JP5262252B2 - Glass fiber for rubber reinforcement and transmission belt using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transmission belt which is prepared by coating glass fiber cords with a glass fiber-coating liquid, drying the coated glass fiber cords to form glass fibers having the coated layers and used for reinforcing a rubber, and then embedding the glass fibers in a hydrogenated nitrile rubber of a base material rubber, is excellent in dimensional stability under severe bending travels in the presence of high temperature, water and an oil, and has good toughness for sustaining a tensile strength. <P>SOLUTION: The glass fibers 6 for reinforcing the rubber is characterized in that forming a primary coating layer containing a phenol compound-formaldehyde condensate and acrylonitrile-butadiene copolymer on a strand prepared by bundling a plurality of glass fiber filaments, and disposing a secondary coating layer containing chlorosulfonated polyethylene and bisallylnadiimide on the primary coating layer. In order to improve durability, vinylpyridine-styrene-butadiene copolymer and chlorosulfonated polyethylene are preferably added to the primary coating layer. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a glass fiber for rubber reinforcement for embedding and reinforcing as a core wire in rubber as a base material when producing a transmission belt, and a rubber product in which the glass fiber for rubber reinforcement is embedded as a core wire for reinforcement. Related to the transmission belt. The rubber reinforcing glass fiber of the present invention is particularly useful as a reinforcing core wire for an automobile timing belt.

  In order to give tensile strength and dimensional stability to rubber products such as transmission belts and tires, fiber with high tensile strength such as glass fiber, nylon fiber, aramid fiber and polyester fiber is embedded as a reinforcing material in the base rubber. In general, the rubber reinforcing fiber embedded in the base rubber is required to have a strong interface with the base rubber and not peel off. However, a glass fiber cord in which a sizing agent containing a silane coupling agent and a resin or the like is dispersed and focused on a number of glass fiber filaments, in other words, even if the strand is embedded in the base rubber as it is, the interface peels off. Do not use as a reinforcing material. For this reason, the glass fiber cord is coated with a coating material for bonding to the base rubber, and a coating layer is provided on the glass fiber for rubber reinforcement that is used by being embedded in the base material rubber when the transmission belt is manufactured.

  For example, since a power transmission belt for automobiles is used in a high-temperature engine room, even a power transmission belt having a core wire in which the glass fiber for rubber reinforcement subjected to the coating treatment is embedded continues to bend at a high temperature. In severe driving conditions, the initial bond strength between the glass fiber for rubber reinforcement and the base rubber is not maintained, and the interface between the glass fiber for rubber reinforcement and the base rubber is peeled off for a long time. Sometimes.

  The power transmission belt for automobiles will maintain its tensile strength and stretch after a long period of bending in a harsh environment where water is splashed in the engine room at high temperatures and oil such as engine oil and lubricating oil adheres. It is required to have excellent dimensional stability. In particular, the timing belt connects the camshaft and crankshaft of the engine and interlocks the opening and closing of the valve with the vertical movement of the piston. A toothed belt is used, and it breaks during long-time bending under severe conditions. Needless to say, little growth is not allowed. As the base rubber of the timing belt, hydrogenated nitrile rubber (hereinafter abbreviated as HNBR), which is a heat-resistant rubber, is used. The core wire has durability and is less expensive than aramid fiber. It is used and further improvement in durability is desired.

  In addition to heat resistance that maintains the initial bond strength between the rubber reinforcing fiber and the base rubber even when the belt is bent for a long time at a high temperature, the coating layer can be applied even if the belt is run for a long time with water on it. However, the development of a transmission belt using a rubber reinforcing glass fiber as a core wire that gives the transmission belt water resistance that maintains the initial adhesive strength by preventing water from penetrating into the glass fiber cord is awaited.

  A coating layer is provided to provide a transmission belt that maintains the initial bond strength between HNBR as the base rubber and the glass fiber cord, does not cause separation of the interface, and is reliable even in bending at high temperatures. As a glass fiber for reinforcing rubber, a glass fiber cord is provided with a primary coating layer, and a glass fiber secondary coating application liquid having a different composition is applied and dried on the primary coating layer to provide a further secondary coating layer. Patent Documents 1 to 4 disclose glass fibers for reinforcing rubber.

  Conventionally, heat-resistant transmission belts such as automobile timing belts are applied to glass fiber cords using a coating solution for coating glass fibers comprising resorcin-formaldehyde condensate, vinylpyridine-styrene-butadiene copolymer, and chlorosulfonated polyethylene. The dried rubber reinforcing glass fiber was embedded in HNBR as a heat-resistant rubber. Further, in order to improve the adhesion between the glass fiber cord and HNBR, and thus heat resistance, the glass fiber for rubber reinforcement was further provided with a secondary coating layer and embedded in HNBR as heat resistant rubber.

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

  Further, Patent Document 2 discloses that even when used under a high temperature condition that is repeatedly subjected to bending stress, the adhesive strength does not decrease with time, the heat resistance is high, and the manufacturing cost is low. A water-soluble condensate of resorcin-formaldehyde on a core wire made of glass fiber as a rubber reinforcing fiber suitable as a reinforcing fiber, particularly as a rubber reinforcing fiber suitable for obtaining a toothed belt having a high tooth root strength, A rubber reinforcing fiber is disclosed in which a layer comprising a vinylpyridine-styrene-butadiene copolymer latex and an acrylonitrile-butadiene copolymer latex is formed.

  Patent Document 3 discloses a fiber treatment agent for rubber reinforcement containing a rubber latex, a resorcin-formaldehyde water-soluble condensate and a triazine thiol.

  Further, in Patent Document 4 relating to the applicant's patent application, a primary coating layer containing an acrylic ester resin, a vinylpyridine-styrene-butadiene copolymer, and a resorcin-formaldehyde condensate in a glass fiber cord is provided. A glass fiber for rubber reinforcement is disclosed, which is provided and a secondary coating layer containing chlorosulfonated polyethylene and bisallylnadiimide is provided thereon.

  Further, in Patent Document 5 relating to the patent application of the present applicant, a primary coating layer containing a resorcin-formaldehyde condensate and a rubber latex is provided, and bisallylnadiimide, a rubber elastomer, a vulcanizing agent, an inorganic filler, A glass fiber for reinforcing rubber provided with a secondary coating layer containing bismuth is disclosed.

  In addition, for the purpose of improving water resistance when used as a transmission belt, Patent Document 6 relating to the applicant's patent application discloses monohydroxybenzene-formaldehyde condensate and vinylpyridine- for coating on a glass fiber cord. A coating solution for coating glass fiber is disclosed in which a styrene-butadiene copolymer and chlorosulfonated polyethylene are dispersed in water to form an emulsion.

  Further, in Patent Documents 7 to 11 related to the applicant's patent application, the glass fiber coating coating solution described in Patent Document 6 is applied to a glass fiber cord to form a primary coating layer, and a halogen-containing polymer is formed on the upper layer A glass fiber for rubber reinforcement characterized by being provided with a secondary coating layer containing bisallylnadiimide, and a secondary coating layer containing a halogen-containing polymer and maleimide as an upper layer of the primary coating layer Rubber reinforcing glass fiber, glass fiber for rubber reinforcing comprising a secondary coating layer containing a halogen-containing polymer, an organic diisocyanate and zinc methacrylate on the upper layer of the primary coating layer, and the primary coating layer A glass fiber for rubber reinforcement is disclosed in which a secondary coating layer containing chlorosulfonated polyethylene and a triazine compound is provided as an upper layer.

  In addition to heat resistance of the engine heat resistance and water resistance in rainy weather, automotive transmission belts also need oil resistance because the engine oil inside the engine oozes from the cylinder head gasket and adheres to it. It is.

Therefore, Patent Document 12 discloses a water-soluble condensate of resorcinol and formaldehyde, a solid acrylonitrile-butadiene co-polymer as a reinforcing fiber for rubber products with excellent oil resistance, which can obtain a timing belt that can be used for a very long time. Disclosed is a glass fiber cord coated with a treating agent containing a latex of a polymer and a latex of a liquid acrylonitrile-butadiene copolymer.

Patent Document 13 discloses a glass fiber for reinforcing rubber that is coated with a treating agent containing a resorcin-formaldehyde water-soluble condensate that improves oil resistance and a soap-free acrylonitrile-butadiene copolymer latex. ing.

  Patent Document 14 includes only a glass fiber treating agent resorcin-formaldehyde water-soluble condensate and a butadiene-acrylonitrile copolymer latex for improving oil resistance, and the butadiene-acrylonitrile copolymer latex has a solid content mass. As a standard, a glass fiber treating agent for reinforcing rubber having a content of acrylonitrile of 31 to 55% by mass is disclosed.

Patent Document 15 describes a reinforcement that has excellent oil resistance, tackiness, and bending fatigue resistance, and is suitable for manufacturing rubber products such as timing belts using HNBR using peroxide as a vulcanizing agent. As the fiber, the first coating layer contains a water-soluble condensate of resorcin and formaldehyde, a latex of solid acrylonitrile-butadiene copolymer, and a latex of liquid acrylonitrile-butadiene copolymer, and the second coating layer of the upper layer. A reinforcing fiber in which the coating layer contains an uncured phenol resin and rubber is disclosed.
Japanese Examined Patent Publication No. 2-4715 JP-A-4-103634 Japanese Patent Laid-Open No. 10-25665 JP 2004-203730 A JP 2004-244785 A JP 2006-104595 A Pamphlet of International Publication WO / 2006/038490 JP 2007-63726 A JP 2007-63727 A JP 2007-63728 A JP 2007-63729 A JP 2002-339255 A Japanese Patent Laid-Open No. 2003-253569 JP 2003-268678 A JP 2004-100059 A

  A transmission belt produced by embedding HNBR with a conventional glass fiber for reinforcing rubber as a core wire is stretched in the transmission belt and has poor heat resistance when it is continuously bent. In particular, the timing belt, which is an automotive transmission belt that continues to bend in an engine room at high temperatures, is not allowed to stretch a little and has excellent dimensional stability, plus excellent heat resistance, water resistance, Oil resistance is required.

  Moreover, the coating layer of the rubber reinforcing glass fiber embedded in the power transmission belt for automobiles easily changes in quality due to contact penetration with engine oil or the like at high temperature, resulting in a decrease in the adhesive strength between the rubber reinforcing glass fiber and HNBR and peeling of the interface. May be connected. This alteration occurs because the vinylpyridine-styrene-butadiene copolymer has poor oil resistance.

  Therefore, in the presence of resorcin-formaldehyde condensate, instead of vinylpyridine-styrene-butadiene copolymer, an acrylonitrile-butadiene copolymer having excellent oil resistance was used as a coating material to produce a glass fiber for rubber reinforcement. However, although the oil resistance of the transmission bolts embedded in the steel was improved, the water resistance was reduced.

  Thus, in the presence of the resorcin-formaldehyde condensate, even if acrylonitrile-butadiene copolymer having excellent oil resistance is simply added as a coating material instead of vinylpyridine-styrene-butadiene copolymer, In bending running of an embedded transmission belt, the balance between water resistance and oil resistance cannot be maintained, and the initial adhesive force cannot be maintained between the glass fiber cord and the base rubber, and the running time of bending running is increased. As a result, the transmission belt stretches and malfunctions occur quickly. In particular, when used as a timing belt, there is a problem that due to elongation, the function of the power transmission mechanism, such as matching the vertical movement of the piston and the opening / closing timing of the valve due to the interlocking of the crankshaft and the camshaft, may be disturbed. all right.

  In the present invention, when a transmission belt is produced by embedding rubber reinforcing glass fibers as a core wire in a base rubber, water is applied at high temperature, and after bending running where oil adheres, the dimensional change is small. It is an object of the present invention to provide a glass fiber for rubber reinforcement that imparts excellent dimensional stability, heat resistance, water resistance, and oil resistance to a transmission belt with low elongation.

  That is, the present invention has a water resistance in which the coating layer maintains the initial adhesive strength even when it is bent for a long time while applying water to the power transmission belt as compared with the conventional power transmission belt. Even if it is bent and run, the coating layer maintains the initial bond strength, and the coating layer maintains the initial bond strength for a long time in the presence of oil. An object of the present invention is to provide a transmission belt that is extremely small in elongation and excellent in dimensional stability even after a long bending run.

  As a result of intensive studies by the present inventors in order to solve the above-described problems, the sizing is performed after applying a sizing agent containing a silane coupling agent and a resin to a plurality of glass fiber filaments, specifically a large number of glass fiber filaments. A primary coating layer containing the phenols-formaldehyde condensate (A) and the acrylonitrile-butadiene copolymer (B) as essential components is formed on the stranded strand, and chlorosulfonated polyethylene (D) is formed on the upper layer. The transmission belt using the glass fiber for rubber reinforcement provided with the secondary coating layer containing bisallyl nadiimide (E) as an essential component is compared with the conventional transmission belt using the glass fiber for rubber reinforcement. In addition to being excellent in dimensional stability during bending running, in other words, not only does it not stretch in the bending running test, Was found to be contacted under alteration is suppressed.

  In addition, in this invention, what provided the coating layer for adhesion | attachment with base material rubber | gum on a strand is called glass fiber for rubber reinforcement.

  A primary coating layer containing the phenols-formaldehyde condensate (A) and acrylonitrile-butadiene copolymer (B) of the present invention as essential components as compared with a conventional transmission belt using glass fibers for reinforcing rubber. The transmission belt using the glass fiber for rubber reinforcement in which the secondary coating layer containing chlorosulfonated polyethylene (D) and bisallylnadiimide (E) as essential components is provided on the upper layer is dimensionally stable. The acrylonitrile is excellent when the coating solution for primary coating containing the phenols-formaldehyde condensate (A) and the acrylonitrile-butadiene copolymer (B) is applied and heated to evaporate and cure the moisture. -The butadiene copolymer (B) has a nitrile group, which accelerates curing by three-dimensional crosslinking, and is a tough polymer matrix. Next, provide excellent coating layer on glass fiber reinforcing rubber, power transmission belt using glass fibers for reinforcing rubber are excellent in dimensional stability be bent running, i.e., does not extend.

