JP2009228194A - Coating liquid for coating glass fiber and glass fiber using the same and used for reinforcing rubber - 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 HNBR 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: Provided is the transmission belt 5 prepared by embedding glass fibers 6 used for reinforcing a rubber and produced by coating the coating liquid containing a monohydroxybenzene-formaldehyde condensate produced by condensation-reacting a monohydroxybenzene and formaldehyde in water, and acrylonitrile-butadiene copolymer as essential components and used for coating the glass fibers on the glass fiber cords, in a hydrogenated nitrile rubber. In order to improve durability, vinyl pyridine-butadiene-styrene copolymer and chlorosulfonated polyethylene are preferably added to a primary coating layer. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention uses a glass fiber coating coating solution for providing a coating layer on a rubber reinforcing glass fiber for embedding and reinforcing it as a core wire in a base material rubber when producing a transmission belt, and the same. The present invention relates to a rubber reinforcing glass fiber and a rubber transmission belt in which the rubber reinforcing glass fiber is embedded as a core wire for reinforcement. The glass fiber coating coating solution and the glass fiber for reinforcing rubber using the same of the present invention are particularly useful as a reinforcing core wire for an automobile timing belt.

  In order to provide tensile strength and dimensional stability to rubber products such as transmission belts and tires, it is common to embed high tensile strength fibers such as glass fibers, nylon fibers and polyester fibers as a reinforcing material in the base rubber. The rubber reinforcing fiber embedded in the base rubber is required to have a strong interface with the base rubber so that it does not peel off. However, even if a glass fiber cord such as a strand obtained by spraying and applying a sizing agent containing a silane coupling agent and a resin to a large number of glass fiber filaments is embedded in the base rubber as it is, the adhesion is weak and the interface is weak. Peels off and does not serve 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 in a driving situation in which a rubber fiber reinforced glass fiber subjected to the coating process is embedded, it continues to bend at high temperatures. The initial bond strength between the rubber reinforcing glass fiber and the base rubber may not be maintained, and the interface between the rubber reinforcing glass fiber and the base rubber may be peeled off after bending for a long time.

  The power transmission belt for automobiles retains its tensile strength and stretches after being bent for a long time 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 to it. No dimensional stability is required. 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 has come to be used, and further improvement in durability is desired.

  In addition to heat resistance that maintains the initial bond strength between the glass fiber cord and the base rubber even when the belt is bent for a long time at high temperatures, it can be covered even if it is bent for a long time while water is applied to the belt. The development of transmission belts with glass fibers for rubber reinforcement that give the transmission belts water resistance that maintains the initial bond strength by preventing water from penetrating into the glass fibers 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 made of resorcin-formaldehyde condensate, vinylpyridine-butadiene-styrene copolymer, chlorosulfonated polyethylene. The dried glass fiber for reinforcing rubber was embedded in HNBR as heat resistant rubber. Further, in order to enhance the adhesion between the glass fiber cord and HNBR, and thus heat resistance, the glass fiber cord for reinforcing rubber 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. As a reinforcing fiber for rubber suitable for reinforcement, particularly as a reinforcing fiber for rubber suitable for obtaining a toothed belt having high tooth root strength, a water-soluble condensate of resorcin formaldehyde on a core made of glass fiber, vinyl A rubber reinforcing fiber formed with a layer comprising a pyridine-butadiene-styrene copolymer latex and an acrylonitrile-butadiene copolymer latex is disclosed.

  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.

  In addition, in Patent Document 4 relating to the patent application of the present applicant, a primary coating layer containing an acrylate resin, a vinylpyridine-butadiene-styrene 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 applicant's patent application, 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.

  Further, for the purpose of improving water resistance when used as a transmission belt, Patent Document 6 relating to the patent application of the present applicant includes monohydroxybenzene-formaldehyde condensate, vinylpyridine-butadiene-styrene copolymer and chlorosulfone. Disclosed is a coating solution for coating glass fibers for coating a glass fiber cord in which a modified polyethylene is dispersed in water to form an emulsion.

  Further, in Patent Documents 7 to 11 relating to the patent application of the present applicant, the glass fiber coating coating liquid 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 processing 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 2006-63726 A JP 2006-63727 A JP 2006-63728 A JP 2006-63729 A JP 2002-339255 A Japanese Patent Laid-Open No. 2003-253569 JP 2003-268678 A JP 2004-100059 A

  A power transmission belt produced by embedding a rubber reinforcing glass fiber provided with a coating layer containing a conventional resorcin-formaldehyde condensate and vinylpyridine-butadiene-styrene copolymer as a core wire in HNBR continues to bend and run. The transmission belt is stretched and heat resistance is poor. In particular, a timing belt that continues to bend in an engine room at a high temperature is not allowed to extend a little, and in addition, excellent heat resistance is required.

  In addition, due to contact penetration with engine oil at high temperatures, the coating layer of the rubber reinforcing glass fiber embedded in the transmission belt for automobiles is likely to be altered, leading to a decrease in the adhesion between the rubber reinforcing glass fiber and HNBR and peeling of the interface. Sometimes. This alteration occurs because the vinylpyridine-butadiene-styrene copolymer has poor oil resistance.

  Therefore, in the presence of resorcin-formaldehyde condensate, instead of vinylpyridine-butadiene-styrene copolymer, an acrylonitrile-butadiene copolymer with excellent oil resistance was used as a coating material to produce rubber reinforcing glass fibers. Although the oil resistance of the bolt is improved, there is a problem that the water resistance is lowered.

  Thus, in the presence of the resorcin-formaldehyde condensate, even if acrylonitrile-butadiene copolymer having excellent oil resistance is added as a coating material instead of vinylpyridine-butadiene-styrene copolymer, In the bending running of the buried 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 usage time for 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. An object of the present invention is to provide a glass fiber for reinforcing rubber that imparts a good balance of 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. Severe bending due to the heat resistance that keeps the initial bond strength even when bent and the oil resistance that keeps the initial bond strength even if the cover layer runs 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 even after running for a long time.

  In order to solve the above problem, the present inventors diligently studied. As a result, a monohydroxybenzene was formed on a strand formed by applying and bundling a sizing agent containing a silane coupling agent and a resin to a plurality of glass fiber filaments. -When a glass fiber coating coating solution prepared by mixing an emulsion of acrylonitrile-butadiene copolymer (B) with an aqueous solution of formaldehyde condensate (A) is applied and dried, the coating layer may be brought into contact with engine oil at a high temperature. It was found that alteration was 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.

  Transmission belt using rubber-reinforced glass fiber containing a resorcin-formaldehyde condensate and vinylpyridine-butadiene-styrene copolymer as components, and forming a primary coating layer not containing acrylonitrile-butadiene copolymer (B) In comparison with the transmission belt, the power transmission belt using the glass fiber for rubber reinforcement formed with the primary coating layer containing the resorcin-formaldehyde condensate and the acrylonitrile-butadiene copolymer (B) as essential components is Excellent dimensional stability.

  Moreover, the glass fiber for rubber reinforcement which provided the primary coating layer which contained a resorcinol-formaldehyde condensate and a vinylpyridine-butadiene-styrene copolymer as a component and did not contain an acrylonitrile-butadiene copolymer (B) was used. Compared with a transmission belt, a transmission belt using a glass fiber for rubber reinforcement in which a primary coating layer containing a resorcin-formaldehyde condensate (A) and an acrylonitrile-butadiene copolymer (B) as essential components is formed. The excellent dimensional stability is that when the coating solution for primary coating containing resorcin-formaldehyde condensate and acrylonitrile-butadiene copolymer (B) is applied to the strand and heated to evaporate and cure the moisture, acrylonitrile-butadiene is used. Because copolymer (B) has a nitrile group, it is due to three-dimensional crosslinking. , Promotes the formation of a tough polymer matrix, gives an excellent coating layer to the glass fiber for rubber reinforcement, and the transmission belt using the glass fiber for rubber reinforcement is excellent in dimensional stability even if it is bent, that is, By not growing.

  However, heat resistance and water resistance cannot be obtained only by forming a primary coating layer containing resorcin-formaldehyde condensate and acrylonitrile-butadiene copolymer (B) as main components on glass fiber for rubber reinforcement.

  In the present invention, a resorcin-formaldehyde condensate obtained by condensation reaction of formaldehyde and water with two OH groups that are hydrophilic groups added to the benzene ring is replaced with 1 OH group that is a hydrophilic group on the benzene ring. By combining the monohydroxybenzene-formaldehyde condensate (A) obtained by condensation reaction of the added monohydroxybenzene with formaldehyde in water and combining the acrylonitrile-butadiene copolymer (B), the glass fiber for rubber reinforcement is formed. Improved heat resistance and water resistance.

