JP6486156B2 - Toothed belt and manufacturing method thereof - Google Patents

Description

  The present invention relates to a toothed belt having a transmission surface (meshing transmission surface) covered with a fiber material (tooth cloth), and relates to a toothed belt capable of reducing the frictional resistance of the fiber material over a long period of time and a method for manufacturing the same.

  In a belt transmission system, a toothed belt (timing belt) having a tooth portion for meshing with a pulley is used as a transmission belt. For example, the toothed belt is used to simultaneously drive auxiliary machines such as a camshaft of an automobile engine and pumps (an injection pump, an oil pump, a water pump, etc.). Such toothed belts (timing belts) are required to be used more severely as the engine output is increased and the engine room is made more compact, and further improvement in durability is required. The same applies to toothed belts used in general industrial machines, and it is required to extend the belt replacement cycle.

  Such a failure mode of the toothed belt is roughly classified into a belt cutting due to fatigue of the core wire and a tooth chip due to overload or tooth wear. For cutting due to fatigue of the core wire, improvement on the belt side (use of aramid core wire or high-strength glass thin core wire, use of hydrogenated nitrile rubber (H-NBR) compound with excellent heat resistance), Improvements have been made by improvements on the engine side (use of an auto tensioner that keeps the belt tension constant at both starting and running), and the occurrence of cutting failures has been reduced.

  In addition, for tooth chipping due to overload and tooth wear, the tooth part that is the pulley contact surface of the toothed belt is reinforced to suppress tooth chipping caused by wear resistance, resulting in durability. The following are prior art techniques for improving the performance.

  JP 2000-240730 (Patent Document 1) impregnates and adheres a rubber composition (rubber glue) in which a fluororubber is mixed with a rubber of the same type as a tooth portion onto a tooth cloth covering the surface of the tooth portion. A vulcanized toothed belt is described, and Japanese Patent Application Laid-Open No. 2013-108564 (Patent Document 2) forms a tooth portion by vulcanizing and molding a rubber composition containing a hydrogenated nitrile rubber, resorcinol, a melamine compound, and the like. It is described to do. JP 2009-127173 A (Patent Document 3) describes a toothed belt in which a tooth cloth including polyethylene naphthalate fibers is arranged in the length direction, and JP 2010-210088 A (Patent Document 4). Describes that a tooth part is covered with a tooth surface protection layer of a canvas and a rubber sheet. JP 2001-32887 A (Patent Document 5) describes an adhesive component, a rubber component, and a fluororesin powder on a tooth fabric. It has been proposed to impregnate a powder-type antifriction material containing, thereby reducing the friction coefficient of the tooth cloth.

  Each of the techniques described in these documents is effective. However, in recent years, the wear resistance is not sufficient from the required high durability level. In particular, high durability (high wear resistance, chipping resistance, etc.) cannot be maintained during traveling under severe conditions (such as high temperature and high load).

  On the other hand, it has also been proposed to modify the rubber surface (improvement of wear resistance, adhesion, water / oil repellency, solvent resistance) with a silane compound. For example, in JP-A-11-166060 (Patent Document 6), a reinforcing agent liquid containing alkoxysilane is applied to a vulcanized rubber, and a mixed liquid containing water and a catalyst is applied to the coated surface. It is described that a hydrolyzed polycondensate of alkoxysilane is produced on the surface layer of vulcanized rubber to modify the surface of the rubber, and International Publication No. 2002/038655 (Patent Document 7) describes silane coupling. JP-A-2004-352742 (Patent Document 8) describes that surface-modified rubber is obtained as a recycled material by immersing waste vulcanized rubber in a solution containing an agent to improve the adhesion of the rubber surface. It describes that a rubber surface is treated with a surface treatment composition containing a fluorine-containing silane coupling agent, a polyfunctional alkoxysilane, a silane coupling agent, and a solvent. In JP-A-11-335493 (Patent Document 9), a crosslinked rubber in which an inorganic filler is dispersed is immersed and swelled in a reinforcing agent solution containing alkoxysilane, and the swollen crosslinked rubber is immersed in catalyst water. The production of hydrolyzed polycondensates of alkoxysilanes is described.

  However, these documents do not describe the relationship between the silane coupling agent and the toothed belt. In particular, there is no description about improving the durability by suppressing the tooth chipping of the tooth portion of the toothed belt. In addition, in the methods described in these documents, it is necessary to use a combination of a plurality of types of compounds, and the process is complicated. Therefore, it is difficult to manufacture a toothed belt with ease and high productivity.

JP 2000-240730 A (Claims) JP 2013-108564 A (Claims) JP 2009-127173 A (Claims) JP 2010-210088 (Claims) JP 2001-32887 A (Claims) JP-A-11-166060 (Claims) International Publication No. 2002/038655 (Claims) JP 2004-352742 A (Claims) JP-A-11-335493 (Claims)

  Accordingly, an object of the present invention is to provide a toothed belt having high durability, particularly wear resistance and chipping resistance, and a method for producing the same.

  Another object of the present invention is to provide a toothed belt capable of maintaining high wear resistance and chipping resistance even when traveling under extremely severe conditions such as high temperature and high load, and a method for manufacturing the same. is there.

  Still another object of the present invention is to provide a method by which a toothed belt having excellent characteristics as described above can be easily produced.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have been able to reduce the friction coefficient of the tooth cloth and improve the wear resistance when the tooth cloth, which is the pulley contact surface of the toothed belt, is impregnated with a silane compound. The present invention has been completed by finding out what can be done.

  That is, the toothed belt of the present invention includes a tooth portion that can mesh with a toothed pulley, and a tooth cloth that covers the tooth portion, and the tooth cloth is a silane compound having a hydrolytic condensable group. It has been treated (impregnated or infiltrated).

  The silane compound may be a silane coupling agent such as a silane coupling agent having an amino group. Such a silane coupling agent may be contained at least on the surface of the tooth cloth. The silane coupling agent may be impregnated in the tooth cloth and may be polycondensed. The silane coupling agent has an organic functional group that interacts with (or can react with) the fiber or rubber composition that constitutes the tooth cloth, and an alkoxy group that can be hydrolyzed and subsequently dehydrated or dealcoholized. Yes. Therefore, by impregnating the tooth cloth with a silane coupling agent and reacting (for example, reaction by heating), the fibers constituting the tooth cloth and / or between the fibers and the rubber composition (poly) It is considered that a siloxane or silsesquioxane skeleton is formed, the fibers and / or the fibers and the rubber composition are firmly bonded, and the tooth cloth surface can be covered with the (poly) siloxane bond. That is, by treating the surface of the tooth cloth and / or between the constituent fibers of the tooth cloth with a silane coupling agent (that is, impregnation and condensation reaction of the silane coupling agent), the tooth cloth can be reinforced and the fiber and rubber composition. The object can be firmly bonded, and the friction coefficient can be reduced. Therefore, it is possible to effectively improve the wear resistance of the tooth portion of the toothed belt and greatly improve the durability of the toothed belt.

