JP2006207600A - Transmission belt - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a transmission belt having high bonding force between a core wire and a bonded rubber layer, having excellent heat resistance, and capable of improving dynamic service life. <P>SOLUTION: This transmission belt is composed of a compressed rubber layer 5 and the bonded rubber layer by burying the core wire 2 made of fiber cords having a bonding treatment layer by resorcinol-formalin-latex (RFL) into the bonded rubber layer. Rubber component of latex in RFL is composed of at least one kind selected from among chlorosulfonated polyethylene and alkylated chlorosulfonated polyethylene by solid of 20 to 80 wt.% and at least one kind selected from among vinylpyridine latex, carboxyl denatured vinylpyridine latex, chloroprene latex, 2,3-dichlorobutadiene latex, nitrile rubber latex, hydrogen added nitrile rubber latex containing carboxyl group, and styrene-butadiene rubber latex of 80 to 20 wt.%. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a transmission belt, and more specifically, has a compression rubber layer and an adhesive rubber layer, and both the compression rubber layer and the adhesive rubber layer are made of an ethylene-α-olefin-diene rubber vulcanizate, and A core wire made of a fiber cord is bonded and embedded in an adhesive rubber layer, and has excellent dynamic adhesiveness between the core wire and the adhesive rubber layer, and therefore relates to a transmission belt having an improved dynamic life. . Furthermore, the present invention relates to a method for manufacturing such a transmission belt.

  Generally, a transmission belt such as a V-belt or a V-ribbed belt has a compression rubber layer and an adhesive rubber layer, and a core wire made of a fiber cord is bonded and embedded in the adhesive rubber layer. Alternatively, a rubberized canvas is adhered to the entire peripheral surface including the lower surface or the side surface as necessary.

  In such transmission belts, conventionally, chloroprene rubber or a vulcanized mixture of hydrogenated nitrile rubber and chlorosulfonated polyethylene rubber has generally been used for the compression rubber layer. From the viewpoint of environmental protection, it has been attempted to use ethylene-α-olefin-diene rubber for the rubber material of the transmission belt and the adhesive rubber layer together with the compression rubber layer based on the demand for dechlorination. Yes.

  However, as already known, ethylene-α-olefin-diene rubber does not have sufficient adhesion to cords made of cords such as polyester, nylon, and aramid fiber, and thus, conventionally, for example, repeated bending It is said that it is difficult to use it for a transmission belt in which dynamic characteristics are important.

  Therefore, in the transmission belt in which the compression rubber layer and the adhesive rubber layer are both made of ethylene-α-olefin-diene rubber, and a core wire made of a fiber cord such as polyester is bonded in the adhesive rubber layer, A core wire and an adhesive rubber layer are obtained by subjecting the core wire to adhesion treatment with a resorcin-formalin-latex (hereinafter referred to as RFL) containing a latex containing a sulfonated polyethylene or an alkylated chlorosulfonated polyethylene as a rubber component. It is known that excellent dynamic adhesive force can be provided between the layers, and thus a transmission belt with excellent dynamic characteristics can be obtained (see Patent Document 1).

However, even in such a transmission belt, when the temperature and time at the time of vulcanization vary during manufacture, particularly when vulcanization is performed at a high temperature for a long time, or when the transmission belt is at a high temperature. When used for a long time in an environment, there is a problem that the adhesive force is likely to be reduced at the interface between the core wire and its RFL treatment layer. This is because chlorosulfonated polyethylene and alkylated chlorosulfonated polyethylene have low polarity, so that it is easy to permeate amine compounds, radicals, moisture, etc. generated from vulcanization accelerators and antioxidants in the rubber layer during vulcanization. For this reason, it seems that this is because the bond at the interface between the surface layer of the core wire and the core wire-adhesion treatment layer is cut.
JP 2001-3991 A

  In order to solve the above-described problems in the transmission belt in which the compression rubber layer and the adhesive rubber layer are both made of ethylene-α-olefin-diene rubber, and the core wire is bonded and embedded in the adhesive rubber layer. It is an object of the present invention to provide a transmission belt that has high adhesion between the core wire and the adhesive rubber layer and is excellent in heat resistance, and thus has improved dynamic life. Moreover, an object of this invention is to provide the manufacturing method of such a transmission belt.

  According to the present invention, the compressed rubber layer and the adhesive rubber layer, both of which are made of ethylene-α-olefin-diene rubber, are vulcanized and bonded, and the fiber cord has an adhesion-treated layer of resorcin-formalin-latex in the adhesive rubber layer. In the transmission belt in which the core wire is bonded and embedded, the rubber component of the latex in the resorcin-formalin-latex is at least one selected from chlorosulfonated polyethylene and alkylated chlorosulfonated polyethylene in the solid content 20-80 % By weight and vinyl pyridine latex, carboxyl modified vinyl pyridine latex, chloroprene latex, 2,3-dichlorobutadiene latex, nitrile rubber latex, carboxyl group-containing hydrogenated nitrile rubber latex and styrene-butadiene rubber Transmission belt characterized in that it consists of at least one 80 to 20% by weight and selected from Tex is provided.

  Further, according to the present invention, a fiber in which a compression rubber layer and an adhesive rubber layer both made of ethylene-α-olefin-diene rubber are vulcanized and bonded, and the adhesive rubber layer is bonded with resorcin-formalin-latex. In the method for producing a transmission belt in which cords made of cords are bonded and buried, at least one kind selected from chlorosulfonated polyethylene and alkylated chlorosulfonated polyethylene as a rubber component of latex in a solid content is 20 to 80% by weight And at least one selected from vinyl pyridine latex, carboxyl-modified vinyl pyridine latex, chloroprene latex, 2,3-dichlorobutadiene latex, nitrile rubber latex, carboxyl group-containing hydrogenated nitrile rubber latex and styrene-butadiene rubber latex The core wire is impregnated with 0 to 20% by weight of resorcin-formalin-latex, heated and dried, and subjected to an adhesion treatment. Thus, the adhesion-treated core wire is unvulcanized to form an adhesive rubber layer. The unvulcanized ethylene-α-olefin-diene rubber sheet is placed between the ethylene-α-olefin-diene rubber sheet and the unvulcanized ethylene-α-olefin-diene rubber sheet is formed into a compressed rubber layer. There is provided a method for producing a transmission belt, characterized by laminating and pressurizing and vulcanizing the laminate thus obtained.