  Specifically, the resorcin-formaldehyde condensate is a condensate formed by condensing resorcin and formaldehyde in which two OH groups as hydrophilic groups are added to the benzene ring, and the monohydroxybenzene-formaldehyde condensate (A) is: It is a compound obtained by condensing monohydroxybenzene having one OH group as a hydrophilic group added to the benzene ring and formaldehyde, and is more hydrophobic than the resorcin-formaldehyde condensate. Therefore, in addition to the acrylonitrile-butadiene copolymer (B), a hydrophobic monohydroxybenzene-formaldehyde condensate (A) is used in place of the resorcin-formaldehyde condensate as the composition of the rubber reinforcing glass fiber coating material. By using it, both water resistance and oil resistance when using a transmission belt were improved. Thus, in the presence of resorcin-formaldehyde condensate, instead of vinylpyridine-butadiene-styrene copolymer, acrylonitrile-butadiene copolymer (B) having excellent oil resistance is used as a coating layer for rubber reinforcing glass fiber. This solves the problem that the water resistance of the transmission belt is improved while the oil resistance of the transmission belt is improved.

  Thus, the water resistance of the monohydroxybenzene-formaldehyde condensate (A) and the monohydroxybenzene-formaldehyde condensate (A) and the oil resistance of the acrylonitrile-butadiene copolymer (B) are given to the coating layer in a well-balanced manner. Therefore, the coating solution for coating glass fibers of the present invention comprises a monohydroxy benzene-formaldehyde condensate (A) produced by a condensation reaction of monohydroxy benzene and formaldehyde in water, and an acrylonitrile-butadiene copolymer (B). And containing. Specifically, an aqueous solution of a monohydroxy benzene-formaldehyde condensate (A) produced by a condensation reaction of monohydroxy benzene and formaldehyde in water and an emulsion of acrylonitrile-butadiene copolymer (B) are contained.

  That is, the present invention provides a glass fiber coating coating solution containing a monohydroxy benzene-formaldehyde condensate (A) and an acrylonitrile-butadiene copolymer (B) produced by condensation reaction of monohydroxy benzene and formaldehyde in water. It is.

  Furthermore, the present invention represents a monohydroxybenzene-formaldehyde condensate represented by a mass percentage based on 100% of the total mass of the monohydroxybenzene-formaldehyde condensate (A) and the acrylonitrile-butadiene copolymer (B). (A), A / (A + B) = 1.0% or more, 55.0% or less, acrylonitrile-butadiene copolymer (B), B / (A + B) = 45.0% or more, 99.0% It contains in the following ranges, It is said glass fiber coating coating liquid characterized by the above-mentioned.

  Further, the vinylpyridine-butadiene-styrene copolymer (C) is added to the glass fiber coating coating solution, and the composition ratio with the acrylonitrile-butadiene copolymer (B) is selected as the composition of the primary coating layer. By this, it becomes possible to obtain water resistance and oil resistance in a balanced manner in a transmission belt in which rubber reinforcing glass fibers are embedded in HNBR as a base rubber.

  Further, the present invention is the above-mentioned coating solution for coating a glass fiber, which further contains a vinylpyridine-butadiene-styrene copolymer (C).

  Furthermore, the present invention provides a mass based on 100% of the total mass of monohydroxybenzene-formaldehyde condensate (A), acrylonitrile-butadiene copolymer (B) and vinylpyridine-butadiene-styrene copolymer (C). Expressed as a percentage, the monohydroxybenzene-formaldehyde condensate (A) is A / (A + B + C) = 1.0% or more and 40.0% or less, and the acrylonitrile-butadiene copolymer (B) is B / (A + B + C). ) = 1.0% or more, 55.0% or less, vinylpyridine-butadiene-styrene copolymer (C) is contained in a range of C / (A + B + C) = 10.0% or more and 70.0% or less. This is a coating solution for coating a glass fiber as described above.

  Furthermore, it has been found that when a coating layer is formed by adding an emulsion of chlorosulfonated polyethylene (D) to a coating solution for coating glass fibers, the heat resistance of the transmission belt using glass fibers for rubber reinforcement as the core wire is improved. As described above, further heat resistance is imparted to the transmission belt formed by embedding the rubber reinforcing glass fiber in which the glass fiber coating coating solution of the present invention is applied to the strand in which a plurality of glass fiber filaments are bundled in the base rubber. For this purpose, an emulsion of chlorosulfonated polyethylene (D) is further added to the coating solution for coating glass fibers.

  Further, the present invention is the above-described coating solution for coating a glass fiber, which further contains chlorosulfonated polyethylene (D).

  Furthermore, the present invention represents a mass percentage based on 100% of the total mass of monohydroxybenzene-formaldehyde condensate (A), acrylonitrile-butadiene copolymer (B) and chlorosulfonated polyethylene (D), The glass fiber coating coating liquid described above, which contains chlorosulfonated polyethylene (D) in a range of D / (A + B + D) = 1.0% or more and 40.0% or less.

  Furthermore, the present invention combines monohydroxybenzene-formaldehyde condensate (A), acrylonitrile-butadiene copolymer (B), vinylpyridine-butadiene-styrene copolymer (C) and chlorosulfonated polyethylene (D). The chlorosulfonated polyethylene (D) is contained in a range of D / (A + B + C + D) = 1.0% or more and 40.0% or less, expressed as a mass percentage based on 100% by mass. It is the coating liquid for glass fiber coating.

  As described above, by adding chlorosulfonated polyethylene (D) to the rubber-reinforced glass fiber coating layer, heat resistance is imparted to the transmission belt having the rubber-reinforced glass fiber as a core wire. In addition to the water resistance of the monohydroxybenzene-formaldehyde condensate (A) in the coating layer, the dimensional stability and oil resistance of the acrylonitrile-butadiene copolymer (B), the vinylpyridine-butadiene-styrene copolymer (C) In order to give the water resistance of chlorosulfonated polyethylene (D) and the heat resistance of the chlorosulfonated polyethylene (D) in a well-balanced manner, the coating liquid for glass fiber coating of the present invention is a monolith produced by condensation reaction of monohydroxybenzene and formaldehyde in water. A vinylpyridine-butadiene-styrene copolymer (C) and a chlorosulfonated polyethylene (D) are contained using the hydroxybenzene-formaldehyde condensate (A) and the acrylonitrile-butadiene copolymer (B) as essential compounds. More specifically, in addition to an aqueous solution of a monohydroxybenzene-formaldehyde condensate (A) produced by condensation reaction of monohydroxybenzene and formaldehyde in water, and an emulsion of acrylonitrile-butadiene copolymer (B), vinylpyridine-butadiene -The styrene copolymer (C) emulsion and the chlorosulfonated polyethylene (D) emulsion are contained in a balanced manner.

  As described above, the present inventors have prepared a monohydroxybenzene-formaldehyde condensate (A) and an acrylonitrile-butadiene co-polymer so that the coating layer of the glass fiber for rubber reinforcement has a good balance of heat resistance, water resistance and oil resistance. The composition ratio in the coating solution for glass fiber coating containing the vinyl pyridine-butadiene-styrene copolymer (C) and the chlorosulfonated polyethylene (D) was studied with the polymer (B) as an essential component. A preferred content range was obtained.

  In addition, instead of the acrylonitrile-butadiene binary copolymer in the glass fiber coating coating solution of the present invention, an acrylonitrile-butadiene copolymer obtained by adding styrene to the polymerization monomer as a terpolymer of acrylonitrile-butadiene-styrene. Even if (B) is used as the primary coating layer of the glass fiber for reinforcing rubber, an equivalent effect is obtained in dimensional stability due to the effect of containing the nitrile group. 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.

  Furthermore, the present invention is the above-mentioned coating solution for coating glass fibers, wherein the acrylonitrile-butadiene copolymer (B) is an acrylonitrile-butadiene-styrene terpolymer.

  Further, the present invention provides a glass for reinforcing rubber, which is provided with a coating layer obtained by applying the above glass fiber coating coating solution to a glass fiber cord in which a plurality of glass fiber filaments are bundled and then drying. Fiber.

  In addition, a glass fiber coating coating solution obtained by adding an emulsion of acrylonitrile-butadiene copolymer (B) to an aqueous solution of monohydroxybenzene-formaldehyde condensate (A) as an essential component is applied to a glass fiber cord and then dried. In addition to an aqueous solution of monohydroxybenzene-formaldehyde condensate (A) and an emulsion of acrylonitrile-butadiene copolymer (B), a vinylpyridine-butadiene-styrene copolymer (C), After the glass fiber coating coating liquid in which the emulsion of chlorosulfonated polyethylene (D) is mixed is applied to the glass fiber cord, it is dried to form a primary coating layer, and chlorosulfonated polyethylene and bisallyl nadiimide are formed on the upper layer. After coating the coating solution for secondary coating dispersed in an organic solvent, dry When a transmission belt was produced by embedding rubber reinforcing glass fibers provided with a secondary covering layer in HNBR, a preferable initial adhesive strength was obtained for the rubber reinforcing glass fibers and HNBR, and the transmission belt had excellent water resistance. In combination with heat resistance, oil resistance and oil resistance, specifically, it maintains tensile strength even after a long bending test under high temperature, lubrication and water injection, and has excellent dimensional stability in the transmission belt It has been found that a glass fiber for reinforcing rubber is provided.