  However, only by forming a primary coating layer containing the phenol-formaldehyde condensate (A) and the acrylonitrile-butadiene copolymer (B) as essential components on the rubber reinforcing glass fiber, excellent heat resistance and water resistance It is difficult to get sex. Chlorosulfonated polyethylene (D) and bisallyl nadiimide (E) are formed on the upper layer of the primary coating layer containing the phenols-formaldehyde condensate (A) and the acrylonitrile-butadiene copolymer (B) as essential components. When the secondary coating layer containing is improved, the heat resistance and water resistance are improved, and the transmission belt embedded with the rubber reinforcing glass fiber has excellent dimensional stability in bending and excellent in running under water injection. Water resistance and excellent oil resistance in running under oil adhesion were given.

  Further, by adding the vinylpyridine-styrene-butadiene copolymer (C) to the composition of the primary coating material and selecting the composition ratio with the acrylonitrile-butadiene copolymer (B), excellent water resistance And oil resistance can be obtained in a well-balanced manner.

  Furthermore, when chlorosulfonated polyethylene (D) is added to the composition contained in the primary coating layer, the heat resistance of the transmission belt in which the glass fibers for rubber reinforcement are embedded is further improved.

  The primary coating layer is obtained by focusing glass fiber filaments with a coating solution for primary coating obtained by adding an emulsion of acrylonitrile-butadiene copolymer (B) to an aqueous solution of phenols-formaldehyde condensate (A). It is formed by applying to a dried strand and then drying.

  In addition, the secondary coating layer is formed by providing a coating solution for secondary coating in which chlorosulfonated polyethylene (D) and bisallyl nadiimide (E) are dispersed in an organic solvent, for example, xylene. It is formed by applying and drying on a glass fiber for rubber reinforcement.

  In the presence of the phenol-formaldehyde condensate (A), an acrylonitrile-butadiene copolymer (B) excellent in oil resistance is contained in the primary coating layer instead of the vinylpyridine-styrene-butadiene copolymer (C). As a result, when the glass fiber for rubber reinforcement was produced, the oil resistance of the transmission bolt embedded as a core wire was improved, but the water resistance was lowered, but the secondary coating layer was coated with chlorosulfonated polyethylene (D) and bisallylna. By containing diimide (E), it became possible to improve water resistance while maintaining the excellent oil resistance that the acrylonitrile-butadiene copolymer (B) gives to the transmission belt. Chlorosulfonated polyethylene (D) is used for improving the heat resistance of a transmission belt in which rubber reinforcing glass fibers are embedded.

  This is because the secondary coating layer to which the coating solution for secondary coating containing chlorosulfonated polyethylene (D) and bisallylnadiimide (E) is applied is excellent in water resistance, so it is excellent in oil resistance but water resistance. This is because water penetrates into the primary coating layer containing the inferior acrylonitrile-butadiene copolymer (B), and water is prevented from coming into contact with the glass fiber having inferior water resistance.

  That is, the present invention forms a primary coating layer containing a phenol-formaldehyde condensate (A) and an acrylonitrile-butadiene copolymer (B) on a strand 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 (D) and bisallylnadiimide (E) is provided on the upper layer.

  Furthermore, the present invention is expressed by a mass percentage based on 100% of the total mass of the phenols-formaldehyde condensate (A) and the acrylonitrile-butadiene copolymer (B) in the primary coating layer. Phenols-formaldehyde condensate (A), A / (A + B) = 1.0% to 55.0%, acrylonitrile-butadiene copolymer (B), B / (A + B) = 45 The glass fiber for rubber reinforcement described above, which is contained in a range of 0.0% or more and 99.0% or less.

  Moreover, this invention is said glass fiber for rubber reinforcement characterized by making the primary coating layer further contain a vinylpyridine-butadiene-styrene copolymer (C).

  Furthermore, the present invention sets the mass of the phenolic-formaldehyde condensate (A), the acrylonitrile-butadiene copolymer (B), and the vinylpyridine-butadiene-styrene copolymer (C) in the primary coating layer to 100. The phenolic-formaldehyde condensate (A) is represented in the primary coating layer by A / (A + B + C) = 1.0% or more and 40.0% or less, and acrylonitrile-butadiene copolymer. (B), B / (A + B + C) = 1.0% or more, 55.0% or less, vinylpyridine-butadiene-styrene copolymer (C), C / (A + B + C) = 10.0% or more, 70 The glass fiber for rubber reinforcement described above, which is contained in a range of 0.0% or less.

  Moreover, this invention is said glass fiber for rubber reinforcement characterized by making the primary coating layer contain chlorosulfonated polyethylene (D) further.

  Furthermore, the present invention provides a mass based on 100% of the total mass of the phenols-formaldehyde condensate (A), the acrylonitrile-butadiene copolymer (B) and the chlorosulfonated polyethylene (D) in the primary coating layer. The rubber described above, characterized in that the chlorosulfonated polyethylene (D) is contained in the primary coating layer in the range of D / (A + B + D) = 1.0% or more and 40.0% or less, expressed as a percentage. Reinforcing glass fiber.

  Furthermore, the present invention provides a phenol-formaldehyde condensate (A), an acrylonitrile-butadiene copolymer (B), a vinylpyridine-butadiene-styrene copolymer (C), and a chlorosulfonated polyethylene (C) in the primary coating layer. The total mass of D) is expressed as a percentage by mass based on 100%, and chlorosulfonated polyethylene (D) is added to the primary coating layer with D / (A + B + C + D) = 1.0% or more and 40.0% or less. The glass fiber for rubber reinforcement described above, which is contained in a range.

  Furthermore, this invention represents the mass of the chlorosulfonated polyethylene (D) contained in the secondary coating layer as a mass percentage based on 100%, and the content of bisallylnadiimide (E) is E / D = 0. It is said glass fiber for rubber reinforcement characterized by being 3% or more and 10.0% or less.

  The resorcin-formaldehyde condensate is a water-soluble condensate obtained by condensing resorcin and formaldehyde in which two OH groups, which are hydrophilic groups, are added to a benzene ring.

  The monohydroxybenzene-formaldehyde condensate is a water-soluble condensate obtained by condensing formaldehyde with monohydroxybenzene having one OH group as a hydrophilic group added to the benzene ring.

  The chlorophenol-formaldehyde condensate is a water-insoluble condensate obtained by condensing chlorophenol and formaldehyde in which one OH group as a hydrophilic group and one Cl group as a hydrophobic group are added to the benzene ring. It is. An aqueous solution of chlorophenol-formaldehyde condensate is obtained by adding an alcohol compound or an amine compound as a solubilizer to dissolve the precipitate of chlorophenol-formaldehyde condensate obtained by condensation reaction of chlorophenol and formaldehyde in water. , Used in the above-mentioned coating solution for primary coating.

  Compared to resorcin-formaldehyde condensate, monohydroxybenzene-formaldehyde condensate is more hydrophobic, and chlorophenol-formaldehyde condensate is more hydrophobic. When the hydrophobicity is compared in this way, resorcin-formaldehyde condensate <monohydroxybenzene-formaldehyde condensate <chlorophenol-formaldehyde condensate.

  For the above reasons, in addition to the acrylonitrile-butadiene copolymer (B) as the composition of the primary coating layer of the glass fiber for reinforcing rubber of the present invention, a hydrophobic monohydroxybenzene is used instead of the resorcin-formaldehyde condensate. -By using formaldehyde condensate, both water resistance and oil resistance when using a transmission belt were improved. In addition to the acrylonitrile-butadiene copolymer (B), the composition of the rubber reinforcing glass fiber coating material of the present invention is replaced with a monohydroxybenzene-formaldehyde condensate and further a hydrophobic chlorophenol-formaldehyde condensate. By using a thing, the water resistance and oil resistance at the time of using a transmission belt improved.

  As described above, the phenols-formaldehyde condensate (A) used in the present invention includes resorcin-formaldehyde condensate, monohydroxybenzene-formaldehyde condensate, chlorophenol-formaldehyde condensate, resorcin-monohydroxybenzene-formaldehyde condensate. And resorcin-chlorophenol-formaldehyde condensates. The resorcin-monohydroxybenzene-formaldehyde condensate is a condensate obtained by condensing resorcin, monohydroxybenzene and formaldehyde. The resorcin-chlorophenol-formaldehyde condensate is a condensate obtained by condensing resorcin, monohydroxybenzene, and formaldehyde. In addition, you may mix and use these phenols-formaldehyde condensates (A).

  That is, in the present invention, the phenols-formaldehyde condensate (A) is resorcin-formaldehyde condensate, monohydroxybenzene-formaldehyde condensate, chlorophenol-formaldehyde condensate, resorcin-monohydroxybenzene-formaldehyde condensate, resorcin- The glass fiber for rubber reinforcement described above, which is selected from chlorophenol-formaldehyde condensates.

  For the reasons described above, the phenols-formaldehyde condensate (A) used in the present invention is compared with resorcin-formaldehyde condensate, resorcin-monohydroxybenzene-formaldehyde condensate and resorcin-chlorophenol-formaldehyde condensate. Hydrophobic monohydroxybenzene-formaldehyde condensate and chlorophenol-formaldehyde condensate are preferred condensates.

  In the primary coating layer of the glass fiber for reinforcing rubber according to the present invention, not only acrylonitrile-butadiene binary but also acrylonitrile-butadiene-styrene terpolymer is obtained by adding styrene to the polymerization monomer. Even if the polymer (B) is used, the same effect can be obtained in the dimensional stability for the reason described above. When the acrylonitrile-butadiene-styrene terpolymer is used as a transmission belt, water resistance can be obtained without reducing heat resistance and oil resistance, and an excellent transmission belt can be easily obtained.

  The present invention also provides the above glass fiber for reinforcing rubber, wherein the acrylonitrile-butadiene copolymer (B) is an acrylonitrile-butadiene-styrene terpolymer.

  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.

  When the glass fiber for rubber reinforcement according to the present invention is embedded in HNBR, which is a heat-resistant rubber, for example, the glass fiber for rubber reinforcement and HNBR have excellent adhesive strength. Furthermore, when it is embedded in the HNBR as a core wire to make a transmission belt, it has heat resistance, water resistance and oil resistance that can withstand long-time bending running, and after long-time bending running as a transmission belt under high temperature and high humidity In this case, there is no concern that the interface between the glass fiber for reinforcing rubber and the heat-resistant rubber is peeled off, and the transmission belt maintains the tensile strength and is excellent in dimensional stability without any elongation.

  Especially when it is used as a timing belt for automobiles among power transmission belts, it keeps the tensile strength after running for a long time in the engine room under high temperature, where water splashes, and oil such as engine oil and lubricating oil adheres. Excellent dimensional stability without any elongation.

  In the present invention, the glass fiber for reinforcing rubber includes, for example, a bundling agent containing a silane coupling agent on a large number of glass fiber filaments, which are fine wires protruding from a bushing of a glass melting furnace in which a raw material of glass fiber is heated. The strands that have been spray-coated and converged are bent and run in a glass fiber coating coating solution, and the glass fiber coating coating solution is forcibly attached, in other words, coated and dried to provide a coating layer.

  In order to form the primary coating layer on the glass fiber for reinforcing rubber of the present invention, a sizing agent containing a silane coupling agent is sprayed and applied to a plurality of glass fiber filaments, and a large number of glass fiber filaments. A primary coating solution prepared by mixing an aqueous solution of a phenols-formaldehyde condensate (A) and an emulsion of an acrylonitrile-butadiene copolymer (B) is applied to the strands and dried.

  In the present invention, a primary coating layer containing a phenols-formaldehyde condensate (A) and an acrylonitrile-butadiene copolymer (B) is formed on a strand obtained by bundling a plurality of glass fiber filaments, and a chlorosilane is formed on the upper layer. It is a glass fiber for rubber reinforcement characterized by providing a secondary coating layer containing sulfonated polyethylene (D) and bisallylnadiimide (E).

  In order to improve the heat resistance of the transmission belt formed by embedding the glass fiber for rubber reinforcement of the present invention in the base rubber at a high temperature, the emulsion of chlorosulfonated polyethylene (D) is further mixed with the above primary emulsion. Add to coating solution. The application of the coating solution for primary coating is carried out by means such as heating and drying after the strand is bent and forced to adhere in the coating solution for primary coating.

  Moreover, this invention contains the phenols-formaldehyde condensate (A), the acrylonitrile-butadiene copolymer (B), and the chlorosulfonated polyethylene (D) in the strand which bundled the several glass fiber filament. It is a glass fiber for rubber reinforcement characterized by forming a secondary coating layer and providing a secondary coating layer containing chlorosulfonated polyethylene (D) and bisallylnadiimide (E) as an upper layer.

  Furthermore, the present invention provides a phenol-formaldehyde condensate (A), an acrylonitrile-butadiene copolymer (B), and a vinylpyridine-styrene-butadiene copolymer (C) on a strand in which a plurality of glass fiber filaments are bundled. A glass fiber for reinforcing rubber comprising a primary coating layer containing chlorosulfonated polyethylene (D) and a bisallyl nadiimide (E) on the upper layer. It is.

  Furthermore, the present invention relates to a phenol-formaldehyde condensate (A), an acrylonitrile-butadiene copolymer (B), and a vinylpyridine-styrene-butadiene copolymer (B) on a strand obtained by bundling a plurality of glass fiber filaments. C) and a primary coating layer containing chlorosulfonated polyethylene (D) is formed, and a secondary coating layer containing chlorosulfonated polyethylene (D) and bisallylnadiimide (E) is provided thereon. It is the glass fiber for rubber reinforcement characterized by becoming.

  In order to obtain the desired adhesive strength for the glass fiber for rubber reinforcement and the base rubber of the present invention when used in a transmission belt, the phenols-formaldehyde condensate (A) contained in the coating liquid for primary coating and Expressed as a mass percentage based on 100% of the total mass of the acrylonitrile-butadiene copolymer (B), the phenols-formaldehyde condensate (A) is 1.0% or more and 55.0% or less, A / (A + B) = 1.0% or more and 55.0% or less, and acrylonitrile-butadiene copolymer (B) is 45.0% or more and 99.0% or less, that is, B / (A + B) = 45. It is preferably contained in the range of 0% or more and 99.0% or less.