  In the transmission belt according to the present invention, both the compression rubber layer and the adhesive rubber layer are made of an ethylene-α-olefin-diene rubber vulcanizate, and a core wire made of a fiber cord is bonded to the adhesive rubber layer by RFL. Are bonded and buried.

  In general, after embedding the core wire bonded with resorcin-formalin-latex in the adhesive rubber layer, when the compression rubber layer and the adhesive rubber layer are vulcanized and bonded, in particular, the amine compound or radical compound from the adhesive rubber layer. It is said that water and the like are generated, and these penetrate through the adhesion treatment layer by RFL on the core wire to cut the fiber molecules of the surface layer of the core wire or deteriorate the adhesion between the fiber and the adhesion treatment layer. Yes.

  Here, according to the present invention, the rubber component of the latex is at least one selected from chlorosulfonated polyethylene and alkylated chlorosulfonated polyethylene in a solid content of 20 to 80% by weight, vinylpyridine latex, carboxyl-modified vinylpyridine latex. A cord with an RFL comprising at least one kind selected from chloroprene latex, 2,3-dichlorobutadiene latex, nitrile rubber latex, carboxyl group-containing hydrogenated nitrile rubber latex and styrene-butadiene rubber latex. By the adhesion treatment, an amine compound generated from the rubber layer at the time of vulcanization adhesion of the compression rubber layer and the adhesion rubber layer to the pyridyl group, carboxyl group, chlorine, nitrile group, phenyl group, etc. of the adhesion treatment layer by the RFL Capturing dical compounds, etc., hindering permeation to the interface between the core wire and the adhesion treatment layer, ensuring vulcanization adhesion between the ethylene-α-olefin-diene rubber and the core wire, and chloro in the latex. With the sulfonated polyethylene and the alkylated chlorosulfonated polyethylene, the adhesion between the RFL adhesion treatment layer and the rubber layer is ensured. Thus, according to the present invention, the compression rubber layer and the adhesive rubber are produced in the production of the transmission belt. Even if the layer is vulcanized and bonded for a long time, it is possible to maintain a strong adhesion between the ethylene-α-olefin-diene rubber and the core wire, and also when the transmission belt runs in a high temperature environment, Such a strong adhesive force can be maintained between the ethylene-α-olefin-diene rubber and the core wire.

  In the present invention, the transmission belt includes a V-ribbed belt and a V-ribbed belt.

  FIG. 1 shows a cross-sectional view of a V-ribbed belt as an example of a transmission belt according to the present invention, and the upper surface of the belt is formed of a single layer or multiple layers of rubberized canvas 1, adjacent to this, An adhesive rubber layer 3 is laminated. In this adhesive rubber layer, a plurality of low-strength core wires 2 made of fiber cords are embedded so as to extend in the longitudinal direction of the belt at intervals. Further, a compressed rubber layer 5 is laminated adjacent to the adhesive rubber layer. The compressed rubber layer is formed with ribs 4 that are spaced from each other so as to extend in the longitudinal direction of the belt. In many cases, short fibers 6 are oriented and dispersed in the width direction of the belt in the compressed rubber layer 5 in order to increase the lateral pressure resistance.

  FIG. 2 shows a cross-sectional view of a V-belt which is an example of a transmission belt according to the present invention. The upper surface of the belt is formed of a single-layered or multiple-layered rubberized canvas 1 as described above, and is necessary. Accordingly, the upper rubber layer 7 is laminated, and the adhesive rubber layer 3 in which the core wire 2 is embedded is laminated adjacently to the upper rubber layer 7, and further, the compressed rubber layer 5 is adjacent to this. Are stacked. In many cases, short fibers 6 are oriented and dispersed in the width direction of the belt in the compressed rubber layer 5 in order to increase the lateral pressure resistance. The compressed rubber layer is usually covered with a single layer or multiple layers of rubberized canvas 1.

  In the transmission belt according to the present invention, as described above, the compression rubber layer and the adhesive rubber layer are vulcanized and bonded, and a core wire made of a fiber cord is bonded to the adhesive rubber layer by RFL, Adhesive and embedded, and if necessary, a rubber-drawn canvas is adhered to the entire peripheral surface including the upper surface, lower surface or side surface thereof, and both the compression rubber layer and the adhesive rubber layer are ethylene-α-olefin-diene rubber. Made of vulcanizate.

  In the present invention, the ethylene-α-olefin-diene rubber is a rubber comprising a copolymer of an α-olefin excluding ethylene and ethylene and a diene (non-conjugated diene), a partial halogen substitution thereof, or two of these. The above mixture is used, and the α-olefin excluding ethylene is preferably at least one selected from propylene, butene, hexene and octene. Among these, preferred ethylene-α-olefin-diene rubbers are ethylene-propylene-diene rubbers, partial halogen substitutions thereof, particularly partial chlorine substitutions, or a mixture of two or more thereof.

In particular, in the present invention, as ethylene-propylene-diene rubber, for example, ethylene is 50 to 80% by weight, propylene is 50 to 20% by weight, and the iodine value of the elastomer is 50 or less, preferably 4 to 40, Mooney. Those having a viscosity ML _{1 + 4} (100 ° C.) of about 20 to 120 are preferably used. Although it does not specifically limit as said diene component, Usually, non-conjugated dienes, such as 1, 4- hexadiene, dicyclopentadiene, or ethylidene norbornene, are used suitably.

  In the transmission belt according to the present invention, a cord made of polyester, aramid, nylon or vinylon fiber is used as the core, and among them, a cord made of polyester fiber made of polyethylene terephthalate, polyethylene naphthalate or the like, nylon 6,6 (Polyhexamethylene adipamide), nylon 6 (polycaproamide), nylon 6,10 (polyhexamethylene sebacate) and other nylon fiber cords, polyparaphenylene terephthalamide, polymetaphenylene isophthalamide, copoly ( A cord made of an aramid fiber such as paraphenylene / 3,4′-oxydiphenylene terephthalamide) is preferably used.