  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 penetrating into the glass fiber inferior in water resistance.

  Furthermore, the present invention forms a primary coating layer obtained by coating and drying the above glass fiber coating coating solution, and a secondary layer containing chlorosulfonated polyethylene (D) and bisallyl nadiimide (E) as an upper layer. A glass fiber for reinforcing rubber, which is provided with a secondary coating layer coated with a coating liquid for coating.

  In the present invention, the content ratio of chlorosulfonated polyethylene (D) and bisallylnadiimide (E) in the secondary coating layer is expressed as a mass percentage based on 100% of the mass of chlorosulfonated polyethylene (D). E / D = 0.3% or more and 10.0% or less.

  Moreover, this invention is a power transmission belt which embeds said glass fiber for rubber reinforcement in base material rubber | gum.

  Moreover, this invention is said transmission belt which uses HNBR for base material rubber | gum.

  In the present invention, the glass fiber for rubber reinforcement contains, for example, a silane coupling agent as a sizing agent in a large number of glass fiber filaments, which are fine wires protruding from a bushing of a glass melting kiln heated from a glass fiber raw material. A coating layer is provided by spraying and applying the sizing agent and bundling the strands in the glass fiber coating solution so that the glass fiber coating solution is forcibly attached, in other words, coated and dried.

  The glass fiber for rubber reinforcement formed by applying the coating solution for coating glass fiber according to the present invention and providing a coating layer on the glass fiber strand is a heat resistant rubber. For example, when embedded in HNBR, the glass fiber cord and HNBR Gives excellent bond strength. Furthermore, when a transmission belt is embedded in HNBR as a core wire, it has excellent heat resistance, water resistance and oil resistance in a well-balanced manner, and after a long period of bending running as a transmission belt under high temperature and high humidity, rubber There is no fear that the interface between the reinforcing glass fiber and the heat-resistant rubber is peeled off, and the transmission belt maintains the tensile strength and has excellent dimensional stability without any elongation.

  Especially when used as a timing belt for automobiles among power transmission belts, the tensile strength is maintained after bending for a long time in the engine room under high temperature, where water splashes and engine oil, lubricating oil, etc. adheres. In addition, it has excellent dimensional stability without any elongation.

  The glass fiber coating solution is, for example, sprayed and applied to a plurality of glass fiber filaments protruding from the bushing of a glass melting furnace, that is, a glass fiber filament containing a silane coupling agent and a resin, and then focused. The strands are coated and coated to make glass fibers for rubber reinforcement. The application is performed by means such as drying after the strand is bent and forced to adhere in the glass fiber coating solution. When producing a power transmission belt, the glass fiber for rubber reinforcement is embedded in HNBR or the like, which is a base rubber, and used as a core wire.

  The present invention is a coating solution for glass fiber coating containing a monohydroxybenzene-formaldehyde condensate (A) and an acrylonitrile-butadiene copolymer (B) as essential components, and an aqueous solution of the monohydroxybenzene-formaldehyde condensate (A). And an emulsion of acrylonitrile-butadiene copolymer (B) is added thereto.

  Monohydroxybenzene-formaldehyde condensate (A) and acrylonitrile contained in the glass fiber coating solution are used to obtain the desired adhesive strength for the glass fiber for rubber reinforcement and the base rubber when used in a transmission belt. Expressed as a mass percentage based on 100% based on the total mass of the butadiene copolymer (B), the monohydroxybenzene-formaldehyde condensate (A) is 1.0% or more and 55.0% or less, that is, A /(A+B)=1.0% or more, 55.0% or less, and acrylonitrile-butadiene copolymer (B) is 45.0% or more and 99.0% or less, that is, B / (A + B) = 45.0 % Or more and 99.0% or less.

  In the glass fiber coating coating solution of the present invention, when the content of the monohydroxybenzene-formaldehyde condensate (A) in the glass fiber coating coating solution is less than A / (A + B) = 1.0%, the rubber reinforcing coating is used. When the glass fiber coating layer is formed, the adhesive strength between the rubber reinforcing glass fiber and the base rubber becomes weak, and it is difficult to obtain preferable water resistance, heat resistance, and oil resistance when the transmission belt is bent and run. When the content of the monohydroxybenzene-formaldehyde condensate (A) exceeds 55.0%, the glass fiber coating liquid tends to cause aggregation and precipitation and cannot be used. Therefore, the suitable content range of the monohydroxybenzene-formaldehyde condensate (A) in the coating solution for glass fiber coating of the present invention is the same as the acrylonitrile-butadiene copolymer (B) contained in the coating solution for glass fiber coating. Expressed as a percentage by mass based on 100%, A / (A + B) = 1.0% or more and 55.0% or less.

  Further, in the glass fiber coating coating solution of the present invention, when the content of the acrylonitrile-butadiene copolymer (B) in the glass fiber coating coating solution is less than B / (A + B) = 45.0%, rubber reinforcement The adhesive strength between the glass fiber for use and the cross-linked HNBR becomes weak, and it is difficult to obtain preferable heat resistance when the power transmission belt is formed. Moreover, the effect which improves oil resistance is scarce. When the content of the acrylonitrile-butadiene copolymer (B) exceeds B / (A + B) = 99.0%, heat resistance and water resistance are deteriorated. Therefore, the suitable content range of the acrylonitrile-butadiene copolymer (B) in the coating solution for glass fiber coating of the present invention is the monohydroxybenzene-formaldehyde condensate (A) and acrylonitrile- contained in the coating solution for glass fiber coating. Expressed as a mass percentage based on 100% of the total mass of the butadiene copolymer (B), B / (A + B) = 45.0% or more and 99.0% or less.

  Balances water resistance and oil resistance to a transmission belt in which a plurality of glass fiber coating coating solutions or a glass fiber for rubber reinforcement coated on the strands of the glass fiber filaments of the present invention are embedded in a base rubber. In order to achieve a good match, the vinylpyridine-butadiene-styrene copolymer (C) is added to the glass fiber coating solution, and the composition ratio with the acrylonitrile-butadiene copolymer (B) is selected.

  When the vinylpyridine-butadiene-styrene copolymer (C) is added to the composition of the primary coating layer of the glass fiber for reinforcing rubber in order to adjust the water resistance and heat resistance when it is used as a transmission belt, Based on 100% of the total mass of monohydroxybenzene-formaldehyde condensate (A), acrylonitrile-butadiene copolymer (B) and vinylpyridine-butadiene-styrene copolymer (C) contained in the coating solution Expressed as a percentage, the monohydroxybenzene-formaldehyde condensate (A) is 1.0% or more and 40.0% or less, that is, A / (A + B + C) = 1.0% or more and 40.0% or less, acrylonitrile- Butadiene copolymer (B) is 1% to 55%, that is, B / (A + B + C) = 1.0% to 55.0%, vinylpyridine- Tajien - styrene copolymer (C) is 10.0% or more 70.0% or less, i.e., C / (A + B + C) = 10.0% or more is preferably contained in the range of less than 70.0.

  In the glass fiber coating coating solution of the present invention, when the content of the monohydroxybenzene-formaldehyde condensate (A) in the glass fiber coating coating solution is less than A / (A + B + C) = 1.0%, the rubber reinforcing coating is used. When the glass fiber coating material is used, the adhesive strength between the rubber reinforcing glass fiber and the base rubber becomes weak, and it is difficult to obtain a good balance of water resistance, heat resistance and oil resistance when used as a transmission belt. When the content of the monohydroxybenzene-formaldehyde condensate (A) exceeds 40.0%, the coating solution for coating glass fibers is liable to cause aggregation and precipitation and cannot be used. Therefore, the preferable content range of the monohydroxybenzene-formaldehyde condensate (A) in the coating solution for glass fiber coating of the present invention is the monohydroxybenzene-formaldehyde condensate (A) contained in the coating solution for glass fiber coating and acrylonitrile. -The mass of the butadiene copolymer (B) and the vinylpyridine-butadiene-styrene copolymer (C) combined is expressed as a mass percentage based on 100%, and A / (A + B + C) = 1.0% or more, 40 0.0% or less.

  Further, in the glass fiber coating coating solution of the present invention, when the content of the acrylonitrile-butadiene copolymer (B) in the glass fiber coating coating solution is less than B / (A + B + C) = 1.0%, glass fiber Adhesive strength between the HNBR and the cross-linked HNBR becomes weak, and it is difficult to obtain excellent heat resistance when a transmission belt is formed. 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 coating solution for glass fiber coating of the present invention is the monohydroxybenzene-formaldehyde condensate (A) and acrylonitrile- contained in the coating solution for glass fiber coating. B / (A + B + C) = 1.0% or more, expressed as a mass percentage based on 100% of the total mass of the butadiene copolymer (B) and the vinylpyridine-butadiene-styrene copolymer (C). 0% or less.