  The fibers forming the tooth cloth may include, for example, at least one selected from cellulosic fibers, polyester fibers, polyamide fibers, polybenzoxazole fibers, and the woven structure of the tooth cloth is a plain weave, A twill or satin weave may be used. Further, the rubber component of the rubber composition forming the tooth part is, for example, from hydrogenated nitrile rubber (H-NBR), chloroprene rubber (CR), chlorosulfonated polyethylene (CSM) and alkylchlorosulfonated polyethylene (ACSM). At least one selected may be included.

The treatment amount (impregnation amount) of the silane compound with respect to the tooth cloth may be about 1 to 60 mg / cm ² per unit area of the tooth cloth. Further, the impregnation depth of the silane compound into the tooth cloth may be about 100 to 1000 μm.

  The present invention also includes a method for manufacturing the toothed belt including an impregnation step of impregnating a tooth cloth of the toothed belt with a silane compound. For example, the surface of the tooth cloth of the toothed belt that can mesh with the toothed pulley is brought into contact with the silane compound for a predetermined time, and the silane compound or a condensation reaction product thereof is contained between the surface of the tooth cloth or the fibers constituting the tooth cloth. Also good.

  The production method of the present invention may include a removing step of removing the silane compound (excess silane compound) adhering to the surface of the tooth cloth after impregnating the silane compound, and reacting the silane compound (or A condensation step, a heat treatment or a heating step). The present invention also includes a toothed belt obtained by this manufacturing method.

  In the present invention, since the tooth cloth of the toothed belt is impregnated with the silane compound, the friction coefficient of the tooth cloth can be reduced, and the wear resistance of the toothed belt can be improved. Therefore, durability (especially wear resistance and tooth chipping resistance) of the toothed belt can be improved. In particular, high durability can be maintained even when traveling under extremely severe conditions such as high temperature and high load. Furthermore, since this toothed belt can be manufactured by a simple method of contacting (impregnating) a silane compound with a tooth cloth, the productivity is high.

FIG. 1 is a cross-sectional perspective view showing an example of a toothed belt according to the present invention. FIG. 2 is a scanning electron micrograph of a test piece after immersion treatment with a silane coupling agent. FIG. 3 is a SiKα ray image of a test piece after immersion treatment with a silane coupling agent. FIG. 4 is a scanning electron micrograph of the toothed belt of Example 1. FIG. 5 is a SiKα ray image of the toothed belt of Example 1. FIG. 6 is a schematic view showing a running test apparatus. FIG. 7 shows a scanning electron micrograph of the cross section of the tooth portion of the toothed belt of Example 1 after the running test (running time: 1500 hours). FIG. 8 shows a scanning electron micrograph of the surface of the tooth section of the toothed belt of Example 1 after the running test (running time: 1500 hours), and FIG. 8 (a) is the front side of the tooth section (in the running direction). A scanning electron micrograph of the front side and FIG. 8B shows a scanning electron micrograph of the rear side of the tooth portion (rear side in the running direction). FIG. 9 shows a scanning electron micrograph of the cross section of the tooth portion of the toothed belt of Example 2 after the running test (running time: 1500 hours). FIG. 10 shows a scanning electron micrograph of the surface of the tooth section of the toothed belt of Example 2 after the running test (running time: 1500 hours), and FIG. 10 (a) is the front side of the tooth section (in the running direction). A scanning electron micrograph of the front side, FIG. 10B shows a scanning electron micrograph of the rear side of the tooth portion (rear side in the running direction). FIG. 11 shows a scanning electron micrograph of the cross section of the tooth portion of the toothed belt of the comparative example after the running test (running time: 200 hours). FIG. 12 shows a scanning electron micrograph of the surface of the tooth section of the toothed belt of the comparative example after the running test (running time: 200 hours), and FIG. 12 (a) is the front side of the tooth part (front side in the running direction). ), And FIG. 12B shows a scanning electron micrograph of the rear side of the tooth portion (rear side in the running direction). FIG. 13 shows a scanning electron micrograph of the cross section of the tooth portion of the toothed belt of the comparative example after the running test (running time: 1500 hours). FIG. 14 shows a scanning electron micrograph of the surface of the tooth section of the toothed belt of the comparative example after the running test (running time: 1500 hours), and FIG. 14 (a) is the front side of the tooth part (front side in the running direction). ), And FIG. 14B shows a scanning electron micrograph of the rear side of the tooth part (rear side in the running direction).

  FIG. 1 is a cross-sectional perspective view showing an example of a toothed belt according to the present invention. The toothed belt 1 has a plurality of tooth portions 2 formed at predetermined intervals along the longitudinal direction of the belt (arrows in the figure). And a back portion 4 in which a plurality of core wires 3 are embedded along the longitudinal direction of the belt, and a tooth cloth 5 is adhered (covered or laminated) on the surface of the tooth portion 2. In addition, the tooth | gear part 2 is formed in the trapezoid shape in the longitudinal cross-section. Further, the tooth cloth 5 is composed of a plurality of wefts 6 extending in the longitudinal direction of the belt 1 and warps 7 extending in the lateral direction of the belt 1.

  The shape of the toothed belt is not limited to the structure shown in FIG. 1, and a plurality of toothed belts are formed on at least one surface of the belt at a predetermined interval in the longitudinal direction of the belt and can mesh with a toothed pulley. What is necessary is just to have the tooth | gear part or convex part. The cross-sectional shape of the tooth portion or the convex portion (the cross-sectional shape in the longitudinal direction or the width direction of the belt) is not limited to the trapezoidal shape. (Triangle, quadrangle (rectangle, etc.), etc.) may be used. Moreover, the space | interval of the tooth | gear part or convex part adjacent to a longitudinal direction may be about 1-10 mm, for example, Preferably about 2-8 mm according to the form of a tooth-like pulley.

  In the following description, the tooth portion and the convex portion are treated synonymously, and each element of the toothed belt having the structure shown in FIG. 1 will be described.

[Tooth part 2 and back part 4]
(Rubber composition)
The belt body (tooth portion 2 and back portion 4) is formed of a rubber composition, and the rubber composition includes a rubber component and an additive contained as necessary.

  The type of rubber component is not particularly limited. For example, diene rubber, olefin rubber, acrylic rubber, fluorine rubber, silicone rubber, urethane rubber, epichlorohydrin rubber, chlorosulfonated polyethylene rubber [chlorosulfone Polyethylene (CSM), alkylchlorosulfonated polyethylene (ACSM), etc.], olefin-vinyl ester copolymer (for example, ethylene-vinyl acetate copolymer (EAM), etc.), and the like. These rubber components can be used alone or in combination of two or more.

  Examples of the diene rubber include diene monomers such as natural rubber (NR), isoprene rubber (IR), isobutylene-isoprene rubber (butyl rubber) (IIR), butadiene rubber (BR), and chloroprene rubber (CR). Polymer; Acrylonitrile-diene copolymer rubber such as acrylonitrile-butadiene rubber (nitrile rubber) (NBR), acrylonitrile-chloroprene rubber (NCR), acrylonitrile-isoprene rubber (NIR), acrylonitrile-isoprene-butadiene rubber (NBIR); styrene -Styrene-diene copolymer rubbers such as butadiene rubber (SBR), styrene-chloroprene rubber (SCR), and styrene-isoprene rubber (SIR).