  According to the present invention, such a core wire is bonded by RFL and, as will be described later, is bonded to the adhesive rubber layer at the same time when the adhesive rubber layer and the compression rubber layer are vulcanized and bonded, Buried. Here, according to the present invention, the RFL has a rubber component of the latex of 20 to 80% by weight selected from chlorosulfonated polyethylene and alkylated chlorosulfonated polyethylene in solid content, vinylpyridine latex, carboxyl It is composed of 80 to 20% by weight of at least one selected from modified vinylpyridine latex, chloroprene latex, 2,3-dichlorobutadiene latex, nitrile rubber latex, carboxyl group-containing hydrogenated nitrile rubber latex and styrene-butadiene rubber latex. Hereinafter, in the present invention, a latex containing at least one selected from chlorosulfonated polyethylene and alkylated chlorosulfonated polyethylene is referred to as a first latex, vinylpyridine latex, carboxyl-modified vinylpyridine latex, chloroprene latex, 2, A latex containing at least one selected from 3-dichlorobutadiene latex, nitrile rubber latex, carboxyl group-containing hydrogenated nitrile rubber latex, and styrene-butadiene rubber latex may be referred to as a second latex.

  The chlorosulfonated polyethylene rubber is a rubber obtained by reacting polyethylene with chlorine and sulfur dioxide, and has a chlorosulfonyl group as a vulcanization point. Usually, the chlorine content is 15 to 45% by weight, preferably 25 to 35% by weight, and the sulfur content is 0.5 to 2.5% by weight. In addition, the alkylated chlorosulfonated polyethylene rubber reduces the amount of polar chlorine introduced in the chlorosulfonated polyethylene rubber, introduces an alkyl group instead, disturbs the crystallinity of the molecule, and lowers the temperature. The balance between characteristics (cold resistance) and rubber elasticity is intended, and the chlorine content is usually in the range of 25-30% by weight, and the sulfur content is 1% by weight or less, preferably 0.6-0. .8% by weight.

  RFL is usually formed by condensing resorcin and formalin in the presence of a basic catalyst at a resorcin / formalin molar ratio of 1/3 to 3/1, and resorcin-formalin resin (resorcin-formalin initial condensate, hereinafter RF It is an aqueous dispersion obtained by preparing an aqueous solution having a concentration of 5 to 80% by weight and mixing it with rubber latex. In RFL, the solid content concentration is not particularly limited, but is usually in the range of 10 to 50% by weight. According to the present invention, the RFL may contain a chlorophenol-resorcin condensate in the RFL, if necessary.

  In the present invention, the RFL used for the bonding process of the core wire is composed of the mixture of the first and second latexes as described above, and therefore, the mixture of the first and second latexes was prepared. Thereafter, if left standing for a long period of time, even if the core wires are separated from each other and processed, there is a possibility that the desired adhesiveness cannot be given to the core wires. Therefore, the RFL made of a mixture of the first and second latexes used in the present invention desirably contains a surfactant as a mutual compatibilizing agent. The surfactant adheres to the surface of the latex particles (rubber component), prevents aggregation of the same type of latex particles, and uniformly disperses different types of latex particles, thus obtaining a stable RFL.

  In preparing the RFL used in the present invention, the surfactant may be added at any stage. However, for example, after the first and second latexes are mixed at a predetermined weight ratio, water is added, and a surfactant is added when diluting to a predetermined solid content concentration, followed by stirring. However, by aging, a stable RFL can be obtained by containing a surfactant together with the first and second latexes.

  As the surfactant, any of cationic, anionic, amphoteric and nonionic surfactants can be used. Examples of the cationic surfactant include aliphatic amine salts, quaternary ammonium salts, alkylpyridinium salts and the like. Examples of the anionic surfactant include fatty acid salts, higher alcohol sulfates, and alkylaryl sulfonates. Examples of the nonionic surfactant include polyoxyethylene alkyl ethers. And polyoxyethylene alkylphenol ether, polyoxyethylene alkyl ester sorbitan alkyl ester, polyoxyethylene sorbitan alkyl ester, and the like. However, according to the present invention, amphoteric or nonionic surfactants are preferably used, and nonionic surfactants are particularly preferably used when the pH of the latex used is significantly different from each other.

  Such a surfactant is usually used in the range of 0.005 to 0.5 parts by weight with respect to 100 parts by weight of the solid content of RFL. When the amount is less than 0.005 parts by weight with respect to 100 parts by weight of the solid content of RFL, the effect as a compatibilizer is not sufficient, and on the other hand, 0.5 parts by weight with respect to 100 parts by weight of the solid content of RFL. When the amount is larger than the above, there is a risk of leaching to the surface of the RFL-treated core wire and hindering the effect of the adhesion treatment by RFL. According to the present invention, the amount of surfactant is preferably in the range of 0.01 to 0.5 parts by weight with respect to 100 parts by weight of RFL solids.

  The bonding treatment of the core wire by such RFL may be performed in accordance with a conventional method. For example, the core wire is immersed in RFL and impregnated with RFL, and then 200 to 300 ° C., preferably 200 to This refers to heating to a temperature in the range of 250 ° C. and drying to insolubilize the solid content of RFL (ie, RF and rubber components) and fix them to the core. In the present invention, such an adhesion process using RFL may be performed in two or more stages as required.

  As described above, according to the present invention, the core wire is bonded with the RFL containing the mixture of the first and second latexes as described above, and this is embedded in the adhesive rubber layer and bonded to form a transmission belt. Thus, during the production, the core wire is vulcanized and bonded into the adhesive rubber layer, and when the compression rubber layer and the adhesive rubber layer are integrally vulcanized and bonded to each other, the rubber component of the first latex on the core wire is formed. Various components that typically have a detrimental effect on the adhesion between the core wire and the RFL treatment layer, typically amine compounds, radical compounds, moisture Etc. are captured by the highly polar rubber component of the second latex and are prevented from penetrating to the side of the cord, thereby maintaining the adhesion between the cord and the RFL. Thus, according to the present invention, when the transmission belt is manufactured, even if the compression rubber layer and the adhesive rubber layer are vulcanized and bonded for a long time, the strong adhesion is obtained between the ethylene-α-olefin-diene rubber and the core wire. Further, such a strong adhesive force can be maintained between the ethylene-α-olefin-diene rubber and the core wire even when the transmission belt is running in a high temperature environment.