  In the glass fiber coating coating solution of the present invention, when the content of the vinylpyridine-butadiene-styrene copolymer (C) in the glass fiber coating coating solution is less than C / (A + B + C) = 10.0% Further, it is difficult to obtain preferable water resistance in bending running when a transmission belt is used. When the content of the vinylpyridine-butadiene-styrene 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. Therefore, the preferred content range of the vinylpyridine-butadiene-styrene copolymer (C) in the coating solution for coating glass fibers of the present invention is a monohydroxybenzene-formaldehyde condensate (A) and an acrylonitrile-butadiene copolymer (B). ) And vinylpyridine-butadiene-styrene copolymer (C) are expressed in terms of mass percentage based on 100%, and C / (A + B + C) = 10.0% or more and 70.0% or less.

  It is also possible to use a styrene-butadiene copolymer in place of the vinylpyridine-butadiene-styrene copolymer. However, if a 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.

  In addition, the glass fiber coating coating solution of the present invention, which essentially contains the monohydroxybenzene-formaldehyde condensate (A) and the acrylonitrile-butadiene copolymer (B) contained in the glass fiber coating coating solution, contains a plurality of glasses. In order to give further heat resistance to a transmission belt formed by embedding rubber reinforcing glass fibers applied to strands in which fiber filaments are bundled in a base rubber, an emulsion of chlorosulfonated polyethylene (D) is further added to the above glass. Add to fiber coating solution.

  When the chlorosulfonated polyethylene (D) is further added to the glass fiber coating coating solution of the present invention, the monochlorobenzene-containing chlorosulfonated polyethylene (D) is contained in the glass fiber coating coating solution. Expressed as a mass percentage based on 100% of the total mass of formaldehyde condensate (A), acrylonitrile-butadiene copolymer (B) and chlorosulfonated polyethylene (D), D / (A + B + D) = 40.0 If it exceeds 50%, the adhesive strength between the glass fiber for rubber reinforcement and the base rubber becomes weak, and it is difficult to obtain preferable heat resistance when it is used as a transmission belt. If D / (A + B + D) is less than 1.0%, there is almost no effect of improving heat resistance.

  In the coating solution for glass fiber coating of the present invention, the suitable range of chlorosulfonated polyethylene (D) for obtaining preferable heat resistance is the monohydroxybenzene-formaldehyde condensate (A) contained in the coating solution for glass fiber coating. Expressing the total mass of the acrylonitrile-butadiene copolymer (B) and the chlorosulfonated polyethylene (D) as a mass percentage based on 100%, D / (A + B + D) = 1.0% or more, 40.0% It is as follows. Preferably, D / (A + B + D) = 15.0% or more and 35.0% or less.

  Glass fiber of the present invention containing monohydroxybenzene-formaldehyde condensate (A), acrylonitrile-butadiene copolymer (B) and vinylpyridine-butadiene-styrene copolymer (C) contained in the coating solution for coating glass fiber In order to give further heat resistance to a power transmission belt in which a glass fiber for rubber reinforcement in which a coating liquid for coating is applied to a strand in which a plurality of glass fiber filaments are bundled is embedded in a base rubber, further chlorosulfonated polyethylene The emulsion of (D) is added to the above glass fiber coating coating solution.

  When the chlorosulfonated polyethylene (D) is further added to the glass fiber coating coating solution of the present invention, the monochlorobenzene-containing chlorosulfonated polyethylene (D) is contained in the glass fiber coating coating solution. In mass percentage based on 100% of the total mass of formaldehyde condensate (A), acrylonitrile-butadiene copolymer (B), vinylpyridine-butadiene-styrene copolymer (C) and chlorosulfonated polyethylene (D) If it is expressed and D / (A + B + C + D) = 40.0% or more, the adhesive strength between the glass fiber for rubber reinforcement and the base material rubber becomes weak, and it is difficult to obtain preferable heat resistance when it is used as a transmission belt. When D / (A + B + C + D) = less than 1.0%, there is almost no effect of improving heat resistance.

  In the coating solution for glass fiber coating of the present invention, the suitable range of chlorosulfonated polyethylene (D) for obtaining preferable heat resistance is the monohydroxybenzene-formaldehyde condensate (A) contained in the coating solution for glass fiber coating. Expressed as a mass percentage based on 100% of the total mass of acrylonitrile-butadiene copolymer (B), vinylpyridine-butadiene-styrene copolymer (C) and chlorosulfonated polyethylene (D), 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.

As described above, the glass fiber coating solution of the present invention is applied to a strand formed by bundling a plurality of glass fiber filaments and then dried to provide a glass fiber for rubber reinforcement. Specifically, after melting the glass raw material, the fine glass fiber filaments discharged from the bush provided under the melting furnace are bundled while applying a sizing agent containing a silane coupling agent and a resin, and the strand. The glass fiber coating coating solution of the present invention is applied to the strand and dried to obtain rubber reinforcing glass fibers. The coating layer of the glass fiber for reinforcing rubber has a function of preventing permeation of oil such as water and engine oil.
The monohydroxybenzene-formaldehyde condensate (A) used in the coating solution for coating glass fibers of the present invention has a molar ratio of formaldehyde to monohydroxybenzene of 0.5 or more and 3.0 or less, in the presence of an alkaline compound. And a reacted resol type monohydroxybenzene-formaldehyde condensate (A). When 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 when it exceeds 3.0, the glass fiber coating solution is easily gelled. Examples of the alkaline compound include lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, and barium hydroxide.

  As the monohydroxybenzene-formaldehyde condensate (A) used in the glass fiber coating coating solution of the present invention, for example, Gunei Chemical Industry Co., Ltd., which is commercially available as an industrial phenol resin, trade name, cash register top, Model number PL-4667 may be mentioned.

  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.

  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 for rubber reinforcement produced by coating using the coating liquid for glass fiber coating using the chlorosulfonated polyethylene (D) deviating from the above-described chlorine content and sulfur content in the sulfone group, Adhesiveness with HNBR which is a base material is inferior.

  In addition, in order to enhance the adhesion between the glass fiber for rubber reinforcement and HNBR, and thus heat resistance and water resistance, the glass fiber coating coating solution of the present invention is applied to the strand and then dried to form a coating layer. It is preferable to apply a glass fiber secondary coating coating solution containing chlorosulfonated polyethylene (D) and bisallylnadiimide (G) to the substrate and dry it to provide a further secondary coating layer. When bisallyl nadiimide (G) is contained in the secondary coating layer, the heat resistance and water resistance of the glass fiber for rubber reinforcement of the present invention are improved. Specifically, a primary coating layer containing an acrylonitrile-butadiene copolymer (B) which is excellent in oil resistance but poor in water resistance by containing bisallylnadiimide (G) in the secondary coating layer. Water permeation to the water is reduced, and deterioration of water resistance due to the inclusion of the acrylonitrile-butadiene copolymer (B) in the primary coating layer is prevented.

  In addition, after applying the glass fiber coating coating solution of the present invention to the strand, the glass fiber for rubber reinforcement used as a coating layer by drying is further coated with chlorosulfonated polyethylene (D) and bisallyl nadiimide (G). When a coating solution for glass fiber secondary coating dispersed in a solvent is applied, a secondary coating layer is provided, and embedded in various base rubbers, particularly heat-resistant rubber such as HNBR, a transmission belt is obtained. 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 rubber reinforcing glass fiber of the present invention is embedded is used for a long period of time in a hot and humid environment, and the coating layer maintains the initial adhesive strength and is excellent in dimensional stability. That is, it is excellent in heat resistance and water resistance. Examples of the organic solvent include xylene.

  In addition to chlorosulfonated polyethylene (D) and bisallylnadiimide (E), as the secondary coating layer provided on the upper layer of the coating layer dried after coating the glass fiber coating coating solution of the present invention on the glass fiber cord, Examples include a secondary coating layer containing chlorosulfonated polyethylene (D) and maleimide, and a secondary coating layer containing chlorosulfonated polyethylene (D) and organic diisocyanate or zinc methacrylate. However, it is preferable to provide a secondary coating layer containing chlorosulfonated polyethylene (D) and bisallylnadiimide (E), because it has the effect of further improving heat resistance and water resistance when used as a transmission belt.

  Bisallyl nadiimide (E) is a kind of thermosetting imide, low molecular weight bisallyl nadiimide (E) is excellent in compatibility with other resins, and bisallyl nadiimide resin after curing is A glass transition point of 300 ° C. or higher has an effect of increasing the heat resistance of the transmission belt.

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

  Bisallyl nadiimide (E) is commercially available from Maruzen Petrochemical Co., Ltd. under trade names such as BANI-M, BANI-H, and BANI-X, and is preferably used in the present invention.

