power transmission belt, wherein the glass fiber for reinforcing rubber according to claim 8 is embedded in heat-resistant rubber. The power transmission belt according to claim 9 , wherein the heat resistant rubber is a hydrogenated nitrile rubber.

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