  The diene rubber may be a hydrogenated product. Examples of the hydrogenated product include hydrogenated nitrile rubber (H-NBR). Furthermore, H-NBR may contain an unsaturated carboxylic acid metal salt. The styrene-diene copolymer rubber such as SBR includes a random copolymer of styrene and a diene (such as butadiene) and a block copolymer of a styrene block and a diene block (such as a butadiene block). These diene rubbers can be used alone or in combination of two or more.

Examples of the olefin rubber include ethylene-α-olefin rubber and ethylene-α-olefin-diene rubber. Examples of the α-olefin include chain α-C _3-12 olefins such as propylene, butene, pentene, methylpentene, hexene, and octene. Of these α-olefins, α-C _3-4 olefins (particularly propylene) such as propylene are preferred. Examples of the diene monomer usually include non-conjugated diene monomers such as dicyclopentadiene, methylene norbornene, ethylidene norbornene, 1,4-hexadiene, and cyclooctadiene. Of these diene monomers, ethylidene norbornene and 1,4-hexadiene (particularly ethylidene norbornene) are preferred.

  Examples of typical olefin rubbers include ethylene-propylene rubber (EPR) and ethylene-propylene-diene copolymers (EPDM, etc.). These olefin rubbers can be used alone or in combination of two or more.

  Furthermore, these rubber components may be modified rubbers (for example, CR, NBR, NCR, SBR, SCR, H-NBR, etc.) into which a functional group such as a carboxyl group or a reactive group has been introduced.

  Of these rubber components, chlorosulfonated polyethylene rubber (CSM, ACSM, etc.), diene rubber (NBR, CR, H-NBR, etc.), olefin rubber (EPDM, EPR, etc.) are often used. . The rubber component forming the belt body (tooth portion 2 and back portion 4) is selected according to the use conditions and the like. For example, toothed belts used for general industrial machines include diene rubber [NR, IR, CR, NBR, SBR, H-NBR, etc.], olefin rubber [EPDM, EPR, etc.], fluoro rubber, silicone rubber, Chlorosulfonated polyethylene rubber [CSM, ACSM, etc.] can be used. Further, in a belt (for example, a toothed belt for an automobile engine or various engines) used under severe conditions, a rubber component having heat resistance and oil resistance, for example, a diene rubber [H-NBR, CR, etc.], chlorosulfonated polyethylene rubber [CSM, ACSM, etc.] can be used.

(Additive or compounding agent)
The rubber composition forming the belt body (tooth portion 2 and back portion 4) may contain various conventional additives (or compounding agents) as necessary.

  Examples of additives include vulcanizing agents or crosslinking agents [for example, oximes (such as quinonedioxime), guanidines (such as diphenylguanidine), metal oxides (such as magnesium oxide and zinc oxide), and organic peroxides (such as Diacyl peroxide, peroxy ester, dialkyl peroxide, etc.)], vulcanization aid, vulcanization accelerator, vulcanization retarder, reinforcing agent (such as silicon oxide such as carbon black and hydrous silica), metal oxide ( For example, zinc oxide, magnesium oxide, calcium oxide, barium oxide, iron oxide, copper oxide, titanium oxide, aluminum oxide), filler (clay, calcium carbonate, talc, mica, etc.), plasticizer, softener (paraffin oil) Oils such as naphthenic oil), processing agents or processing aids (stearic acid, stearic acid) Metal salts, waxes, paraffins, etc.), anti-aging agents (aromatic amines, benzimidazole anti-aging agents, etc.), adhesion improvers (resorcin-formaldehyde cocondensates, melamine resins such as hexamethoxymethyl melamine, these Cocondensates (resorcinol-melamine-formaldehyde cocondensate, etc.)], colorants, tackifiers, coupling agents (silane coupling agents, etc.), stabilizers (antioxidants, UV absorbers, heat stabilizers, etc.) ), Lubricants, flame retardants, antistatic agents and the like. If necessary, the rubber composition may be short fibers (cellulosic fibers such as cotton and rayon, polyester fibers (PET fibers, etc.), polyamide fibers (aliphatic polyamide fibers such as polyamide 6, aramid fibers, etc.), etc. Short fibers) may be included. These additives can be used singly or in combination of two or more, and can be selected according to the type, application, performance, etc. of the rubber component.

  The proportion of the additive can be appropriately selected according to the type of rubber component. For example, the ratio of the reinforcing agent (carbon black or the like) is 10 parts by mass or more (for example, 20 to 150 parts by mass), preferably 25 to 120 parts by mass, more preferably 35 to 100 parts by mass with respect to 100 parts by mass of the rubber. Part (for example, 35 to 80 parts by mass).

  In addition, as long as the adhesiveness of the tooth part 2 and the back part 4 is not impaired, a different rubber composition may be sufficient as the rubber composition which forms the tooth part 2 and the back part 4, and it is the same rubber composition. Also good. Usually, the tooth part 2 and the back part 4 may contain the same series of rubbers (for example, rubbers belonging to a diene rubber and different types) or the same type of rubber components (for example, the same type of diene rubbers). Many.

(Core 3)
In the belt body, core wires (usually a plurality of core wires) extending along the longitudinal direction of the belt are embedded from the viewpoint of running stability and belt strength.

  The fiber forming the core wire is not particularly limited, and examples thereof include polyester fibers (polyalkylene arylate fibers, polyparaphenylene naphthalate), polybenzoxazole fibers, acrylic fibers, polyamide fibers, and aramid fibers. Examples thereof include inorganic fibers such as synthetic fibers, glass fibers, carbon fibers, and metal fibers (steel fibers). These fibers can be used alone or in combination of two or more. As the fiber forming the core wire, from the viewpoint of low elongation and high strength, for example, synthetic fibers such as polyester fibers, polyamide fibers and aramid fibers, inorganic fibers such as glass fibers and carbon fibers, etc. are generally used. Glass cores and aramid cores are used. The composition of the glass core is not particularly limited, and may be E glass, S glass (high strength glass), C glass, or the like.

  As the core wire (tensile body), a multifilament yarn twisted cord (for example, various twists, single twists, Lang twists, etc.) can be used. The thickness of the filament, the number of filaments converged, and the number of strands are not particularly limited, and the average wire diameter (fiber diameter of the twisted cord) of the core wire is, for example, 0.5 to 3 mm, preferably 0.6 to 1 mm. Preferably, it may be about 0.7 to 0.8 mm.

  The plurality of core wires may be embedded at a predetermined interval (or pitch) (or at equal intervals) in the width direction of the belt. The interval (spinning pitch) between adjacent core wires may be, for example, about 0.5 to 2 mm, preferably about 0.8 to 1.5 mm, depending on the diameter of the core wires.

  The core wire may be subjected to adhesion treatment with various adhesion treatment agents (for example, epoxy compounds, isocyanate compounds, etc.) in order to improve the adhesion with the rubber component. You may surface-treat with a coating agent etc. A glass fiber or the like may be coated with a protective agent (such as the sizing agent, the RFL treatment liquid, or the overcoat agent) to suppress breakage of the glass fiber due to bending.

(Tooth cloth 5)
A tooth cloth 5 is coated or laminated on the tooth portion 2 of the toothed belt 1 which is a pulley contact surface, and the tooth cloth 5 is integrated with the tooth portion 2.