  In the glass fiber for rubber reinforcement of the present invention, when the content of the phenols-formaldehyde condensate (A) in the primary coating layer is less than A / (A + B) = 1.0%, the glass fiber for rubber reinforcement is coated. When used as a material, the adhesive strength between the glass fiber for reinforcing rubber and the base rubber becomes weak, and it is difficult to obtain preferable water resistance, heat resistance, and oil resistance in bending running when used as a transmission belt. If the content of the phenols-formaldehyde condensate (A) exceeds 55.0%, the glass fiber coating solution is liable to cause aggregation and precipitation and is difficult to use. Therefore, the suitable range of the phenols-formaldehyde condensate (A) in the primary coating layer of the glass fiber for reinforcing rubber of the present invention is the phenols-formaldehyde condensate (A) and acrylonitrile contained in the primary coating layer. -The total mass of the butadiene copolymer (B) is expressed as a mass percentage based on 100%, and A / (A + B) = 1.0% or more and 55.0% or less.

  Moreover, in the glass fiber for rubber reinforcement of the present invention, when the content of the acrylonitrile-butadiene copolymer (B) in the primary coating layer is less than B / (A + B) = 45.0%, the glass fiber for rubber reinforcement The adhesive strength between the base material rubber and the base rubber becomes weak, and it is difficult to obtain preferable heat resistance in bending running when a transmission belt is used. When the content of the acrylonitrile-butadiene copolymer (B) exceeds B / (A + B) = 99.0%, the heat resistance is lowered.

  Therefore, the suitable content range of the acrylonitrile-butadiene copolymer (B) in the primary coating layer of the glass fiber for rubber reinforcement of the present invention is preferably a suitable chlorophenol-formaldehyde condensate (A) and acrylonitrile in the primary coating layer. -Expressing the total mass of the butadiene copolymer (B) as a mass percentage based on 100%, B / (A + B) = 45.0% or more and 99.0% or less.

  In order to improve water resistance, it is effective to add a vinylpyridine-styrene-butadiene copolymer (C) to the composition of the primary coating material, and the composition with the acrylonitrile-butadiene copolymer (B). By selecting the ratio, the transmission belt in which the glass fiber for rubber reinforcement of the present invention is embedded as a core wire is balanced in a region where the balance of water resistance and oil resistance is high, and excellent water resistance and oil resistance are given. It becomes possible.

  In order to obtain the desired adhesive strength for the glass fiber for rubber reinforcement and the base rubber of the present invention when used in a transmission belt, the phenols-formaldehyde condensate (A) contained in the coating liquid for primary coating and The phenols-formaldehyde condensate (A) is represented by a mass percentage based on 100% of the total mass of the acrylonitrile-butadiene copolymer (B) and the vinylpyridine-styrene-butadiene copolymer (C). 0% or more, 40.0% or less, that is, A / (A + B + C) = 1.0% or more, 40.0% or less, acrylonitrile-butadiene copolymer (B) is 1.0% or more, 55.0% Hereinafter, B / (A + B + C) = 1.0% or more, 55.0% or less, vinylpyridine-styrene-butadiene copolymer (C) is 10.0% or more and 70.0% or less, C / (A + B + C) 10.0% or more is preferably contained in the range of less than 70.0.

  In the glass fiber for rubber reinforcement of the present invention, when the content of the phenols-formaldehyde condensate (A) in the primary coating layer is less than A / (A + B + C) = 1.0%, the glass fiber for rubber reinforcement is coated. When used as a material, the adhesive strength between the glass fiber for reinforcing rubber and the base rubber becomes weak, and it is difficult to obtain preferable water resistance, heat resistance, and oil resistance in bending running when used as a transmission belt. If the content of the phenols-formaldehyde condensate (A) exceeds 40.0%, the glass fiber coating solution is liable to cause aggregation and precipitation and is difficult to use. Therefore, the suitable range of the phenols-formaldehyde condensate (A) in the primary coating layer of the glass fiber for reinforcing rubber of the present invention is the phenols-formaldehyde condensate (A) and acrylonitrile contained in the primary coating layer. -Expressing the total mass of the butadiene copolymer (B) and the vinylpyridine-styrene-butadiene copolymer (C) as a mass percentage based on 100%, A / (A + B + C) = 1.0% or more, 40 0.0% or less.

  In the glass fiber for reinforcing rubber of the present invention, when the content of the acrylonitrile-butadiene copolymer (B) in the primary coating layer is less than B / (A + B + C) = 1.0%, the glass fiber for rubber reinforcement The adhesive strength between the base material rubber and the base rubber becomes weak, and it is difficult to obtain preferable heat resistance in bending running when a transmission belt is used. When the content of the acrylonitrile-butadiene copolymer (B) exceeds B / (A + B + C) = 55.0%, the heat resistance is lowered. Therefore, the suitable content range of the acrylonitrile-butadiene copolymer (B) in the primary coating layer of the glass fiber for rubber reinforcement of the present invention is preferably a suitable chlorophenol-formaldehyde condensate (A) and acrylonitrile in the primary coating layer. -Representing the total mass of the butadiene copolymer (B) and the vinylpyridine-styrene-butadiene copolymer (C) as a mass percentage based on 100%, B / (A + B + C) = 1.0% or more, 55 0.0% or less.

  Further, in the glass fiber for reinforcing rubber of the present invention, when the content of the vinylpyridine-styrene-butadiene copolymer (C) in the primary coating layer is less than C / (A + B + C) = 10.0%, a transmission belt It is difficult to obtain preferable water resistance in the bending running at that time. When the content of the vinylpyridine-styrene-butadiene copolymer (C) exceeds C / (A + B + C) = 70.0%, it is difficult to obtain preferable oil resistance in bending running when a transmission belt is used. Accordingly, the preferred content range of the vinylpyridine-styrene-butadiene copolymer (C) in the primary coating layer of the glass fiber for reinforcing rubber of the present invention is chlorophenol-formaldehyde condensate (A) and acrylonitrile-butadiene copolymer. Expressed as a mass percentage based on 100% of the combined mass of the blend (B) and the vinylpyridine-styrene-butadiene copolymer (C), C / (A + B + C) is 10.0% or more and 70.0% or less. is there.

  It is also possible to use a styrene-butadiene copolymer in place of the vinylpyridine-styrene-butadiene copolymer. However, when the styrene-butadiene copolymer is used, the adhesive strength with the base rubber tends to decrease. However, there is an advantage that there is no stickiness after application.

  Chlorosulfonated polyethylene (D) is applied to the primary coating layer containing the chlorophenol-formaldehyde condensate (A) and the acrylonitrile-butadiene copolymer (B) in order to improve heat resistance in bending running when it is used as a transmission belt. When contained, the total mass of the phenols-formaldehyde condensate (A), acrylonitrile-butadiene copolymer (B) and chlorosulfonated polyethylene (D) contained in the primary coating layer is based on 100%. Expressed as a percentage by mass, the primary coating layer preferably contains chlorosulfonated polyethylene (D) in a range of D / (A + B + D) = 1.0% or more and 40.0% or less.

  When the content of chlorosulfonated polyethylene (D) is greater than D / (A + B + D) = 40.0%, the adhesive strength between the rubber fiber for rubber reinforcement and the base rubber becomes weak, and the belt runs when used as a transmission belt. It is difficult to obtain preferable heat resistance. If it is less than 1.0%, there is almost no effect of improving heat resistance. Therefore, the suitable content range of chlorosulfonated polyethylene (D) in the primary coating layer of the glass fiber for reinforcing rubber of the present invention is D / (A + B + D) = 1.0% or more and 40.0% or less. Preferably, D / (A + B + D) = 15.0% or more and 35.0% or less.

  In order to improve heat resistance in bending running when it is used as a transmission belt, it contains chlorophenol-formaldehyde condensate (A), acrylonitrile-butadiene copolymer (B), and vinylpyridine-styrene-butadiene copolymer (C). When the chlorosulfonated polyethylene (D) is contained in the primary coating layer, the phenols-formaldehyde condensate (A), acrylonitrile-butadiene copolymer (B), and vinylpyridine-styrene- contained in the primary coating layer. Expressing the total mass of the butadiene copolymer (C) and the chlorosulfonated polyethylene (D) as a mass percentage based on 100%, the primary coating layer contains chlorosulfonated polyethylene (D) and D / (A + B + C + D). It is preferably included in the range of 1.0% or more and 40.0% or less.

  When the content of chlorosulfonated polyethylene (D) is more than D / (A + B + C + D) = 40.0%, the adhesive strength between the rubber fiber for rubber reinforcement and the base rubber becomes weak, and the bent running when the transmission belt is made It is difficult to obtain preferable heat resistance. If it is less than 1.0%, there is almost no effect of improving heat resistance. Therefore, the suitable content range of chlorosulfonated polyethylene (D) in the primary coating layer of the glass fiber for reinforcing rubber of the present invention is D / (A + B + C + D) = 1.0% or more and 40.0% or less. Preferably, D / (A + B + C + D) = 15.0% or more and 35.0% or less.

  In order to form the secondary coating layer of the glass fiber for rubber reinforcement of the present invention, chlorosulfonated polyethylene (D) and bisallyl nadiimide (E) are formed on the primary coating layer with an organic solvent such as xylene. The secondary coating solution dispersed in is applied to provide a secondary coating layer. The application of the coating solution for secondary coating is performed by a means such as forcing the rubber reinforcing glass fiber to be bent and running in the coating solution for secondary coating, forcing it, and then drying.

  On the primary coating layer containing the phenols-formaldehyde condensate (A) and the acrylonitrile-butadiene copolymer (B), the phenols-formaldehyde condensate (A) and the acrylonitrile-butadiene copolymer (B) On the primary coating layer containing chlorosulfonated polyethylene (D), phenols-formaldehyde condensate (A), acrylonitrile-butadiene copolymer (B), and vinylpyridine-styrene-butadiene copolymer (C). Or a phenol-formaldehyde condensate (A), an acrylonitrile-butadiene copolymer (B), a vinylpyridine-styrene-butadiene copolymer (C), and a chlorosulfonated polyethylene ( On the primary coating layer containing D), chlorosulfonated polyethylene Providing a secondary coating layer containing (D) and bisallylnadiimide (E) is a dimensional stability, heat resistance, water resistance when used as a transmission belt on the glass fiber for rubber reinforcement of the present invention, It has the effect of combining oil resistance.

  Expressed as a mass percentage based on 100% of the mass of chlorosulfonated polyethylene (D) contained in the secondary coating layer, the content of bisallylnadiimide (E) is E / D = 0.3% or more, 10 It is preferably 0.0% or less.

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

  Next, the phenol-formaldehyde condensate (A) contained in the primary coating layer and the bisallyl nadiimide (E) contained in the secondary coating layer in the glass fiber for rubber reinforcement of the present invention will be described.

  The phenols-formaldehyde condensate (A) to be contained in the primary coating layer includes resorcin-formaldehyde condensate, monohydroxybenzene-formaldehyde condensate, chlorophenol-formaldehyde condensate, resorcin-monohydroxybenzene-formaldehyde condensate, Resorcin-chlorophenol-formaldehyde condensates and mixtures thereof.

  As these phenols-formaldehyde condensates (A), the molar ratio of formaldehyde to phenols is 0.5 or more and 3.0 or less, and the resol type phenols-formaldehyde condensate reacted in the presence of alkali. It is preferable to use (A) because there is an effect of stabilizing the coating liquid without precipitation of solids. If the molar ratio of formaldehyde is less than 0.5, the adhesive strength between the glass fiber for reinforcing rubber and the heat-resistant rubber is inferior, and if it exceeds 3.0, the coating solution for primary coating tends to gel. In this invention, the liquid stability of the coating liquid for glass fiber coating improves by using a resol type phenols-formaldehyde condensate (A). Examples of the alkali include lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, and barium hydroxide.

  The resorcin-formaldehyde condensate and the monohydroxybenzene-formaldehyde condensate are water-soluble. When preparing a coating solution for primary coating, the acrylonitrile-butadiene copolymer (B) is added to the aqueous solution of these condensates. Add emulsion and emulsion of chlorosulfonated polyethylene (D).

  The chlorophenol-formaldehyde condensate is a condensate that is hardly soluble in water. When preparing a coating solution for primary coating, the chlorophenol-formaldehyde condensate obtained by the condensation reaction of chlorophenol and formaldehyde in water. An aqueous solution of a chlorophenol-formaldehyde condensate is obtained by adding an alcohol compound or an amine compound as a solubilizer to dissolve the precipitate of the product, and an emulsion of acrylonitrile-butadiene copolymer (B), vinylpyridine-styrene-butadiene Mix with emulsion of copolymer (C), emulsion of chlorosulfonated polyethylene (D). Therefore, the chlorophenol-formaldehyde condensate is preferably a resol type chlorophenol-formaldehyde condensate condensed in the presence of an alkali catalyst. In that case, the chlorophenol is preferably para-type chlorophenol because the para-type is highly reactive and the condensate is stable when used as a coating solution.

  Examples of the alcohol compound to be dissolved in the precipitate of the chlorophenol-formaldehyde condensate include n-propanol, isopropanol, propylene glycol, 2-methoxyethanol, 2-methoxymethylethoxypropanol, 1-methoxy-2-propanol, ethylene glycol, Examples include diethylene glycol and 1,2-diethoxyethane. In particular, 2-methoxyethanol and propylene glycol are diffused when a coating layer is formed on a strand by drying after coating a glass fiber coating coating solution. It is a particularly preferred alcohol compound for use in the preparation of a coating solution for primary coating because it does not remain in the solution and has a high effect of stabilizing the aqueous solution of the chlorophenol-formaldehyde condensate. In addition, when alcohol is used in the coating solution for primary coating for the purpose of dissolving the precipitate of chlorophenol-formaldehyde condensate, a gelled product is formed when water is added to adjust the concentration of the coating solution. However, there is no concern for 2-methoxyethanol and propylene glycol in adjusting the concentration in the necessary area. In addition, there is safety from fire, low toxicity and low boiling point. There is no fear of suction, it is excellent in environmental safety, its commercial price is low, and its practicality is high.

  The precipitation of the chlorophenol-formaldehyde condensate is dissolved by adding these alcohol compounds, the aqueous solution of the chlorophenol-formaldehyde condensate is stabilized, and the chlorophenol-formaldehyde condensate is not precipitated. It seems that the OH group of the product and the OH group of the alcohol compound form a three-dimensionally strong hydrogen bond. In addition, since the dipole moment and dielectric constant of the alcohol compound are high, long-range interactions such as dispersion force work strongly, and the effect of stabilizing the chlorophenol-formaldehyde condensate in aqueous solution, (Charge transfer) Since the interaction energy is large, strong solvation occurs due to association not only between the solvent and solute but also between the solvent and the solvent, and stable in an aqueous solution so that the chlorophenol-formaldehyde condensate does not precipitate. It seems that there is an effect to make it.