  According to the present invention, by including a certain metal oxide and sulfur-containing vulcanization accelerator in RFL, the time for vulcanization adhesion between the core wire and the adhesive rubber layer can be shortened. Thus, the productivity of the transmission belt can be increased.

  As the metal oxide, for example, zinc oxide, magnesium oxide, lead oxide or a mixture of two or more of these is preferably used, and zinc oxide is particularly preferably used. Further, as the sulfur-containing vulcanization accelerator, thiazoles, sulfenamides, thiurams, dithiocarbamates or a mixture of two or more thereof are preferably used.

  Examples of the thiazoles include 2-mercaptobenzothiazole (M) and salts thereof (for example, zinc salt, sodium salt, cyclohexylamine salt, etc.), dibenzothiazyl disulfide (DM), and the like. Examples of amides include N-cyclohexyl-2-benzothiazylsulfenamide (CZ) and the like, and examples of thiurams include tetramethylthiuram monosulfide (TS) and tetramethylthiuram disulfide ( TT), dipentamethylene thiuram tetrasulfide (TRA), and the like. Examples of dithiocarbamate salts include sodium di-n-butyldithiocarbamate (TP), zinc dimethyldithiocarbamate (PZ), and diethyl. Dithiocarbamine Zinc (EZ), and the like can be given.

  The blending ratio in the RFL is usually in the range of 0.1 to 10 parts by weight of the metal oxide with respect to 100 parts by weight of the solid content of the latex component in the RFL, and the sulfur-containing vulcanization accelerator is usually in the range of 0.1 to 20 parts by weight.

  In the present invention, before the core wire is bonded by RFL, the core wire is immersed in a solution containing an isocyanate compound or an epoxy compound, and then, if necessary, the core wire is pretreated by heating and drying. You may do it.

  Although it does not specifically limit as said isocyanate compound, For example, tolylene diisocyanate, m-phenylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, polymethylene polyphenyl polyisocyanate etc. are used preferably. In addition, polyisocyanate added polyisocyanate obtained by reacting such an isocyanate compound with a compound having two or more active hydrogens in the molecule, such as trimethylolpropane, pentaerythritol, etc., phenols to the isocyanate compound, Blocked polyisocyanates obtained by reacting blocking agents such as tertiary alcohols and secondary amines to block the isocyanate group of the isocyanate compound can also be suitably used as the isocyanate compound.

  On the other hand, the epoxy compound is not particularly limited as long as it is a polyepoxy compound having two or more epoxy groups in the molecule. For example, polyhydric alcohols such as ethylene glycol, glycerin, sorbitol, and pentaerythritol are used. Reaction products of polyalkylene glycols such as polyethylene glycol and halogen-containing epoxy compounds such as epichlorohydrin, resorcin, bis (4-hydroxyphenyl) dimethylethane, phenol-formaldehyde resins, resorcin-formaldehyde resins A reaction product of a polyhydric phenol such as the above or a phenol resin and a halogen-containing epoxy compound such as epichlorohydrin is preferably used.

  The solvent for forming a solution of such an isocyanate compound or epoxy compound is not particularly limited, and water or an appropriate organic solvent is used depending on the isocyanate compound or epoxy compound to be used. Usually, isocyanate compounds are chemically very active, so they are non-aqueous solutions. However, for example, as described above, those in which isocyanate groups are blocked with phenols can also be used as aqueous solutions. Can do. As the organic solvent, usually, aromatic hydrocarbons such as benzene, xylene and toluene, aliphatic ketones such as methyl ethyl ketone and methyl isobutyl ketone, and aliphatic carboxylic acid alkyl esters such as ethyl acetate and amyl acetate are preferably used. The concentration of the isocyanate compound or epoxy compound in such a solution is usually in the range of 5 to 50% by weight.

  Further, in the present invention, the core wire may be post-treated with rubber paste after being subjected to the adhesion treatment with RFL. The rubber paste used in this post-treatment is usually a solution obtained by dissolving ethylene-α-olefin-diene rubber for forming a compression rubber layer and an adhesive rubber layer in an appropriate organic solvent. What is necessary is just to heat-dry, after immersing in a solution.

  In the present invention, the ethylene-α-olefin-diene rubber used for forming the compression rubber layer and the adhesive rubber layer may be a reinforcing agent such as carbon black, silica, glass fiber, ceramic fiber, calcium carbonate, talc as necessary. It is used as a blend containing various chemicals used in the normal rubber industry, such as fillers, plasticizers, stabilizers, processing aids, colorants and the like.

  An ethylene-α-olefin-diene rubber compound for forming a compression rubber layer or an adhesive rubber layer is usually an ethylene-α-olefin-diene rubber, roll, banbury, etc. It can obtain by mixing uniformly using the mixing means.

  The power transmission belt according to the present invention can be manufactured by a conventionally known method. For example, in the case of a V-ribbed belt, one or more rubber coated canvases and an unvulcanized sheet for an adhesive rubber layer are wound around the circumferential surface of a cylindrical molding drum having a smooth surface, The core wire is spun into a spiral shape, and further, an unvulcanized sheet for the adhesive rubber layer is wound thereon, and then an unvulcanized sheet for the compressed rubber layer is wound to form a laminate, which is vulcanized. It is heated and pressurized in a can and vulcanized to obtain an annular product. Next, the annular member is stretched between a driving roll and a driven roll, and a plurality of ribs are formed on the surface by a grinding wheel while running under a predetermined tension. Then, if this annular material is further cut between a driving roll and a driven roll and cut into a predetermined width while running, a V-ribbed belt as a product can be obtained.

  EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In the following, a compound having the following composition was used as the compound for the adhesive rubber layer of the belt.

