Transmission belt, method for manufacturing a transmission belt, belt transmission mechanism, and method for improving adhesion

Abstract

The present invention provides a power transmission belt with excellent adhesion (bonding strength) between the silicone rubber layer on the conveying surface and the hydrogenated nitrile rubber layer laminated on the inner circumferential surface of the silicone rubber layer. [Solution] A transmission belt 1 for transporting articles, comprising a core wire 3 extending along the circumferential direction of the belt and an outer peripheral rubber layer 2 formed on the outer peripheral side of the belt relative to the core wire 3, wherein the outer peripheral surface of the outer peripheral rubber layer 2 is used for transporting articles. The outer periphery rubber layer 2 has a laminated structure including a first rubber layer 2a that forms the transport surface which is the outer periphery, an intermediate layer 2b laminated on the inner periphery of the first rubber layer 2a, and a second rubber layer 2c laminated on the inner periphery of the intermediate layer 2b. The first rubber layer 2a is formed from a crosslinked product of a first rubber composition containing silicone rubber, The intermediate layer 2b contains a crosslinked binder component containing an unsaturated carboxylic acid metal salt. The second rubber layer 2c is formed from a crosslinked product of a second rubber composition containing hydrogenated nitrile rubber.

Description

[Technical Field]

[0001] The present invention relates to a power transmission belt for transmitting power and transporting articles using the back surface of the belt, a method for manufacturing a power transmission belt, a belt transmission mechanism, and a method for improving adhesion. [Background technology]

[0002] Power transmission belts are broadly classified into friction belts and meshing belts. Examples of friction belts include flat belts, V-belts, and V-ribbed belts, while examples of meshing belts include toothed belts. These transmission belts consist of a rubber layer and a core (core wire) embedded in the rubber layer. Hydrogenated nitrile rubber (HNBR) is used as one of the polymer components that make up the rubber layer. Hydrogenated nitrile rubber is a highly saturated rubber in which the butadiene unit of nitrile rubber is hydrogenated, and it is an elastomer that combines oil resistance due to the nitrile group with heat resistance due to hydrogenation. For example, Japanese Patent Publication No. 8-118507 (Patent Document 1) and Japanese Patent Publication No. 2014-70644 (Patent Document 2) disclose toothed belts and V-belts using HNBR.

[0003] A power transmission belt is wrapped around the shafts of a drive pulley and a driven pulley and rotates to transmit power. However, depending on the application, it may also serve to transport goods using the back surface of the belt in addition to transmitting power.

[0004] Generally, a conveying surface for conveying an article is formed of a polymer layer containing a silicone component because appropriate grip (friction coefficient), non-sticking property, etc. are required in relation to the conveyed object. For example, as a flat conveyor belt for a belt conveyor, Japanese Patent Application Laid-Open No. 2016-183049 (Patent Document 3) discloses a conveyor belt having a conveying surface formed of a thermoplastic resin or a thermoplastic elastomer containing a silicone component. Further, Japanese Patent Application Laid-Open No. 2016-37338 (Patent Document 4) discloses a conveyor belt including a peroxide vulcanized rubber layer made of a peroxide vulcanized rubber other than silicone rubber and a peroxide vulcanized thermosetting silicone rubber layer laminated on the surface of the peroxide vulcanized rubber layer via a silane coupling agent layer.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0006] The flat conveyor belts of Patent Documents 3 and 4 are belts solely for the purpose of conveying articles, with a relatively small overall thickness and the layer containing a silicone component also being a thin film. On the other hand, in the case of a transmission belt that not only transmits power but also plays a role in conveying articles using the back surface of the belt, since it is necessary to add a layer serving as the conveying surface with the framework for power transmission as the base, the thickness becomes larger compared to the flat conveyor belt. When forming the part of the framework for power transmission with a rubber layer using the aforementioned hydrogenated nitrile rubber, it is necessary to laminate a polymer layer containing a silicone component (for example, a silicone rubber layer) that forms the conveying surface.

[0007] However, silicone components such as silicone rubber are known as difficult-to-adhere materials with low adhesiveness to other components, as they are widely used as release agents and non-sticking materials. In particular, silicone rubber has been selected as a rubber with low adhesiveness also from the aspect of the function where non-stickiness to the conveyed object is required, and there is a trade-off relationship between the function and adhesiveness of the silicone rubber required as the conveying surface, and it is very difficult to adhere (join) the silicone rubber layer and the hydrogenated nitrile rubber layer. Therefore, in the conveyor belt of Patent Document 4, a silane coupling agent layer is interposed as an adhesive layer between the peroxide vulcanized rubber layer and the thermosetting silicone rubber layer, but the adhesiveness is not sufficient.

[0008] Therefore, an object of the present invention is to provide a transmission belt excellent in adhesiveness (bonding strength) between a silicone rubber layer on the conveying surface and a hydrogenated nitrile rubber layer laminated on the inner peripheral surface of this silicone rubber layer, and a manufacturing method thereof.

[0009] Another object of the present invention is to provide a transmission belt with a long endurance running life and a manufacturing method thereof.

Means for Solving the Problems

[0010] As a result of diligent research to achieve the above objectives, the present inventors have discovered that by interposing an intermediate layer containing a crosslinked binder component containing an unsaturated carboxylic acid metal salt between the silicone rubber layer forming the conveying surface of the transmission belt and the hydrogenated nitrile rubber layer, the adhesion (bonding strength) between the silicone rubber layer and the hydrogenated nitrile rubber layer can be improved, thus completing the present invention.

[0011] In other words, the present invention includes the following embodiments.

[0012] Embodiment [1]: A transmission belt comprising a core wire extending along the circumferential direction of the belt and an outer peripheral rubber layer formed on the outer peripheral side of the belt relative to the core wire, wherein the outer peripheral surface of the outer peripheral rubber layer is used to transport articles, The outer periphery rubber layer has a laminated structure including a first rubber layer that forms the transport surface which is the outer periphery, an intermediate layer laminated on the inner periphery of the first rubber layer, and a second rubber layer laminated on the inner periphery of the intermediate layer. The first rubber layer is formed of a crosslinked product of a first rubber composition containing silicone rubber, The aforementioned intermediate layer comprises a crosslinked product of a binder component containing an unsaturated carboxylic acid metal salt, A power transmission belt in which the second rubber layer is formed of a crosslinked product of a second rubber composition containing hydrogenated nitrile rubber.

[0013] Embodiment [2]: The transmission belt according to Embodiment [1], wherein the unsaturated carboxylic acid metal salt comprises zinc methacrylate.

[0014] Embodiment [3]: The transmission belt according to Embodiment [1] or [2], wherein the intermediate layer is formed of a crosslinked product of the binder component, and the binder component is the unsaturated carboxylic acid metal salt.

[0015] Embodiment [4]: ​​The basis weight of the binder component is 50 g / m² 2 The transmission belt according to the above embodiment [3].

[0016] Embodiment [5]: The transmission belt according to Embodiment [1] or [2], wherein the intermediate layer is an intermediate layer formed of a crosslinked product of the binder component, or an intermediate layer formed of a cloth containing a crosslinked product of the binder component, and the binder component is a third rubber composition containing a rubber component and the unsaturated carboxylic acid metal salt.

[0017] Embodiment [6]: The transmission belt according to Embodiment [5], wherein the rubber component comprises silicone rubber and / or hydrogenated nitrile rubber.

[0018] Embodiment [7]: The transmission belt according to Embodiment [5] or [6], wherein the rubber component comprises hydrogenated nitrile rubber, and the proportion of the unsaturated carboxylic acid metal salt is 3 parts by mass or more per 100 parts by mass of the rubber component.

[0019] Embodiment [8]: The average thickness of the cloth is 0.05 to 1 mm, The aforementioned fabric is formed from a woven fabric consisting of warp threads extending in the belt width direction and weft threads extending in the belt circumferential direction, and A transmission belt according to any one of the embodiments [5] to [7], wherein the woven fabric contains polyamide fibers, and the average diameter of the warp threads is 0.3 times or more the average diameter of the weft threads.

[0020] Embodiment [9]: A transmission belt according to any of Embodiments [1] to [8], wherein the average thickness of the first rubber layer is 50 to 80% of the average thickness of the outer rubber layer.

[0021] Embodiment

[10] : A transmission belt according to any of Embodiments [1] to [9], wherein the peel strength between the first rubber layer and the intermediate layer is 30 N / 25 mm or more.

[0022] Embodiment

[11] : A transmission belt according to any of Embodiments [1] to

[10] , which is a toothed belt.

[0023] Embodiment

[12] : A method for manufacturing a power transmission belt according to any one of Embodiments [1] to

[11] , comprising a joining step of joining the first rubber layer and the second rubber layer by crosslinking a first rubber layer precursor formed of the first rubber composition, an intermediate layer precursor containing the binder component, and a second rubber layer precursor formed of the second rubber composition in this order, thereby interposing an intermediate layer between the first rubber layer and the second rubber layer.

[0024] Embodiment

[13] : A transmission belt comprising a core wire extending along the circumferential direction of the belt and an outer rubber layer formed on the outer circumferential side of the belt relative to the core wire, wherein the outer surface of the outer rubber layer is used to transport articles, The outer periphery rubber layer has a laminated structure including a first rubber layer that forms the transport surface which is the outer periphery, an intermediate layer laminated on the inner periphery of the first rubber layer, and a second rubber layer laminated on the inner periphery of the intermediate layer. The first rubber layer is formed from a crosslinked product of a first rubber composition containing silicone rubber, The intermediate layer contains a crosslinked binder component containing an unsaturated carboxylic acid metal salt. A method for improving the adhesion between the first rubber layer and the second rubber layer by forming the second rubber layer with a crosslinked product of a second rubber composition containing hydrogenated nitrile rubber.

[0025] Embodiment

[14] : A belt transmission mechanism for transporting articles, comprising a transmission belt according to any of Embodiments [1] to

[11] and a pulley.

[0026] In this application, the numerical range represented by "A~B" means "A or greater and B or less," and is used to include the values ​​A and B at both ends of that range.

[0027] Furthermore, in this application, "inner surface" means the "inner surface of the belt" in each layer or belt, and "outer surface" means the "outer surface of the belt" in each layer or belt. [Effects of the Invention]

[0028] In this invention, an intermediate layer containing a crosslinked binder component containing an unsaturated carboxylic acid metal salt is interposed between the silicone rubber layer and the hydrogenated nitrile rubber layer that form the conveying surface of the transmission belt. Therefore, despite the combination of materials that are difficult to bond together, the adhesion (bonding strength) between the silicone rubber layer and the hydrogenated nitrile rubber layer can be improved. Furthermore, the transmission belt of this invention has a long lifespan, and in particular, failures due to long-term use (cracks on the back surface, peeling of the back layer) can be suppressed. [Brief explanation of the drawing]

[0029] [Figure 1] Figure 1 is a schematic partial cross-sectional perspective view showing an example of a toothed belt according to the present invention. [Figure 2] Figure 2 is a schematic cross-sectional view of the toothed belt shown in Figure 1. [Figure 3] Figure 3 is a schematic diagram illustrating the measurement method for the adhesion test in the example. [Modes for carrying out the invention]

[0030] [Transmission belt] The power transmission belt of the present invention is not particularly limited, as long as it is a power transmission belt that transmits power and can transport articles using the back surface (outer surface) of the belt. The type of power transmission belt of the present invention is also not particularly limited, as long as it is a belt that transmits power by contacting a pulley, and may be a friction transmission belt or a meshing transmission belt.

[0031] Examples of friction transmission belts include flat belts, V-belts (wrapped V-belts, raw edge V-belts, raw edge cogged V-belts with cogs formed on the inner circumference, raw edge double cogged V-belts with cogs formed on both the inner and outer circumferences), and V-ribbed belts.

[0032] Examples of interlocking power transmission belts include toothed belts and double-sided toothed belts.