  Compared to a conventional transmission belt, the coating solution for coating glass fibers of the present invention comprising a monohydroxybenzene-formaldehyde condensate (A) obtained by reacting monohydroxybenzene with formaldehyde, an acrylonitrile-butadiene copolymer (B), Alternatively, the glass fiber coating coating solution of the present invention consisting of a monohydroxybenzene-formaldehyde condensate (A), an acrylonitrile-butadiene copolymer (B) and a chlorosulfonated polyethylene (D) is used to coat and dry the glass fiber cord. Then, expressed as a mass percentage based on 100% of chlorosulfonated polyethylene (D), 0.3% or more and 10.0% or less of bisallylnadiimide (E), that is, E / D = 0. Glass fiber secondary coating added in the range of 3% to 10.0% and dispersed in organic solvent The transmission belt produced by embedding the glass fiber for reinforcing rubber of the present invention, which is coated with a coating solution and having a secondary coating layer, as a core wire in a cross-linked HNBR rubber, runs for a long time under high humidity and high temperature. Later, the initial bonding strength of the HNBR crosslinked with the glass fiber by the coating layer is maintained, the tensile strength is maintained and the dimensional stability is excellent, and the water resistance, heat resistance, and oil resistance are combined. When the content of bisallylnadiimide (E) is less than E / D = 0.3%, it is difficult to obtain the above-described excellent heat resistance, water resistance and oil resistance. If E / D = 10.0% is exceeded, the adhesive strength between the glass fiber cord and the base rubber becomes weak, and the produced transmission belt is inferior in durability.

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

  For heat resistance, it is preferable to use chlorosulfonated polyethylene (D) for the secondary coating layer of the glass fiber for rubber reinforcement of the present invention. Further, a nitroso compound as a vulcanizing agent such as p-nitrosobenzene, an inorganic filler such as carbon black or magnesium oxide is added to the glass fiber secondary coating solution, and a secondary coating layer is formed on the rubber reinforcing glass fiber. In addition to the above, there is a further effect of increasing the heat resistance of a transmission belt produced by embedding the rubber reinforcing glass fiber in rubber. In the coating solution for glass fiber secondary coating, the mass of 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 and 20.0% or less. When the inorganic filler is added in the range of 10.0% or more and 70.0% or less, the produced transmission belt exhibits further heat resistance. When the content of the vulcanizing agent is less than 0.5% and the content of the inorganic filler is less than 10.0%, the effect of improving the heat resistance is not exhibited, and the vulcanizing agent exceeds 20.0%, It is not necessary to add more than 70.0% inorganic filler.

  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 power transmission belt for automobiles refers to the heat and oil resistant transmission belts used in the engine room of automobiles. A timing belt is a pulley tooth used in an engine having a camshaft to transmit the crankshaft to the timing gear and drive the camshaft to open and close the valve in the automobile transmission belt. It is a toothed belt provided with meshing teeth. Automotive transmission belts must be resistant to engine heat and exposed to engine oil, so they must be oil-resistant and water-resistant in rainy weather. Tensile strength after running for a long time at high temperatures and high humidity And having excellent dimensional stability, that is, water resistance, heat resistance and oil resistance are required.

  A glass fiber coating coating solution of the present invention containing an aqueous solution of a monohydroxybenzene-formaldehyde condensate (A), an acrylonitrile-butadiene copolymer (B) and an emulsion of chlorosulfonated polyethylene (D) is applied to a glass fiber cord. A glass fiber for reinforcing rubber which is post-dried and coated with a coating solution for secondary coating of glass fiber in which chlorosulfonated polyethylene (D) and bisallylnadiimide (E) are dispersed in an organic solvent is used as a coating layer. It produced (Examples 1-3).

An aqueous solution of a monohydroxybenzene-formaldehyde condensate (A), an emulsion of acrylonitrile-butadiene-styrene terpolymer as an acrylonitrile-butadiene copolymer (B), and a vinylpyridine-butadiene-styrene copolymer (C). The glass fiber coating coating solution of the present invention containing an emulsion and an emulsion of chlorosulfonated polyethylene (D) is applied to the strands and then dried, and further, chlorosulfonated polyethylene (D) and bisallyl nadiimide (E) are added. The glass fiber secondary coating coating solution dispersed in an organic solvent was applied to prepare rubber reinforcing glass fibers as coating layers (Examples 4 to 6).

Next, glass fibers for rubber reinforcement not within the scope of the present invention were produced (Comparative Examples 1 and 2). The adhesion strength evaluation test with respect to the oil-resistant heat-resistant rubber of the glass fibers for rubber reinforcement of the present invention (Examples 1 to 6) and the glass fibers for rubber reinforcement not in the category of the present invention (Comparative Examples 1 and 2) was conducted and the evaluation results 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 coating glass fiber of the present invention)
Using an aqueous solution of a monohydroxybenzene-formaldehyde condensate (A), ammonia water and water are added to a commercially available acrylonitrile-butadiene copolymer (B) emulsion and a chlorosulfonated polyethylene (D) emulsion, and the glass of the present invention. A coating solution for fiber coating was prepared. In order to obtain liquid stability by adding ammonia, the monohydroxybenzene-formaldehyde condensate (A) was a resol-type monohydroxybenzene-formaldehyde condensate (A) reacted in the presence of an alkali catalyst.

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 a predetermined amount of chlorosulfonated polyethylene (D) (trade name, TS-430, manufactured by Tosoh Corporation), and 22 parts by weight of aqueous ammonia (concentration, 25.0% by mass) as a pH adjuster. Then, water was added so that the total amount was 1000 parts by weight to prepare a coating solution for coating glass fibers of the present invention.

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%. Chlorosulfonated polyethylene (D) is a mass percentage based on 100% of the total mass of monohydroxybenzene-formaldehyde condensate (A), acrylonitrile-butadiene copolymer (B) and chlorosulfonated polyethylene (D). Expressed as D / (A + B + D) = 28%. 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.
(Preparation of glass fiber for rubber reinforcement of the present invention)
Next, the rubber reinforcement of the present invention, in which carbon black was added to chlorosulfonated polyethylene (D), p-dinitrobenzene, and hexamethylene diallyl nadiimide belonging to bisallyl nadiimide (E) and dispersed in xylene. A glass fiber secondary coating coating solution for providing a secondary coating layer on the glass fiber was prepared.

Specifically, as Tosoh 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, are dispersed in glass fiber secondary coating solution. Prepared. 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 of glass fiber was prepared so that p-dinitrobenzene was 40% by mass and carbon black as an inorganic filler was 30% by mass.

  After sprinkling and applying a sizing agent containing a silane coupling agent to a glass fiber filament having a diameter of 9 μm protruding from a bushing provided under a glass melting furnace, 200 glass fiber strands that have been bundled 200 are aligned, The glass fiber coating coating solution prepared in the above-described procedure was applied, and then dried at a temperature of 280 ° C. for 22 seconds to provide a coating layer to prepare 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 rubber reinforcing glass fiber is subjected to 2.0 twists per 2.54 cm, and further 13 wires are aligned and twisted 2.0 times per 2.54 cm in the opposite direction to the twist. gave. Then, after applying the glass fiber secondary coating coating solution prepared in the above-described procedure, drying was performed at 110 ° C. for 1 minute to provide a secondary coating layer, and the glass fiber for rubber reinforcement of the present invention (Example 1) ) Was produced. In this way, two types of glass fibers for reinforcing rubber were prepared in which the directions of lower kneading and upper kneading were reversed. These are called S-kneading and Z-kneading, respectively.

The solid content adhesion rate at this time, that is, the mass ratio of the secondary coating layer was 3.5% by mass with respect to the total mass of the glass fiber for rubber reinforcement provided with the primary and secondary coating layers.
Example 2
100 parts by weight of an aqueous solution of the monohydroxybenzene-formaldehyde condensate (A) with respect to the glass fiber coating coating solution of Example 1, an emulsion of acrylonitrile-butadiene copolymer (B) (Nippon Zeon Corporation) Product name, Nipol L1562
A glass fiber coating coating solution of the present invention was prepared in the same manner as in Example 1 except that the addition amount of the solid content concentration (41.0% by mass) was changed to 347 parts by weight. That is, the monohydroxybenzene-formaldehyde condensate (A) and the acrylonitrile-butadiene copolymer (B) in the coating solution for coating glass fiber are expressed in terms of mass percentage based on 100%, and monohydroxybenzene- The formaldehyde condensate (A) was A / (A + B) = 15.2%, and the acrylonitrile-butadiene copolymer (B) was B / (A + B) = 84.8%. Chlorosulfonated polyethylene (D) is a mass percentage based on 100% of the total mass of monohydroxybenzene-formaldehyde condensate (A), acrylonitrile-butadiene copolymer (B) and chlorosulfonated polyethylene (D). Expressed as D / (A + B + D) = 28%.

Next, a secondary solution for glass fiber coating similar to that in Example 1 is prepared by the procedure shown in Example 1, and the operation is performed in the same procedure as in Example 1 to further add a secondary coating layer to the glass fiber cord. A glass fiber for reinforcing rubber of the present invention (Example 2) was produced.
Example 3
32 parts by weight of an aqueous solution of the monohydroxybenzene-formaldehyde condensate (A) was added to the glass fiber coating coating solution of Example 1, and an emulsion of acrylonitrile-butadiene copolymer (B) (Nippon Zeon Corporation) The glass fiber coating coating solution of the present invention was prepared in the same manner as in Example 1 except that the addition amount of the product made by the company, trade name, Nipol L1562 solid content concentration, 41.0% by mass) was changed to 493 parts by weight. . That is, the monohydroxybenzene-formaldehyde condensate (A) and the acrylonitrile-butadiene copolymer (B) in the coating solution for coating glass fiber are expressed in terms of mass percentage based on 100%, and monohydroxybenzene- The formaldehyde condensate (A) was adjusted to A / (A + B) = 3.8%, and the acrylonitrile-butadiene copolymer (B) was adjusted to B / (A + B) = 96.2%. Chlorosulfonated polyethylene (D) is a mass percentage based on 100% of the total mass of monohydroxybenzene-formaldehyde condensate (A), acrylonitrile-butadiene copolymer (B) and chlorosulfonated polyethylene (D). Expressed as D / (A + B + D) = 28%.