Examples of fibers forming the weft 6 and the warp 7 of the tooth cloth 5 include, for example, cellulose fibers [cellulose fibers (cellulose fibers derived from plants such as cotton, animals or bacteria), regenerated cellulose fibers such as rayon, cellulose ester fibers, etc. ], Polyolefin fiber (polyethylene fiber, polypropylene fiber, etc.), vinyl alcohol fiber (polyvinyl alcohol, ethylene-vinyl alcohol copolymer fiber, vinylon, etc.), polyamide fiber (polyamide 6 fiber, polyamide 66 fiber, polyamide 46 fiber) Aliphatic polyamide fiber such as aromatic polyamide fiber such as aramid fiber), polyester fiber [eg, polyethylene terephthalate (PET) fiber, polypropylene terephthalate (PPT) fiber, polytrimethylene terephthalate PTT) fibers, _{C 2-4} alkylene _{C 6-14} arylate fibers such as polyethylene naphthalate (PEN) fibers, polyarylate fibers, including full aromatic polyester fibers such as liquid crystal polyester fibers, polyphenylene ether fibers Examples thereof include polyether ether ketone fibers, polyether sulfone fibers, polybenzoxazole fibers (such as polyparaphenylene benzobisoxazole (PBO) fibers), polyurethane fibers, and inorganic fibers such as carbon fibers. These fibers can be used alone or in combination of two or more.

  Among these fibers, cellulose fibers such as cotton and rayon, polyester fibers (PET fibers, etc.), polyamide fibers (aliphatic polyamide fibers such as polyamide 66 fibers, aramid fibers, etc.), polybenzoxazole fibers, etc. General purpose. In particular, at least polyamide-based fibers (aliphatic polyamide fibers such as polyamide 66 fibers, aramid fibers, etc.) are preferably used in order to extend the life of the belt even under severe conditions.

  The form of the fiber is not particularly limited, and may be either a filament yarn or a spun yarn, and may be a twisted yarn, a mixed twisted yarn, a blended yarn, or the like of a single composition fiber.

  The average diameter of the fibers (or yarns) constituting the tooth cloth may be any thickness that allows the silane compound to penetrate or impregnate between the fibers, and may be, for example, about 5 to 100 μm, preferably about 10 to 50 μm. Good. Moreover, the average fiber diameter (thickness) of the yarn (twisted yarn) formed from the fibers is, for example, about 100 to 1000 dtex (for example, 200 to 800 dtex), preferably about 300 to 700 dtex (for example, 400 to 600 dtex) for the weft. It may be 50 to 500 dtex (for example, 75 to 400 dtex), preferably about 100 to 300 dtex (for example, 100 to 200 dtex) in the warp.

  The woven structure (woven structure) of the tooth cloth is not limited as long as the silane compound can permeate or impregnate. For example, the structure of twill weave (oblique texture), satin weave (lion cloth, satin), plain weave, etc. Good. Such a woven structure is useful for impregnating a silane compound. Note that the twill and satin weave structures have fewer contact points of fibers (or yarns) than the plain weave structures, and the impregnation of the silane compound seems to be higher.

  The density (w / cm) of the weft may be, for example, about 5 to 50 (for example, 10 to 40), preferably about 15 to 35 (for example, 20 to 30), and the density of the warp (w / cm). May be, for example, about 10 to 300 (for example, 20 to 250), preferably about 25 to 100 (for example, 30 to 70).

  The thickness of the tooth cloth is not particularly limited, and may be, for example, about 0.3 to 1.5 mm (for example, 0.5 to 1.3 mm), preferably about 0.6 to 1.2 mm.

  In order to enhance the adhesion between the belt body (tooth portion 2 and back portion 4) and the tooth cloth, the tooth cloth may be subjected to an adhesion treatment. Examples of the adhesion treatment include a treatment liquid containing a reactive adhesion component such as an epoxy compound (or resin), an isocyanate compound (or polyisocyanate), a silane coupling agent, and an organic solvent (toluene, xylene, methyl ethyl ketone, etc.). A method of immersing the cloth; a method of immersing the tooth cloth in an aqueous treatment liquid such as an RFL treatment liquid; a rubber composition obtained by dissolving the rubber composition in an organic solvent; Examples thereof include a method of impregnating and adhering a rubber composition to a cloth. These methods can be performed alone or in combination, and the processing order and the number of processing are not particularly limited. In order to further improve the adhesion between the adhesive-treated tooth cloth and the rubber of the belt main body, the tooth cloth and the rubber composition are passed through a calender roll, and the rubber composition of the belt main body is imprinted on the tooth cloth. You may perform the process which laminates | stacks a rubber composition on the adhesion surface side with a tooth | gear part among cloth. In addition, as the rubber composition impregnated in the tooth cloth (or the rubber composition imprinted on the tooth cloth or laminated on the adhesive surface with the tooth part), the rubber composition forming the belt body (the tooth part 2 and the back part 4). The same or different rubber composition can be used. As the rubber composition, the same rubber composition as that of the belt main body (tooth portion 2 and back portion 4) is often used.

  The RFL treatment liquid is a mixture in which an initial condensate of resorcin and formalin is mixed with latex, and the latex is not particularly limited. For example, styrene-butadiene-vinylpyridine terpolymer, hydrogenated nitrile rubber Chlorosulfonated polyethylene, epichlorohydrin rubber, and the like.

(Silane treatment of tooth cloth)
(Silane compound)
When the tooth cloth is treated with the impregnating agent containing the silane compound, the friction resistance between the tooth cloth and the pulley can be reduced, the tooth cloth can be reinforced or strengthened, and the wear resistance of the toothed belt can be improved. Furthermore, the durability between the tooth cloth and the tooth portion can be improved, and the wear resistance and chipping resistance of the toothed belt can be greatly improved even when the toothed belt is run under severe conditions.

  As the silane compound, a silane compound having a hydrolytic condensable group can be used to reduce the friction coefficient between the tooth cloth and the pulley and reinforce or strengthen the tooth cloth.

Examples of the hydrolytic condensable group of the silane compound include a hydroxyl group (silanol group); a linear or branched C _1-4 alkoxy group such as a methoxy group, an ethoxy group, and a butoxy group (particularly, a C _1-2 alkoxy group). ); Halogen atoms such as chlorine atom and bromine atom. The hydrolytic condensable group is often a methoxy group or an ethoxy group.

Silane compounds having a hydrolytic condensable group include tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane; alkylalkoxysilanes such as methyltrimethoxysilane (and corresponding alkylhydroxysilanes and alkylhalosilanes such as methyl Di- or tri-C _1-4 silanols such as trisilanol and dimethyldisilanol, C _1-4 alkyltrichlorosilanes such as methyltrichlorosilane); arylalkoxysilanes such as phenyltrimethoxysilane and diphenyldimethoxysilane (and corresponding to these) Arylhalosilanes and arylhalosilanes); trihalo C _1-4 alkyl tri C _1-4 alfa such as trifluoropropyltrimethoxysilane, trichloropropyltrimethoxysilane Kokishishiran, perfluorooctyl ethyl trimethoxysilane, perhaloalkyl C _1-4 alkyl tri C _1-4 alkoxysilane such as perchlorethylene octyl trimethoxysilane, chloro C _1-4 alkyl birds such as 2-chloroethyl trimethoxysilane C _1-4 alkoxysilane and the like may be used. A preferred silane compound is a silane coupling agent having an organic functional group (polar group) that interacts with the fiber and / or rubber component of the tooth cloth, particularly a reactive functional group capable of reacting.