[0033] In the present invention, these power transmission belts have a laminated structure in which the outer rubber layer formed on the outer circumference side of the belt relative to the core wire includes a first rubber layer (silicone rubber layer) that forms the conveying surface which is the outer circumference, an intermediate layer laminated on the inner circumference surface of the first rubber layer, and a second rubber layer (hydrogenated nitrile rubber layer) laminated on the inner circumference surface of the intermediate layer. By including a crosslinked binder component containing an unsaturated carboxylic acid metal salt in the intermediate layer, the adhesion (bonding strength) between the silicone rubber layer and the hydrogenated nitrile rubber layer can be improved.

[0034] In the power transmission belt of the present invention, the outer periphery rubber layer may include the first rubber layer, the intermediate layer, and the second rubber layer, and one or more other rubber layers (for example, an adhesive rubber layer to improve the adhesion between the second rubber layer and the core wire) may be further interposed between the second rubber layer and the core wire. As the adhesive rubber layer, adhesive rubber layers commonly used in power transmission belts can be used depending on the type of rubber. Of these, the outer periphery rubber layer is preferably a combination of the first rubber layer, the intermediate layer, the second rubber layer, and the third rubber layer (especially the adhesive rubber layer), or a combination of the first rubber layer, the intermediate layer, and the second rubber layer (an outer periphery rubber layer consisting only of the first rubber layer, the intermediate layer, and the second rubber layer), and the combination of the first rubber layer, the intermediate layer, and the second rubber layer is particularly preferred. In the power transmission belt of the present invention, the details of the first rubber layer, the intermediate layer, and the second rubber layer are as follows.

[0035] (First rubber layer) The first rubber layer is formed of a crosslinked product of the first rubber composition containing silicone rubber.

[0036] (1A) Silicone rubber The silicone rubber may be conventional silicone rubber, or for example, polyorganosiloxane. Polyorganosiloxane is a linear, branched, or network compound having Si-O bonds (siloxane bonds), and is of formula R a SiO (4-a) / 2 It may consist of units represented by (wherein R is a substituent and a is a number from 0 to 3).

[0037] In addition, since silicone rubber mainly consists of two-dimensional siloxane bonds (D units), it is superior in flexibility compared to silicone resin mainly consisting of three-dimensional siloxane bonds (T units). On the other hand, the silicone-modified resin disclosed in Patent Document 3 is a thermoplastic resin or a thermoplastic elastomer and melts by heating, so it can be adhered to other rubbers relatively easily. In contrast, silicone rubber is thermosetting and does not melt by heating, and its adhesiveness to other rubbers is extremely low. Therefore, silicone rubber is a polymer containing a silicone component that is widely used as a release agent or a non-sticking material, and is a polymer with particularly low adhesiveness.

[0038] In the above formula, as the substituent R, for example, C 1-10 alkyl groups such as methyl group, ethyl group, propyl group, butyl group, halogenated C 1-10 alkyl groups such as 3-chloropropyl group, 3,3,3-trifluoropropyl group, C 2-10 alkenyl groups such as vinyl group, allyl group, butenyl group, C 6-20 aryl groups such as phenyl group, tolyl group, naphthyl group, C 3-10 cycloalkyl groups such as cyclopentyl group, cyclohexyl group, C 6-12 aryl-C 1-4 alkyl groups and the like can be mentioned. These substituents can be used alone or in combination of two or more. Among these, as R, a methyl group, a phenyl group, an alkenyl group (such as a vinyl group), and a fluoro C 1-6 alkyl group are preferred.

[0039] Examples of the polyorganosiloxane include polydialkylsiloxane (polydialkylsiloxane such as polydimethylsiloxane), polyalkylalkenylsiloxane (polyalkylalkenylsiloxane such as polymethylvinylsiloxane), polyalkylarylsiloxane (polyalkylarylsiloxane such as polymethylphenylsiloxane) 1-10 alkylsiloxane), polyalkylalkenylsiloxane (polyalkylalkenylsiloxane such as polymethylvinylsiloxane), poly C 1-10 alkyl C 2-10 alkenylsiloxane), polyalkylarylsiloxane (polyalkylarylsiloxane such as polymethylphenylsiloxane), poly C 1-10 alkyl C 6-20Arylsiloxanes, polydiarylsiloxanes (polydiphenylsiloxanes, etc.) 6-20 Examples include arylsiloxanes, copolymers composed of the polyorganosiloxane units [dimethylsiloxane-methylvinylsiloxane copolymer, dimethylsiloxane-methylphenylsiloxane copolymer, dimethylsiloxane-methyl(3,3,3-trifluoropropyl)siloxane copolymer, dimethylsiloxane-methylvinylsiloxane-methylphenylsiloxane copolymer; dimethylsiloxane-diphenylsiloxane copolymer, etc.]. These polyorganosiloxanes may be used individually or in combination of two or more types.

[0040] Polyorganosiloxanes may also be polyorganosiloxanes having substituents such as epoxy groups, hydroxyl groups, alkoxy groups, carboxyl groups, amino groups or substituted amino groups (such as dialkylamino groups), or (meth)acryloyl groups at the molecular ends or main chain. Furthermore, both ends of the polyorganosiloxane may have substituents such as trimethylsilyl groups, dimethylvinylsilyl groups, silanol groups, or tri-C groups. 1-2 It may also be an alkoxysilyl group, etc.

[0041] Of these polyorganosiloxanes, polydiC is chosen based on its mechanical properties and availability. 1-10 It is preferable that the material contains alkylsiloxanes, particularly polydimethylsiloxane (PDMS).

[0042] The polyorganosiloxane structure forming the silicone rubber may be branched or networked, but a linear structure is preferred from the viewpoint of mechanical properties. Examples of silicone rubbers include dimethyl silicone rubber (MQ), vinyl methyl silicone rubber (VMQ), phenyl methyl silicone rubber (PMQ), phenyl vinyl methyl silicone rubber (PVMQ), and fluorovinyl methyl silicone rubber (FVMQ). Of these, dimethyl silicone rubber composed of PDMS is preferred. Furthermore, the silicone rubber may be a combination of linear polyorganosiloxane (such as methyl silicone rubber) and branched or networked polyorganosiloxane (such as MQ resin).

[0043] The silicone rubber may be either room-temperature curing or thermosetting, and may be either one-component curing or two-component curing. Of these, thermosetting silicone rubber is preferred in terms of handling ease and heat resistance.

[0044] The rubber hardness of the silicone rubber (crosslinked silicone rubber) is a Type A hardness, for example, A10 to A90 (particularly A10 to A75), preferably A20 to A80, even more preferably A25 to A75, more preferably A30 to A70, and most preferably A40 to A65 (particularly A40 to A60). If the rubber hardness of the silicone rubber is too low, the first rubber layer may wear down easily, and if it is too high, the friction with the conveyed material may be insufficient, and sufficient grip may not be obtained. In order to improve the durability and running performance of the belt, the rubber hardness of the silicone rubber may be a Type A hardness, preferably A52 to A65, and even more preferably A53 to A63.

[0045] In this application, the Type A hardness of each rubber layer is expressed as the value measured using a Type A durometer in accordance with the spring durometer hardness test specified in JIS K 6253 (2012) (Vulcanized rubber and thermoplastic rubber - Method for determining hardness).

[0046] The proportion of silicone rubber may be 50% by mass or more (for example, 50 to 99.9% by mass) in the first rubber composition, for example, 80 to 99.9% by mass, preferably 90 to 99.9% by mass, more preferably 95 to 99.8% by mass, more preferably 98 to 99.7% by mass, and most preferably 99 to 99.6% by mass. If the proportion of silicone rubber is too low, the transportability of the article may decrease.

[0047] (1B) First crosslinking agent The first rubber composition preferably further contains a crosslinking agent (first crosslinking agent). Examples of the first crosslinking agent include organic peroxides.

[0048] Examples of organic peroxides include diacyl peroxides (e.g., dilauroyl peroxide, dibenzoyl peroxide, etc.), peroxyketals [e.g., 1,1-di(t-butylperoxy)cyclohexane, 2,2-di(t-butylperoxy)butane, 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane, etc.], and dialkyl peroxides [di-t-butyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyl peroxide]. Examples include [1,3-bis(2-t-butylperoxyisopropyl)benzene, etc.], alkyl peroxyesters [t-butylperoxybenzoate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, etc.], dialkyl peroxides (dicumyl peroxide, t-butylcumyl peroxide, etc.), peroxycarbonates (t-butylperoxyisopropyl carbonate, t-butylperoxy-2-ethyl-hexyl carbonate, t-amylperoxy-2-ethyl-hexyl carbonate, etc.). Furthermore, the organic peroxide may be a peroxide that has a decomposition temperature of 150-250°C (e.g., 175-225°C) at which it obtains a half-life of 1 minute by thermal decomposition. These organic peroxides can be used individually or in combination of two or more.

[0049] Among these organic peroxides, dialkyl peroxides such as 2,5-dimethyl-2,5-di(t-butylperoxy)hexane are particularly preferred.

[0050] The proportion of the first crosslinking agent (especially organic peroxide) may be 0.05 parts by mass or more per 100 parts by mass of silicone rubber, for example, 0.05 to 5 parts by mass, preferably 0.1 to 3 parts by mass, more preferably 0.15 to 1 part by mass, more preferably 0.2 to 0.8 parts by mass, and most preferably 0.3 to 0.7 parts by mass. If the proportion of the first crosslinking agent is too low, the rubber hardness may decrease, and if it is too high, the flexibility of the belt may decrease, and bloom (precipitation on the surface) may occur.

[0051] (1C) Other ingredients The first rubber composition may further contain other components (first other components), such as rubber other than silicone rubber, and conventional additives used in rubber compositions for power transmission belts. Examples of conventional additives include crosslinking aids (cocrosslinking agents, crosslinking accelerators, crosslinking retarders, etc.), filling agents (fillers, short fibers, etc.), softeners, antioxidants, flex crack inhibitors, ozone degradation inhibitors, colorants, adhesion improvers, tackifiers, coupling agents (silane coupling agents, etc.), stabilizers (ultraviolet absorbers, heat stabilizers, etc.), flame retardants, and antistatic agents. These other components can be used individually or in combination of two or more.

[0052] The total proportion of the other components is 100 parts by mass or less, preferably 50 parts by mass or less, more preferably 30 parts by mass or less, more preferably 10 parts by mass or less, and most preferably 1 part by mass or less, per 100 parts by mass of silicone rubber.

[0053] (Second rubber layer) The second rubber layer is formed of a crosslinked product of the second rubber composition, which includes hydrogenated nitrile rubber.

[0054] (2A) Hydrogenated nitrile rubber Hydrogenated nitrile rubber (HNBR) may be partially hydrogenated nitrile rubber or fully hydrogenated nitrile rubber. The hydrogenation rate of the hydrogenated nitrile rubber can be selected from a range of approximately 50-100%, and may be 70-100%. The hydrogenated nitrile rubber may be carboxylated.

[0055] In this application, hydrogenated nitrile rubber refers to rubber that maintains the oil resistance, which is an advantage of conventional nitrile rubber, while preventing the deterioration of rubber elasticity due to sulfur recombination reactions during thermal aging. This is achieved by chemically hydrogenating the unsaturated bonds (carbon-carbon double bonds) present in conventional nitrile rubber, thereby making recombination reactions during thermal aging less likely to occur and improving heat resistance.

[0056] The iodine value (unit: mg / 100 mg) of hydrogenated nitrile rubber is, for example, 5 to 60 (for example, 7 to 50), preferably 8 to 40 (for example, 8 to 35), and more preferably 10 to 30.

[0057] In this application, the iodine value is an indicator of the amount of unsaturated bonds, and a higher iodine value indicates a greater amount of unsaturated bonds in the polymer molecular chain. The iodine value is determined by adding an excess of iodine to the sample and allowing it to react completely (reacting iodine with unsaturated bonds), and then quantifying the amount of remaining iodine by redox titration. If the iodine value of hydrogenated nitrile rubber is low, the crosslinking reaction between hydrogenated nitrile rubbers is insufficient, resulting in lower rigidity of the crosslinked rubber, which may reduce deformation resistance during belt operation. On the other hand, if the iodine value of hydrogenated nitrile rubber is high, the amount of unsaturated bonds becomes excessively high, which may lead to thermal and oxidative degradation of the crosslinked rubber, shortening the belt life.