Next, a secondary solution for glass fiber coating similar to that in Example 1 is prepared by the procedure shown in Example 1, and the operation is performed in the same procedure as in Example 1 to further add a secondary coating layer to the glass fiber cord. A glass fiber for reinforcing rubber of the present invention (Example 3) was prepared.
Example 4
(Preparation of coating solution for coating glass fiber of the present invention)
Using an aqueous solution of a monohydroxybenzene-formaldehyde condensate (A), an emulsion of acrylonitrile-butadiene-styrene copolymer as a commercially available acrylonitrile-butadiene copolymer (B) and a vinylpyridine-butadiene-styrene copolymer (C ) And an emulsion of chlorosulfonated polyethylene (D) were added with aqueous ammonia and water to prepare a coating solution for coating glass fibers of the present invention. In order to obtain liquid stability by adding ammonia, the monohydroxybenzene-formaldehyde condensate (A) was a resol-type monohydroxybenzene-formaldehyde condensate (A) reacted in the presence of an alkali catalyst.

  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. An aqueous solution of monohydroxybenzene-formaldehyde condensate (A), 77 parts by weight, and an emulsion of acrylonitrile-butadiene-styrene terpolymer as acrylonitrile-butadiene copolymer (B) (trade name, manufactured by Nippon Zeon Co., Ltd.) , Nipol L1577K solid concentration, 38.0% by mass) 233 parts by weight and vinylpyridine-butadiene-styrene copolymer (C) emulsion (manufactured by Nippon A & L Co., Ltd., trade name, pilatex, solid content, 41. 0 mass%) To 345 parts by weight, a predetermined amount of a chlorosulfonated polyethylene (D) emulsion (trade name, TS-430, manufactured by Tosoh Corporation) is added, and aqueous ammonia (concentration: 25.0 mass%) is used as a pH adjuster. ) Add 22 parts by weight of water to 1000 parts by weight as a whole. It was prepared fiberglass coating the coating solution of the present invention.

  The content ratio of each component in the coating solution for coating glass fiber is acrylonitrile-butadiene-styrene terpolymer and vinylpyridine as monohydroxybenzene-formaldehyde condensate (A) and acrylonitrile-butadiene copolymer (B). -The total weight of the butadiene-styrene copolymer (C) is expressed as a mass percentage based on 100%, and the monohydroxybenzene-formaldehyde condensate (A) is A / (A + B + C) = 11.7%, acrylonitrile. -Acrylonitrile-butadiene-styrene terpolymer as butadiene copolymer (B) is B / (A + B + C) = 35.6%, vinylpyridine-butadiene-styrene copolymer (C) is C / ( A + B + C) = 52.7%. The chlorosulfonated polyethylene (D) is composed of a monohydroxybenzene-formaldehyde condensate (A), an acrylonitrile-butadiene-styrene terpolymer as an acrylonitrile-butadiene copolymer (B), and a vinylpyridine-butadiene-styrene 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) = 22.5%. 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.

Next, a secondary solution for glass fiber coating similar to that in Example 1 is prepared by the procedure shown in Example 1, and the same procedure as in Example 1 is performed. A layer was provided to produce a glass fiber for reinforcing rubber.
Example 5
100 parts by weight of an aqueous solution of the monohydroxybenzene-formaldehyde condensate (A) with respect to the glass fiber coating coating solution of Example 4, and acrylonitrile-butadiene-as the acrylonitrile-butadiene copolymer (B) Except changing the addition amount of the emulsion of the styrene terpolymer emulsion (made by Nippon Zeon Co., Ltd., trade name, Nipol L1577K solid content concentration, 38.0 mass%) to 288 parts by weight, the same as in Example 4 A glass fiber coating coating solution of the present invention was prepared.

  The content ratio of each component in the coating solution for coating glass fiber is acrylonitrile-butadiene-styrene terpolymer and vinylpyridine as monohydroxybenzene-formaldehyde condensate (A) and acrylonitrile-butadiene copolymer (B). -The mass of the butadiene-styrene copolymer (C) combined is expressed as a mass percentage based on 100%, and the monohydroxybenzene-formaldehyde condensate (A) is A / (A + B + C) = 13.6%, acrylonitrile. -Acrylonitrile-butadiene-styrene terpolymer as butadiene copolymer (B) is B / (A + B + C) = 39.2%, vinylpyridine-butadiene-styrene copolymer (C) is C / ( A + B + C) = 47.2%. The chlorosulfonated polyethylene (D) is composed of a monohydroxybenzene-formaldehyde condensate (A), an acrylonitrile-butadiene-styrene terpolymer as an acrylonitrile-butadiene copolymer (B), and a vinylpyridine-butadiene-styrene 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) = 20.7%. 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.

Next, a secondary solution for glass fiber coating similar to that in Example 1 is prepared by the procedure shown in Example 1, and the operation is performed in the same procedure as in Example 1 to further add a secondary coating layer to the glass fiber cord. A glass fiber for reinforcing rubber of the present invention (Example 2) was produced.
Example 6
32 parts by weight of an aqueous solution of the monohydroxybenzene-formaldehyde condensate (A) is added to the coating solution for coating glass fibers of Example 4, and acrylonitrile-butadiene-as the acrylonitrile-butadiene copolymer (B). Except for changing the addition amount of the styrene terpolymer emulsion (manufactured by Nippon Zeon Co., Ltd., trade name, Nipol L1577K solid content concentration, 38.0 mass%) to 313 parts by weight, A glass fiber coating coating solution of the present invention was prepared.
Next, a secondary solution for glass fiber coating similar to that in Example 1 is prepared by the procedure shown in Example 1, and the operation is performed in the same procedure as in Example 1 to further add a secondary coating layer to the glass fiber cord. A glass fiber for reinforcing rubber of the present invention (Example 6) was prepared.

The content ratio of each component in the coating solution for coating glass fiber is acrylonitrile-butadiene-styrene terpolymer and vinylpyridine as monohydroxybenzene-formaldehyde condensate (A) and acrylonitrile-butadiene copolymer (B). -The total weight of the butadiene-styrene copolymer (C) is expressed as a mass percentage based on 100%, and the monohydroxybenzene-formaldehyde condensate (A) is A / (A + B + C) = 4.6%, acrylonitrile. -Acrylonitrile-butadiene-styrene terpolymer as butadiene copolymer (B) is B / (A + B + C) = 45.4%, vinylpyridine-butadiene-styrene copolymer (C) is C / ( A + B + C) = 50.0%. The chlorosulfonated polyethylene (D) is composed of a monohydroxybenzene-formaldehyde condensate (A), an acrylonitrile-butadiene-styrene terpolymer as an acrylonitrile-butadiene copolymer (B), and a vinylpyridine-butadiene-styrene 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) = 18.8%. 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.
Comparative Example 1
In place of the monohydroxybenzene-formaldehyde condensate (A), a glass fiber coating solution for reinforcing rubber containing a resorcin-formaldehyde condensate and an acrylonitrile-butadiene copolymer (B) was prepared. Specifically, a rubber reinforcement comprising an aqueous solution of resorcin-formaldehyde condensate 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) A glass fiber coating solution was prepared. A rubber coating glass fiber primary coating layer was provided in the same procedure as in Example 1 using the rubber reinforcing glass fiber coating solution.

Next, a secondary solution for glass fiber coating similar to that in Example 1 is prepared by the procedure shown in Example 1, and the operation is performed in the same procedure as in Example 1 to further add a secondary coating layer to the glass fiber cord. A glass fiber for rubber reinforcement (Comparative Example 1) was prepared.
Comparative Example 2
A vinylpyridine-butadiene-styrene polymer emulsion obtained by polymerizing monohydroxybenzene-formaldehyde condensate (A) and vinylpyridine-butadiene-styrene so as to have a vinylpyridine-butadiene-styrene = 15: 15: 70 mass ratio (Japan) A glass fiber coating solution for rubber reinforcement consisting of A & L Co., Ltd., trade name, pyrexate solid concentration, 41.0% by mass) was prepared.