Ethylene-propylene-diene rubber ¹⁾ 100 parts by weight HAF carbon (Mitsubishi Chemical Co., Ltd.) 50 parts by weight silica (Tokuyama Co., Ltd. Toxeal Gu) 20 parts by weight paraffin oil (Nihon Sun Chemical Co., Ltd. Sunflex 2280) 20 parts by weight vulcanizing agent (oil sulfur manufactured by Hosoi Chemical Co., Ltd.) 3 parts by weight vulcanization accelerator (EP-150 ² manufactured by Ouchi Shinsei Chemical Co., Ltd.) 2.5 parts by weight vulcanizing aid (Kao ( 1 part by weight vulcanization aid (Zinc oxide manufactured by Sakai Chemical Industry Co., Ltd.) 5 parts by weight anti-aging agent (224 ³ manufactured by Ouchi Shinsei Chemical Co., Ltd. ⁾ ) 2 parts by weight anti-aging agent ( MB, manufactured by Ouchi Shinsei Chemical Co., Ltd. ⁴⁾ ) 1 part by weight tackifier (manufactured by Nippon Zeon Co., Ltd., petroleum resin quinton A-100) 5 parts by weight Short fiber (cotton powder) 2 parts by weight

  Moreover, what has the following composition was used as a compound for the compression rubber layer of a belt.

Ethylene-propylene-diene rubber ¹⁾ 100 parts by weight HAF carbon (Mitsubishi Chemical Corporation) 70 parts by weight paraffin oil (Nihon Sun Chemical Co., Ltd. Sunflex 2280) 20 parts by weight vulcanizing agent (Hosoi Chemical Co., Ltd.) Oil sulfur) 1.6 parts by weight vulcanization accelerator (EP-150 manufactured by Ouchi Shinsei Chemical Co., Ltd. ²⁾ ) 2.8 parts by weight vulcanization accelerator (Ouchi Shinsei Chemical Co., Ltd. MSA ⁵⁾ ) 2 parts by weight vulcanization aid (stearic acid manufactured by Kao Corporation) 1 part by weight vulcanization aid (zinc oxide manufactured by Sakai Chemical Industry Co., Ltd.) 5 parts by weight anti-aging agent (224 manufactured by Ouchi Shinsei Chemical Co., Ltd.) ³⁾ ) 2 parts by weight anti-aging agent (MB, manufactured by Ouchi Shinsei Chemical Co., Ltd. ⁴⁾

(Note) 1) Ethylene content 56% by weight, propylene content 36.1% by weight, ethylidene norbornene (ENB) 5.5% by weight, dicyclopentadiene (DCPD) 2.4% by weight, Mooney viscosity ML _{1 + 4} ( 100 ° C) 60
2) Vulcanization accelerator DM (dibenzothiadisulfide), TT (tetramethylthiuram disulfide), and EZ (mixture of zinc diethyldithiocarbamate)
3) TMDQ (2,2,4-trimethyl-1,2-dihydroquinoline)
4) 2-mercaptobenzimidazole 5) N-oxydiethylene-2-benzothiazylsulfenamide

Preparation of RFL RFL (1) to (10) used for the bonding treatment of the core wire were prepared as follows.

RFL (1)
(RFL containing only chlorosulfonated polyethylene (CSM) latex as latex)
7.31 parts by weight of resorcin and 10.77 parts by weight of formalin (37% by weight concentration) were mixed and stirred, and an aqueous sodium hydroxide solution (solid content: 0.33 parts by weight) was added thereto, followed by stirring. 160.91 parts by weight of water was added and aged for 5 hours to prepare an aqueous solution of resorcin-formalin resin (resorcin-formalin initial condensate (referred to as RF), R / F ratio of 0.5). To this RF aqueous solution, 45.2 parts by weight of CSM latex (solid content: 40%) was added so that the RF / L ratio was 0.25, and then water was added to obtain a solid content of 20% by weight. It adjusted so that it might become. While stirring, the mixture was aged for 12 hours to prepare RFL (1).

RFL (2)
(RFL containing CSM latex and 2,3-dichlorobutadiene (DCB) latex) 7.31 parts by weight of resorcin and 10.77 parts by weight of formalin (37% by weight concentration) are mixed and stirred, and an aqueous sodium hydroxide solution is added thereto. (Solid content 0.33 parts by weight) was added and stirred, and then 160.91 parts by weight of water was added and aged for 5 hours to prepare an RF aqueous solution with an R / F ratio of 0.5. In this RF aqueous solution, CSM latex (solid content: 40%) and DCB latex (solid content: 32%) are added at a solid content ratio of 5/5, and the total solid content is 45.2 so that the RF / L ratio is 0.25. After adding parts by weight, water was added to adjust the solid content to 20% by weight. While stirring, the mixture was aged for 12 hours to prepare RFL (2).

RFL (3)
(RFL containing CSM latex and carboxylated vinylpyridine latex)
7.31 parts by weight of resorcin and 10.77 parts by weight of formalin (37% by weight concentration) were mixed and stirred, and an aqueous sodium hydroxide solution (solid content: 0.33 parts by weight) was added thereto, followed by stirring. Then, 160.91 parts by weight of water was added and aged for 5 hours to prepare an RF aqueous solution with an R / F ratio of 0.5. CSM latex (solid content 40%) and vinylpyridine-ethylenically unsaturated carboxylic acid-styrene-butadiene copolymer (carboxylated VP) latex (LX603, Nippon Zeon Co., Ltd., solid content 36%) are added to this RF aqueous solution. After adding a total of 45.2 parts by weight so that the RF / L ratio is 0.25 at a solid content ratio of 6/4, water is added so that the solid content becomes 20% by weight. It was adjusted. While stirring, the mixture was aged for 12 hours to prepare RFL (3-1).

  Similarly, in the above RF aqueous solution, CSM latex (solid content 40%) and carboxylated VP latex (LX603 manufactured by Nippon Zeon Co., Ltd., solid content 36%) were mixed at a solid content ratio of 2/8 and the RF / L ratio was 0. After adding a total of 45.2 parts by weight with a solid content so as to be .25, water was added to adjust the solid content to 20% by weight. While stirring, the mixture was aged for 12 hours to prepare RFL (3-2).

RFL (4)
(RFL containing CSM latex and vinylpyridine-styrene-butadiene copolymer (VP) latex)
7.31 parts by weight of resoronoresin and 10.77 parts by weight of formalin (37% by weight concentration) were mixed and stirred, and an aqueous sodium hydroxide solution (solid content: 0.33 parts by weight) was added thereto, followed by stirring. Then, 160.91 parts by weight of water was added and aged for 5 hours to prepare an RF aqueous solution with an R / F ratio of 0.5. CSM latex (solid content 40%) and VP latex (JSR0650 manufactured by JSR Corporation, solid content 40%) are solidified in this RF aqueous solution so that the RF / L ratio is 0.25 at a solid content ratio of 6/4. After adding 45.2 parts by weight in minutes, water was added to adjust the solid content to 20% by weight. While stirring, the mixture was aged for 12 hours to prepare RFL (4-1).