  Silane coupling agents include halogen-containing silane coupling agents, amino group-containing silane coupling agents, epoxy group-containing silane coupling agents, isocyanate group-containing silane coupling agents, ureido group-containing silane coupling agents, and mercapto group-containing silanes. A coupling agent, a carboxyl group-containing silane coupling agent, an ethylenically unsaturated bond group-containing silane coupling agent, and the like are included.

Examples of the amino group-containing silane coupling agent include amino C _2-4 alkyl-C _1-4 alkyldiC _1-4 alkoxysilane such as 3-aminopropylmethyldimethoxysilane, 2-aminoethyltrimethoxysilane, 3- Amino C _2-4 alkyltri C _1-4 alkoxysilanes such as aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- [N- (2-aminoethyl) amino] propylmethyldimethoxysilane [or N- (2-aminoethyl) -3-aminopropyl amino _{C 2-4} alkylamino _{-C 2-4} alkyl _{-C 1-4} alkyl di _{C 1-4} alkoxysilane such as methyl dimethoxysilane], 3- [N- (2 -Aminoethyl) amino] propyltrimethoxysilane [or N-2- (aminoethyl) Le) -3-aminopropyltrimethoxysilane] amino _{C 2-4} alkylamino _{C 2-4} alkyl tri _{C 1-4} alkoxysilane such as, such as N- phenyl-3-aminopropyltrimethoxysilane N- arylamino _C2-4 alkyltri _C1-4 alkoxysilane etc. are mentioned.

Examples of the epoxy group-containing silane coupling agent include C _2-4 alkyltri C _1-4 alkoxysilane having an alicyclic epoxy group such as 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3- glycidyloxy _{C 2-4} alkyl _{-C 1-4} alkyl di _{C 1-4} alkoxysilane such as glycidyloxypropyl methyl diethoxy silane, 2- glycidyloxy ethyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyl (Glycidyloxy C _1-4 alkoxy) C _2-4 such as glycidyloxy C _2-4 alkyltri C _1-4 alkoxysilane such as oxypropyltriethoxysilane, 3- (2-glycidyloxyethoxy) _{propyltrimethoxysilane} Alkyltri C _Examples include _1-4 alkoxysilane.

Examples of the isocyanate group-containing silane coupling agent include isocyanate C _2-4 alkyltri C _1-4 alkoxysilanes such as 3-isocyanatepropyltrimethoxysilane and 3-isocyanatepropyltriethoxysilane.

Examples of the ureido group-containing silane coupling agent include ureido C _2-4 alkyl C _1-4 alkoxysilanes such as 3-ureidoisopropyltrimethoxysilane and 3-ureidoisopropyltriethoxysilane.

Examples of the mercapto group-containing silane coupling agent include mercapto C _2-4 alkyltri C _1-4 alkoxysilanes such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane.

Examples of the carboxyl group-containing silane coupling agent include carboxy C _2-4 alkyltri C _1-4 alkoxysilane such as 2-carboxyethyltrimethoxysilane.

Examples of the ethylenically unsaturated bond group-containing silane coupling agent include compounds having a vinyl group or (meth) acryloyl group, for example, vinyl tri-C _1-4 alkoxysilane such as vinyltrimethoxysilane, 2- (meth) acrylic. (Meth) acryloxy C _2-4 alkyltri C _1-4 alkoxysilane such as loxyethyltrimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) (meth) acryloxy _{C 2-4} alkyl _{-C 1-4} alkyl di _{C 1-4} alkoxysilane such as acryloxypropyl methyl dimethoxy silane.

These silane compounds (or silane coupling agents) can be used alone or in combination of two or more. Among these silane coupling agents, a silane coupling agent having a functional group having a strong interaction with the fiber and rubber component of the tooth cloth (for example, a functional group having reactivity with the fiber), such as an amino group, A silane coupling agent having an epoxy group, an isocyanate group, a ureido group, a mercapto group, or a carboxyl group is preferable, and an amino group-containing silane coupling agent such as an amino C _2-4 alkyl C _1-4 alkoxysilane [for example, 3- Particularly preferred are amino C _2-4 alkyltri C _1-4 alkoxysilanes (especially amino C _2-4 alkyltri C _1-2 alkoxysilanes) such as aminopropyltriethoxysilane.

  Such a silane coupling agent is impregnated in the tooth cloth and polycondensed. That is, by impregnating a tooth cloth with a silane coupling agent and reacting (for example, reacting by heating), fibers of the tooth cloth and / or fibers and a rubber composition are generated by polycondensation ( While being able to bond firmly through a poly) siloxane or silsesquioxane skeleton, the surface of a tooth cloth can be covered with a (poly) siloxane bond. More specifically, when a silane coupling agent is used, it remains in the fibers of the tooth cloth (for example, fibers of polyamide, polyester, cellulose, etc.) and / or the rubber component (for example, rubber of NBR, H-NBR, CR, etc.). Polar groups (for example, reactive groups such as carboxyl group, amino group, hydroxyl group, halogen atom, cyano group, halosulfonyl group) and the reactive functional group of the silane coupling agent can be reacted, It can be cross-linked or cured by using a decomposable group and can effectively reinforce a tooth cloth. Moreover, a silane coupling agent may react with the fiber and / or rubber component of a tooth cloth with the hydrolysis and condensation reaction of a hydrolytic condensable group. Therefore, a reinforcing effect can be expressed by a short impregnation and subsequent treatment.

  If an impregnation agent containing an ethylenically unsaturated bond group-containing silane coupling agent contains a radical polymerization initiator such as an organic peroxide (such as a diacyl peroxide, a peroxy ester, or a dialkyl peroxide), It is also possible to co-vulcanize with the rubber component of the belt body by impregnating the cloth and heating to polymerize.

  Furthermore, the impregnation treatment agent containing a silane compound may be used in combination with a catalyst. For example, in order to promote the condensation reaction of the hydrolytic condensable group, an appropriate amount of water (for example, about 3 to 25% by mass of water) or a catalyst (an acid catalyst such as an inorganic acid such as hydrochloric acid or an organic acid such as acetic acid) May be included. Further, the impregnation treatment agent has a polar group (reactive group) and a functional group according to the combination of the polar group (reactive group) of the fiber and / or rubber component of the tooth cloth and the functional group of the silane coupling agent. The catalyst for promoting reaction with may be contained.

  The silane compound that is liquid at room temperature may be used as it is for the treatment of the tooth cloth, and the silane compound may be diluted with a solvent (water, organic solvent, etc.) and used in the form of a liquid diluted mixture. In the diluted mixed solution, the concentration of the silane compound is, for example, 0.5% by mass or more, preferably 2% by mass or more (for example, 5% by mass or more), more preferably 10% by mass or more (for example, 20% by mass or more). It is. The concentration of the silane compound in the diluted mixed solution is usually 30% by mass or more (particularly 50% by mass or more). In addition, you may use the silane compound (especially silane coupling agent) which has a hydrolytic condensable group in the form of the precondensate condensed beforehand in the solvent, if necessary.