[0058] The proportion of hydrogenated nitrile rubber may be 10% by mass or more in the second rubber composition, for example, 10 to 90% by mass, preferably 30 to 80% by mass, more preferably 40 to 75% by mass, more preferably 50 to 70% by mass, and most preferably 60 to 65% by mass. If the proportion of hydrogenated nitrile rubber is too low, the flexural strength of the transmission belt may decrease.

[0059] (2B) Second crosslinking agent The second rubber composition preferably further contains a second crosslinking agent. Examples of the second crosslinking agent include organic peroxides and metal oxides. These crosslinking agents can be used individually or in combination of two or more.

[0060] Examples of organic peroxides include those exemplified as organic peroxides for the first crosslinking agent.

[0061] Examples of metal oxides include magnesium oxide, zinc oxide, and lead oxide. These metal oxides can be used individually or in combination of two or more.

[0062] The crosslinking agents can be used alone or in combination of two or more. Among the crosslinking agents, organic peroxides and / or metal oxides are preferred, and a combination of organic peroxides (especially dialkyl peroxides such as 1,3-bis(2-t-butylperoxyisopropyl)benzene) and metal oxides (especially zinc oxide) is particularly preferred.

[0063] The proportion of organic peroxide may be 0.3 parts by mass or more per 100 parts by mass of hydrogenated nitrile rubber, for example, 0.3 to 10 parts by mass, preferably 0.5 to 5 parts by mass, more preferably 0.8 to 4 parts by mass, more preferably 1 to 3 parts by mass, and most preferably 1.5 to 2.5 parts by mass. If the proportion of organic peroxide is too low, the rubber hardness may decrease, and if it is too high, the flexibility of the belt may decrease.

[0064] The proportion of metal oxide may be 0.3 parts by mass or more per 100 parts by mass of hydrogenated nitrile rubber, for example, 0.3 to 10 parts by mass, preferably 0.5 to 5 parts by mass, more preferably 0.8 to 4 parts by mass, more preferably 1 to 3 parts by mass, and most preferably 1.5 to 2.5 parts by mass. If the proportion of metal oxide is too low, the rubber hardness may decrease, and if it is too high, the flexibility of the belt may decrease.

[0065] The proportion of the second crosslinking agent may be 0.5 parts by mass or more per 100 parts by mass of hydrogenated nitrile rubber, for example, 0.5 to 15 parts by mass, preferably 1 to 10 parts by mass, more preferably 1.5 to 8 parts by mass, more preferably 2 to 7 parts by mass, and most preferably 3 to 5 parts by mass. If the proportion of the second crosslinking agent is too low, the rubber hardness may decrease, and if it is too high, the flexibility of the belt may decrease.

[0066] (2C) Second cocrosslinking agent The second rubber composition may further contain a second co-crosslinking agent (crosslinking aid or co-vulcanizing agent). Examples of the second co-crosslinking agent include polyfunctional (iso)cyanurates [e.g., triallyl isocyanurate (TAIC), triallyl cyanurate (TAC), etc.], polydienes (e.g., 1,2-polybutadiene, etc.), oximes (e.g., quinone dioxime, etc.), guanidines (e.g., diphenylguanidine, etc.), polyfunctional (meth)acrylates [e.g., ethylene glycol di(meth)acrylate, alkanediol di(meth)acrylates such as butanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and other alkane polyol poly(meth)acrylates]. Examples include bismaleimides [for example, alkylene bismaleimides such as N,N'-1,2-ethylenedimaleimide, N,N'-hexamethylenebismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)cyclohexane; N,N'-m-phenylenedimaleimide (MPBM), 4-methyl-1,3-phenyledimaleimide, 4,4'-diphenylmethanedimaleimide, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 4,4'-diphenyletherdimaleimide, 4,4'-diphenylsulfonedimaleimide, and arene bismaleimides such as 1,3-bis(3-maleimidophenoxy)benzene].

[0067] These cocrosslinking agents can be used individually or in combination of two or more. Of these, bismaleimides such as MPBM are preferred because they can improve abrasion resistance and lateral pressure resistance.

[0068] The proportion of the second co-crosslinking agent may be 0.3 parts by mass or more per 100 parts by mass of hydrogenated nitrile rubber, for example, 0.3 to 10 parts by mass, preferably 0.5 to 5 parts by mass, more preferably 0.8 to 4 parts by mass, more preferably 1 to 3 parts by mass, and most preferably 1.5 to 2.5 parts by mass. If the proportion of the second co-crosslinking agent is too low, the rubber hardness may decrease, and if it is too high, the flexibility of the belt may decrease.

[0069] (2D) Second filler The second rubber composition may further contain a second filler. The second filler includes reinforcing inorganic fillers, non-reinforcing fillers, and the like.

[0070] Examples of reinforcing inorganic fillers include carbon black and silica. The reinforcing inorganic filler may also be in particulate (powder) form.

[0071] Carbon black can generally be classified into hard carbon black, which has a relatively small particle size, and soft carbon black, which has a relatively large particle size. While the classification of carbon black is sometimes based on the average particle size (average primary particle size) in the raw material state, in this application, the classification is based on the primary particle size of the carbon black contained in the rubber composition (particularly in the crosslinked rubber composition). That is, in this application, the primary particle size of each primary particle of carbon black contained in the rubber composition is measured, and carbon black with a primary particle size of 1 nm or more and less than 40 nm is referred to as hard carbon black (or hard carbon), and carbon black with a primary particle size of 40 nm or more (e.g., 40 to 300 nm) is referred to as soft carbon black (or soft carbon).

[0072] The average primary particle size of hard carbon black may be, for example, 10 to 38 nm, preferably 15 to 35 nm, more preferably 20 to 33 nm, and more preferably 25 to 30 nm. On the other hand, the average primary particle size of soft carbon black may be, for example, 40 to 100 nm, preferably 50 to 80 nm, more preferably 60 to 70 nm, and more preferably 65 to 68 nm.

[0073] In this application, the average particle diameter of particulate fillers such as carbon black can be measured using, for example, a scanning electron microscope (SEM) or a transmission electron microscope (TEM), and the arithmetic mean particle diameter of an appropriate number of samples (for example, any 50 samples) can be calculated by image analysis.

[0074] In this invention, the carbon black may be either hard carbon black or soft carbon black, and can be appropriately selected depending on the application, or both may be combined.

[0075] The amount of iodine adsorbed by carbon black is, for example, 5 to 200 g / kg, preferably 15 to 150 g / kg, and more preferably 20 to 140 g / kg.

[0076] In this application, the amount of iodine adsorbed by carbon black can be measured in accordance with the standard test method of ASTM D1510-17.

[0077] The BET specific surface area of ​​carbon black using the BET method is, for example, 10 to 400 m². 2 / g, preferably 15-200m 2 / g, more preferably 20-150m 2 It is / g.

[0078] In this application, the BET specific surface area of ​​a filler such as carbon black refers to the specific surface area measured using nitrogen gas by the BET method.

[0079] Silica includes dry silica, wet silica, and surface-treated silica. Furthermore, silica can be classified by its manufacturing method into, for example, dry-process white carbon, wet-process white carbon, colloidal silica, and precipitated silica. These silicas can be used individually or in combination of two or more types. Among these silicas, silica having surface silanol groups (anhydrous silicic acid, hydrated silicic acid) is preferred, and hydrated silicic acid with a high number of surface silanol groups is particularly preferred due to its strong chemical bonding ability with rubber components.

[0080] The average particle diameter (average primary particle diameter) of silica is, for example, 1 to 500 nm, preferably 3 to 300 nm, more preferably 5 to 100 nm, and more preferably 10 to 50 nm.

[0081] Furthermore, the specific surface area for nitrogen adsorption of silica by the BET method is, for example, 50 to 400 m². 2 / g, preferably 100-300m 2 / g, more preferably 150-200m 2 It is / g.

[0082] Examples of non-reinforcing fillers include metal oxides (magnesium oxide, zinc oxide, lead oxide, calcium oxide, barium oxide, iron oxide, copper oxide, titanium oxide, aluminum oxide, etc.), polyvalent metal carbonates (calcium carbonate, magnesium carbonate, etc.), polyvalent metal hydroxides (aluminum hydroxide, etc.), polyvalent metal sulfates (barium sulfate, etc.), silicates (natural or synthetic silicates in which some of the silicon atoms are replaced by polyvalent metal atoms, such as aluminum silicate, magnesium silicate, and aluminum magnesium silicate; minerals mainly composed of silicates, such as clay containing aluminum silicate, and silicate minerals such as talc and mica containing magnesium silicate), lithopone, and silica sand. These non-reinforcing fillers can be used alone or in combination of two or more. Of these, metal oxides are preferred, and zinc oxide is particularly preferred.

[0083] These fillers can be used individually or in combination of two or more. The second filler preferably contains carbon black and / or silica, more preferably contains carbon black and silica, and a combination of carbon black, silica and a metal oxide is particularly preferred.

[0084] The proportion of carbon black (especially soft carbon black) is, for example, 0.3 to 50 parts by mass, preferably 0.5 to 30 parts by mass, more preferably 1 to 10 parts by mass, more preferably 1.2 to 5 parts by mass, and most preferably 1.5 to 3 parts by mass, per 100 parts by mass of hydrogenated nitrile rubber.

[0085] The amount of silica is, for example, 1 to 150 parts by mass, preferably 5 to 100 parts by mass, more preferably 10 to 80 parts by mass, more preferably 20 to 70 parts by mass, and most preferably 30 to 50 parts by mass, per 100 parts by mass of hydrogenated nitrile rubber.

[0086] The proportion of the second filler is, for example, 5 to 200 parts by mass, preferably 10 to 150 parts by mass, more preferably 20 to 100 parts by mass, more preferably 30 to 80 parts by mass, and most preferably 35 to 60 parts by mass, per 100 parts by mass of hydrogenated nitrile rubber.

[0087] (2E) Second softening agent The second rubber composition may further contain a second softening agent (processing agent or processing aid) to improve the flexibility of the belt. The second softening agent may include mineral oil-based softening agents, vegetable oil-based softening agents, synthetic softening agents, and the like.

[0088] Examples of mineral oil-based softeners include petroleum-based softeners [paraffinic oils, alicyclic oils (naphthenic oils), aromatic oils, etc.] and coal tar-based softeners (coal tar, coumarone-indene resin, etc.).

[0089] Examples of vegetable oil-based softeners include fatty oil-based softeners (such as stearic acid, fatty acids or their metal salts, fatty acid esters, fatty acid amides, and fatty oils).

[0090] Examples of synthetic softeners include synthetic resin softeners (phenol-aldehyde resins, hydrocarbon synthetic oils such as liquid ethylene-α-olefin copolymers, liquid polybutene, liquid polybutadiene, liquid isoprene rubber, etc.), and synthetic plasticizers [aliphatic carboxylic acid plasticizers (adipate ester plasticizers, sebacate ester plasticizers, etc.), aromatic carboxylic acid ester plasticizers (phthalate ester plasticizers, trimellitic acid ester plasticizers, etc.), oxycarboxylic acid ester plasticizers, phosphate ester plasticizers, ether plasticizers, ether ester plasticizers, etc.].

[0091] These softeners can be used individually or in combination of two or more. Of these, petroleum-based softeners such as paraffinic oils, vegetable oil-based softeners such as stearic acid, and synthetic plasticizers such as ether ester plasticizers are preferred, with vegetable oil-based softeners and synthetic plasticizers being particularly preferred.