  Add only the amount of sodium hydroxide required for the condensation reaction to the mixed aqueous solution of chlorophenol and formaldehyde, and heat it to 30 ° C or higher and 95 ° C or lower without adding it. An alcohol compound is added to the reaction solution in which the precipitate of the resol-type chlorophenol-formaldehyde condensate is formed, and the precipitate is dissolved by stirring to obtain an aqueous solution of the resol-type chlorophenol-formaldehyde condensate. Is obtained.

Moreover, as an amine compound for making it melt | dissolve in precipitation of a chlorophenol-formaldehyde condensate, the amine compound whose basicity constant (Kb) is 5 * 10 < ^-5 > or more and 1 * 10 < ^-3 > or less is used. If the basicity constant (Kb) is smaller than 5 × 10 ⁻⁵ , even if the precipitate of the chlorophenol-formaldehyde condensate does not dissolve but dissolves, the chlorophenol-formaldehyde condensation is performed in order to prepare a coating solution for primary coating. When an emulsion of acrylonitrile-butadiene copolymer (B) and an emulsion of chlorosulfonated polyethylene (D) are mixed in an aqueous solution of the product, a precipitate of chlorophenol-formaldehyde condensate (A) is deposited. When the basicity constant (Kb) is larger than 1 × 10 ⁻³ , the adhesive strength between the rubber reinforcing glass fiber and the base rubber is lowered. 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.

  Specific examples of the amine compound include methylamine, ethylamine, t-butylamine, dimethylamine, diethylamine, triethylamine, tri-n-butylamine, methanolamine, dimethanolamine, monoethanolamine, and diethylamine. Is dimethylamine, diethylamine, dimethanolamine, or diethanolamine, and more preferably dimethylamine or diethanolamine. Dimethylamine is inexpensive and diethanolamine has no amine-specific odor and is easy to handle. In particular, when 2-methoxyethanol is applied after the coating solution for primary coating is dried to form a coating layer on the strand, it is diffused and does not remain in the coating layer, and is also an alcohol compound. Since the effect of stabilizing the aqueous solution of formaldehyde condensate is great, it is a particularly preferred compound for use in the primary coating layer of the glass fiber for rubber reinforcement of the present invention.

  Add only the amount of sodium hydroxide required for the condensation reaction to the mixed aqueous solution of chlorophenol and formaldehyde, and heat it to 30 ° C or higher and 95 ° C or lower without adding it. An amine compound is added to the reaction solution in which a precipitate of the resol-type chlorophenol-formaldehyde condensate is formed, and then the precipitate is dissolved by stirring to obtain an aqueous solution of the chlorophenol-formaldehyde condensate. It was.

  The amount of the alcohol compound or amine compound added when the precipitation of the chlorophenol-formaldehyde condensate is dissolved by adding the alcohol compound or amine compound is based on the mass of the chlorophenol-formaldehyde condensate as 100%. Expressed as a mass percentage, it is 50% or more and 500% or less. In other words, the mass to which the alcohol compound or amine compound is added is ½ or more and 5 or less in terms of mass ratio with respect to the mass of the chlorophenol-formaldehyde condensate. When the amount of the alcohol compound or amine compound added is less than 50%, there is no effect of dissolving the chlorophenol-formaldehyde condensate, and it is not necessary to add more than 500%. When the amount of the alcohol compound or amine compound added exceeds 500%, the emulsion of chlorophenol-formaldehyde condensate and acrylonitrile-butadiene copolymer (B) in the primary glass fiber coating solution and chlorosulfonated polyethylene (D ), The glass fiber for rubber reinforcement formed by applying the primary coating solution onto the strands becomes inflexible. Moreover, since an amine compound is added for liquid stabilization, it is preferable that a chlorophenol-formaldehyde condensate is a resol type.

  In the glass fiber for reinforcing rubber of the present invention, the bisallylnadiimide (E) contained in the secondary coating layer is a kind of thermosetting imide, and the low molecular weight bisallylnadiimide (E) is different from other resins. The bisallyl nadiimide resin after curing has a glass transition point of 300 ° C. or higher.

  The bisallylnadiimide (E) is represented by the structural formula of Chemical Formula 2 before curing, and the alkyl group of the structural formula of Chemical Formula 2 is represented by the structural formula of Chemical Formula 3 or Chemical Formula 4, and in particular, N—N '-Hexamethylene diallyl nadiimide is preferably used.

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

  When bisallyl nadiimide (E) is contained in the secondary coating layer, when the rubber-reinforced glass fiber is embedded in the base rubber or subsequently formed into a transmission belt, the double bond site can be seen from the structural formula of Chemical Formula 2. Acts as a reaction site to form a matrix in the secondary coating layer, and suppresses water from penetrating into the acrylonitrile-butadiene copolymer (B) which has excellent oil resistance but poor water resistance in the primary coating layer. The rubber reinforcing glass fiber of the present invention plays a role of combining heat resistance, water resistance and oil resistance.

  As the secondary coating layer, in addition to chlorosulfonated polyethylene (D) and bisallylnadiimide (E), a secondary coating layer containing chlorosulfonated polyethylene (D) and maleimide, chlorosulfonated polyethylene (D) And a secondary coating layer containing organic diisocyanate and zinc methacrylate. However, compared with these secondary coating layers, the secondary coating layer containing chlorosulfonated polyethylene (D) and bisallyl nadiimide (E) is used in the transmission belt embedded with the glass fiber for rubber reinforcement of the present invention. Combines excellent heat resistance, water resistance and oil resistance. Chlorosulfonated polyethylene (D) is necessary for heat resistance.

  When the glass fiber for rubber reinforcement of the present invention provided with the primary coating layer and the secondary coating layer is embedded in various base rubbers, particularly heat resistant rubber such as HNBR, and used as a transmission belt, Excellent adhesion of the base rubber is obtained, and the glass fiber for rubber reinforcement of the present invention works effectively as a reinforcing material for the transmission belt. Furthermore, the transmission belt in which the glass fiber for reinforcing rubber according to the present invention is embedded is a coating belt having a glass fiber for reinforcing rubber and a base rubber in a long-time bending running in an environment where high temperature and humidity and oil adhere. By maintaining the initial adhesive strength, it has excellent dimensional stability and has excellent heat resistance, water resistance and oil resistance.

  As monohydroxybenzene-formaldehyde condensate (A) used for the primary covering layer of the glass fiber for rubber reinforcement of the present invention, for example, trade name made by Gunei Chemical Industry Co., Ltd. marketed as industrial phenol resin , Cash register top, model number PL-4667.

  Examples of the acrylonitrile-butadiene copolymer (B) used for the primary covering layer of the glass fiber for reinforcing rubber of the present invention include Nippon Zeon Co., Ltd., trade names, Nipol L1560, Nipol L1562, and Nipol SX1503. It is done.

  In the primary coating layer of the glass fiber for reinforcing rubber of the present invention, not only the acrylonitrile-butadiene binary but also the acrylonitrile-butadiene-styrene terpolymer is obtained by adding styrene to the polymerization monomer. Even if (B) is used, the same effect can be obtained in the dimensional stability for the reason described above. When the acrylonitrile-butadiene-styrene terpolymer is used as a transmission belt, water resistance can be obtained without reducing heat resistance and oil resistance, and an excellent transmission belt can be easily obtained.

  Examples of the acrylonitrile-butadiene-styrene copolymer (B) used for the primary coating layer of the glass fiber for rubber reinforcement of the present invention include Nippon Zeon Co., Ltd., trade names, Nipol L1577K, Nipol L1571CL, and the like.

  The chlorosulfonated polyethylene (D) used as a composition for the coating solution for coating glass fibers of the present invention is represented by mass percentage and has a chlorine content of 20.0% or more and 40.0% or less, and sulfur in the sulfone group. Those having a content of 0.5% or more and 2.0% or less are suitably used. For example, as a latex having a solid content of about 40% by mass, a product name, CSM-450, manufactured by Sumitomo Seika Co., Ltd. is commercially available. And used for the coating solution for coating glass fiber of the present invention. In addition, the glass fiber coating coating solution using the chlorosulfonated polyethylene (D) with the chlorine content and the sulfur content in the sulfone group deviating from the above is used for rubber reinforcement produced by coating the glass fiber cord. Glass fiber is inferior in adhesiveness with the cross-linked HNBR which is a base material.

  The primary coating layer or the secondary coating layer of the glass fiber for reinforcing rubber of the present invention may contain an antiaging agent, 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.

  For heat resistance, chlorosulfonated polyethylene (D) is used in the coating solution for secondary coating of the rubber reinforcing glass fiber of the present invention, and a nitroso compound as a vulcanizing agent such as p-nitrosobenzene, The addition of an inorganic filler such as carbon black or magnesium oxide to form a secondary coating layer of rubber reinforcing glass fiber improves the heat resistance of a transmission belt produced by embedding the rubber reinforcing glass fiber in rubber. There is a further effect. In the coating solution for secondary coating, the mass of the chlorosulfonated polyethylene (D) in the coating solution is expressed as a mass percentage based on 100%, and the vulcanizing agent is 0.5% or more, 20.0% or less, inorganic When the 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%, Moreover, it is not necessary to add an inorganic filler exceeding 70.0%.

  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 above-mentioned transmission belt having heat resistance, water resistance and oil resistance used in the engine room of the automobile. A timing belt is a pulley tooth used in an engine having a camshaft to transmit the crankshaft to the timing gear and drive the camshaft to open and close the valve in the automobile transmission belt. It is a toothed belt provided with meshing teeth. Power transmission belts for automobiles require heat resistance against engine heat, water resistance in rainy weather, and oil resistance because they are exposed to engine oil. Dimensional stability is maintained after a long period of flexing. In other words, heat resistance, water resistance and oil resistance are required.

Example 1
Chlorosulfonated polyethylene (D) on the primary coating layer containing resorcinol-formaldehyde condensate as phenols-formaldehyde condensate (A), acrylonitrile-butadiene copolymer (B) and chlorosulfonated polyethylene (D) A glass fiber for reinforcing rubber having a secondary coating layer containing bisallylnadiimide (E) was prepared.
(Example 2)
Next, chlorosulfonated on the primary coating layer containing monohydroxybenzene-formaldehyde condensate as phenols-formaldehyde condensate (A), acrylonitrile-butadiene copolymer (B) and chlorosulfonated polyethylene (D). A glass fiber for rubber reinforcement in which a secondary coating layer containing polyethylene (D) and bisallylnadiimide (E) was formed was produced.
(Examples 3 and 4)
Next, chlorosulfonated polyethylene on the primary coating layer containing chlorophenol-formaldehyde condensate as phenols-formaldehyde condensate (A), acrylonitrile-butadiene copolymer (B) and chlorosulfonated polyethylene (D). A glass fiber for reinforcing rubber having a secondary coating layer containing (D) and bisallylnadiimide (E) was produced. When preparing a coating solution for primary coating for obtaining a primary coating layer, each rubber reinforcing glass fiber using an alcohol compound and an amine compound was prepared to obtain an aqueous solution of a chlorophenol-formaldehyde condensate.

A glass fiber for rubber reinforcement using a coating solution for primary coating using an aqueous solution of a chlorophenol-formaldehyde condensate using an alcohol compound is used in Example 3, and an aqueous solution of a chlorophenol-formaldehyde condensate using an amine compound is used. Example 4 is a glass fiber for rubber reinforcement using the coating solution for primary coating.
(Example 5)
Resorcinol-formaldehyde condensate as phenols-formaldehyde condensate (A), acrylonitrile-butadiene-styrene copolymer as acrylonitrile-butadiene copolymer (B), and vinylpyridine-styrene-butadiene copolymer (C And a glass fiber for rubber reinforcement in which a secondary coating layer containing chlorosulfonated polyethylene (D) and bisallylnadiimide (E) is formed on the primary coating layer containing chlorosulfonated polyethylene (D). Produced.
(Example 6)
Subsequently, monohydroxybenzene-formaldehyde condensate as phenols-formaldehyde condensate (A), acrylonitrile-butadiene-styrene copolymer as acrylonitrile-butadiene copolymer (B), and vinylpyridine-styrene-butadiene copolymer For rubber reinforcement in which a secondary coating layer containing chlorosulfonated polyethylene (D) and bisallylnadiimide (E) is formed on a primary coating layer containing coalesced (C) and chlorosulfonated polyethylene (D) Glass fiber was produced.
(Examples 7 and 8)
Next, a chlorophenol-formaldehyde condensate as a phenols-formaldehyde condensate (A), an acrylonitrile-butadiene-styrene copolymer as an acrylonitrile-butadiene copolymer (B), and a vinylpyridine-styrene-butadiene copolymer For rubber reinforcement in which a secondary coating layer containing chlorosulfonated polyethylene (D) and bisallylnadiimide (E) is formed on a primary coating layer containing coalesced (C) and chlorosulfonated polyethylene (D) Glass fiber was produced. When preparing a coating solution for primary coating for obtaining a primary coating layer, each rubber reinforcing glass fiber using an alcohol compound and an amine compound was prepared to obtain an aqueous solution of a chlorophenol-formaldehyde condensate.

Example 7 is a glass fiber for rubber reinforcement using a coating solution for primary coating using an aqueous solution of a chlorophenol-formaldehyde condensate using an alcohol compound, and an aqueous solution of a chlorophenol-formaldehyde condensate using an amine compound is used. A glass fiber for rubber reinforcement using the coating solution for primary coating was used as Example 8.
(Comparative Example 1)
Subsequently, chlorosulfonated polyethylene (D) and bisallyl nadiimide (E) are coated on the primary coating layer containing the conventional resorcin-formaldehyde condensate, vinylpyridine-styrene-butadiene copolymer and chlorosulfonated polyethylene (D). The glass fiber for rubber reinforcement which provided the secondary coating layer containing) was produced.
(Comparative Example 2)
Subsequently, chlorosulfonated polyethylene (D) and bisallyl nadiimide (E) were formed on the primary coating layer containing monohydroxybenzene-formaldehyde condensate, vinylpyridine-styrene-butadiene copolymer and chlorosulfonated polyethylene (D). The glass fiber for rubber reinforcement which provided the secondary coating layer containing) was produced.
(Comparative Examples 3 and 4)
Next, chlorosulfonated polyethylene (D) and bisallyl nadiimide (E) are formed on the primary coating layer containing chlorophenol-formaldehyde condensate, vinylpyridine-styrene-butadiene copolymer and chlorosulfonated polyethylene (D). The glass fiber for rubber reinforcement which provided the secondary coating layer containing this was produced. A glass fiber for rubber reinforcement using a coating solution for primary coating using an aqueous solution of a chlorophenol-formaldehyde condensate using an alcohol compound is used in Comparative Example 3, and an aqueous solution of a chlorophenol-formaldehyde condensate using an amine compound is used. The glass fiber for rubber reinforcement using the coating solution for primary coating was referred to as Comparative Example 4.