(Impregnation with silane compound)
By contacting (or treating) a silane compound with the tooth cloth, the tooth cloth can be impregnated or infiltrated with the silane compound. The contact or treatment method (or impregnation method) with a silane compound is not particularly limited, and may be a method of immersing a tooth cloth in a liquid silane compound, a method of applying or spraying by spraying or brushing, or the like. A simple method is an immersion method. In the dipping method, at least a part of the surface of the tooth cloth may be immersed, or at least the entire surface, particularly the entire tooth cloth may be immersed. When a highly volatile silane compound is used, the contact or impregnated surface may be covered with a cover or the like in order to suppress evaporation of the silane compound. Further, the contact temperature (or impregnation temperature) is not particularly limited, and the tooth cloth and / or the silane compound is heated to about 30 to 70 ° C. in order to promote penetration or impregnation of the silane compound into the tooth cloth. Although it may be heated, it is usually room temperature in many cases. Further, the contact (or impregnation) of the silane compound with the tooth cloth may be performed under normal pressure, under pressure, or under reduced pressure. For example, the silane compound may be introduced into a container that accommodates the tooth cloth under reduced pressure. .

  The contact time (or impregnation time) between the tooth cloth and the silane compound is not particularly limited, and may be, for example, about 1 minute to 6 hours. In order to allow the silane compound to penetrate into the tooth cloth, for example, It may be about 10 minutes to 3 hours, preferably about 30 minutes to 2 hours.

  The treatment of the tooth cloth with the silane compound may be performed in any step of the belt forming process. For example, (a) the tooth cloth may be contact-treated (impregnated with the silane compound in advance) for belt forming. Well, (b) the tooth cloth part of the vulcanized sleeve obtained by vulcanizing the belt body provided with the tooth cloth may be contact-treated with a silane compound, and (c) the vulcanized sleeve is cut to a predetermined width and prepared. The tooth cloth portion of the toothed belt may be contact-treated with a silane compound. In the method (a), when the tooth cloth is contact-treated with a silane compound in advance and the tooth cloth treated with the silane compound is laminated on the unvulcanized belt body, the tooth cloth and the tooth are formed on the toothed belt. If the silane compound remains on the bonding surface with the part, bonding at the bonding surface may not be sufficient due to the low surface free energy due to the siloxane bond. In order to avoid such a situation, after the vulcanization sleeve or belt is formed as in the methods (b) and (c), the tooth cloth part is contact-treated with a silane compound, and the tooth cloth part is treated with silane. It is preferred to impregnate the compound.

  The silane compound only needs to be impregnated in the tooth cloth, and may be impregnated in at least a part of the tooth cloth. The area ratio of 50% or more (preferably 80% or more) of the entire area of the tooth cloth, particularly It is preferable that substantially the entire surface (100%) is impregnated.

  The impregnation depth of the silane compound in the tooth cloth of the toothed belt is, on average, 10 μm or more, preferably 100 μm or more, more preferably 300 μm or more from the surface of the tooth cloth, and there is no particular upper limit, usually about 1000 μm. It is. The impregnation depth of the silane compound may be, for example, about 60 to 1000 μm, preferably 100 to 1000 μm, and more preferably about 400 to 1000 μm (particularly 500 to 1000 μm) from the viewpoint of improving the durability of the tooth cloth. The impregnation depth of the silane compound can be measured using an energy dispersive X-ray spectrometer (EDS) attached to a scanning electron microscope (SEM), and the portion containing the silane compound relative to the portion not containing the silane compound. Is expressed as a SiKα ray image and can be measured by visual identification.

The impregnation amount (or adhesion ratio) of the silane compound to the tooth cloth is 0.6 to 60 mg / cm ² (for example, 1 to 40 mg / cm ² ), preferably ^{2 to} 30 mg / cm, with respect to the unit area of the tooth cloth. ² (for example, 2.5 to 25 mg / cm ² ), more preferably about 3 to 20 mg / cm ² (for example, 5 to 15 mg / cm ² ). The impregnation amount of the silane compound is, for example, 1 to 60 mg / cm ² , preferably ² to 60 mg / cm ² , more preferably 3 to 60 mg / cm ² (particularly 5 to 60 mg) from the viewpoint of improving the durability of the tooth cloth. / Cm ² ). If the amount of the silane compound impregnated in the tooth cloth is too small, the effect of improving the wear resistance is lowered. If the amount is too large, the reaction product of the silane compound (polysiloxane or silsesquioxane) may be peeled off. The amount of impregnation (or impregnation ratio) of the silane compound with respect to the tooth cloth can be calculated based on the area of the tooth cloth and the weight of the silane compound calculated from the weight difference before and after the impregnation.

  The silane compound may be uniformly dispersed in the tooth cloth, but is often dispersed non-uniformly, and is usually dispersed with an inclination so that the concentration becomes higher as it approaches the tooth cloth surface. .

  The silane compound may be contained at least in the tooth cloth, and may be impregnated in a portion other than the pulley contact surface (tooth cloth) of the belt.

(Removal process)
After being subjected to the impregnation step with the silane compound, if the silane compound is subjected to the subsequent step with the excess silane compound adhering to the surface of the tooth cloth, siloxane and silsesquioxane, which are reaction products of the silane compound, remain attached, and the tooth The adhesion between the part and the tooth cloth may be reduced, or may be peeled off when the belt is operated. Therefore, it is preferable to remove excess silane compound adhering to the tooth cloth.

  The removal method is not particularly limited, and may be, for example, a method of wiping using a fiber structure such as a woven fabric or a nonwoven fabric, a method of rinsing with a solvent such as alcohol, a centrifugal separation method, or the like. From the viewpoint of simplicity, a wiping method is preferred.

  After removing the silane coupling agent, it may be dried by natural drying such as air drying. The reaction of the silane compound usually proceeds with time. Therefore, it is not particularly necessary, but if necessary, heat treatment (for example, heat treatment at about 30 to 120 ° C., preferably about 50 to 100 ° C.) may be performed to promote the reaction of the silane compound.

(Toothed belt molding method)
The toothed belt can be formed by a known method. For example, a step of winding a canvas forming a tooth cloth around a cylindrical mold having a plurality of recesses corresponding to tooth portions of a toothed belt, and a cylindrical cord around which a tooth cloth is wound, a cord forming a cord Unwrapped rubber for forming a back portion and a tooth portion, a step of winding at a predetermined pitch (predetermined pitch with respect to the axial direction of the cylindrical mold) in the longitudinal direction (circumferential direction) of the cylindrical mold, a step of spinning spirally The step of forming an unvulcanized sleeve (unvulcanized laminate) by winding a sheet, the cylindrical sheet around which the unvulcanized sleeve is wound is transferred into a vulcanizing can, and heated and pressurized to thereby form the rubber sheet. Is pressed into a mold groove (outer mold groove) and vulcanized to form teeth (step of forming a vulcanized laminate having teeth), and the obtained sleeve-shaped molded body has a predetermined cut width. According to Through the step of cutting by the cutting blade Te can produce toothed belts. As described above, the impregnation of the tooth cloth with the silane compound may be performed in any step.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

[Raw materials]
H-NBR: “Zetpole 2021” manufactured by Nippon Zeon Co., Ltd.
Zinc oxide: “Zinc oxide 3 types” manufactured by Shodo Chemical Industry Co., Ltd.
Carbon black: “Seast V” manufactured by Tokai Carbon Co., Ltd., average particle size 55 nm
Vulcanization accelerator: “N-cyclohexyl-2-benzothiazole sulfenamide” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.