[0092] The proportion of the vegetable oil-based softener is, for example, 0.1 to 10 parts by mass, preferably 0.2 to 5 parts by mass, more preferably 0.3 to 3 parts by mass, more preferably 0.5 to 2 parts by mass, and most preferably 0.8 to 1.5 parts by mass, per 100 parts by mass of hydrogenated nitrile rubber.

[0093] The proportion of the synthetic plasticizer is, for example, 1 to 100 parts by mass, preferably 2 to 50 parts by mass, more preferably 3 to 30 parts by mass, more preferably 5 to 20 parts by mass, and most preferably 8 to 15 parts by mass, per 100 parts by mass of hydrogenated nitrile rubber.

[0094] The proportion of the second softening agent is, for example, 1 to 100 parts by mass, preferably 3 to 50 parts by mass, more preferably 5 to 40 parts by mass, more preferably 8 to 30 parts by mass, and most preferably 10 to 20 parts by mass, per 100 parts by mass of hydrogenated nitrile rubber.

[0095] (2F) Second Anti-aging Agent The second rubber composition may further contain a second antioxidant, as this can improve its heat aging resistance. Examples of the second antioxidant include benzimidazole-based antioxidants, diarylamine-based antioxidants, and p-phenylenediamine-based antioxidants.

[0096] Examples of benzimidazole-based antioxidants include benzimidazole compounds such as 2-mercaptobenzimidazole (MBI), 2-mercapto-5-methylbenzimidazole, 2-mercapto-5-methoxybenzimidazole, 2-mercapto-5-carboxybenzimidazole, 2-mercapto-5-nitrobenzimidazole, 1,3-dihydro-1-phenyl-2H-benzimidazole-2-thion, and mixtures of 2-mercaptobenzimidazole and phenol condensates. Benzimidazole-based antioxidants may also be in the form of salts with metals such as zinc.

[0097] Examples of diarylamine-based antioxidants include bis(C) such as di(4-octylphenyl)amine (ODPA). 4-18 Alkyl C 6-10 Examples include arylamines; bis(aralkyl-aryl)amines such as 4,4'-bis(α,α-dimethylbenzyl)diphenylamine (DCD); and styrene-diphenylamine (SDPA).

[0098] Examples of p-phenylenediamine-based antioxidants include N-isopropyl-N'-phenyl-p-phenylenediamine (IPPD), N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD), and N-(1,3-methylheptyl)-N'-phenyl-p-phenylenediamine (8PPD), which are N-linear or branched C-cells. 1-10 Alkyl-N'-C 6-10 Aryl-p-phenylenediamine; N,N'-diphenyl-p-phenylenediamine, N,N'-di-2-naphthyl-p-phenylenediamine (DNPD), etc., N,N'-diC 6-10 Examples include aryl-p-phenylenediamines.

[0099] These antioxidants can be used individually or in combination of two or more. Among these, diarylamine antioxidants, in particular, such as ODPA and other bis(C) compounds, are available. 4-18 Alkyl C 6-10 Arylamines are preferred.

[0100] The proportion of the second antioxidant is, for example, 0.3 to 10 parts by mass, preferably 0.5 to 8 parts by mass, more preferably 1 to 5 parts by mass, and more preferably 1.5 to 3 parts by mass, per 100 parts by mass of hydrogenated nitrile rubber. If the proportion of the second antioxidant is too low, the crack resistance of the belt may decrease, and if it is too high, the mechanical properties of the belt may decrease.

[0101] (2G) Second Other Component The second rubber composition may further contain, as a second other component, rubber other than hydrogenated nitrile rubber, and conventional additives used in rubber compositions for power transmission belts. Examples of conventional additives include crosslinking accelerators, crosslinking retarders, short fibers, antioxidants, flex crack inhibitors, ozone degradation inhibitors, colorants, adhesion improvers, tackifiers, coupling agents (such as silane coupling agents), stabilizers (such as UV absorbers and heat stabilizers), flame retardants, and antistatic agents. These other components can be used individually or in combination of two or more.

[0102] The total proportion of the second other component is 100 parts by mass or less, preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and more preferably 10 parts by mass or less, per 100 parts by mass of hydrogenated nitrile rubber.

[0103] (Middle class) The intermediate layer is interposed between the first rubber layer and the second rubber layer and, by including a crosslinked binder component containing an unsaturated carboxylic acid metal salt, can firmly bond the first rubber layer and the second rubber layer. Preferred embodiments for including the crosslinked binder component in the intermediate layer include an embodiment in which the intermediate layer is formed by a crosslinked binder component consisting of an unsaturated carboxylic acid metal salt (first embodiment), an embodiment in which the intermediate layer is formed by a crosslinked binder component which is a third rubber composition containing a rubber component and an unsaturated carboxylic acid metal salt (second embodiment), and an embodiment in which the intermediate layer is formed by a cloth containing the crosslinked binder component which is the third rubber composition (third embodiment).

[0104] (First aspect) In the first embodiment, the binder component consists of an unsaturated carboxylic acid metal salt, and the intermediate layer consists of a crosslinked product of the binder component. The unsaturated carboxylic acid metal salt, which is the binder component, exists in the transmission belt primarily in the form of a self-crosslinked product of the unsaturated carboxylic acid metal salt, and it can be presumed that at the boundaries between the first rubber layer and the second rubber layer, it partially crosslinks with the silicone rubber and the hydrogenated nitrile rubber at each boundary.

[0105] Unsaturated carboxylate metal salts may also be compounds in which an unsaturated carboxylic acid having one or more carboxyl groups is ionically bonded to a metal.

[0106] Examples of unsaturated carboxylic acids in metal salts of unsaturated carboxylic acids include monocarboxylic acids such as (meth)acrylic acid and crotonic acid, dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid, and monoalkyl esters of these dicarboxylic acids. These unsaturated carboxylic acids can be used alone or in combination of two or more. A preferred unsaturated carboxylic acid is (meth)acrylic acid.

[0107] Examples of metals used in unsaturated carboxylate metal salts include alkali metals such as sodium and potassium; polyvalent metals such as group 2 elements of the periodic table (magnesium, calcium, etc.), group 4 elements (titanium, zirconium, etc.), and group 8 to 14 elements of the periodic table (e.g., iron, cobalt, nickel, copper, zinc, aluminum, tin, lead, etc.). These metals can be used individually or in combination of two or more. Preferred metals are polyvalent metals such as group 2 elements of the periodic table (magnesium, etc.) and group 12 elements of the periodic table (zinc, etc.).

[0108] These unsaturated carboxylate metal salts can be used individually or in combination of two or more.

[0109] As unsaturated carboxylate metal salts, zinc (meth)acrylate and magnesium (meth)acrylate are preferred, zinc (meth)acrylate is more preferred, and zinc methacrylate is most preferred.

[0110] In the intermediate layer of the first embodiment, the basis weight of the binder component (unsaturated carboxylic acid metal salt) is 10 g / m². 2 (especially 50g / m) 2 (The above) may also be acceptable, for example, 10-300 g / m² 2 Preferably 30-250 g / m² 2 More preferably 50-200 g / m² 2 Comfortably 70-150g / m 2 Most preferably 90-120 g / m² 2 When high bonding strength is required, the basis weight is 80 g / m². 2 It may be greater than or equal to 80-300 g / m², preferably 80-300 g / m². 2 More preferably 100-270 g / m² 2 , comfortably 150~250g / m 2 Most preferably 180-220 g / m² 2 If the basis weight of the binder component is too low, there is a risk that the adhesion between the first rubber layer and the second rubber layer will decrease.

[0111] (Second aspect) In the second embodiment, the binder component is a third rubber composition comprising a rubber component and an unsaturated carboxylate metal salt.

[0112] (3A) Rubber component Examples of rubber components include diene rubbers [natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), chloroprene rubber (CR), butyl rubber (IIR), styrene-butadiene rubber (SBR), vinylpyridine-styrene-butadiene rubber, acrylonitrile-butadiene rubber (nitrile rubber: NBR), acrylonitrile-chloroprene rubber, hydrogenated nitrile rubber (HNBR), etc.], ethylene-α-olefin elastomers (ethylene-propylene copolymer (EPM), ethylene-propylene-diene terpolymer (EPDM), etc.), chlorosulfonated polyethylene rubber (CSM), alkylated chlorosulfonated polyethylene rubber (ACSM), epichlorohydrin rubber, acrylic rubber, silicone rubber, urethane rubber, and fluororubber. These rubber components can be used individually or in combination of two or more.

[0113] Of these, from the viewpoint of adhesion to the first and second rubber layers, the rubber component preferably contains silicone rubber and / or hydrogenated nitrile rubber, more preferably contains hydrogenated nitrile rubber, and most preferably consists of hydrogenated nitrile rubber alone.

[0114] The silicone rubber can be selected from the silicone rubbers exemplified as the first rubber layer, including preferred embodiments. Furthermore, the hydrogenated nitrile rubber can be selected from the hydrogenated nitrile rubbers exemplified as the second rubber layer, including preferred embodiments.

[0115] When the rubber component includes silicone rubber and / or hydrogenated nitrile rubber, the total amount of silicone rubber and hydrogenated nitrile rubber may be 50% by mass or more of the rubber component, preferably 80% by mass or more, more preferably 90% by mass or more, more preferably 95% by mass or more, and most preferably 100% by mass.

[0116] The proportion of the rubber component may be 10% by mass or more in the third rubber composition, for example, 10 to 95% by mass, preferably 20 to 90% by mass, more preferably 30 to 80% by mass, more preferably 50 to 70% by mass, and most preferably 53 to 60% by mass. If the proportion of the rubber component is too low, the flexibility of the transmission belt may decrease.

[0117] (3B) Unsaturated carboxylic acid metal salts The unsaturated carboxylate metal salt can be selected from the unsaturated carboxylate metal salts exemplified in the first embodiment, including preferred embodiments.

[0118] The proportion of the unsaturated carboxylic acid metal salt (especially zinc methacrylate) should be 1 part by mass or more (preferably 3 parts by mass or more, more preferably 8 parts by mass or more, more preferably 10 parts by mass or more, and most preferably 12 parts by mass or more) per 100 parts by mass of the rubber component (especially hydrogenated nitrile rubber). For example, it can be selected from a range of about 1 to 50 parts by mass (especially 3 to 40 parts by mass), preferably 5 to 35 parts by mass, more preferably 8 to 30 parts by mass, more preferably 10 to 25 parts by mass, and most preferably 12 to 20 parts by mass. If the proportion of the unsaturated carboxylic acid metal salt is too low, the adhesion between the first rubber layer and the second rubber layer may decrease.

[0119] (3C) Third crosslinking agent The third rubber composition may further contain a third crosslinking agent. Examples of the third crosslinking agent include organic peroxides, metal oxides, and sulfur-based crosslinking agents.

[0120] Examples of organic peroxides include the organic peroxides exemplified as the first crosslinking agent. These organic peroxides can be used alone or in combination of two or more types.

[0121] Examples of metal oxides include the metal oxides exemplified as the first crosslinking agent. These metal oxides can be used alone or in combination of two or more types.

[0122] Examples of sulfur-based crosslinking agents include powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, highly dispersible sulfur, and sulfur chloride (sulfur monochloride, sulfur dichloride, etc.). These sulfur-based crosslinking agents can be used individually or in combination of two or more.

[0123] The crosslinking agents can be used alone or in combination of two or more. Among the crosslinking agents, organic peroxides and / or metal oxides are preferred, and a combination of organic peroxides (especially dialkyl peroxides such as 1,3-bis(2-t-butylperoxyisopropyl)benzene) and metal oxides (especially zinc oxide) is particularly preferred.

[0124] The range of the ratio of the third crosslinking agent (including organic peroxides and metal oxides) to the rubber component can be selected from the range of the ratio of the second crosslinking agent to the hydrogenated nitrile rubber, including a preferred range.

[0125] (3D) Third Filler The third rubber composition may further contain a third filler. The third filler can be selected from the fillers exemplified as the second filler, including preferred embodiments. The range of the ratio of the third filler (including carbon black and silica) to the rubber component can also be selected from the range of the ratio of the second filler to the hydrogenated nitrile rubber, including preferred embodiments.