  Unlike Example 1, instead of the acrylonitrile-butadiene copolymer (B), an emulsion of vinylpyridine-butadiene-styrene polymer (manufactured by Nippon A & L Co., Ltd., trade name, solid concentration of pilatex, 41.0% by mass) ) Was used in the same manner as in Example 1 except that acrylonitrile-butadiene copolymer (B) was not used, and the procedure shown in Example 1 was repeated. A glass fiber coating coating solution was prepared. That is, the monohydroxybenzene-formaldehyde is expressed in terms of mass percentage based on 100% of the monohydroxybenzene-formaldehyde condensate (A) and the vinylpyridine-butadiene-styrene copolymer (C) in the coating solution for glass fiber coating. The condensate (A) was adjusted to A / (A + C) = 8.2%, and the vinylpyridine-butadiene-styrene polymer (C) was adjusted to C / (A + C) = 91.8%.

Next, a secondary solution for glass fiber coating similar to that in Example 1 is prepared by the procedure shown in Example 1, and the operation is performed in the same procedure as in Example 1 to further add a secondary coating layer to the glass fiber cord. A glass fiber for rubber reinforcement (Comparative Example 2) was produced.
(Evaluation test of adhesive strength between glass fibers 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 is a 3 mm thick, 25 mm wide rubber sheet made of HNBR and 20 rubber reinforcing glass fibers (Examples 1 to 6 and Comparative Examples 1 and 2) are arranged on top of each other. Under the condition of 196 Newton / cm ² (hereinafter, Newton is abbreviated as N) under the condition of C and pressed at the end, and molded while being vulcanized for 30 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)
In Table 1, 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 had been separated from the interface was defined as interface peeling. Rubber destruction is superior in adhesion strength to interfacial peeling.

As shown in Table 1, the glass fiber for rubber reinforcement of Example 1 was measured for adhesion strength to be 302N, Example 2 was 333N, Example 3 was 315N, and Example 4 was 325N. Example 5 was 318N, Example 6 was 323N, and both Examples 1 to 6 had good adhesion to HNBR and excellent adhesion strength. The glass fiber for rubber reinforcement of Comparative Example 1 was 306N, and Comparative Example 2 was 300N. The adhesiveness to rubber was good and the adhesive strength was excellent.
(MIT flex test of each glass fiber for rubber reinforcement, water resistance, heat resistance, oil resistance)
Using the glass fibers for rubber reinforcement produced in Examples 1 to 6 and Comparative Examples 1 and 2 as a reinforcing material, the above-mentioned HNBR is used as a base rubber, and two pieces are used in rubber having a width of 50 mm, a length of 250 mm, and a thickness of 20 mm. A cord was embedded to prepare a test piece for the MIT bending test, and the water resistance, heat resistance and oil resistance of the MIT bending test of the glass fiber for rubber reinforcement 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 for 2 hours, remove it after wiping off the moisture, and attach a 3 kg weight to the end of the test piece at an angle of 210 degrees. The bending was repeated 1200 times, and then the tensile strength was measured.

  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, attaching a 3 kg weight to the end of the test piece, and setting the angle to 210 degrees at 1200 degrees. The fold bending was repeated, and then the tensile strength was measured.

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

  As shown in FIG. 1, the size of the test piece 1 is 2 mm in height, 5 mm in width, and 250 mm in length, and the glass fiber 3 for rubber reinforcement according to Examples 1 to 3 and Comparative Examples 1 and 2 is provided inside the HNBR. Is buried.

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

  As shown in FIG. 2, the bending angle of the clamp is 120 degrees, and the clamp 4 is bent 1200 times with the weight 4 attached.

  The results of the MIT flex test are shown in Table 2. The numerical values in Table 2 are the tensile strength retention ratios, and were obtained by the following equation (1).

  As shown in Table 2, in the measurement results of the tensile strength retention rate and heat resistance, the test piece of Example 1 was 35.4%, the test piece of Example 2 was 33.5%, and The test piece was 34.8%, the test piece of Example 4 was 41.2%, the test piece of Example 5 was 43.8%, the test piece of Example 6 was 39.5%, the test piece of Comparative Example 1 Was 38.7%, and the test piece of Comparative Example 2 was 39.5%, which was equivalent or better.

  In terms of water resistance, the test piece of Example 1 was 91.5%, the test piece of Example 2 was 92.3%, the test piece of Example 3 was 90.1%, and the test piece of Example 4 was 92.3%. 4%, test piece of Example 5 91.3%, test piece of Example 6 91.8%, test piece of Comparative Example 1 92.0%, test piece of Comparative Example 2 85.5% The test piece using the glass fiber for rubber reinforcement of the present invention (Examples 1 to 6) is compared with the test piece using the conventional test piece (Comparative Examples 1 and 2) not in the category of the present invention. The same tensile strength retention was shown. This is because the primary coating layer of the glass fiber for reinforcing rubber contains the hydrophobic monohydroxybenzene-formaldehyde condensate (A) and the secondary coating layer contains bisallyl nadiimide (E). By doing, it is based on the effect which suppressed that water permeate | transmits a primary coating layer.

  Moreover, in oil resistance, the test piece of Example 1 is 80.3%, the test piece of Example 2 is 82.3%, the test piece of Example 3 is 81.5%, and the test piece of Example 4 is 87.8%, the test piece of Example 5 is 88.0%, the test piece of Example 6 is 89.2%, the test piece of Comparative Example 1 is 64.5%, and the test piece of Comparative Example 2 is 50.%. The test piece using the glass fiber for rubber reinforcement (Examples 1 to 6) of the present invention (Examples 1 to 6) is 5%, and the test piece using the glass fiber for conventional rubber reinforcement not within the scope of the present invention (Comparative Example 1, In contrast to 2), an excellent tensile strength retention was shown.

The tensile strength after the MIT bending test for evaluating the heat resistance, water resistance and oil resistance of each of these rubber reinforcing glass fibers is determined by bending the transmission belt in which the rubber reinforcing glass fibers are embedded in HNBR. It becomes an index of heat resistance, water resistance and oil resistance after the subsequent bending run.
(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 1-6 and Comparative Examples 1 and 2.
(Water resistance evaluation by bending running test)
Using the glass fibers for rubber reinforcement produced in Examples 1 to 6 and Comparative Examples 1 and 2 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 with each other.

  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 manufactured using the rubber reinforcing glass 6 of Examples 1 to 6 and Comparative Examples 1 and 2 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 above equation (1).

  Table 3 shows the running time until breakage and the tensile strength retention after the water-resistant running fatigue test of each transmission belt.

As shown in Table 3, after applying a coating solution for primary coating comprising a monohydroxybenzene-formaldehyde condensate (A), an acrylonitrile-butadiene copolymer (B) and a chlorosulfonated polyethylene (D) as a composition NN'-hexamethylene diallyl nadiimide having a primary coating layer dried and having a composition of chlorosulfonated polyethylene (D), p-dinitrosolobenzene, and bisallyl nadiimide (G) The tensile strength retention after running test of the transmission belt 6 provided with a further secondary coating layer made of carbon black and carbon black was 42% in Example 1, 38% in Example 2, and 40% in Example 3. It was. Further, the time until the belt broke was 45 to 50 hr.
Further, monohydroxybenzene-formaldehyde condensate (A), acrylonitrile-butadiene-styrene terpolymer as acrylonitrile-butadiene copolymer (B), vinylpyridine-butadiene-styrene copolymer (C) and chlorosulfone. Having a primary coating layer formed by applying and then drying a coating solution for primary coating comprising a sulfonated polyethylene (D) as a composition (Examples 4 to 6), and the composition is chlorosulfonated polyethylene (D), Tensile strength after running test of power transmission belt 6 provided with a further secondary coating layer composed of p-dinitosolobenzene, NN'-hexamethylenediallylnadiimide belonging to bisallylnadiimide (G) and carbon black The retention was 47% in Example 4, 43% in Example 5, and 45% in Example 6. Further, the time until the belt broke was 56 to 62 hr.

  On the other hand, the transmission belt 5 which is not in the category of the present invention shown in Comparative Examples 1 and 2 was 42% in Comparative Example 1 and 39% in Comparative Example 2. The time until the belt breaks was 46 hours for Comparative Example 1 and 45 hours for Comparative Example 2.

From the results of this water resistance running fatigue test, compared with the conventional glass fiber for rubber reinforcement, monohydroxybenzene-formaldehyde condensate (A), vinylpyridine-butadiene-styrene copolymer (B) and chlorosulfonated polyethylene ( D) as the composition (Examples 1 to 3), or acrylonitrile-butadiene-styrene as monohydroxybenzene-formaldehyde condensate (A) and acrylonitrile-butadiene copolymer (B) It has a primary coating layer composed of a terpolymer, vinylpyridine-butadiene-styrene copolymer (C) and chlorosulfonated polyethylene (D) (Examples 4 to 6), and bisallylnadiimide. NN'-hexamethylenediallylnadiimide belonging to (E), chloros as halogen-containing polymer The transmission belt 5 using the glass fiber 6 for rubber reinforcement of the present invention having a further secondary coating layer comprising a composition of lufonated polyethylene (C) and p-dinitrosolobenzene has an equivalent water resistance. It was found to have. This is because the primary coating layer of the glass fiber for reinforcing rubber contains the hydrophobic monohydroxybenzene-formaldehyde condensate (A) and the secondary coating layer contains bisallyl nadiimide (E). By doing, it is based on the effect which suppressed that water permeate | transmits a primary coating layer.
(Heat resistance evaluation)
Subsequently, the glass fiber for rubber reinforcement produced in Examples 1 to 6 and Comparative Examples 1 and 2 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 water resistance evaluation test described above. 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 the 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 rubber reinforcement of Examples 1 to 6 and Comparative Examples 1 and 2, that is, heat resistance, were comparatively evaluated.