[Silane treatment of dentition (impregnation treatment of silane compound) and confirmation of silane compound]
As a tooth cloth, a canvas (manufactured by Asahi Kasei Co., Ltd.) having the following configuration was used.

-Composition Weft: 66 nylon + urethane yarn, warp: 66 nylon-Thread composition Weft: 465 dtex, Warp: 155 dtex
Density Weft: 80 / 3cm, Warp: 150 / 3cm
・ Weave structure Twill weave ・ Thickness 0.85mm
A rubber composition having a formulation shown in Table 1 was dissolved in methyl ethyl ketone to prepare a rubber paste, and this tooth paste was impregnated with the rubber paste. Moreover, the rubber sheet (sheet thickness: 2.0 mm) of the rubber composition of the mixing | blending prescription shown in Table 1 was prepared. Then, the tooth cloth impregnated with the rubber paste and the rubber sheet were laminated, and press vulcanized at 153 ° C. for 30 minutes to prepare a test piece (size: 50 mm × 50 mm × 2.5 mm). After immersing this test piece in the silane coupling agent shown in Table 2 at room temperature and normal pressure for 30 minutes, excess silane coupling agent shown in Table 2 adhering to the surface was wiped off with clean cloth and air-dried for about 1 hour. .

The impregnation amount (ratio) of the silane compound was calculated from a weight difference before and after the silane treatment at a site of 20 mm × 40 mm from the test piece. The results are shown in Table 2. The impregnation amount (ratio) of the silane compound was 4.0 to 15.0 mg / cm ² per unit area of the tooth cloth.

[Measurement of dynamic friction coefficient]
Table 2 shows the dynamic friction coefficient of the tooth cloth surface of the test piece before and after the immersion treatment with respect to the stainless steel plate (SUS plate). The coefficient of dynamic friction is such that the test piece is placed on the moving table with the tooth cloth surface facing the moving table, a weight (load) of 200 to 700 g is placed on the test piece, and the moving table is moved at 10 mm / s. The frictional force was calculated by measuring with a load cell connected to the test piece. The dynamic friction coefficient was calculated from the equation F = μW (F: friction force, μ: dynamic friction coefficient, W: load). The results are shown in Table 2.

  In addition, although the dynamic friction coefficient of the test piece before processing with a silane coupling agent was 0.19, it turns out that a dynamic friction coefficient becomes small by silane processing.

[Cross-sectional SEM observation of test piece]
When 3-aminopropyltriethoxysilane is used as the silane coupling agent, a cross section of the vicinity of the tooth cloth including the interface between the rubber sheet and the tooth cloth of the test piece after the immersion treatment is taken with a scanning electron microscope (SEM) (JEOL) (JSM5900LV) manufactured by Co., Ltd.) and the number of counts of SiKα rays that are characteristic X-rays from each measurement point was heat mapped. FIG. 2 shows a scanning electron microscope (SEM), and FIG. 3 shows a heat-mapped image (SiKα ray image).

  The SiKα line image in FIG. 3 is a heat map of the number of counts of SiKα rays that are characteristic X-rays from each measurement point. From the point where the number of counts is large, white → red → green → blue → black It is expressed in order. Therefore, the distribution of silicon Si can be determined from this SiKα ray image. As is apparent from FIG. 3, a silane compound (Si) is present in the vicinity of the tooth cloth (yarn). In particular, since many counts of SiKα rays (especially white and red) are distributed between the surface of the tooth cloth and the fibers constituting the tooth cloth, these portions are impregnated with 3-aminopropyltriethoxysilane. You can see that In addition, since the test piece before the silane treatment does not contain silicon Si, all detected SiKα rays are derived from 3-aminopropyltriethoxysilane.

[Production of toothed belt]
[Example 1]
As the tooth cloth, the tooth cloth used in the section [Silane treatment of tooth cloth] was used. Similarly to the section of [Silane treatment of tooth cloth], this tooth cloth is impregnated with a rubber paste prepared by dissolving the rubber composition of the formulation shown in Table 1 in methyl ethyl ketone, and the tooth cloth impregnated with the rubber paste; A rubber sheet (sheet thickness: 2.0 mm) of the rubber composition having the formulation shown in 1 was laminated to prepare a laminate.

  The laminate is wound around a mold so that the tooth cloth surface becomes the surface of the belt, and a glass fiber cord (raw yarn: ECG150, strand configuration: 3/11, core diameter: 1.20 mm, treated) on the laminate. : Coated with RFL and rubber), and then a rubber sheet (sheet thickness: 3.0 mm) made of the rubber composition shown in Table 1 was wound. The wound body wound around the mold was vulcanized at 161 ° C. for 20 minutes, and the obtained sleeve was cut into a predetermined width to obtain a belt. The produced belt has a belt width of 19.1 mm, a belt circumferential length of 840 mm, a belt tooth profile HTD, a number of teeth of 105 teeth, and a tooth pitch of 8.000 mm, and is usually indicated as a Y tooth profile. The produced toothed belt was immersed in 3-aminopropyltriethoxysilane at room temperature and normal pressure for 30 minutes. After immersion, excess 3-aminopropyltriethoxysilane adhering to the surface was wiped off with a clean cloth and air-dried for about 1 hour.

[Example 2]
A toothed belt was produced in the same manner as in Example 1 except that the produced toothed belt was immersed in 3-aminopropyltriethoxysilane for 120 minutes at room temperature and normal pressure.

[Example 3]
A toothed belt was produced in the same manner as in Example 1 except that the produced toothed belt was immersed in 3-aminopropyltriethoxysilane at normal temperature and normal pressure for 480 minutes.

[Example 4]
A toothed belt was produced in the same manner as in Example 1 except that the produced toothed belt was immersed in 3-aminopropyltriethoxysilane at room temperature and normal pressure for 5 minutes.

[Example 5]
A toothed belt was produced in the same manner as in Example 1 except that the produced toothed belt was immersed in 3-aminopropyltriethoxysilane at room temperature and normal pressure for 1440 minutes.

[Example 6]
A toothed belt was produced in the same manner as in Example 1 except that the produced toothed belt was immersed in 3-glycidoxypropyltrimethoxysilane at room temperature and normal pressure for 30 minutes.

[Example 7]
A toothed belt was produced in the same manner as in Example 1 except that the produced toothed belt was immersed in 3-isocyanatopropyltriethoxysilane at room temperature and normal pressure for 60 minutes.

[Comparative example]
A toothed belt was produced in the same manner as in Example 1 without immersing the produced toothed belt in 3-aminopropyltriethoxysilane.

[SEM observation of cross section of toothed belt]
The cross section near the tooth cloth surface including the interface between the rubber sheet and the tooth cloth of the toothed belt of Example 1 is observed with a scanning electron microscope (SEM), and SiKα rays, which are characteristic X-rays from each measurement point, are observed. The count number was heat mapped. FIG. 4 shows a scanning electron microscope (SEM), and FIG. 5 shows a heat-mapped image (SiKα ray image).