  Similarly, CSM latex (40% solid content) and VP latex (JSR0650 manufactured by JSR Corporation, 40% solid content) are added to the above RF aqueous solution so that the RF / L ratio is 0.25 at a solid content ratio of 2/8. After adding a total of 45.2 parts by weight as solid content, water was added to adjust the solid content to 20% by weight. While stirring, the mixture was aged for 12 hours to prepare RFL (4-2).

RFL (5)
(RFL including CSM latex and DCB latex)
7.31 parts by weight of resorcin and 10.77 parts by weight of formalin (37% by weight concentration) were mixed and stirred, and an aqueous sodium hydroxide solution (solid content: 0.33 parts by weight) was added thereto, followed by stirring. Then, 160.91 parts by weight of water was added and aged for 5 hours to prepare an RF aqueous solution having an R / F ratio of 0.25. CSM latex (solid content 40%) and DCB latex (LH430 manufactured by Tosoh Corporation, solid content 32%) are solidified in this RF aqueous solution so that the RF / L ratio is 0.25 at a solid content ratio of 6/4. After adding 45.2 parts by weight in minutes, water was added to adjust the solid content to 20% by weight. While stirring, the mixture was aged for 12 hours to prepare RFL (5).

RFL (6)
(RFL containing CSM latex and chloroprene rubber (CR) latex)
7.31 parts by weight of resorcin and 10.77 parts by weight of formalin (37% by weight concentration) were mixed and stirred, and an aqueous sodium hydroxide solution (solid content: 0.33 parts by weight) was added thereto, followed by stirring. Then, 160.91 parts by weight of water was added and aged for 5 hours to prepare an RF aqueous solution with an R / F ratio of 0.5. In this RF aqueous solution, CSM latex (solid content 40%) and chloroprene rubber (CR) latex (CR842 manufactured by DDE Japan Co., Ltd., solid content 50%) are mixed at a solid content ratio of 6/4 and RF / L ratio is 0.25. After adding a total of 45.2 parts by weight as solid content, water was added to adjust the solid content to 20% by weight. While stirring, the mixture was aged for 12 hours to prepare RFL (6).

RFL (7)
(RFL containing CSM latex and nitrile rubber (NBR) latex)
7.31 parts by weight of resorcin and 10.77 parts by weight of formalin (37% by weight concentration) were mixed and stirred, and an aqueous sodium hydroxide solution (solid content: 0.33 parts by weight) was added thereto, followed by stirring. Then, 160.91 parts by weight of water was added and aged for 5 hours to prepare an RF aqueous solution with an R / F ratio of 0.5. In this RF aqueous solution, CSM latex (solid content 40%) and NBR latex (Nipol 1562 manufactured by Nippon Zeon Co., Ltd., solid content 40%) are added so that the RF / L ratio is 0.25 at a solid content ratio of 6/4. After adding a total of 45.2 parts by weight in terms of solid content, water was added to adjust the solid content to 20% by weight. While stirring, the mixture was aged for 12 hours to prepare RFL (7).

RFL (8)
(RFL containing CSM latex and styrene-butadiene rubber (SBR) latex)
7.31 parts by weight of resorcin and 10.77 parts by weight of formalin (37% by weight concentration) were mixed and stirred, and an aqueous sodium hydroxide solution (solid content: 0.33 parts by weight) was added thereto, followed by stirring. Then, 160.91 parts by weight of water was added and aged for 5 hours to prepare an RF aqueous solution with an R / F ratio of 0.5. In this RF aqueous solution, CSM latex (solid content 40%) and SBR latex (Japan A & L Co., Ltd. J9049, solid content 40%) are set so that the RF / L ratio is 0.25 at a solid content ratio of 6/4. After adding a total of 45.2 parts by weight in solid content, water was added to adjust the solid content to 20% by weight. While stirring, the mixture was aged for 12 hours to prepare RFL (8).

RFL (9)
(RFL containing CSM latex and carboxylated VP latex)
7.31 parts by weight of resorcin and 10.77 parts by weight of formalin (37% by weight concentration) were mixed and stirred, and an aqueous sodium hydroxide solution (solid content: 0.33 parts by weight) was added thereto, followed by stirring. Then, 160.91 parts by weight of water was added and aged for 5 hours to prepare an RF aqueous solution with an R / F ratio of 0.5. In this RF aqueous solution, CSM latex (solid content 40%) and carboxylated VP latex (Nihon Zeon Co., Ltd. LX603, solid content 36%) are obtained, and the RF / L ratio becomes 0.25 at a solid content ratio of 6/4. After adding a total of 45.2 parts by weight in the solid content, water was added to adjust the solid content to 20% by weight. While stirring, the mixture was aged for 12 hours to prepare RFL (9).

RFL (10)
(RFL containing CSM latex, carboxylated VP latex, zinc oxide and vulcanization accelerator)
7.31 parts by weight of resorcin and 10.77 parts by weight of formalin (37% by weight concentration) were mixed and stirred, and an aqueous sodium hydroxide solution (solid content: 0.33 parts by weight) was added thereto, followed by stirring. Then, 160.91 parts by weight of water was added and aged for 5 hours to prepare an RF aqueous solution with an R / F ratio of 0.5. In this RF aqueous solution, CSM latex (solid content 40%) and carboxylated VP latex (Nihon Zeon Co., Ltd. LX603, solid content 36%) are obtained, and the RF / L ratio becomes 0.25 at a solid content ratio of 6/4. In addition, 45.2 parts by weight in total as solid content was added, and Dispon DZ (Sumitomo Seika Co., Ltd. vulcanization accelerator DM / zinc oxide = 5/1 aqueous dispersion, solid content 43%) 6 After adding 5 parts by weight, water was added to adjust the solid content of the latex to 20% by weight. While stirring, the mixture was aged for 12 hours to prepare RFL (10).