Further, the length of the transmission belt 5 after the heat resistance running fatigue test was measured, and the difference from the length of the transmission belt 5 before the heat resistance running fatigue test was defined as elongation.
(Elongation measurement)
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 4 shows the elongation of each.

  As shown in Table 4, monohydroxybenzene-formaldehyde condensate (A), acrylonitrile butadiene (B) and chlorosulfonated polyethylene (D) were used for the primary coating layer, and chlorosulfonated polyethylene was used for the secondary coating layer. The elongation retention after a 36-hour running test of the transmission belt 5 produced using the rubber reinforcing glass fiber 6 using (D) and bisallyl nadiimide (E) is 0.09 mm in Example 1, and Example 2 Was 0.08 mm, and Example 3 was 0.06 mm.

  In addition, the primary coating layer is formed of a monohydroxybenzene-formaldehyde condensate (A) and an acrylonitrile-butadiene copolymer (B) as an acrylonitrile-butadiene-styrene terpolymer and a vinylpyridine-butadiene-styrene copolymer. Using (C) and chlorosulfonated polyethylene (D), the secondary coating layer is made of chlorosulfonated polyethylene (D) and bisallylnadiimide (E). The rate was 0.05 mm in Example 4, 0.04 mm in Example 5, and 0.03 mm in Example 6.

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

  This is due to the progress of the three-dimensional crosslinking of the primary coating layer by the acrylonitrile-butadiene copolymer contained in the primary coating layer, thereby maintaining the initial adhesive strength of the glass fiber cord and the base rubber HNBR. It seems to be due to the effect of increased sex.

  Table 5 shows the tensile strength retention rate of each transmission belt after the heat-resistant and bending-resistant running fatigue test.

  As shown in Table 5, monohydroxybenzene-formaldehyde condensate (A), acrylonitrile butadiene (B) and chlorosulfonated polyethylene (D) were used for the primary coating layer, and chlorosulfonated polyethylene was used for the secondary coating layer. (D) and the tensile strength retention after the heat-resistant bending-resistant running fatigue test of the transmission belt 6 produced using the glass fiber 6 for rubber reinforcement using bisallyl nadiimide (E) is 95% in Example 1. Example 2 was 98% and Example 3 was 103%.

  In addition, the primary coating layer is formed of a monohydroxybenzene-formaldehyde condensate (A) and an acrylonitrile-butadiene copolymer (B) as an acrylonitrile-butadiene-styrene terpolymer and a vinylpyridine-butadiene-styrene copolymer. (C) and a chlorosulfonated polyethylene (D), and a belt made of rubber reinforcing glass fiber 6 using chlorosulfonated polyethylene (D) and bisallylnadiimide (E) as a secondary coating layer. The tensile strength retention after heat-resistant bending resistance fatigue test of No. 5 was 103% in Example 4, 105% in Example 5, and 102% in Example 6.

  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 fibers 6 for rubber reinforcement of Comparative Examples 1 and 2 not belonging to the category of the present invention is 93%, It was 91%. In contrast to the transmission belt 5 using the glass fibers 6 for rubber reinforcement of Comparative Examples 1 and 2, the transmission belt 5 using the glass fibers 6 for rubber reinforcement of Examples 1 to 6 has a high tensile strength retention and is excellent. Heat resistance.

  In Examples 3 to 6, 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 primary composition comprising a monohydroxybenzene-formaldehyde condensate (A), a vinylpyridine-butadiene-styrene copolymer (B) and a chlorosulfonated polyethylene (D) was used. It has a primary coating layer formed by applying and then drying a coating solution for coating, NN'-hexamethylenediallylnadiimide belonging to bisallylnadiimide (E), chlorosulfonated polyethylene belonging to halogen-containing polymer (D ) And p-dinitosolobenzene as a composition, the power transmission belt 5 using the glass fibers 6 for rubber reinforcement of Examples 1 to 3 having a secondary coating layer has excellent heat resistance in bending running. It was found to have

  Further, monohydroxybenzene-formaldehyde condensate (A), acrylonitrile-butadiene-styrene terpolymer as acrylonitrile-butadiene copolymer (B), vinylpyridine-butadiene-styrene copolymer (C) and chlorosulfone. NN′-hexamethylene diallylna belonging to bisallylnadiimide (E), which has a primary coating layer obtained by applying a coating solution for primary coating, which is made of a modified polyethylene (D), and then drying. The rubber reinforcing glass fibers 6 of Examples 1 to 3 having a further secondary coating layer composed of diimide and a chlorosulfonated polyethylene (D) belonging to a halogen-containing polymer and p-dinitosolobenzene were used. It was found that the transmission belt 5 had excellent heat resistance in bending running.

  The glass fibers 6 for rubber reinforcement of Examples 1 to 6 have excellent adhesive strength with HNBR, and the transmission belts produced using the glass fibers 6 for rubber reinforcement of Examples 1 to 6 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 power transmission belt for automobiles such as a timing belt used for a long time under high temperature and high humidity.

  According to the present invention, 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 (13)

A coating solution for coating glass fibers containing a monohydroxy benzene-formaldehyde condensate (A) produced by a condensation reaction of monohydroxy benzene and formaldehyde in water and an acrylonitrile-butadiene copolymer (B). The monohydroxybenzene-formaldehyde condensate (A) and the acrylonitrile-butadiene copolymer (B) are expressed in terms of mass percentage based on 100%. /(A+B)=1.0% or more, 55.0% or less, acrylonitrile-butadiene copolymer (B) is contained in the range of B / (A + B) = 45.0% or more and 99.0% or less. The glass fiber coating coating solution according to claim 1 or 2, characterized in that The glass fiber coating coating solution according to claim 1, further comprising a vinylpyridine-butadiene-styrene copolymer (C). The monohydroxybenzene-formaldehyde condensate (A), the acrylonitrile-butadiene copolymer (B), and the vinylpyridine-butadiene-styrene copolymer (C) combined are expressed in terms of mass percentage based on 100%. Hydroxybenzene-formaldehyde condensate (A), A / (A + B + C) = 1.0% to 40.0%, acrylonitrile-butadiene copolymer (B), B / (A + B + C) = 1.0% Or more, 55.0% or less, vinylpyridine-butadiene-styrene copolymer (C) is contained in a range of C / (A + B + C) = 10.0% or more and 70.0% or less. Claim | item 1 or the coating liquid for glass fiber coating of Claim 3. The glass fiber coating coating solution according to any one of claims 1 to 4, further comprising chlorosulfonated polyethylene (D). The mass of the monohydroxybenzene-formaldehyde condensate (A), the acrylonitrile-butadiene copolymer (B) and the chlorosulfonated polyethylene (D) is expressed as a mass percentage based on 100%, and the chlorosulfonated polyethylene (D ) In the range of D / (A + B + D) = 1.0% or more and 40.0% or less. 6. The glass fiber coating coating solution according to claim 5. The total mass of the monohydroxybenzene-formaldehyde condensate (A), the acrylonitrile-butadiene copolymer (B), the vinylpyridine-butadiene-styrene copolymer (C), and the chlorosulfonated polyethylene (D) is defined as 100%. The glass according to claim 5, which contains chlorosulfonated polyethylene (D) in a range of D / (A + B + C + D) = 1.0% or more and 40.0% or less. Coating liquid for fiber coating. The coating liquid for glass fiber coating according to any one of claims 1 to 11, wherein the acrylonitrile-butadiene copolymer (B) is an acrylonitrile-butadiene-styrene terpolymer. A coating layer obtained by coating the glass fiber coating coating solution according to any one of claims 1 to 8 on a glass fiber cord in which a plurality of glass fiber filaments are bundled and then drying is provided. Characteristic glass fiber for rubber reinforcement. A primary coating layer obtained by coating and drying the glass fiber coating coating solution according to any one of claims 1 to 9 is formed, and chlorosulfonated polyethylene (D) and bisallyl nadiimide ( A glass fiber for rubber reinforcement, comprising a secondary coating layer coated with a coating solution for secondary coating containing E). The content ratio of chlorosulfonated polyethylene (D) and bisallylnadiimide (E) in the secondary coating layer is expressed as a mass percentage based on 100% of the mass of chlorosulfonated polyethylene (D), and E / D = 0. The glass fiber for rubber reinforcement according to claim 6, wherein the glass fiber is 3% or more and 10.0% or less. A power transmission belt in which the glass fiber for rubber reinforcement according to any one of claims 9 to 11 is embedded in a base rubber. The power transmission belt according to claim 12, wherein hydrogenated nitrile rubber is used as the base rubber.

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