[0126] (3E) Third softening agent The third rubber composition may further contain a third softening agent. The third softening agent can be selected from the softening agents exemplified as the second softening agent, including preferred embodiments. The range of the ratio of the third softening agent to the rubber component can also be selected from the range of the ratio of the second softening agent to the hydrogenated nitrile rubber, including preferred embodiments.

[0127] (3F) Third Anti-aging Agent The third rubber composition may further contain a third antioxidant. The third antioxidant can be selected from the antioxidants exemplified as the second antioxidant, including preferred embodiments. The range of the ratio of the third antioxidant to the rubber component can also be selected from the range of the ratio of the second antioxidant to the hydrogenated nitrile rubber, including preferred embodiments.

[0128] (3G) Third Other Component The third rubber composition may further contain, as a third other component, conventional additives used in rubber compositions for power transmission belts. Examples of conventional additives include those exemplified as the second other component. The total proportion of the third other component is 100 parts by mass or less, preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and more preferably 10 parts by mass or less, per 100 parts by mass of the rubber component.

[0129] (Third aspect) In a third embodiment, by interposing an intermediate layer formed of a cloth containing a crosslinked binder component of the third rubber composition (hereinafter referred to as the "intermediate cloth") between the first rubber layer and the second rubber layer, the first rubber layer and the second rubber layer can be firmly bonded together. In addition, in a toothed belt, it is possible to suppress the flow of the first rubber layer into the teeth from the back side through the space between the core wires during the manufacturing process. As a result, it is possible to suppress the occurrence of appearance defects and a decrease in tooth shear strength in a toothed belt. The intermediate cloth only needs to contain the third rubber composition, and is usually a cloth to which the third rubber composition is attached (a cloth to which the third rubber composition is attached to the surface of the fibers constituting the cloth).

[0130] Examples of fabrics (cloths or fabric materials) include woven fabrics, knitted fabrics, and nonwoven fabrics. Conventionally, the fabric is often a woven fabric (canvas), which is composed of a fabric woven from warp threads extending in the belt width direction and weft threads extending in the belt circumference direction. The weave structure of the woven fabric is not particularly limited as long as the warp and weft threads intersect regularly in the vertical and horizontal directions, and may be any of plain weave, twill weave (or diagonal weave), satin weave, or a weave structure that combines these structures. Preferred woven fabrics have a twill weave and / or satin weave structure (especially a twill weave structure). The twill weave structure may be a random twill weave structure.

[0131] The fibers forming the fabric may be organic or inorganic. Examples of organic fibers include polyolefin fibers (polyethylene fibers, polypropylene fibers, etc.), polyamide fibers [aliphatic polyamide fibers such as polyamide 6 fibers, polyamide 66 fibers, polyamide 46 fibers (nylon fibers), aramid fibers, etc.], polyester fibers [polyalkylene arylate fibers (e.g., polyethylene terephthalate (PET) fibers, polytrimethylene terephthalate (PTT) fibers, polybutylene terephthalate (PBT) fibers, polyethylene naphthalate (PEN) fibers, etc.)]. 2-4 Alkilen C 8-14 Synthetic fibers include: arylate fibers (such as polyarylate fibers and fully aromatic polyester fibers like liquid crystal polyester fibers), vinylon fibers, polyvinyl alcohol fibers, poly(p-phenylenebenzobisoxazole) (PBO) fibers, polyphenylene ether fibers, polyether ether ketone fibers, polyether sulfone fibers, polyurethane fibers, etc.; natural fibers such as cotton, linen, and wool; regenerated cellulose fibers such as rayon; and cellulose ester fibers. Inorganic fibers include, for example, carbon fibers and glass fibers. These fibers can be used individually or in combination of two or more types.

[0132] Of these fibers, organic fibers are commonly used, with cellulose fibers such as cotton and rayon, polyester fibers (such as PET fibers), polyamide fibers (aliphatic polyamide fibers such as polyamide 6 fibers and polyamide 66 fibers, aramid fibers, etc.), and PBO fibers being preferred, with aliphatic polyamide fibers being more preferred, and polyamide 66 fibers being even more preferred. Furthermore, composite yarns of these fibers and elastic yarns with elasticity [for example, elastic polyurethane-based elastic yarns such as spandex made of polyurethane, processed yarns that have undergone stretch processing (for example, woolly processing, crimping processing, etc.)] are also preferred.

[0133] If the fabric is woven, the form of the warp and weft threads is not particularly limited and may be monofilament yarn, which is a single long fiber; multifilament yarn, which is made by aligning or twisting filaments (long fibers); or spun yarn, which is made by twisting short fibers. The multifilament yarn or spun yarn may be a blended yarn or blended yarn using multiple types of fibers. The weft threads preferably contain elastic yarn, while the warp threads usually do not contain elastic yarn from the viewpoint of weaving. In order to ensure the elasticity of the intermediate fabric in the belt circumferential direction, the weft threads containing elastic yarn extend in the belt circumferential direction, and the warp threads extend in the belt width direction.

[0134] The average diameter of the fibers is, for example, 1 to 100 μm (for example, 3 to 50 μm), preferably 5 to 30 μm, and more preferably 7 to 25 μm.

[0135] Regarding the average diameter (thickness) of the yarn (twisted yarn), if the fabric is woven, the average diameter of the warp threads can be selected from a range of about 10 to 1000 dtex, for example, 30 to 700 dtex, preferably 50 to 500 dtex, more preferably 100 to 400 dtex, more preferably 150 to 350 dtex, and most preferably 200 to 300 dtex. If the average diameter of the warp threads is too small, the unevenness of the woven fabric surface may decrease, reducing the anchoring effect, and if it is too large, the amount of rubber component that penetrates between the fibers may decrease, reducing the bonding strength.

[0136] The average diameter of the weft yarn can be selected from a range of approximately 10 to 1000 dtex, for example, 20 to 500 dtex, preferably 30 to 300 dtex, more preferably 35 to 200 dtex, more preferably 40 to 100 dtex, and most preferably 40 to 70 dtex. If the average diameter of the weft yarn is too small, the surface irregularities of the woven fabric may become smaller, reducing the anchoring effect, and if it is too large, the amount of rubber component that penetrates between the fibers may decrease, reducing the bonding strength.

[0137] The average diameter of the warp threads may be 0.3 times or more the average diameter of the weft threads, for example, 0.3 to 30 times, preferably 0.5 to 20 times, more preferably 1 to 15 times, more preferably 3 to 10 times, and most preferably 4 to 7 times.

[0138] The warp density (threads / 3cm) can be selected from a range of approximately 30 to 500, for example, 40 to 300, preferably 50 to 200, more preferably 60 to 150, more preferably 70 to 110, and most preferably 80 to 100. If the warp density is too low, there is a risk that the silicone rubber will penetrate the intermediate fabric, and if it is too high, there is a risk that the amount of rubber component that penetrates between the fibers will decrease, reducing the bonding strength.

[0139] The density of the warp threads may be 5 times or less the density of the weft threads, for example, 0.3 to 3 times, preferably 0.4 to 2 times, more preferably 0.5 to 1 time, more preferably 0.6 to 0.9 times, and most preferably 0.7 to 0.8 times.

[0140] (Characteristics of the outer rubber layer) In the power transmission belt of the present invention, the first rubber layer and the second rubber layer constituting the outer periphery rubber layer are a combination of silicone rubber and hydrogenated nitrile rubber, which have low adhesive properties. However, by interposing an intermediate layer containing a crosslinked binder component containing an unsaturated carboxylic acid metal salt, a strong bond can be achieved.

[0141] The peel strength between the first rubber layer and the intermediate layer may be 30 N / 25 mm or more, preferably 50 N / 25 mm or more, and more preferably 100 N / 25 mm or more.

[0142] In this application, the peel strength between the first rubber layer and the intermediate layer can be measured by the method described in the examples below.

[0143] (Toothed belt) The transmission belt of the present invention is not particularly limited as long as it has the outer rubber layer, but among the transmission belts, a toothed belt is preferred because it requires an outer layer with a large thickness on the conveying surface and offers greater benefits from the present invention.

[0144] Below, an example of a power transmission belt of the present invention will be described in detail, with reference to the attached drawings as necessary. In the following description, identical or functionally common elements (or components) may be denoted by the same reference numeral.

[0145] Figure 1 is a schematic partial cross-sectional perspective view showing an example of a toothed belt of the present invention, and Figure 2 is a schematic cross-sectional view of the toothed belt of Figure 1.

[0146] The toothed belt 1 in this example is an endless interlocking transmission belt, comprising a back portion 1c in which a core wire 3 extending in the belt circumferential direction (longitudinal direction) is embedded, and a plurality of teeth 1a provided at predetermined intervals on the inner circumferential surface of the back portion 1c and extending in the belt width direction, with the belt surface (inner circumferential surface) on the tooth side being made of tooth fabric 5. The back portion 1c has a back rubber layer (outer rubber layer) 2 disposed on the outer circumferential side of the belt of the core wire 3, and this back rubber layer 2 consists of a first rubber layer 2a that forms the outer circumferential surface (conveying surface) of the belt, an intermediate layer 2b located on the inner circumferential side of the first rubber layer 2a, and a second rubber layer 2c located on the inner circumferential side of the intermediate layer 2b. Furthermore, the toothed belt 1 has a tooth rubber layer (rubber layer forming the teeth) 4 between the tooth fabric 5 and the core wire 3 on the inner circumferential side of the belt of the core wire 3.

[0147] Between adjacent tooth portions 1a, there is a flat tooth root portion 1b, and the tooth portions 1a and tooth root portions 1b are alternately formed along the circumferential direction (belt longitudinal direction) on the inner surface of the belt. That is, the surface of the tooth portion 1a and the inner surface of the back portion 1c (i.e., the surface of the tooth root portion 1b) are made of the continuous tooth fabric 5.

[0148] In the embodiment shown in Figure 1, the tooth fabric 5 that constitutes the surface of the tooth portion is a constituent element of the tooth portion, while the tooth fabric 5 that constitutes the surface of the tooth root portion is a constituent element of the back portion. Furthermore, each tooth fabric 5 that constitutes the tooth portion is part of a continuous tooth fabric 5 (part of the tooth fabric 5 in Figure 2).

[0149] In this example, the tooth portion 1a has a substantially trapezoidal cross-sectional shape in the circumferential direction of the belt. Furthermore, the tooth portion 1a with a substantially trapezoidal cross-section has a circumferential surface formed of the tooth fabric 5, and its interior is formed of a tooth rubber layer 4 interposed between the tooth fabric 5 and the core wire 3.

[0150] Furthermore, in the tooth root portion 1b, a tooth rubber layer 4 is interposed between the tooth cloth 5 and the core wire 3 (not shown). The thickness of the tooth rubber layer 4 in the tooth root portion 1b is extremely thin compared to the thickness of the tooth rubber layer 4 in the tooth portion 1a.

[0151] The core wires 3 extend in the longitudinal direction (circumferential direction) of the belt and are arranged at intervals in the width direction of the belt. The gaps between adjacent core wires 3 may be formed by crosslinked rubber compositions (particularly the rubber compositions constituting the back rubber layer 2) and / or the tooth rubber layer 4.

[0152] The toothed belt of the present invention is not limited to the form and structure shown in Figures 1 and 2. For example, the multiple teeth only need to be able to mesh with a toothed pulley, and the cross-sectional shape of the teeth (the cross-sectional shape of the toothed belt in the circumferential direction) is not limited to a substantially trapezoidal shape, but may be, for example, semicircular, semielliptical, polygonal [triangle, quadrilateral (rectangle, trapezoid, etc.)], etc. Of these, a trapezoidal or substantially trapezoidal shape is preferred from the viewpoint of meshing and power transmission.