Core wire The following fiber cord was used as the core wire.
(A) Polyester fiber cord Polyester fiber manufactured by Teijin Limited, 1000d / 2 × 3, upper twist 9.5T / 10cm (Z), lower twist 2.19T / 10cm
(B) Aramid fiber cord Technora manufactured by Teijin Limited, 1000d / 1 × 3, Upper twist (Z) 16.4T / 10cm, Lower twist (S) 28.5T / 10cm
(C) Nylon fiber cord Leona 66, 1260d / 1 × 5, Asahi Kasei Co., Ltd., Upper twist (Z) 9.3 T / 10 cm, Lower twist (S) 20.7 T / 10 cm
(D) Vinylon fiber cord Kuraray Kuraray Vinylon Co., Ltd., 1800d / 1 × 3, Upper twist (Z) 10T / 10cm, Lower twist 17.3T / 10cm

A. Examples used for bonding of core wires within 24 hours after preparation of RFL

Example 1
(Preparation of adhesive between polyester core and adhesive rubber layer and measurement of adhesive strength of this adhesive)
The polyester core wire was immersed in a toluene solution of isocyanate (isocyanate solid content 20% by weight) and then dried by heating at 240 ° C. for 40 seconds to pretreat the core wire.

  Next, the polyester core wire thus pretreated is immersed in RFL (3-1), and then heated and dried at 200 ° C. for 80 seconds, and then the polyester core wire thus bonded is treated with the same ethylene as the adhesive rubber. -After being immersed in an adhesive solution obtained by dissolving propylene-diene rubber in toluene, the polyester core wire was post-treated by heating and drying at 60 ° C for 40 seconds.

  The polyester core wire thus treated is sandwiched between unvulcanized sheets of an ethylene-propylene-diene rubber blend for the adhesive rubber, and these are heated under pressure at a surface pressure of 3920 kPa and a temperature of 160 ° C. for 35 minutes. Press vulcanized. Thus, the adhesive force of the polyester core wire in the adhesive obtained was measured. The results are shown in Table 1 as the properties (1) of the adhesive. Moreover, the adhesive force of the polyester core wire was measured for the adhesive obtained in the same manner except that the vulcanization conditions were set at a surface pressure of 3920 kPa and a temperature of 170 ° C. for 50 minutes. The results are shown in Table 1 as the properties (2) of the adhesive.

(Manufacture of transmission belt and evaluation of its dynamic life)
As described above, a rubber-coated canvas and an unvulcanized sheet of the ethylene-propylene-diene rubber compound for the adhesive rubber layer are wound around the peripheral surface of a cylindrical molding drum having a smooth surface, and then bonded onto this. The treated polyester cord was spun into a spiral. Further, after wrapping the unvulcanized sheet of the rubber compound for the same adhesive rubber layer as above, the unvulcanized sheet of the ethylene-propylene-diene rubber compound for the compressed rubber layer is wound. A laminate was obtained.

The laminate pressure 6 kgf / cm ^2, the external pressure 9 kgf / cm ^2, temperature of 165 ° C., heated and pressurized at a vulcanizer in under conditions of time 35 minutes, then steam vulcanized to obtain an annular substance. Next, the annular object is attached to a first drive system composed of a driving roll and a driven roll, and the annular object is ground using a grinding wheel while traveling under a predetermined tension, and a plurality of surfaces are ground on the surface. Ribs were formed. After that, this annular object is attached to a second drive system composed of another drive roll and a driven roll, and is cut into a predetermined width while running to obtain a product having three ribs and a circumferential length of 1000 mm. V-ribbed belt was obtained.

  As shown in FIG. 3, the V-ribbed belt thus obtained has a driving pulley 11 (diameter 120 mm), a driven pulley 12 (diameter 120 mm), an idler pulley 13 (diameter 70 mm) disposed between these pulleys, and a tension pulley. 14 (55 mm diameter). However, the back of the belt was engaged with the idler pulley.

  Under an ambient temperature of 130 ° C., the load of the driven pulley is 16 horsepower, the initial tension of the tension pulley is 85 kgf, the driving pulley is driven at a rotational speed of 4900 rpm, the belt is run, and the core wire is exposed from the belt. The running time until the rubber layer was cracked was defined as the dynamic life of the belt. The results are shown in Table 1.

Examples 2-14
Adhesive treatment was performed on the core wire in the same manner as in Example 1 except that the fiber cord shown in Table 1 or Table 2 was used as the core wire, and the RFL shown in Table 1 or Table 2 was used. Using the core wire thus treated, an adhesive was prepared in the same manner as in Example 1, and the adhesive strength was measured. The results are shown in Tables 1 and 2.

  Next, a V-ribbed belt as a product having three ribs and a circumferential length of 1000 mm was obtained in the same manner as in Example 1 using the core wire subjected to the adhesion treatment in this manner. Thus, the dynamic life of the belt was examined. The results are shown in Tables 1 and 2.

Comparative Example 1
In Example 1, an adhesive treatment was performed on the core wire in the same manner as in Example 1 except that RFL (1) was used. Using the core wire thus treated, an adhesive was prepared in the same manner as in Example 1, and the adhesive strength was measured. The results are shown in Table 2.

  Next, a V-ribbed belt as a product having three ribs and a circumferential length of 1000 mm was obtained in the same manner as in Example 1 using the core wire subjected to the adhesion treatment in this manner. Thus, the dynamic life of the belt was examined. The results are shown in Table 2.

Comparative Examples 2-4
In Example 1, the fiber cord shown in Table 2 was used instead of the polyester core wire, and the core wire was subjected to adhesion treatment in the same manner as in Example 1 except that RFL (1) was used. Using the core wire thus treated, an adhesive was prepared in the same manner as in Example 1, and the adhesion was measured. The results are shown in Table 2.

  Next, a V-ribbed belt as a product having three ribs and a circumferential length of 1000 mm was obtained in the same manner as in Example 1 using the core wire subjected to the adhesion treatment in this manner. Thus, the dynamic life of the belt was examined. The results are shown in Table 2.

B. Example used for adhesion treatment of core wire 5 days after preparation of RFL

Preparation of RFL (3-3) to (3-8) Nonionic surfactant polyoxyethylene distyrenated phenyl ether (Kao Co., Ltd.) based on 100 parts by weight of the solid content of RFL in the aforementioned RFL (3-1) 1.0 parts by weight of Emulgen A-500) was added and aged for 12 hours while stirring, and then allowed to stand for 5 days to prepare RFL (3-3). Moreover, after preparing RFL (3-1) mentioned above, what was left as it was for 5 days was made into RFL (3-0).