  As described above, the compositions of the primary coating layers of Examples 1 to 8 and Comparative Examples 1 to 4 are summarized in Table 1. The secondary coating layer contains chlorosulfonated polyethylene (D) and bisallyl nadiimide (E).

  These rubber reinforcing glass fibers of the present invention (Examples 1 to 8) and rubber reinforcing glass fibers not in the scope of the present invention (Comparative Examples 1 to 4) were subjected to an adhesive strength evaluation test for heat-resistant rubber, and the evaluation results were obtained. Compared.

  In addition, a test piece for MIT bending test in which the glass fiber for rubber reinforcement of the present invention or the glass fiber for rubber reinforcement of the present invention was embedded in HNBR was prepared. Using this test piece, water resistance, heat resistance, and oil resistance were measured.

Details will be described below.
Example 1
(Preparation of coating solution for primary coating)
To the aqueous solution of resorcinol-formaldehyde condensate belonging to the phenols-formaldehyde condensate (A), aqueous ammonia and water were added to the acrylonitrile-butadiene copolymer (B) emulsion to prepare a coating solution for primary coating.

  Specifically, an aqueous solution of resorcin-formaldehyde condensate obtained by diluting an aqueous solution of resorcin-formaldehyde condensate (A) (solid content, 50% by mass) with a concentration of 1% by mass with a sodium hydroxide aqueous solution twice as much is used. It was. An aqueous solution of resorcin-formaldehyde condensate (A), 63 parts by weight, and an emulsion of acrylonitrile-butadiene copolymer (B) (manufactured by Nippon Zeon Co., Ltd., trade name, Nipol L1562 solid content concentration, 41.0% by mass) 433 A predetermined amount of chlorosulfonated polyethylene (D) (trade name, TS-430, manufactured by Tosoh Corporation) is added to 22 parts by weight of ammonia water (concentration, 25.0% by mass) as a pH adjuster, As a result, water was added so as to be 1000 parts by weight to prepare a coating solution for primary coating.

The content ratio of each component in the coating solution for primary coating is expressed as a mass percentage based on 100% of the total mass of the resorcin-formaldehyde condensate and the acrylonitrile-butadiene copolymer (B), and resorcin-formaldehyde condensation. The product is A / (A + B) = 8.2%, and the acrylonitrile-butadiene copolymer (B) is B / (A + B) = 91.8%. The chlorosulfonated polyethylene (D) is a mass percentage based on 100% of the total mass of resorcin-formaldehyde condensate (A), acrylonitrile-butadiene copolymer (B) and chlorosulfonated polyethylene (D). Expressed as C / (A + B + C) = 28%. In addition, the mass of the resorcinol-formaldehyde condensate (A) and the acrylonitrile-butadiene copolymer (B) in the glass fiber coating liquid was obtained by converting the solid content into the solid content. It becomes the primary coating layer of the glass fiber for rubber reinforcement with this content rate.
(Preparation of secondary coating solution)
Next, a coating solution for secondary coating in which carbon black is added to chlorosulfonated polyethylene (D), p-dinitrobenzene, and hexamethylene diallyl nadiimide belonging to bisallyl nadiimide (E) and dispersed in xylene. Was prepared.

Specifically, as Tosoh Corporation product name as chlorosulfonated polyethylene (D), TS-430, 100 parts by weight, p-dinitrobenzene, 40 parts by weight, and NN′-hexamethylene diallyl nadiimide Made by Maruzen Petrochemical Co., Ltd., trade name, BANI-H, 0.3 parts by weight, carbon black, 30 parts by weight, and xylene, 1315 parts by weight were dispersed to prepare a coating solution for secondary coating. . That is, NN′-hexamethylene diallyl nadiimide belonging to bisallyl nadiimide (E) is E / D = 0.3% by mass with respect to the mass of chlorosulfonated polyethylene (D), and is a vulcanizing agent. A coating solution for secondary coating was prepared such that p-dinitrobenzene was 40% by mass and carbon black as an inorganic filler was 30% by mass. The secondary coating layer of the glass fiber for reinforcing rubber becomes the content ratio as it is.
(Preparation of glass fiber for rubber reinforcement of the present invention)
After aligning three strands of 200 μm glass fiber filaments with a diameter of 9 μm using a sizing agent containing an acrylic silane coupling agent and a resin, the primary coating solution prepared by the above-described procedure is applied. Then, it was dried at a temperature of 280 ° C. for 22 seconds to provide a primary coating layer to produce one rubber reinforcing glass fiber.

  At this time, the solid content adhesion rate, that is, the mass ratio of the coating layer was 19.0 mass% with respect to the total mass of the glass fiber for rubber reinforcement.

The glass fiber for rubber reinforcement provided with the primary coating layer is subjected to 2.0 twists per 2.54 cm, and 13 are further aligned to 2.0 times per 2.54 cm in the opposite direction to the twist. Work to twist the top. 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 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.
Example 2
(Preparation of coating solution for primary fiber coating)
To an aqueous solution of monohydroxybenzene-formaldehyde condensate belonging to phenols-formaldehyde condensate (A), an acrylonitrile-butadiene copolymer (B) emulsion, a chlorosulfonated polyethylene (D) emulsion, aqueous ammonia and water are added. A coating solution for primary coating was prepared.

    Specifically, a commercially available aqueous solution of monohydroxybenzene-formaldehyde condensate (A) (manufactured by Gunei Chemical Industry Co., Ltd., trade name, cash register top, model number PL-4667, solid content, 50% by mass) with 1% by mass water An aqueous solution of monohydroxybenzene-formaldehyde condensate (A) diluted with an aqueous sodium oxide solution at a mass ratio of 2 was used. Aqueous solution of monohydroxybenzene-formaldehyde condensate (A), 63 parts by weight, emulsion of acrylonitrile-butadiene copolymer (B), manufactured by Nippon Zeon Co., Ltd., trade name, Nipol L1562 solid content concentration, 41.0% by mass ) 433 parts by weight and 22 parts by weight of aqueous ammonia (concentration, 25.0 mass%) as a pH adjuster, and a predetermined amount of chlorosulfonated polyethylene (D) (trade name, TS-430, manufactured by Tosoh Corporation) In addition, water was added to a total of 1000 parts by weight to prepare a primary coating solution.

  The content ratio of each component in the coating solution for glass fiber coating is expressed as a mass percentage based on 100% of the total mass of the monohydroxybenzene-formaldehyde condensate (A) and the acrylonitrile-butadiene copolymer (B). The monohydroxybenzene-formaldehyde condensate (A) is A / (A + B) = 8.2%, and the acrylonitrile-butadiene copolymer (B) is B / (A + B) = 91.8%. The chlorosulfonated polyethylene (D) is a mass percentage based on 100% of the total mass of resorcin-formaldehyde condensate (A), acrylonitrile-butadiene copolymer (B) and chlorosulfonated polyethylene (D). Expressed C / (A + B + C) = 32%. In addition, the mass of the monohydroxybenzene-formaldehyde condensate (A) and the acrylonitrile-butadiene copolymer (B) in the coating solution for glass fiber coating was obtained by converting the solid content into the solid content. It becomes the primary coating layer of the glass fiber for rubber reinforcement with this content rate.

Subsequently, the glass fiber for rubber reinforcement (Example 2) of this invention was produced in the same procedure as Example 1 using the coating liquid for secondary coating prepared in Example 1.
Examples 3 and 4
(Preparation of aqueous solution of chlorophenol-formaldehyde condensate using alcohol compound)
First, preparation of an aqueous solution of a chlorophenol-formaldehyde condensate belonging to the phenols-formaldehyde condensate (A) using an alcohol compound will be described.

To a three-necked separable flask equipped with a reflux condenser, a thermometer, and a stirrer, chlorophenol, 138 parts by weight, concentration, 37.0% by mass aqueous formaldehyde solution, 87 parts by weight (in terms of molar ratio, 1.0 ), 20 parts by weight of an aqueous solution of sodium hydroxide having a concentration of 1.0% by mass, and the mixture was stirred for 3 hours while being heated to 80 ° C. to cause a condensation reaction. In this way, a resol type chlorophenol-formaldehyde condensate was produced and obtained as a precipitate in the reaction solution. Propylene glycol as an alcohol compound was added to 100 parts by weight of the reaction solution to dissolve the precipitate of the chlorophenol-formaldehyde condensate, thereby preparing an aqueous solution of the chlorophenol-formaldehyde condensate. In addition, the said addition of the density | concentration and 1.0 mass% sodium hydroxide aqueous solution is not added more than the amount required for the condensation reaction for carrying out the condensation reaction of chlorophenol and formaldehyde to make a chlorophenol-formaldehyde condensate. . In addition, P-chlorophenol was used for chlorophenol. In addition, it melt | dissolved so that the mass of propylene glycol might be 200 mass% with respect to the mass of a chlorophenol-formaldehyde condensate.
(Preparation of aqueous solution of chlorophenol-formaldehyde condensate using amine compound)
Next, preparation of an aqueous solution of a chlorophenol-formaldehyde condensate belonging to the phenols-formaldehyde condensate (A) using an amine compound will be described.

To a three-necked separable flask equipped with a reflux condenser, a thermometer, and a stirrer, chlorophenol, 138 parts by weight, concentration, 37.0% by mass aqueous formaldehyde solution, 87 parts by weight (in terms of molar ratio, 1.0 ), 20 parts by weight of an aqueous solution of sodium hydroxide having a concentration of 1.0% by mass, and the mixture was stirred for 3 hours while being heated to 80 ° C. to cause a condensation reaction. In this way, a resol type chlorophenol-formaldehyde condensate was produced and obtained as a precipitate in the reaction solution. Dimethylamine as an amine compound was added to 100 parts by weight of the reaction solution to dissolve the precipitate of the chlorophenol-formaldehyde condensate, thereby preparing an aqueous solution of the chlorophenol-formaldehyde condensate. In addition, the addition of the sodium hydroxide aqueous solution having a concentration of 1.0% by mass should be added more than the amount necessary for the condensation reaction to condense chlorophenol and formaldehyde into a chlorophenol-formaldehyde condensate. Not in. In addition, P-chlorophenol was used for chlorophenol. The basicity constant (Kb) of dimethylamine is 5.4 × 10 ⁻⁴ . In addition, it melt | dissolved so that the mass of a dimethylamine might be 200 mass% with respect to the mass of a chlorophenol-formaldehyde condensate.
(Preparation of coating solution for primary coating)
Commercially available acrylonitrile-butadiene copolymer using the above-mentioned aqueous solution of the chlorophenol-formaldehyde condensate dissolved using the alcohol compound or the aqueous solution of the chlorophenol-formaldehyde condensate dissolved using the amine compound. The combined (B) emulsion and chlorosulfonated polyethylene (D) were added, and aqueous ammonia and water were added to prepare a coating solution for primary coating.

Specifically, each aqueous solution of a chlorophenol formaldehyde condensate adjusted to a solid content concentration of 25% by mass, 63 parts by weight, and an acrylonitrile-butadiene copolymer (B) emulsion (manufactured by Zeon Corporation, trade name, Nipol L1562 solid) 433 parts by weight of a partial concentration, 41.0% by mass), 22 parts by weight of ammonia water (concentration, 25.0% by mass) as a pH adjuster, chlorosulfonated polyethylene (D) (trade name, manufactured by Tosoh Corporation) , TS-430) was added in a predetermined amount, and water was added to a total of 1000 parts by weight to prepare a coating solution for primary coating.

  The content ratio of each component in the coating solution for primary coating is represented by mass percentage based on 100% of the total mass of the chlorophenol formaldehyde condensate and the acrylonitrile-butadiene copolymer (B), and phenols-formaldehyde The chlorophenol formaldehyde condensate belonging to the condensate (A) is A / (A + B) = 8.2%, and the acrylonitrile-butadiene copolymer (B) is B / (A + B) = 91.8%. The chlorosulfonated polyethylene (D) is a mass percentage based on 100% of the total mass of resorcin-formaldehyde condensate (A), acrylonitrile-butadiene copolymer (B) and chlorosulfonated polyethylene (D). Expressed as C / (A + B + C) = 28%. In addition, the mass of the chlorophenol formaldehyde condensate and the acrylonitrile-butadiene copolymer (B) in the coating solution for primary coating was obtained by converting the solid content into the solid content. It becomes the primary coating layer of the glass fiber for rubber reinforcement with this content rate.

  Next, glass fibers for rubber reinforcement (Example 3 and Example 4) were produced in the same procedure as in Example 1 using the coating solution for secondary coating prepared in Example 1.

A glass fiber for rubber reinforcement using a coating solution for primary coating using an aqueous solution of a chlorophenol-formaldehyde condensate using an alcohol compound is used in Example 3, and an aqueous solution of a chlorophenol-formaldehyde condensate using an amine compound is used. Example 4 is a glass fiber for rubber reinforcement using the coating solution for primary coating.
Example 5
(Preparation of coating solution for primary coating)
An aqueous solution of resorcinol-formaldehyde condensate belonging to phenols-formaldehyde condensate (A) is added to an emulsion of acrylonitrile-butadiene-styrene copolymer as acrylonitrile-butadiene copolymer (B) and vinylpyridine-styrene-butadiene copolymer. Ammonia water and water were added to the polymer (C) emulsion to prepare a coating solution for primary coating.