[0153] In the toothed belt of the present invention, the average distance between the centers of adjacent teeth in the circumferential direction (tooth pitch, see Figure 2) can be selected from a range of approximately 2 to 25 mm, depending on the shape of the toothed pulley, etc. The tooth pitch value corresponds to the scale of the teeth (length of the teeth in the belt circumferential direction, and tooth height). That is, the larger the tooth pitch, the larger the scale of the teeth becomes. The tooth pitch is preferably 3 to 20 mm, more preferably 4 to 15 mm, more preferably 5 to 12 mm, and most preferably 6 to 10 mm.

[0154] (Back rubber layer) The back portion has the teeth and tooth roots formed on its inner circumferential surface, and on its outer circumferential side, it has a back rubber layer that forms the outer surface of the belt.

[0155] In a toothed belt, the back rubber layer corresponds to the outer rubber layer; therefore, the back rubber layer can be selected from the outer rubber layer, including preferred embodiments.

[0156] In addition, in the cross-section of the toothed belt shown in Figures 1 and 2, when cut along the belt circumferential direction, the layer shape of the intermediate layer interposed at the interface between the first rubber layer 2a and the second rubber layer 2c is a gentle wave shape (wavy shape) corresponding to the uneven shape of the teeth 1a and tooth roots 1b, but it may also be a flat shape along the belt length direction. The toothed belt of the present invention can usually be manufactured by the first method (a method in which the teeth are not formed in advance during the molding process) or the second method (a method in which the teeth are formed in advance during the molding process), as described later. In the first method, a toothed belt with a wave-shaped intermediate layer is obtained, and in the second method, a toothed belt with a flat layer shape is obtained. Since the layer shape of the intermediate layer of the toothed belt obtained by the first method is a gentle wave shape, the adhesion between the first rubber layer and the second rubber layer can be considered the same for the toothed belt obtained by the first method and the toothed belt obtained by the second method.

[0157] In the toothed belt of the present invention, the average thickness of the back rubber layer (outer rubber layer) is, for example, 1 to 9 mm, preferably 2 to 8 mm, more preferably 3 to 7.5 mm, and most preferably 4 to 7.2 mm.

[0158] The average thickness of the first rubber layer is, for example, 0.8 to 7 mm (particularly 0.8 to 5 mm), preferably 0.9 to 4.5 mm, more preferably 1 to 4 mm, more preferably 1.5 to 3.8 mm, and most preferably 1.7 to 3.5 mm (particularly 2.3 to 3.2 mm).

[0159] The average thickness of the first rubber layer is, for example, 35-90%, preferably 40-85%, and more preferably 50-80%, of the average thickness of the outer rubber layer. If the ratio of the average thickness of the first rubber layer to the average thickness of the outer rubber layer (back rubber layer) is too small, the hardness of the second rubber layer will become dominant throughout the outer rubber layer, increasing the overall hardness of the outer rubber layer, which may result in insufficient grip (coefficient of friction) on the conveyed object. On the other hand, if the ratio of the average thickness of the first rubber layer to the average thickness of the outer rubber layer (back rubber layer) is too large, the second rubber layer may become too thin, which may result in insufficient mechanical strength of the belt.

[0160] The average thickness of the second rubber layer is, for example, 0.2 to 4 mm (particularly 1 to 4 mm), preferably 0.3 to 3.5 mm, more preferably 0.4 to 3 mm, more preferably 0.5 to 2.5 mm, and most preferably 0.8 to 2 mm.

[0161] In the second embodiment, the average thickness of the intermediate layer is, for example, 0.05 to 2 mm, preferably 0.1 to 1 mm, more preferably 0.2 to 0.8 mm, more preferably 0.3 to 0.7 mm, and most preferably 0.4 to 0.6 mm.

[0162] In the third embodiment, the average thickness of the intermediate fabric (intermediate fabric in the transmission belt) is, for example, 0.05 to 1 mm, preferably 0.08 to 0.8 mm, more preferably 0.1 to 0.6 mm, more preferably 0.12 to 0.4 mm, and most preferably 0.15 to 0.35 mm.

[0163] In this application, the average thickness of each layer is the average of the measured thicknesses at any six points in an image of the cross-section of the transmission belt taken with a microscope. Furthermore, if the intermediate layer is corrugated, the average thickness of the first and second rubber layers is the average of the measured thicknesses at three arbitrarily selected peaks and three bottoms of the corrugated shape.

[0164] The toothed belt of the present invention only needs to have a back rubber layer formed from the outer rubber layer, and conventional core wires and teeth can be used, but for example, the following core wires and teeth may be used.

[0165] (Core wire) On the back of the belt, a core wire extending along the belt circumferential direction is embedded on the inner circumference side of the back rubber layer. This core wire acts as a tensile body, improving the running stability and strength of the toothed belt. Furthermore, on the back, the core wire, which is usually a twisted cord extending along the belt circumferential direction, is embedded at predetermined intervals in the belt width direction. Multiple core wires parallel to the longitudinal direction may be arranged, but from the viewpoint of productivity, they are usually embedded in a spiral shape. When arranged in a spiral shape, the angle of the core wire with respect to the longitudinal direction of the belt may be, for example, 5° or less, and from the viewpoint of belt running performance, it is preferable that it is as close to 0° as possible.

[0166] More specifically, the core wires may be embedded at predetermined intervals (or pitches) (or at equal intervals) from one end to the other in the belt width direction on the back, as shown in Figure 1. The spacing (spinning pitch), which is the distance between the centers of adjacent core wires, should be greater than the core wire diameter, and depending on the core wire diameter, it may be, for example, 0.5 to 3.5 mm, preferably 0.8 to 3 mm, and more preferably 1 to 2.8 mm.

[0167] The core wire may be formed from a twisted cord made by twisting together multiple strands or multifilament threads. Of these, a twisted cord of strands is preferred, and one strand may be formed by bundling filaments (long fibers). There are no particular limitations on the thickness of the filaments forming the twisted cord, the number of filaments converged, the number of strands, and the twist configuration.

[0168] The twisted cord forming the core wire may be a single-strand, double-strand, or Lang-strand cord. By using a Lang-strand core wire, where the twist direction of the lower twist and the twist direction of the upper twist are the same, the bending stiffness is lower compared to double-strand or single-strand cords, resulting in excellent bending fatigue resistance.

[0169] The fibers forming the core are not particularly limited, and examples include synthetic fibers such as polyester fibers (polyalkyl arylate fibers, poly(p-phenylene naphthalate) fibers), PBO fibers, acrylic fibers, and polyamide fibers (aliphatic polyamide fibers, aramid fibers, etc.), as well as inorganic fibers such as glass fibers, carbon fibers, and metal fibers (steel fibers). These fibers can be used individually or in combination of two or more types. As fibers forming the core, synthetic fibers such as polyester fibers and polyamide fibers, and inorganic fibers such as glass fibers and carbon fibers are commonly used due to their low elongation and high strength.

[0170] The core wire may be treated with an adhesive treatment to enhance its adhesion to the crosslinked material of the rubber composition. For example, the adhesive treatment may involve immersing the stranded cord in a resorcinol-formaldehyde-latex treatment solution (RFL treatment solution), followed by heating and drying to form a uniform adhesive layer on the surface of the stranded cord. The RFL treatment solution is a mixture of latex and an initial condensate of resorcinol and formalin. The latex may be, for example, chloroprene rubber, styrene-butadiene-vinylpyridine terpolymer (VP latex), nitrile rubber, or hydrogenated nitrile rubber. Furthermore, the adhesive treatment may involve pre-treating with an epoxy compound or isocyanate compound before treatment with the RFL treatment solution.

[0171] The average diameter (average wire diameter) of the stranded cord (or core wire) is, for example, 0.2 to 2.5 mm, preferably 0.5 to 2.3 mm, and more preferably 0.7 to 2.2 mm. If the core wire diameter is too small, the elongation of the core wire will increase, which may cause tooth breakage (loss of teeth). If the core wire diameter is too large, the fatigue resistance of the core wire will decrease, which may cause the core wire to break.

[0172] (Tooth rubber layer) The teeth include a tooth rubber layer positioned on the inner circumference of the core wire. In the embodiment shown in Figure 1, the surface of the tooth rubber layer is covered with tooth cloth, but the tooth rubber layer may not be covered with tooth cloth, and the inner circumference of the belt may be formed of the tooth rubber layer.

[0173] The tooth rubber layer may be formed of a crosslinked material of a fourth rubber composition containing hydrogenated nitrile rubber. In the fourth rubber composition, the hydrogenated nitrile rubber is preferably the same as or of the same type as the hydrogenated nitrile rubber in the second rubber composition, and is particularly preferably the same hydrogenated nitrile rubber, in order to improve the adhesion between the back rubber layer and the tooth rubber layer.

[0174] The fourth rubber composition may further contain, in addition to hydrogenated nitrile rubber, a crosslinking agent exemplified as the second crosslinking agent of the second rubber composition, a filler exemplified as the second filler, a softener exemplified as the second softener, an antioxidant exemplified as the second anti-aging agent, and other components exemplified as the second other component. The fourth rubber composition may also be the same rubber composition as the second rubber composition.

[0175] The tooth rubber layer is not limited to a single-layer tooth rubber layer as shown in Figure 1, but may also be a tooth rubber layer having a laminated structure of two or more layers.

[0176] (Tooth cloth) If the teeth include a tooth fabric, the tooth fabric laminated on the inner circumferential surface of the belt (teeth and tooth roots) may be made of a fabric such as a woven fabric, knitted fabric, or nonwoven fabric. Conventionally, it is often a woven fabric (canvas), and is composed of a fabric woven from warp threads extending in the belt width direction and weft threads extending in the belt circumferential direction. The woven fabric can be selected from the woven fabrics exemplified as intermediate fabrics, including preferred embodiments.

[0177] The fibers forming the weft and warp threads of the toothed fabric may be organic or inorganic fibers. Examples of organic and inorganic fibers include those exemplified as organic and inorganic fibers forming the intermediate layer of fabric. These fibers can be used individually or in combination of two or more types.

[0178] Of the aforementioned fibers, organic fibers are commonly used, and preferred are cellulose fibers such as cotton and rayon, polyester fibers (such as PET fibers), polyamide fibers (such as aliphatic polyamide fibers like polyamide 66 fibers, aramid fibers, etc.), PBO fibers, and fluororesin fibers [such as polytetrafluoroethylene (PTFE) fibers]. Also preferred are composite yarns of these fibers and elastic yarns with elasticity [for example, elastic polyurethane-based elastic yarns such as spandex made of polyurethane, and processed yarns that have undergone stretch processing (for example, woolly processing, crimping processing, etc.)].

[0179] The form of the warp and weft threads is not particularly limited and may be monofilament yarn, which is a single long fiber; multifilament yarn, which is made by aligning or twisting filaments (long fibers); or spun yarn, which is made by twisting short fibers. The multifilament yarn or spun yarn may be a blended yarn or blended yarn using multiple types of fibers. The weft threads preferably contain elastic yarn, while the warp threads usually do not contain elastic yarn from the viewpoint of weaving. In order to ensure the elasticity of the tooth fabric in the circumferential direction of the belt, the weft threads containing elastic yarn extend in the circumferential direction of the belt, and the warp threads extend in the width direction of the belt.

[0180] The average diameter of the fibers is, for example, 1 to 100 μm (e.g., 3 to 50 μm), preferably 5 to 30 μm, and more preferably 7 to 25 μm. Regarding the average diameter (thickness) of the yarn (twisted yarn), the weft may be, for example, 100 to 1000 dtex (particularly 300 to 700 dtex), and the warp may be, for example, 50 to 500 dtex (particularly 100 to 300 dtex). The density of the weft (threads / cm) may be, for example, 5 to 50 (particularly 10 to 30), and the density of the warp (threads / cm) may be, for example, 10 to 300 (particularly 20 to 100).