As indicated by the arrows in FIG. 5, the impregnation of the silane compound can be confirmed in the tooth cloth portion of the belt. Moreover, the impregnation amount (ratio) of the silane compound was calculated from the belt weight difference before and after the immersion treatment. In Example 1 of the present invention, the belt weight difference before and after the immersion treatment was 1.11 g. Moreover, it was 210 cm < ² > when the toothbrush area of the belt was calculated. Therefore, the impregnation amount (ratio) of the silane compound in the belt of Example 1 was 5.3 mg / cm ² per unit area of the tooth cloth. Similarly, the impregnation amounts (ratio) of 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane in the belts obtained in Examples 2 to 7 were also calculated. The results are shown in Table 3.

  In addition, since the impregnation process of the silane compound is performed by immersing the entire belt in the silane coupling agent, the impregnation of a portion (rubber portion) other than the tooth cloth is also considered. However, since there is a gap between fibers that can be attached by penetration or penetration of the silane coupling agent into the tooth cloth, the impregnation rate is high, whereas the silane coupling agent is present in parts other than the tooth cloth (rubber part). Since the gap into which the water penetrates is small, the impregnation speed is small. Therefore, even if the entire belt is immersed, the tooth cloth is preferentially impregnated, and compared with the amount of the silane compound impregnated in the tooth cloth, the silane compound impregnated in the portion other than the tooth cloth (rubber part) The amount of is so small that it can be ignored in terms of weight. Therefore, the increase in the belt weight before and after the dipping treatment can be regarded as the weight of the silane compound impregnated in the tooth cloth.

  Moreover, the impregnation depth of 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane was measured from the heat-mapped images (SiKα ray images) of Examples 1 to 7. did. The results are shown in Table 3.

[Toothed belt running test]
A running test was performed using the toothed belts obtained in the examples and comparative examples. As a running test device, as shown in FIG. 6, a toothed belt is bridged between a 21-tooth drive pulley (Dr) and a 42-tooth driven pulley (Dn), and a diameter 52 mmφ capable of contacting the back (back) A test apparatus equipped with a tension pulley (Ten) was used. Under the conditions of an atmospheric temperature of 120 ° C., a load of 3.68 kW, an initial tension of 147 N, and a driving side rotational speed of 7200 rpm, a running test was performed for 1500 hours for Examples 1 to 7 and 200 hours for Comparative Examples. The state of the tooth cloth of the toothed belt after the running test was observed with a scanning electron microscope and evaluated according to the following criteria. The results are shown in Table 3.

(Criteria)
◎: Less wear on tooth cloth and no fiber cutting ○: A little wear on tooth cloth and some fiber cutting △: High wear on tooth cloth and many fibers cutting ×: Teeth The fabric wears a lot, and many fibers are cut and frayed

  As apparent from the results in Table 3, when the amount of impregnation of the silane compound into the tooth cloth is reduced and the impregnation depth of the silane compound is reduced, the effect of improving the wear resistance is lowered. In addition, if the impregnation amount of the silane compound is too large, the reaction product of the silane compound (polysiloxane or silsesquioxane) may be peeled off, and the abrasion resistance may not be improved in the peeled portion. The amount of useless silane compounds that do not contribute to wear increases, and the cost for processing increases.

  Scanning electron micrographs of the tooth part after the running test (running time: 1500 hours) of Example 1 are shown in FIGS. 7 and 8, and the tooth part after the running test (running time: 1500 hours) of Example 2 is shown. Scanning electron micrographs are shown in FIGS. Moreover, the scanning electron micrograph of the tooth part after the 200-hour running test of the toothed belt of the comparative example is shown in FIGS. 11 and 12, and the scanning electron micrograph of the tooth part after the 1500-hour running test is shown in FIG. 13 and FIG. The traveling direction of the toothed belt is from right to left in the figure.

  As is apparent from FIGS. 7 to 10, the toothed belts of Examples 1 and 2 both include the surface of the tooth cloth at the front and rear of the tooth part, even after the 1500-hour running test. There was little abrasion, and the constituent fibers of the tooth cloth were not cut.

  On the other hand, as is apparent from FIGS. 11 to 12, the toothed belt of the comparative example is a 200-hour running test, and the tooth cloth surfaces of the front and rear portions of the tooth part compared to the toothed belt of the example. In addition, the wear of the tooth cloth increased, and many of the constituent fibers of the tooth cloth were cut. Furthermore, compared to the toothed belt of the example, in the running test for 1500 hours, the tooth cloth wear including the tooth cloth surfaces of the front and rear parts of the tooth part (in particular, the upstream side of the tooth part of the belt in the running direction (see FIG. In the middle, the right inclined side part) the tooth cloth was more worn), the constituent fibers were not only frequently cut, but the constituent fibers were frayed.

  Thus, the abrasion resistance of a tooth cloth part improves by processing with a silane compound. Therefore, even if the toothed belt is operated, durability against the wear of the tooth portion is improved, and the life of the toothed belt can be extended. In addition, it is possible to extend the life even when used under more severe conditions.

  The toothed belt of the present invention is combined with a toothed pulley in various fields where synchronization between input and output is required, for example, power transmission of engines such as automobiles and motorcycles, power transmission of motors and pumps, It can be used for machinery such as automatic doors and automation machines, copying machines, and printing machines. In particular, it can be used as peripheral equipment (peripheral parts) such as a power transmission belt (timing belt or cogged belt) of an automobile engine.

DESCRIPTION OF SYMBOLS 1 ... Toothed belt 2 ... Tooth part 3 ... Core wire 4 ... Back part 5 ... Tooth cloth 6 ... Weft 7 ... Warp

Claims (9)

A toothed belt that can be meshed with a toothed pulley, and a tooth cloth that covers the tooth part, wherein the tooth cloth is treated with a silane coupling agent having an amino group , A toothed belt wherein the tooth cloth is impregnated with the silane coupling agent, and the impregnation depth of the silane coupling agent with respect to the tooth cloth is 100 to 1000 µm . Toothed belt according to claim 1, wherein the silane coupling agent having an amino group is polycondensed. The toothed belt according to claim 1 or 2 , wherein the fibers forming the tooth cloth include at least one selected from cellulosic fibers, polyester fibers, polyamide fibers, and polybenzoxazole fibers. The toothed belt according to any one of claims 1 to 3 , wherein the woven structure of the tooth cloth is a plain weave, a twill weave, or a satin weave. Rubber component of the rubber composition forming the toothing, hydrogenated nitrile rubber, according to the chloroprene rubber, claim 1-4 comprising at least one selected from chlorosulfonated polyethylene and alkylated chlorosulfonated polyethylene Toothed belt. The toothed belt according to any one of claims 1 to 5 , wherein an impregnation amount of the silane coupling agent having an amino group with respect to the tooth cloth is 1 to 60 mg / cm ² per unit area of the tooth cloth. A method for producing a toothed belt, comprising a step of impregnating a tooth cloth covering a tooth part engageable with a toothed pulley with a silane coupling agent having an amino group. After impregnating a silane coupling agent having an amino group, a removal step of removing the silane coupling agent attached to the tooth cloth, The method of claim 7 further comprising the step of reacting the silane coupling agent. A toothed belt obtained by the production method according to claim 7 or 8 .