  Specifically, an aqueous solution of resorcin-formaldehyde condensate obtained by diluting an aqueous solution of resorcin-formaldehyde condensate (A) (solid content, 50% by mass) with a concentration of 1% by mass with a sodium hydroxide aqueous solution twice as much is used. It was. An aqueous solution of resorcin-formaldehyde condensate (A), 63 parts by weight, and an acrylonitrile-butadiene-styrene copolymer emulsion as an acrylonitrile-butadiene copolymer (B) (trade name, Nipol L1577K manufactured by Nippon Zeon Co., Ltd.) 233 parts by weight of solid content concentration (38.0% by mass) and an emulsion of vinylpyridine-styrene-butadiene copolymer (C) (manufactured by Nippon A & L Co., Ltd., trade name, pilatex, solid content, 41.0% by mass) ) To 345 parts by weight, a predetermined amount of chlorosulfonated polyethylene (D) (trade name, TS-430, manufactured by Tosoh Corporation) is added to 22 parts by weight of ammonia water (concentration: 25.0 mass%) as a pH adjuster. Then, water was added so as to be 1000 parts by weight as a whole, and a coating solution for primary coating was prepared.

  The content ratio of each component in the coating solution for primary coating is such that resorcinol-formaldehyde condensate, acrylonitrile-butadiene copolymer (B), acrylonitrile-butadiene-styrene copolymer and vinylpyridine-styrene-butadiene copolymer. When the total mass of (C) is expressed as a mass percentage based on 100%, the resorcin-formaldehyde condensate is A / (A + B + C) = 9.8%, the acrylonitrile-butadiene copolymer (B) is B / (A + B + C) = 36.3%, vinylpyridine-styrene-butadiene copolymer (C) is C / (A + B + C) = 53.9%.

The chlorosulfonated polyethylene (D) is composed of a resorcin-formaldehyde condensate (A), an acrylonitrile-butadiene-styrene copolymer and a vinylpyridine-styrene-butadiene copolymer (B) as an acrylonitrile-butadiene copolymer (B). When the total mass of C) and chlorosulfonated polyethylene (D) is expressed as a mass percentage based on 100%, D / (A + B + C + D) = 21.9%. An acrylonitrile-butadiene-styrene copolymer and a vinylpyridine-styrene-butadiene copolymer (C) as resorcin-formaldehyde condensate (A) and acrylonitrile-butadiene copolymer (B) in the coating solution for coating glass fiber (C) ) Was determined by converting the solid content concentration to the solid content. It becomes the primary coating layer of the glass fiber for rubber reinforcement with this content rate.
(Preparation of secondary coating solution)
Next, in the same manner as in Example 1, carbon black was added to chlorosulfonated polyethylene (D), p-dinitrobenzene, and hexamethylene diallyl nadiimide belonging to bisallyl nadiimide (E), and dispersed in xylene. A secondary coating solution was prepared, a secondary coating layer was provided, and the glass fiber for rubber reinforcement of the present invention was prepared.
Example 6
(Preparation of coating solution for primary fiber coating)
An aqueous solution of monohydroxybenzene-formaldehyde condensate belonging to phenols-formaldehyde condensate (A), an emulsion of acrylonitrile-butadiene-styrene copolymer as acrylonitrile-butadiene copolymer (B), vinylpyridine-styrene-butadiene An emulsion of copolymer (C) and an emulsion of chlorosulfonated polyethylene (D) were added, and aqueous ammonia and water were added to prepare a coating solution for primary coating.

  Specifically, an aqueous solution of a commercially available monohydroxybenzene-formaldehyde condensate (A) (manufactured by Gunei Chemical Industry Co., Ltd., trade name, cash register top, model number PL-4667, solid content, 50% by mass) with a concentration of 1% by mass. An aqueous solution of monohydroxybenzene-formaldehyde condensate (A) diluted with a sodium hydroxide aqueous solution at a mass ratio of 2 times was used. An aqueous solution of monohydroxybenzene-formaldehyde condensate (A), 77 parts by weight, and an acrylonitrile-butadiene-styrene copolymer emulsion (trade name, Nipol, manufactured by Nippon Zeon Co., Ltd.) as acrylonitrile-butadiene copolymer (B) L1577K solid content concentration, 38.0 mass%) 233 parts by weight and vinylpyridine-styrene-butadiene copolymer (C) emulsion (manufactured by Nippon A & L Co., Ltd., trade name, pilatex, solid content, 41.0 mass %) In addition to 345 parts by weight, 22 parts by weight of ammonia water (concentration, 25.0 mass%) was added as a pH adjuster, and chlorosulfonated polyethylene (D) (trade name, TS-430, manufactured by Tosoh Corporation) Add a predetermined amount of water and add water to make 1000 parts by weight as a whole. The use coating solution was prepared.

  The content of each component in the coating solution for glass fiber coating is as follows: monohydroxybenzene-formaldehyde condensate (A), acrylonitrile-butadiene-styrene copolymer as acrylonitrile-butadiene copolymer (B), vinylpyridine-styrene -Representing the total mass of the butadiene copolymer (C) as a mass percentage based on 100%, the monohydroxybenzene-formaldehyde condensate (A) is A / (A + B + C) = 9.8%, acrylonitrile-butadiene Copolymer (B) is B / (A + B + C) = 36.3%. , Vinylpyridine-styrene-butadiene copolymer (C) is C / (A + B + C) = 53.9%.

  Further, chlorosulfonated polyethylene (D) is an emulsion of acrylonitrile-butadiene-styrene copolymer as resorcin-formaldehyde condensate (A) and acrylonitrile-butadiene copolymer (B), vinylpyridine-styrene-butadiene copolymer The total mass of the combined (C) emulsion and the chlorosulfonated polyethylene (D) is expressed as a mass percentage based on 100%, and D / (A + B + C + D) = 21.9%. In addition, the monohydroxybenzene-formaldehyde condensate (A) and the acrylonitrile-butadiene copolymer (B) in the coating solution for glass fiber coating, acrylonitrile-butadiene-styrene copolymer, vinylpyridine-styrene-butadiene copolymer The mass of (C) was calculated by converting the solid content concentration to the solid content. It becomes the primary coating layer of the glass fiber for rubber reinforcement with this content rate.

Subsequently, the glass fiber for rubber reinforcement of this invention was produced in the same procedure as Example 1 using the coating liquid for secondary coating prepared in Example 1.
Examples 7 and 8
(Preparation of coating solution for primary coating)
Chlorophenol-formaldehyde condensation dissolved with an aqueous solution of the aforementioned chlorophenol-formaldehyde condensate dissolved with an alcohol compound according to the procedure shown in Example 3 or with an amine compound according to the procedure shown in Example 4. An aqueous acrylonitrile-butadiene copolymer (B) emulsion, an acrylonitrile-butadiene-styrene copolymer emulsion, a vinylpyridine-styrene-butadiene copolymer (C) emulsion, In addition to the emulsion of sulfonated polyethylene (D), aqueous ammonia and water were added to prepare a coating solution for primary coating.

  Specifically, each aqueous solution of chlorophenol-formaldehyde condensate adjusted to a solid content concentration of 25% by mass, 85 parts by weight, and an emulsion of acrylonitrile-butadiene-styrene copolymer (B) as acrylonitrile-butadiene copolymer (B) Nippon Zeon Co., Ltd., trade name, Nipol L1577K solid concentration, 38.0 mass%) 255 parts by weight and vinylpyridine-styrene-butadiene copolymer (C) emulsion (manufactured by Nippon A & L Co., Ltd., trade name, In addition to 343 parts by weight of pyrexate, solid content, 41.0% by mass), 22 parts by weight of aqueous ammonia (concentration, 25.0% by mass) as a pH adjuster, chlorosulfonated polyethylene (D) (Tosoh Corporation) Product, trade name, TS-430) is added in a predetermined amount to make 1000 parts by weight as a whole. By adding water as to prepare a primary coating coating liquid.

  The content ratio of each component in the coating liquid for primary coating is such that the chlorophenol-formaldehyde condensate, the acrylonitrile-butadiene-styrene copolymer as the acrylonitrile-butadiene copolymer (B), and the vinylpyridine-styrene-butadiene copolymer. The chlorophenol formaldehyde condensate belonging to the phenols-formaldehyde condensate (A) is represented by A / (A + B + C) = 12.4%, expressed as a mass percentage based on 100% of the total mass of the polymer (C). The acrylonitrile-butadiene copolymer (B) is B / (A + B + C) = 37.3%. , Vinylpyridine-styrene-butadiene copolymer (C) is C / (A + B + C) = 50.3%.

  The chlorosulfonated polyethylene (D) is composed of resorcin-formaldehyde condensate (A), acrylonitrile-butadiene-styrene copolymer as acrylonitrile-butadiene copolymer (B), and vinylpyridine-styrene-butadiene copolymer. The mass of the combined (C) and chlorosulfonated polyethylene (D) is expressed as a mass percentage based on 100%, and D / (A + B + C + D) = 20.3%. In addition, the chlorophenol-formaldehyde condensate and the acrylonitrile-butadiene copolymer (B) in the coating solution for primary coating, acrylonitrile-butadiene-styrene copolymer as the acrylonitrile-butadiene copolymer (B), and vinylpyridine- The mass of the styrene-butadiene copolymer (C) was calculated from the solid content concentration in terms of solid content. It becomes the primary coating layer of the glass fiber for rubber reinforcement with this content rate.

  Next, glass fibers for rubber reinforcement (Example 7 and Example 8) were produced in the same procedure as in Example 1 using the coating solution for secondary coating prepared in Example 1.

Example 7 is a glass fiber for rubber reinforcement using a coating solution for primary coating using an aqueous solution of a chlorophenol-formaldehyde condensate using an alcohol compound, and an aqueous solution of a chlorophenol-formaldehyde condensate using an amine compound is used. A glass fiber for rubber reinforcement using the coating solution for primary coating was used as Example 8.
Comparative Example 1
Unlike Example 1, Example 1 was used except that instead of the acrylonitrile-butadiene copolymer (B), a vinylpyridine-styrene-butadiene copolymer was used so as to have the same content ratio in the primary coating layer. Similarly, a primary coating solution was prepared. The mass of the resorcin-formaldehyde condensate and the vinylpyridine-styrene-butadiene copolymer is expressed as a mass percentage based on 100%, and the resorcin-formaldehyde condensate is 8.2%, and the vinylpyridine-styrene-butadiene polymer. Was adjusted to 91.8%.

Next, a coating solution for secondary coating similar to that in Example 1 is prepared according to the procedure shown in Example 1, and the operation is performed according to the same procedure as in Example 1 to further add a secondary coating layer to the glass fiber for rubber reinforcement. A glass fiber for rubber reinforcement was prepared.
Comparative Example 2
Unlike Example 2, Example 2 was used except that instead of the acrylonitrile-butadiene copolymer (B), an emulsion of vinylpyridine-styrene-butadiene polymer was used so as to have the same content ratio in the primary coating layer. A primary coating solution was prepared in the same manner as described above. Expressed as a mass percentage based on 100% based on the total mass of the monohydroxybenzene-formaldehyde condensate and vinylpyridine-styrene-butadiene copolymer, the monohydroxybenzene-formaldehyde condensate is 8.2%, vinylpyridine-styrene. -It adjusted so that a butadiene polymer might be 91.8%.

  Next, a coating solution for secondary coating similar to that in Example 1 is prepared according to the procedure shown in Example 1, and the operation is performed according to the same procedure as in Example 1 to further add a secondary coating layer to the glass fiber for rubber reinforcement. A glass fiber for rubber reinforcement was prepared.

Thus, 2 containing chlorosulfonated polyethylene (D) and bisallyl nadiimide (E) on the primary coating layer containing monohydroxybenzene-formaldehyde condensate and vinylpyridine-styrene-butadiene copolymer. A glass fiber for rubber reinforcement (Comparative Example 2) provided with a next coating layer was produced.
Comparative Examples 3 and 4
Unlike Example 3, it replaced with the acrylonitrile butadiene copolymer (B), and it was the same as Example 2 except having used the vinyl pyridine styrene butadiene polymer so that it might become the same content rate in a primary coating layer. A primary coating solution was prepared. The mass of the chlorophenol-formaldehyde condensate and the vinylpyridine-styrene-butadiene copolymer is expressed as a mass percentage based on 100%, and the chlorophenol-formaldehyde condensate is 8.2%, vinylpyridine-styrene-butadiene. The polymer was adjusted to 91.8%.

  Next, a coating solution for secondary coating similar to that in Example 1 is prepared according to the procedure shown in Example 1, and the operation is performed according to the same procedure as in Example 1 to further add a secondary coating layer to the glass fiber for rubber reinforcement. A glass fiber for rubber reinforcement was prepared.

Thus, chlorosulfonated polyethylene (D) and bisallyl nadiimide (E) were formed on the primary coating layer containing chlorophenol-formaldehyde condensate, vinylpyridine-styrene-butadiene copolymer and chlorosulfonated polyethylene. A glass fiber for rubber reinforcement (Comparative Examples 3 and 4) provided with a secondary coating layer containing bismuth was prepared. A glass fiber for rubber reinforcement using a coating solution for primary coating using an aqueous solution of a chlorophenol-formaldehyde condensate using an alcohol compound is used in Comparative Example 3, and an aqueous solution of a chlorophenol-formaldehyde condensate using an amine compound is used. The glass fiber for rubber reinforcement using the coating solution for the primary coating was referred to as Comparative Example 4 (Evaluation test of adhesive strength between each glass fiber for rubber reinforcement and HNBR)
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 were blended.

The test piece was a 20 mm rubber reinforcing glass fiber (Examples 1 to 8 and Comparative Examples 1 to 4) on a 3 mm thick and 25 mm wide rubber sheet made of HNBR. Under the condition of 196 Newton / cm ² at 0 ° C., the end portion was pressed and molded while vulcanizing for 35 minutes to obtain a test piece for evaluating the adhesive strength. 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 adhesive strength. The greater the adhesive strength, the better the adhesive strength.
(Adhesion strength evaluation results)
The evaluation results of the adhesive strength are shown in Table 2. In Table 2, the destruction state in which the glass fiber and HNBR were not peeled from the interface was defined as rubber failure, and the destruction state in which only a part of the glass fiber and HNBR were separated from the interface was defined as interface peeling. Rubber destruction is superior in adhesion strength to interfacial peeling. Table 2 shows the adhesive strength of each rubber reinforcing glass fiber to HNBR.