[0181] The woven fabric may have a multi-layered structure (such as a double-layered structure), and in a woven structure comprising warp and weft threads, at least some of the weft threads may be made of low-friction fibers (or low-friction fibers) such as fluororesin-containing fibers (such as composite yarns containing fibers formed from fluororesins such as PTFE). For example, the warp threads may be made of polyamide fibers such as polyamide 66, polyester fibers, etc., and the weft threads may be made of fluororesin-formed fibers alone; composite yarns of fluororesin-formed fibers and second fibers such as polyamide fibers or polyurethane fibers (elastic yarns); or composite yarns of this composite yarn and a second composite yarn formed from a plurality of the aforementioned second fibers.

[0182] In woven fabrics with a multi-layered weave structure, it is preferable to use fluorine-based fibers (e.g., PTFE fibers) with a low coefficient of friction as the weft threads located on the surface side of the toothed fabric (the side that engages with the toothed pulley) (exposed side) in order to reduce friction between the toothed fabric and the toothed pulley. On the other hand, by using fibers other than fluorine-based fibers for the weft threads located on the back side of the toothed fabric (the side that adheres to the first rubber layer), it is possible to increase the adhesive strength between the toothed fabric and the rubber that constitutes the teeth.

[0183] Furthermore, when using fluorine-based fibers, it is preferable that low-melting-point fibers that melt at the cross-linking (vulcanization) temperature of the teeth and back, with rubber as the base material, be arranged around the fluorine-based fibers. Specifically, the form of the composite yarn containing fluorine-based fibers includes forms in which fluorine-based fibers and low-melting-point fibers are mixed and twisted together, or forms in which fluorine-based fibers are covered by low-melting-point fibers. The cross-linking (vulcanization) conditions of the teeth and back are not particularly limited, but generally, the cross-linking (vulcanization) temperature is 100 to 200°C and the cross-linking (vulcanization) time is 1 minute to 5 hours.

[0184] In an embodiment in which low-melting-point fibers are arranged around fluorine-based fibers, the low-melting-point fibers melt during cross-linking (vulcanization) of the teeth and back portions, flow into the spaces between the fibers constituting the tooth fabric, and then crystallize when cooled to below their melting point. Therefore, the cutting and scattering of fluorine-based fibers due to impact and abrasion on the surface of the tooth fabric during engagement with or disengagement from a toothed pulley is suppressed.

[0185] The average thickness of the tooth fabric (the tooth fabric in the toothed belt) is, for example, 0.1 to 2 mm, preferably 0.2 to 1.5 mm. The average thickness of the tooth fabric as raw material (the tooth fabric before molding) is, for example, 0.5 to 3 mm, preferably 0.75 to 2.5 mm.

[0186] To improve the adhesion between the tooth cloth and the tooth rubber layer, the cloth forming the tooth cloth may be treated with an adhesive. Examples of adhesive treatments include immersing the cloth in an RFL treatment solution followed by heat drying; treating with an epoxy compound or isocyanate compound; or dissolving a rubber composition in an organic solvent to make a rubber glue, immersing the cloth in this rubber glue, and then heat drying. These methods can be performed individually or in combination, and the order and number of treatments are not limited. For example, after immersion in an RFL treatment solution, the cloth may be further immersed in rubber glue and then heat dried.

[0187] Furthermore, to enhance the adhesion between the tooth cloth and the tooth rubber layer, an uncrosslinked rubber sheet, formed by rolling a rubber composition, may be laminated onto the back surface (the side that adheres to the tooth rubber layer) of the cloth forming the tooth cloth. This rubber composition can be appropriately selected from the rubber compositions exemplified above as the fourth rubber composition for forming the tooth rubber layer, or it may be a conventional adhesive rubber composition. In addition, the uncrosslinked rubber sheet made of this rubber composition may form an adhesive rubber layer interposed between the tooth cloth and the tooth rubber layer in the toothed belt.

[0188] The average tooth height of the teeth is, for example, 25-70%, preferably 30-50%, and more preferably 35-40%, of the average value of the total belt thickness [thickness (distance or height) from the back surface (outer surface) to the tooth crown].

[0189] In this application, as shown in Figure 2, the average tooth height of the teeth refers to the average height of the protruding teeth on the inner surface of the belt [the average value of the thickness (distance or height) from the tooth root surface to the tooth apex].

[0190] (Tooth root) When the tooth portion includes a tooth cloth, the tooth cloth constitutes the surface of the tooth portion and also forms the surface on the tooth side of the back (the surface of the tooth root).

[0191] If the tooth portion includes a tooth cloth, a tooth rubber layer may be interposed between the tooth cloth and the core wire in the dorsal portion corresponding to the tooth root, or the tooth cloth and core wire may be in contact without the tooth rubber layer being interposed. Even if a tooth rubber layer is interposed in the dorsal portion corresponding to the tooth root, the thickness of the tooth rubber layer is formed to be thinner than that of the tooth portion.

[0192] If the tooth portion does not include a tooth cloth, the dorsal portion corresponding to the tooth root may be formed of a tooth rubber layer. In the dorsal portion corresponding to the tooth root, the thickness of the tooth rubber layer is formed to be thinner than that of the tooth portion.

[0193] [Manufacturing method for power transmission belts] The method for manufacturing the power transmission belt of the present invention is not particularly limited, and conventional methods can be used depending on the type of belt. In the case of a toothed belt, it can be manufactured by a first method that does not involve pre-forming only the teeth, or by a second method that does involve the aforementioned pre-forming. Specifically, a toothed belt having a toothed fabric and in which the outer rubber layer consists of a first rubber layer, an intermediate layer, and a second rubber layer may be manufactured, for example, by the method shown below.

[0194] (a) Method 1 (Method in which the teeth are not formed in advance during the molding process) A toothed belt can be obtained by a method that includes a crosslinking molding step in which an uncrosslinked molded body is formed by laminating precursors of tooth cloth, core wire, intermediate layer, tooth rubber layer, and back rubber layer (outer rubber layer). Specifically, the method includes a precursor preparation step in which each precursor is prepared; a molding step in which an uncrosslinked molded body is formed by laminating the precursors of tooth cloth, core wire, intermediate layer, tooth rubber layer, and back rubber layer; a crosslinking molding step in which the uncrosslinked molded body is crosslinked to obtain a crosslinked molded body; and a cutting step in which the crosslinked molded body is cut to obtain a toothed belt.

[0195] (Precursor preparation process) In the precursor preparation step, the core wire precursor, the tooth cloth precursor, and the intermediate layer precursor for forming the third intermediate layer (third intermediate layer precursor) may be prepared by bonding treatment as described above.

[0196] The precursors for the tooth rubber layer and the back rubber layer (the first and second rubber layers that form the outer periphery) are uncrosslinked rubber sheets. The uncrosslinked rubber sheets are prepared by conventional methods, for example, by kneading a rubber composition in a Banbury mixer and rolling it with a roll or calender to prepare uncrosslinked rubber sheet A for forming the tooth rubber layer and the second rubber layer, and uncrosslinked rubber sheet B for forming the first rubber layer.

[0197] In the case of forming the intermediate layer according to the first embodiment, the intermediate layer may be formed by pre-laminating an intermediate layer precursor (first intermediate layer precursor) onto one side of the obtained uncrosslinked rubber sheet A and then subjecting it to the next step. Methods for laminating the first intermediate layer precursor include scattering powdered unsaturated carboxylate metal salt and applying a solution containing the unsaturated carboxylate metal salt to one side of the obtained uncrosslinked rubber sheet A. Of these, the method of applying a solution containing the unsaturated carboxylate metal salt is preferred because it is easier to form a uniform intermediate layer and improve interlayer adhesion.

[0198] Furthermore, when forming the intermediate layer of the second embodiment, an uncrosslinked rubber sheet C (second intermediate layer precursor) for forming the intermediate layer is prepared in the same manner as uncrosslinked rubber sheets A and B.

[0199] Furthermore, when forming an intermediate layer (intermediate cloth) according to the third embodiment, an uncrosslinked third rubber composition is attached to the cloth. Methods for attaching the uncrosslinked third rubber composition to the cloth include, for example, a method of soaking (immersing) the cloth in a rubber glue made by dissolving the uncrosslinked rubber composition in a solvent to form a rubber glue adhesive layer (soaking method), a method of applying (coating) the rubber glue to the cloth to form a rubber glue adhesive layer (coating method), and a method of friction-adhesive rubber layer being formed by friction-rubbing (rubbing) the solid uncrosslinked rubber composition into the cloth (frictioning method). Of these, the soaking method and the coating method are preferred.

[0200] In soaking and coating methods, suitable solvents for preparing rubber adhesives include, for example, aromatic hydrocarbons (e.g., aliphatic hydrocarbons such as hexane and cyclohexane; aromatic hydrocarbons such as toluene and xylene), ketones (e.g., aliphatic ketones such as acetone, diacetone alcohol, methyl ethyl ketone, and methyl isobutyl ketone; alicyclic ketones such as cyclohexanone and isophorone), ethers (e.g., dioxane and tetrahydrofuran), and esters (e.g., acetate esters such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, and amyl acetate). These solvents can be used individually or in combination of two or more. Of these, aromatic hydrocarbons and aliphatic ketones are commonly used.

[0201] In the soaking method, the proportion of solvent may be 50% by mass or more in the rubber adhesive, for example, 50 to 99% by mass, preferably 70 to 98% by mass, and more preferably 80 to 95% by mass. In the coating method, the proportion of solvent may be 10% by mass or more in the rubber adhesive, for example, 10 to 90% by mass, preferably 50 to 85% by mass, and more preferably 70 to 80% by mass.

[0202] In the soaking method, after immersing the cloth in rubber cement, the cloth impregnated with rubber cement may be passed between rollers to remove excess rubber cement and allow the rubber cement to penetrate into the fabric. The cloth impregnated with rubber cement may be dried by heating at a temperature of 50°C or higher (for example, 60-100°C).

[0203] In the coating method, rubber adhesive may be applied to the surface of the fabric using a coater or similar device, and then dried by heating at a temperature of 50°C or higher (for example, 60-100°C).

[0204] To improve the adhesion between the intermediate fabric and the first and second rubber layers, the fabric forming the intermediate fabric may be subjected to an adhesive treatment as a pretreatment before applying the third rubber composition. Examples of adhesive treatments include immersing the fabric in an RFL treatment solution followed by heat drying, or treating it with an epoxy compound or isocyanate compound. These methods can be performed individually or in combination, and the order and number of treatments are not limited.

[0205] (molding process) In the molding process, a tooth cloth precursor for forming the tooth cloth is wound around the outer surface of a cylindrical mold having multiple grooves (recesses) corresponding to the teeth. Subsequently, a twisted cord for forming the core wire is wound spirally around its outer surface at a predetermined pitch (with a predetermined pitch in the axial direction of the cylindrical mold). Furthermore, an uncrosslinked rubber sheet A for forming the tooth rubber layer and the second rubber layer, and an uncrosslinked rubber sheet B for forming the first rubber layer are sequentially wound around its outer surface to form an uncrosslinked belt molded body (uncrosslinked molded body).

[0206] When forming the intermediate layer according to the first embodiment, an uncrosslinked rubber sheet A is used, which has the first intermediate layer precursor laminated on one side, and is arranged so that the first intermediate layer precursor is in contact with the uncrosslinked rubber sheet B.

[0207] On the other hand, when forming the intermediate layer of the second embodiment, an uncrosslinked rubber sheet C is wrapped between the uncrosslinked rubber sheet A and the uncrosslinked rubber sheet B. Similarly, when forming the intermediate layer of the third embodiment, a third intermediate layer precursor (intermediate fabric precursor) is wrapped between the uncrosslinked rubber sheet A and the uncrosslinked rubber sheet B.

[0208] (Crosslinking molding process) Next, in the cross-linking molding process, the uncrosslinked belt molded body is placed on the outer circumference of the cylindrical mold, and a rubber jacket, which acts as a vapor barrier, is then placed over its outer circumference. Subsequently, the belt molded body with the jacket and the cylindrical mold are housed inside a cross-linking molding device such as a vulcanizing can. When the belt molded body is heated and pressurized inside the cross-linking molding device, a portion of the softened uncrosslinked rubber sheet A is extruded (press-fitted) into the inner circumference through the gaps in the twisted cord.