  Similarly, 0.1 part by weight of the nonionic surfactant is added to RFL (3-1) with respect to 100 parts by weight of the solid content of RFL to prepare RFL (3-4), and the nonionic surfactant is obtained. 0.03 part by weight was added to prepare RFL (3-5).

  Further, to the above-mentioned RFL (3-2), 1.0 part by weight of the above nonionic surfactant was added to 100 parts by weight of the solid content of RFL, and the mixture was aged for 12 hours with stirring, and then allowed to stand for 5 days. RFL (3-6) was prepared.

  Similarly, 0.1 part by weight of the nonionic surfactant is added to RFL (3-2) with respect to 100 parts by weight of the solid content of RFL to prepare RFL (3-7), and the nonionic surfactant is obtained. 0.03 part by weight was added to prepare RFL (3-8).

Examples 15-18
In Example 1, as shown in Table 3, except that RFL (3-4), (3-5), (3-7) or (3-8) was used, it was bonded to the core wire in the same manner. Treated. Using the core wire thus treated, an adhesive was prepared in the same manner as in Example 1, and the adhesive strength was measured. The results are shown in Table 3.

  Next, a V-ribbed belt as a product having three ribs and a circumferential length of 1000 mm was obtained in the same manner as in Example 1 using the core wire subjected to the adhesion treatment in this manner. Thus, the dynamic life of the belt was examined. The results are shown in Table 3.

Comparative Examples 5-7
In Example 1, as shown in Table 3, the core wire was subjected to adhesion treatment in the same manner except that the above-described RFL (3-1), (3-3) or (3-6) was used. . Using the core wire thus treated, an adhesive was prepared in the same manner as in Example 1, and the adhesive strength was measured. The results are shown in Table 3.

  Next, a V-ribbed belt as a product having three ribs and a circumferential length of 1000 mm was obtained in the same manner as in Example 1 using the core wire subjected to the adhesion treatment in this manner. Thus, the dynamic life of the belt was examined. The results are shown in Table 3.

The cross-sectional view of an example of a V-ribbed belt is shown. The cross-sectional view of an example of a V belt is shown. It is a figure which shows the belt drive system for performing the dynamic test of a transmission belt.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Rubber-drawn canvas 2 ... Core wire 3 ... Adhesive rubber layer 4 ... Rib 5 ... Compression rubber layer 6 ... Short fiber 7 ... Upper rubber layer 11 ... Drive pulley 12 ... Drive pulley 13 ... Idler pulley 14 ... Tension pulley

Claims (12)

  Both a compression rubber layer made of ethylene-α-olefin-diene rubber and an adhesive rubber layer are vulcanized and bonded, and a core cord made of a fiber cord bonded with resorcin-formalin-latex is bonded to the adhesive rubber layer. In the power transmission belt embedded, the rubber component of the latex in the resorcin-formalin-latex is 20-80% by weight selected from chlorosulfonated polyethylene and alkylated chlorosulfonated polyethylene in solid content, and vinylpyridine latex , Carboxyl-modified vinylpyridine latex, chloroprene latex, 2,3-dichlorobutadiene latex, nitrile rubber latex, carboxyl group-containing hydrogenated nitrile rubber latex and styrene-butadiene rubber latex Transmission belt, characterized in that consisting of one 80 to 20% by weight even without.   The power transmission belt according to claim 1, wherein the resorcin-formalin-latex contains a nonionic surfactant as a compatibilizing agent.   The power transmission belt according to claim 1, wherein the resorcin-formalin-latex contains a metal oxide and a sulfur-containing vulcanization accelerator.   The power transmission belt according to claim 3, wherein the metal oxide is zinc oxide, magnesium oxide, or lead oxide.   The transmission belt according to claim 3, wherein the sulfur-containing vulcanization accelerator is thiazoles, sulfenamides, thiurams, dithiocarbamates or a mixture of two or more thereof.   The power transmission belt according to claim 1, wherein the core wire comprises at least one cord selected from polyester fiber, aramid fiber, vinylon fiber, and nylon fiber.   Both a compression rubber layer made of ethylene-α-olefin-diene rubber and an adhesive rubber layer are vulcanized and bonded, and a core cord made of a fiber cord bonded with resorcin-formalin-latex is bonded to the adhesive rubber layer. In the method for producing an embedded transmission belt, the rubber component of the latex is 20 to 80% by weight selected from chlorosulfonated polyethylene and alkylated chlorosulfonated polyethylene in solid content, vinylpyridine latex, carboxyl-modified vinyl From 80 to 20% by weight of at least one selected from pyridine latex, chloroprene latex, 2,3-dichlorobutadiene latex, nitrile rubber latex, carboxyl group-containing hydrogenated nitrile rubber latex and styrene-butadiene rubber latex The core is impregnated with resorcin-formalin-latex, dried by heating, and subjected to an adhesion treatment. Thus, the unvulcanized ethylene-α-olefin-diene for forming the adhesion rubber layer is formed on the adhesion-treated core. Placed between the rubber sheets, this unvulcanized ethylene-α-olefin-diene rubber sheet is laminated on the unvulcanized ethylene-α-olefin-diene rubber sheet to form the compression rubber layer, and thus A method for producing a transmission belt, wherein the obtained laminate is heated under pressure and vulcanized.   The method for producing a transmission belt according to claim 7, wherein the resorcin-formalin-latex contains a nonionic surfactant as a compatibilizing agent.   The method for producing a transmission belt according to claim 7, wherein the resorcin-formalin-latex contains a metal oxide and a sulfur-containing vulcanization accelerator.   The method for manufacturing a transmission belt according to claim 9, wherein the metal oxide is zinc oxide, magnesium oxide, or lead oxide.   The method for producing a transmission belt according to claim 9, wherein the sulfur-containing vulcanization accelerator is thiazoles, sulfenamides, thiurams, dithiocarbamates or a mixture of two or more thereof. The method for manufacturing a transmission belt according to claim 7, wherein the core wire is made of at least one cord selected from polyester fiber, aramid fiber, vinylon fiber, and nylon fiber.

Images