As shown in Table 2, the glass fibers for rubber reinforcement (Examples 1 to 8) of the present invention and the glass fibers for rubber reinforcement (Comparative Examples 1 to 4) not within the scope of the present invention have the same adhesive strength ( 300-318N), and the peeled state was rubber destruction, which was the same result.
(Evaluation results of water resistance, heat resistance and oil resistance by MIT bending test of glass fibers for rubber reinforcement)
Using the glass fibers for rubber reinforcement produced in Examples 1 to 8 and Comparative Examples 1 to 4 as a reinforcing material, using the HNBR as a base rubber , two cords were embedded, and then vulcanized at 150 ° C. for 35 minutes A test piece sample for the MIT flex test was prepared. Water resistance, heat resistance and oil resistance were evaluated.

  For heat resistance, the test piece was heated to 150 ° C. for 240 hours in a heating furnace and returned to room temperature, and then the end of the test piece was attached with a 3 kg weight and bent at an angle of 210 degrees 1200 times, and then Tensile strength was measured.

  For water resistance, immerse the test piece in a beaker containing water, boil it over a gas burner for 2 hours, remove it, wipe off the water, attach a 3 kg weight to the end of the test piece, and place it at an angle of 210 degrees. Then, bending was repeated 1200 times, and then the tensile strength was measured.

  Also, for oil resistance, after immersing the test piece in automotive engine oil heated to 120 ° C. for 100 hours and taking it out, wiping off the engine oil and attaching a 3 kg weight to the end of the test piece, an angle of 210 degrees Then, bending was repeated 1200 times, and then the tensile strength was measured.

  As described above, in order to evaluate heat resistance, water resistance, and oil resistance, after accelerating the deterioration, the MIT bending test was repeated 1200 times at an angle of 210 degrees, and the heat resistance when the transmission belt was formed. It was used as an index for evaluation of water resistance, water resistance and oil resistance.

  FIG. 1 is a schematic view of a test piece of the MIT flex test.

  The size of the test piece 1 is 2 mm in height, 5 mm in width, and 250 mm in length, and the glass fibers 3 for rubber reinforcement according to Examples 1 to 8 and Comparative Examples 1 to 4 are embedded in the HNBR 2.

  FIG. 2 is a schematic diagram of the test situation of the MIT flex test.

  The bending angle of the clamp is 120 degrees, and the test piece 1 is bent 1200 times with the weight 4 attached.

  The results of the MIT flex test are shown in Table 3. The numerical values in Table 3 are tensile strength retention ratios, and were obtained by the following equation (1).

  In Table 3, an aqueous solution of resorcin-formaldehyde condensate, an aqueous solution of monohydroxybenzene-formaldehyde condensate, an aqueous solution of the aforementioned chlorophenol-formaldehyde condensate dissolved using an alcohol compound, or an amine compound were used. Water resistance, heat resistance, oil resistance by MIT bending test of test piece 1 using each glass fiber 3 for rubber reinforcement using each coating liquid for primary coating prepared using an aqueous solution of chlorophenol-formaldehyde condensate as described above. The evaluation result of sex is shown. In order to evaluate water resistance, heat resistance, and oil resistance, the tensile strength retention of each test piece 1 after the MIT flex test was measured.

  As shown in Table 3, the heat resistance is the tensile strength of both the rubber reinforcing glass fibers of the present invention shown in Examples 1 to 8 and the rubber reinforcing glass fibers not in the category of the present invention shown in Comparative Examples 1 to 4. The thickness retention was in the range of 35.4% to 41.5%, which was an equivalent measurement result.

  Further, the water resistance of the rubber reinforcing glass fibers of the present invention shown in Examples 1 to 8 and the rubber reinforcing glass fibers of Comparative Examples 1 to 4 which are not in the category of the present invention are 82. It was in the range of 0.0% to 92.3% and was the same measurement result. This is due to the effect that the bisallylnadiimide (E) contained in the secondary coating layer of the glass fiber for reinforcing rubber suppressed water from penetrating into the primary coating layer.

  In comparison, the oil resistance is in the range of 64.5% to 88.8% tensile strength retention of the glass fiber for rubber reinforcement of the present invention shown in Examples 1-8. The tensile strength retention rate of the glass fiber for reinforcing rubber not included in the category of the present invention shown in No. 4 was in the range of 46.7% to 52.6%, and the glass fiber for rubber reinforcing of the present invention was excellent.

  The rubber reinforcement of Examples 1 to 4 using a phenol-formaldehyde condensate (A), an acrylonitrile-butadiene copolymer (B), and a chlorosulfonated polyethylene (D) as the composition of the primary coating layer The glass fiber for rubber reinforcement of Example 1 using resorcinol-formaldehyde condensate as the phenols-formaldehyde condensate (A) in the glass fiber for use has a tensile strength retention of 64.5%, and monohydroxybenzene -Tensile strength retention of rubber reinforcing glass fiber of Example 2 using formaldehyde condensate is 80.3%, and using chlorophenol-formaldehyde condensate as phenols-formaldehyde condensate (A) The tensile strength retention rates of the glass fibers for rubber reinforcement of Examples 3 and 4 were 85.3% and 85.6%, respectively.

  Further, the composition of the primary coating layer of the glass fiber for rubber reinforcement includes an acrylonitrile-butadiene-styrene copolymer as a phenols-formaldehyde condensate (A) and an acrylonitrile-butadiene copolymer (B), vinyl In the glass fiber for rubber reinforcement of Examples 5-8 using pyridine-styrene-butadiene copolymer (C) and chlorosulfonated polyethylene (D), resorcinol-formaldehyde condensation was performed on phenols-formaldehyde condensate (A). The tensile strength retention rate of the glass fiber for rubber reinforcement of Example 5 using a product is 87.5%, and the tensile strength of the glass fiber for rubber reinforcement of Example 6 using a monohydroxybenzene-formaldehyde condensate is used. The retention is 88.8%, and the phenols-formaldehyde condensate (A) Phenol - Each tensile strength retention of rubber-reinforcing glass fiber of the formaldehyde condensates of Examples 7 and 8 used was 88.3% and 85.5%.

Thus, the oil resistance was in the order of resorcin-formaldehyde condensate <monohydroxybenzene-formaldehyde condensate <chlorophenol-formaldehyde condensate.
(Bending test)
Subsequently, the bending running test was implemented about the power transmission belt which embedded the glass fiber for rubber reinforcement produced in Examples 1-8 and Comparative Examples 1-4.
(Water resistance evaluation by bending running test)
Using the glass fiber for rubber reinforcement produced in Examples 1 to 8 and Comparative Examples 1 to 4 as a reinforcing material, using the above heat-resistant rubber as a base rubber, winding it in a loop shape, and then embedding it in a compound of heat-resistant rubber. It put in the stick | sticker type | mold, was hardened by applying heat, each produced the transmission belt as a toothed belt of width 19mm and length 876mm, and the water-resistant running fatigue test for evaluating water resistance was implemented. For water resistance, the transmission belt is run using gears, that is, pulleys under water injection, and the elongation after a certain period of time and the tensile strength retention ratio after a certain period of time, that is, the water resistance running fatigue performance is evaluated.

  FIG. 3 is a perspective view when a transmission belt produced by embedding rubber reinforcing glass fibers in heat-resistant rubber is cut.

  As shown in FIG. 3, the transmission belt 5 has a large number of projections 5A having a height of 3.2 mm for meshing with pulleys, and the thickness of the back part 5B excluding the projections is 2.0 mm. In 5B, as shown in the cross section, S twist, 6 Z twist, 6 and 12 glass reinforcing fibers 6 in total, which have different twist directions of the upper twist and the lower twist, are S twist and Z twist. Are buried in a state of being wound on a loop so as to alternate.

  FIG. 4 is a schematic side view of a water resistance running fatigue tester for a transmission belt.

  As shown in FIG. 4, each transmission belt 5 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 5 travels while the driven pulleys 8 and 9 are rotated by the driving force of the driving pulley 7 that is rotationally driven by a driving motor (not shown). The driven pulley 8 is connected to a generator (not shown), and drives the generator to generate 1 kW of electric power. The idler 10 has a role of tensioning the transmission belt 5 while rotating during traveling in the water resistance traveling fatigue test, and gives 50 N to the transmission belt 5 as a load for tensioning the transmission belt 5. The driven pulleys 8 and 9 have a diameter, 60 mm, the number of teeth, and 20T, and the driving pulley 7 has a diameter of 120 mm, and the number of teeth, 40T. The rotational speed per minute of the driving pulley 7 during the water resistance running fatigue test is 3000 rpm, and the rotational speed per minute of the driven pulleys 8 and 9 is 6000 rpm. The direction of rotation is indicated by an arrow parallel to the transmission belt 5.

  At normal temperature, as shown in FIG. 4, 6000 ml of water 11 per hour is dropped evenly on the transmission belt 1 between the driving pulley 7 and the driven pulley 8 while rotating the driving pulley 7 at 3000 rpm to transmit power. The belt 1 was run using driven pulleys 8 and 9 and an idler 10. In this way, a water-resistant running fatigue test was conducted in which the transmission belt 5 was run until it broke.

The tensile strength of the transmission belt 5 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 5 produced using the rubber reinforcing glass 6 of Examples 1 to 8 and Comparative Examples 1 to 4 was comparatively evaluated.
(Tensile strength measurement)
The length of the test piece used for the measurement of tensile strength is 257 mm, and three pieces can be cut from one transmission belt 5. Each end of these test pieces was clamped with a clamp having a distance of 145 mm between the clamps, the pulling speed was 50 mm / min, and the maximum resistance value until the transmission belt 5 was broken was the tensile strength. The resistance value was measured three times from one transmission belt 5, and the average value was taken as the tensile strength of the transmission belt 5. In addition, the tensile strength before a test measured the resistance value 3 times from ten similarly produced | generated transmission belts 5, and used the average value as an initial value.

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

  Table 4 shows the running time until belt breakage and the tensile strength retention after the water-resistant running fatigue test of each transmission belt in the water-resistant running fatigue test.

  As shown in Table 4, the coating for primary coating comprising the phenols-formaldehyde condensate (A) acrylonitrile-butadiene copolymer (B) and chlorosulfonated polyethylene (D) shown in Examples 1 to 8 as compositions. A primary coating layer that is applied to the strand and then dried, and the composition of the secondary coating layer is composed of chlorosulfonated polyethylene (D), p-dinitosolobenzene, bisallylna Tensile strength retention after a running test of the transmission belt 6 using a coating solution for secondary coating of rubber reinforcing glass fiber consisting of NN′-hexamethylene diallyl nadiimide belonging to diimide (E) and carbon black is: Example 1 was 42%, Example 2 was 38%, Example 3 was 43%, and Example 4 was 40%. Further, the time until the belt broke was 53 to 57 hr.

  As shown in Table 4, the phenols-formaldehyde condensate (A), acrylonitrile-butadiene copolymer (B) as shown in Examples 5 to 8, and vinylpyridine-styrene- A primary coating layer obtained by coating a butadiene copolymer (C) and a chlorosulfonated polyethylene (D) coating solution for the primary coating on a strand and then drying, and a secondary coating layer; The composition of the next coating layer is for reinforcing rubber comprising chlorosulfonated polyethylene (D), p-dinitosolobenzene, NN'-hexamethylene diallyl nadiimide belonging to bisallyl nadiimide (E) and carbon black. The tensile strength retention after the running test of the transmission belt 6 using the glass fiber secondary coating coating solution was 44% in Example 5, Example 6 was 47%, Example 7 was 45%, and Example 8 was 46%. The time until the belt breaks was 58 to 63 hr.

  On the other hand, the transmission belt 5 not included in the category of the present invention shown in Comparative Examples 1 to 4 is 44% for Comparative Example 1, 38% for Comparative Example 2, 42% for Comparative Example 3, and 39% for Comparative Example 4. there were. Further, the time until the belt broke was 50 to 53 hr.

  From the results of this water resistance running fatigue test, the phenols-formaldehyde condensate (A) of Examples 1 to 4 and the vinylpyridine-styrene-butadiene copolymer (B) as compared with the conventional rubber reinforcing glass fiber. And NN'-hexamethylene belonging to bisallylnadiimide (E), which has a primary coating layer formed by applying a coating solution for primary coating comprising chlorosulfonated polyethylene (D) and drying after coating The rubber reinforcing glass fiber 6 of the present invention having a further secondary coating layer composed of diallyl nadiimide, chlorosulfonated polyethylene (D) as a halogen-containing polymer, and p-dinitosolobenzene was used. It has been found that the transmission belt 5 has equivalent or higher water resistance.

  Furthermore, the phenols-formaldehyde condensate (A) of Examples 5 to 8, the acrylonitrile-butadiene-styrene copolymer as the acrylonitrile-butadiene copolymer (B), and the vinylpyridine-styrene-butadiene copolymer ( C) and NN ′ belonging to bisallylnadiimide (E), which has a primary coating layer formed by applying and drying a coating solution for primary coating comprising chlorosulfonated polyethylene (D) as a composition. -Hexamethylene diallyldiimide, chlorosulfonated polyethylene (D) as a halogen-containing polymer, and a glass fiber for reinforcing rubber 6 of the present invention having a further secondary coating layer composed of p-dinitosolobenzene It has been found that the transmission belt 5 using the belt has further water resistance.

This is due to the effect that the bisallyl nadiimide (E) contained in the secondary coating layer suppresses the penetration of water into the primary coating layer.
Further, the difference in water resistance between Examples 1 to 4 and Examples 5 to 8 shown in Table 4 is that Examples 5 to 8 are acrylonitrile instead of acrylonitrile-butadiene binary copolymer in the primary coating layer. -By using butadiene-styrene terpolymer and containing vinylpyridine-styrene-butadiene copolymer (C) (heat resistance evaluation)
Subsequently, the glass fiber for rubber reinforcement produced in Examples 1 to 8 and Comparative Examples 1 to 4 was used as a reinforcing material, and the above heat resistant rubber was used as a base rubber, and the width was 19 mm in the same manner as in the above water resistance evaluation test. Each of the transmission belts 5 having a length of 876 mm was produced and subjected to a heat-resistant and bending-resistant running fatigue test for evaluating heat resistance. The heat resistance is evaluated by running the transmission belt 5 while bending it using a plurality of gears, that is, pulleys, at a high temperature, and maintaining the tensile strength retention rate after a certain period of time, that is, the heat resistance bending resistance running fatigue performance. .

  FIG. 5 is a schematic side view of a heat-resistant bending-resistant running fatigue tester for a transmission belt.

As shown in FIG. 5, each transmission belt 5 is mounted on a heat-resistant and bending-resistant running fatigue tester equipped with a drive motor (not shown), and heat resistance is measured. Transmission belt 5 by the driving force of the driving pulley 12 which is rotated by a driving motor, the three driven pulleys 13 and 13 ', travels while rotating the 13 ^〃. The idler 14 is for tensioning the transmission belt 5 during traveling in the heat-resistant bending resistance running fatigue test, has a role of tensioning the transmission belt 5, and gives 50 N to the transmission belt 1 as a load for tensioning the transmission belt 5. . The driving pulley 12 has a diameter of 120 mm and the number of teeth of 40 T, and the driven pulleys 13, 13 ′ and 13 ^〃 have a diameter of 60 mm and the number of teeth of 20 T. The rotational speed per minute of the driving pulley 12 during the heat resistance and bending resistance fatigue test is 3000 rpm, and the rotational speed per minute of the driven pulleys 13, 13 ′, and 13 ^〃 is 6000 rpm. The direction of rotation is indicated by an arrow parallel to the transmission belt 5.

Temperature, under 130 ° C. of environment, as shown in FIG. 5, the drive pulley 12, is rotated at 3000 rpm, the transmission belt 5 driven pulley 13, 13 ', 13 ^〃, was run while bending with the idler 14 It was. In this way, the power transmission belt 5 was run for 50 hours, and a heat-resistant and bending-proof running fatigue test was performed. The tensile strength of the transmission belt 5 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 5 produced using the glass fibers 6 for reinforcing rubber of Examples 1 to 8 and Comparative Examples 1 to 4, that is, heat resistance, were comparatively evaluated.
(Elongation measurement)
The length after the heat-resistant bending-resistant running fatigue test was measured, and the difference from the length of the transmission belt 5 before the heat-resistant bending-resistant running fatigue test was defined as elongation. Specifically, the length of the transmission belt 5 after traveling for 300 hours was measured, and the difference from the length of the transmission belt 5 before traveling was defined as elongation. Table 5 shows the measurement results of the elongation of each transmission belt 5.

  As shown in Table 5, for the primary coating comprising the phenols-formaldehyde condensate (A), acrylonitrile-butadiene copolymer (B) and chlorosulfonated polyethylene (D) shown in Examples 1 to 4 as compositions. The coating liquid is applied to the strand and then dried, and has a primary coating layer and an additional secondary coating layer. The composition of the secondary coating layer is chlorosulfonated polyethylene (D), p-dinitrosolobenzene, The elongation retention after a 36-hour running test of the transmission belt 5 using a coating liquid for secondary coating of rubber fibers for rubber reinforcement consisting of NN'-hexamethylenediallylnadiimide belonging to Lunadiimide (E) and carbon black is Example 1 was 0.07 mm, Example 2 was 0.05 mm, Example 3 was 0.09 mm, and Example 4 was 0.07 mm.

  Further, the phenols-formaldehyde condensate (A) shown in Examples 5 to 8, the acrylonitrile-butadiene-styrene copolymer as the acrylonitrile-butadiene copolymer (B), and the vinylpyridine-styrene-butadiene copolymer. A primary coating layer obtained by applying (C) and a coating solution for primary coating composed of chlorosulfonated polyethylene (D) to the strand and then drying the strand; and a secondary coating layer, and a secondary coating layer. A glass fiber secondary fiber for rubber reinforcement comprising a composition comprising chlorosulfonated polyethylene (D), p-dinitrosolobenzene, NN'-hexamethylenediallylnadiimide belonging to bisallylnadiimide (E) and carbon black The elongation retention after the 36-hour running test of the transmission belt 5 using the coating liquid for coating is 0.06 mm in Example 5, and Example 6 was 0.03 m, Example 7 was 0.05 mm, and Example 8 was 0.04 mm.

  Compared with Examples 1 to 4, Examples 5 to 8 showed less elongation. Thus, as a result of the bending running test, a transmission belt having a well-balanced combination of dimensional stability, heat resistance, water resistance and oil resistance was obtained.

  On the other hand, the transmission belt 5 which is not in the category of the present invention shown in Comparative Examples 1 to 4 is that Comparative Example 1 is 0.34 mm, Comparative Example 2 is 0.36 mm, Comparative Example 3 is 0.35 mm, and Comparative Example 4 is It was 0.37 mm, and was inferior in dimensional stability in bending running of the transmission belt.

Comparative example in which the acrylonitrile-butadiene copolymer (B) is contained in the primary coating layer and the transmission belt of Examples 1 to 8 has little elongation and the primary coating layer does not use the acrylonitrile-butadiene copolymer (B). The elongation of the transmission belts 1 to 8 was large because the three-dimensional crosslinking of the primary coating layer proceeded with the acrylonitrile-butadiene copolymer (B) contained in the primary coating layer. This seems to be due to the effect of increasing the durability of the initial adhesive strength of the glass fiber 6 and the base rubber HNBR.
(Tensile strength retention rate)
Tables 9 and 10 show the tensile strength retention ratios of the respective transmission belts after the heat-resistant and bending-resistant running fatigue test.

  As shown in Table 6, phenols-formaldehyde condensate (A), acrylonitrile butadiene (B) and chlorosulfonated polyethylene (D) were used for the primary coating layer, and chlorosulfonated polyethylene ( D) and bisallyl nadiimide (E) using the glass fiber 6 for rubber reinforcement of Examples 1 to 4 were used, and the tensile strength retention after the heat-resistant and bending-resistant running fatigue test of the transmission belt 1 was 97 respectively. %, 98%, 101%, and 103%.

  In the primary coating layer, phenols-formaldehyde condensate (A), acrylonitrile-butadiene-styrene copolymer (C) as acrylonitrile butadiene (B), vinylpyridine-styrene-butadiene copolymer (C), and chloro Transmission produced using the glass fiber 6 for reinforcing rubber of Examples 5 to 8 using sulfonated polyethylene (D) and chlorosulfonated polyethylene (D) and bisallylnadiimide (E) in the secondary coating layer. The tensile strength retention ratios of the belt 1 after the heat-resistant bending-resistant running fatigue test were 99%, 104%, 103%, and 101%, respectively.

  On the other hand, the tensile strength retention after the heat-resistant bending-resistant running fatigue test of the transmission belt 5 using the glass fiber 6 for rubber reinforcement of Comparative Examples 1 to 4 not belonging to the category of the present invention is 93%, They were 91%, 92%, and 93%. In contrast to the transmission belt 5 using the glass fibers 6 for rubber reinforcement of Comparative Examples 1 to 4, the transmission belt 5 using the glass fibers 6 for rubber reinforcement of Examples 1 to 8 has a high tensile strength retention rate and is excellent. Heat resistance.

  In Examples 3 and 4, the tensile strength retention exceeded 100% because the three-dimensional crosslinking of the primary coating layer was heated by the acrylonitrile-butadiene copolymer (B) contained in the primary coating layer. This seems to be an effect of the progress made.

  From the results of this heat and bending resistance running fatigue test, a coating solution for primary coating comprising a phenols-formaldehyde condensate (A), an acrylonitrile-butadiene copolymer (B) and a chlorosulfonated polyethylene (D) as a composition. NN'-hexamethylene diallyldiimide belonging to bisallylnadiimide (E), chlorosulfonated polyethylene (D) belonging to halogen-containing polymer, p -The transmission belt 5 using the glass fiber 6 for rubber reinforcement of the present invention of Examples 1 to 4 having a further secondary coating layer composed of dinitrosolobenzene has excellent heat resistance and bending resistance. I found out.

  In addition, the primary coating layer includes phenols-formaldehyde condensate (A), acrylonitrile-butadiene-styrene copolymer as acrylonitrile butadiene (B), vinylpyridine-styrene-butadiene copolymer (C), And NN'-hexamethylene belonging to bisallylnadiimide (E), which has a primary coating layer formed by applying a coating solution for primary coating comprising chlorosulfonated polyethylene (D) and drying after coating For reinforcing rubber according to the present invention of Examples 5 to 8 having a further secondary coating layer composed of diallyl nadiimide, chlorosulfonated polyethylene (D) belonging to a halogen-containing polymer, and p-dinitrosolobenzene It was found that the transmission belt 5 using the glass fiber 6 has further excellent heat resistance and bending resistance.

  The glass fibers 6 for rubber reinforcement of Examples 1 to 8 have excellent adhesive strength with HNBR, and the transmission belts produced using the glass fibers 6 for rubber reinforcement of Examples 1 to 8 have excellent dimensional stability. Since it has heat resistance, water resistance and oil resistance, it is suitable for use as a core wire of a transmission belt for automobiles such as a timing belt which is used for a long time under high temperature and high humidity. In particular, the transmission belts shown in Examples 5 to 8 can be a timing belt that has a high level of dimensional stability, heat resistance, water resistance, and oil resistance and is extremely excellent in durability.

  According to the present invention, there is obtained a glass fiber coating coating solution for providing a glass fiber cord coating layer that gives a preferable adhesive strength to the adhesion of the glass fiber cord and the crosslinked HNBR as the base rubber. , Excellent dimensional stability in bending when the rubber fiber reinforcing glass fiber coated with the glass fiber coating solution is dried and coated on the glass fiber cord to form a transmission belt embedded in a cross-linked HNBR Heat resistance, water resistance and oil resistance were imparted, and the transmission belt was provided with dimensional stability, heat resistance, water resistance and oil resistance. Therefore, the glass fiber for rubber reinforcement of the present invention is used by being embedded in a transmission belt for transmitting a driving force of a driving source such as an engine or a motor for reinforcement. Especially when used as a power transmission belt for automobiles by embedding in HNBR to be used for power transmission belts for cars such as timing belts. Maintains tensile strength and provides dimensional stability even after severe bending under high temperature and high humidity or in the presence of oil.

It is a schematic diagram of the test piece of a MIT bending test. It is a schematic diagram of the test condition of a MIT bending test. 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

1 Test piece 2 HNBR
3 Glass fiber for rubber reinforcement 4 Weight 5 Transmission belt 5A Protruding part 5B Back part 6 Glass fiber for rubber reinforcement 7 Drive pulley (connected to drive motor)
8 Driven pulley 9 Driven pulley (connected to generator)
10 idler
11 Water 12 Drive pulley 13, 13 ', 13 ^〃 Follow pulley 14 Idler

Claims (6)

Phenols-formaldehyde condensate (A) selected from chlorophenol-formaldehyde condensate, resorcin-monohydroxybenzene-formaldehyde condensate, resorcin-chlorophenol-formaldehyde condensate on a strand in which a plurality of glass fiber filaments are bundled And forming a primary coating layer containing acrylonitrile-butadiene copolymer (B), and providing a secondary coating layer containing chlorosulfonated polyethylene (D) and bisallylnadiimide (E) as an upper layer. In the glass fiber for rubber reinforcement
The total mass of (A) and (B) in the primary coating layer is expressed as a mass percentage based on 100%, and (A) is expressed as A / (A + B) = 1 in the primary coating layer. 0.0% or more and 55.0% or less, and (B) is contained in the range of B / (A + B) = 45.0% or more and 99.0% or less, for reinforcing a transmission belt rubber Glass fiber. Phenols-formaldehyde condensate (A) selected from chlorophenol-formaldehyde condensate, resorcin-monohydroxybenzene-formaldehyde condensate, resorcin-chlorophenol-formaldehyde condensate on a strand in which a plurality of glass fiber filaments are bundled Primary coating layer containing acrylonitrile-butadiene copolymer (B) and vinylpyridine-butadiene-styrene copolymer (C) is formed, and chlorosulfonated polyethylene (D) and bisallyl nadiimide are formed thereon. In a glass fiber for reinforcing rubber of a transmission belt provided with a secondary coating layer containing (E),
The mass of the (A), (B) and (C) in the primary coating layer is expressed as a mass percentage based on 100%, and the (A) is added to the primary coating layer by A / ( A + B + C) = 1.0% or more, 40.0% or less, (B) is B / (A + B + C) = 1.0% or more, 55.0% or less, (C) is C / (A + B + C) = Glass fiber for reinforcing rubber of a transmission belt, characterized by containing in the range of 10.0% or more and 70.0% or less . Phenols-formaldehyde condensate (A) selected from chlorophenol-formaldehyde condensate, resorcin-monohydroxybenzene-formaldehyde condensate, resorcin-chlorophenol-formaldehyde condensate on a strand in which a plurality of glass fiber filaments are bundled Forming a primary coating layer containing acrylonitrile-butadiene copolymer (B) and chlorosulfonated polyethylene (D), and containing chlorosulfonated polyethylene (D) and bisallylnadiimide (E) as an upper layer In the glass fiber for rubber reinforcement formed by providing the secondary coating layer, the mass (%) based on 100% of the total mass of (A), (B) and (D) in the primary coating layer is expressed. And (D) is added to the primary coating layer, D / (A + B + D) = 1.0% Furthermore, rubber-reinforcing glass fiber of the driving belt, characterized in that it contains in the range of less than 40.0%. Phenols-formaldehyde condensate (A) selected from chlorophenol-formaldehyde condensate, resorcin-monohydroxybenzene-formaldehyde condensate, resorcin-chlorophenol-formaldehyde condensate on a strand in which a plurality of glass fiber filaments are bundled A primary coating layer containing acrylonitrile-butadiene copolymer (B), vinylpyridine-butadiene-styrene copolymer (C) and chlorosulfonated polyethylene (D) is formed, and chlorosulfonated polyethylene is formed thereon. In the glass fiber for rubber reinforcement formed by providing a secondary coating layer containing (D) and bisallylnadiimide (E), (A), (B), and (C) in the primary coating layer Mass percentage based on 100% of the combined mass of (D) Expressed in, the (D) to the first covering layer, D / (A + B + C + D) = 1.0% or more, rubber-reinforcing glass fiber of the driving belt, characterized in that is contained in the range of less than 40.0% . Expressing the mass of the chlorosulfonated polyethylene (D) contained in the secondary coating layer as a mass percentage based on 100%, the content of bisallylnadiimide (E) is E / D = 0.3% or more, 10 The glass fiber for reinforcing rubber of a transmission belt according to any one of claims 1 to 4 , wherein the glass fiber is 0.0% or less. The glass for reinforcing rubber of a power transmission belt according to any one of claims 1 to 5 , wherein the acrylonitrile-butadiene copolymer (B) is an acrylonitrile-butadiene-styrene terpolymer. fiber.

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