[0209] By press-fitting, the tooth cloth precursor is stretched to conform to the contour of the tooth and positioned on the innermost circumference, a rubber layer derived from the uncrosslinked rubber sheet A is positioned on its outer circumference along the contour of the tooth, twisted cords are arranged on the outer circumference of the rubber layer, the remaining rubber layer is positioned on the outer circumference of the twisted cords, an intermediate layer is positioned further on its outer circumference, and a rubber layer derived from the uncrosslinked rubber sheet B (back) is positioned on the outermost circumference, forming a layered structure.

[0210] Simultaneously with the formation of this layered structure, the cross-linking reaction of the uncrosslinked and semi-crosslinked rubber components contained in the belt molded body causes each component to be integrally joined, forming a sleeve-shaped crosslinked molded body (crosslinked belt sleeve).

[0211] Thus, in the first method, which does not involve pre-forming, the uncrosslinked rubber sheet A (a single uncrosslinked rubber sheet) wrapped around the outer circumference of the twisted cord during the molding process forms both the teeth and the back. In other words, in the first method, a portion of the rubber composition for forming the second rubber layer and the teeth (tooth rubber layer) flows from the back side through the space between the core wires to the teeth side to form the teeth.

[0212] (cutting process) Finally, in the cutting process, multiple toothed belts are obtained by cutting the bridging belt sleeve, which has been demolded from the cylindrical mold, to a predetermined width.

[0213] (b) Second method (a method in which the teeth are formed in advance during the molding process) The first method described above may also be manufactured by adding a step to prepare a pre-formed body in which only the teeth are formed during the molding process.

[0214] (Precursor preparation process) In the precursor preparation step, the core wire precursor, tooth cloth precursor, and third intermediate layer precursor may be prepared by bonding treatment as described above.

[0215] The precursors for the tooth rubber layer and the back rubber layer (the first and second rubber layers that form the outer periphery) are uncrosslinked rubber sheets. The uncrosslinked rubber sheets are prepared by conventional methods, for example, by rolling a rubber composition kneaded in a Banbury mixer or the like, using rolls or a calender, to prepare uncrosslinked rubber sheet a for forming the tooth rubber layer, uncrosslinked rubber sheet b for forming the second rubber layer, and uncrosslinked rubber sheet c for forming the first rubber layer.

[0216] Furthermore, when forming the intermediate layer according to the first embodiment, the intermediate layer may be formed by pre-laminating an intermediate layer precursor onto one side of the obtained uncrosslinked rubber sheet b and then subjecting it to the next step.

[0217] Furthermore, when forming the intermediate layer of the second embodiment, an uncrosslinked rubber sheet d for forming the intermediate layer is prepared in the same manner as the uncrosslinked rubber sheets a to c.

[0218] (molding process) In the molding process, a tooth cloth precursor for forming the tooth cloth is wrapped around the outer surface of a cylindrical mold having multiple grooves (recesses) corresponding to the teeth of a toothed belt. Subsequently, a laminate is formed by wrapping an uncrosslinked rubber sheet a around its outer surface. While heating the laminate to a temperature sufficient to soften the rubber composition (for example, about 70-90°C) using a predetermined device, pressure is applied to the laminate from the outer side, causing the rubber composition of the uncrosslinked rubber sheet a and the tooth cloth precursor to be pressed into the grooves (recesses) of the cylindrical mold to form the teeth and obtain a semi-crosslinked pre-molded body (pre-laminated body). In this process of pressing to form the teeth, the tooth cloth is stretched to a shape that follows the contour of the teeth and is positioned on the outermost surface, and a layer structure is formed on the outer side where the rubber layer is positioned along the contour of the teeth.

[0219] Alternatively, instead of using a cylindrical mold, a flat press mold (flat mold) having multiple grooves (recesses) corresponding to the teeth may be used to form the teeth by press-fitting the rubber composition of an uncrosslinked rubber sheet and a tooth fabric precursor into the grooves (recesses) of the flat mold using the above procedure. In this method, after demolding the preformed body from the flat mold, the preformed body is wrapped around and attached to a cylindrical mold having multiple grooves (recesses) corresponding to the teeth (fitting the teeth and grooves).

[0220] In either method, a stranded cord forming the core is wound spirally around the outer surface of the obtained preformed body at a predetermined pitch (with a predetermined pitch in the axial direction of the cylindrical mold). Furthermore, an uncrosslinked rubber sheet b forming the second rubber layer and an uncrosslinked rubber sheet c forming the first rubber layer are sequentially wound around its outer surface to form an uncrosslinked belt molded body (uncrosslinked laminate).

[0221] (Crosslinking molding process) Next, in the crosslinking molding process, the uncrosslinked belt molded body is placed on the outer circumference of a cylindrical mold, and a rubber jacket, which acts as a vapor barrier, is then placed over its outer circumference. Subsequently, the belt molded body with the jacket and the cylindrical mold are housed inside a crosslinking molding apparatus such as a vulcanizing vessel. When the belt molded body is heated and pressurized inside the crosslinking molding apparatus, the desired shape is formed, and the crosslinking reaction of the uncrosslinked and semi-crosslinked rubber components contained in the belt molded body causes each component to be joined together integrally, forming a sleeve-shaped crosslinked molded body (crosslinked belt sleeve).

[0222] When forming the intermediate layer according to the first embodiment, an uncrosslinked rubber sheet b is used, which has an intermediate layer precursor (first intermediate layer precursor) laminated on one side, and is arranged so that the intermediate layer precursor is in contact with the uncrosslinked rubber sheet c.

[0223] On the other hand, when forming the intermediate layer of the second embodiment, an uncrosslinked rubber sheet d (second intermediate layer precursor) is wrapped between the uncrosslinked rubber sheet b and the uncrosslinked rubber sheet c. Similarly, when forming the intermediate layer of the third embodiment, a third intermediate layer precursor (intermediate fabric precursor) is wrapped between the uncrosslinked rubber sheet b and the uncrosslinked rubber sheet c.

[0224] (cutting process) Finally, in the cutting process, multiple toothed belts are obtained by cutting the bridging belt sleeve, which has been demolded from the cylindrical mold, to a predetermined width. [Examples]

[0225] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. The raw materials used, preparation methods, methods for producing the measurement laminate (crosslinked molded body), and evaluation methods for the measurement laminate are shown below.

[0226] [HNBR composition] Table 1 shows the formulations of the HNBR compositions (R1, R6) as the second rubber composition for forming the second rubber layer and the HNBR compositions (R2~R5) as the third rubber composition for forming the intermediate layer.

[0227] [Table 1]

[0228] [Materials of HNBR composition] HNBR1: Zetpol2010, manufactured by Nippon Zeon Co., Ltd., iodine value 11mg / 100mg HNBR2: ARLANXEO's "Therban3446", residual double bond content 5.5% Zinc methacrylate: "R-20S" manufactured by Asada Chemical Industries, Ltd., purity 85% by mass Stearic acid: "Stearic acid Tsubaki" manufactured by NOF Corporation. Carbon black: "Seas S" manufactured by Tokai Carbon Co., Ltd., average particle size 66 nm, iodine adsorption capacity 26 mg / g Silica: "UltraZil VN3" manufactured by Evonik Degussa Japan Co., Ltd., BET specific surface area 175 m² 2 / g Zinc oxide: "Zinc Oxide Type 2" manufactured by Sakai Chemical Industry Co., Ltd., average particle size 0.55 μm Anti-aging agent: p,p'-dioctyldiphenylamine, manufactured by Seiko Chemical Co., Ltd. ("Nonflex OD3") Organic peroxide 1: NOF Corporation's "Perbutyl P-40MB", 1,3-bis(2-t-butylperoxyisopropyl)benzene, active ingredient 40% by mass Co-crosslinking agent: N,N'-m-phenylenedimaleimide, manufactured by Ouchi Shinko Chemical Co., Ltd. ("Balnock PM") Plasticizer: ADEKA Corporation's "ADEKA Sizer RS700"

[0229] [Silicone rubber composition] Table 2 shows the formulation of the first rubber composition (silicone rubber composition) for forming the first rubber layer.

[0230] [Table 2]

[0231] [Materials for silicone rubber composition] Silicone rubber 1: "TSE270-5U" manufactured by Momentive Performance Materials Japan LLC. Silicone rubber 2: "TSE261-6U" manufactured by Momentive Performance Materials Japan LLC. Organic Peroxide 2: "TC-8" manufactured by Momentive Performance Materials Japan LLC.

[0232] [Tooth cloth] A 2 / 2 twill canvas was woven using 155 dtex nylon 66 yarn as the warp and a composite yarn of 155 dtex nylon 66 yarn and 122 dtex urethane elastic yarn as the weft. The warp density was 137 threads / 3cm and the weft density was 81 threads / 3cm. The woven canvas was immersed in the RFL treatment solution shown in Table 3 and dried. Then, the dried canvas was further immersed in a rubber adhesive prepared by dissolving the uncrosslinked HNBR composition for rubber adhesive shown in Table 4 in methyl ethyl ketone at a ratio of 10% by mass, and dried to obtain a bonded canvas (tooth cloth precursor) with a thickness of 0.85 mm.

[0233] [Table 3]

[0234] [Table 4]

[0235] [Intermediate section] A 2 / 2 twill canvas was woven using 235 dtex nylon 6 yarn as the warp and 44 dtex woolly processed nylon 6 yarn as the weft. The warp density was 90 threads / 3cm and the weft density was 120 threads / 3cm. The uncrosslinked HNBR composition for rubber adhesive shown in Table 5 was kneaded in a Banbury mixer, and 100 parts by mass of the HNBR composition was dissolved in 900 parts by mass of toluene to prepare the rubber adhesive. The woven canvas was immersed in the RFL treatment solution shown in Table 3 and dried, and then immersed in the rubber adhesive and dried to obtain an adhesive-treated intermediate fabric (intermediate fabric precursor) with a thickness of 0.75 mm.

[0236] [Table 5]

[0237] [Reinforcement fabric] 0.5mm thick nylon canvas

[0238] [Core wire (processing code)] Three strands of a strand (strand of ECG150 as described in JIS R 3413 (2012)) in which 200 E-glass filaments with a diameter of 9 μm are bundled were aligned and passed through the RFL treatment liquid (18 to 23°C) shown in Table 3 for 3 seconds for immersion, and then heated and dried at 200 to 280°C for 3 minutes to form an adhesive film of RFL. After this adhesion treatment, a lower-twisted yarn (lower-twisted yarn S) twisted in the S direction at a lower twist number of 8 turns / 10 cm and a lower-twisted yarn (lower-twisted yarn Z) twisted in the Z direction at the same number of turns were prepared. Next, 13 lower-twisted yarns S were aligned and twisted in the Z direction at a twist number of 8 turns / 10 cm to obtain a multi-twisted cord (multi-twisted cord Z). Similarly, 13 lower-twisted yarns Z were aligned and twisted in the S direction at a twist number of 8 turns / 10 cm to obtain a multi-twisted cord (multi-twisted cord S). Each multi-twisted cord was passed through an overcoat liquid (a rubber paste obtained by dissolving an uncrosslinked rubber composition shown in Table 4 in methyl ethyl ketone at a ratio of 10% by mass) and then dried to produce a treated cord (treated cord S and treated cord Z) provided with an adhesive film of the rubber composition. The total fineness of the treated cord was 1300 to 1400 tex, and the outer diameter was 1.2 mm.

[0239] [Production of Uncrosslinked Rubber Sheet] As the uncrosslinked rubber sheet A for forming the tooth rubber layer and the second rubber layer used in the toothed belt produced in the examples and comparative examples, a rubber composition having the composition shown in Table 1 was used, and as the uncrosslinked rubber sheet B for forming the first rubber layer, a rubber composition having the composition shown in Table 2 was used. Each rubber composition was kneaded with a Banbury mixer and rolled with calender rolls to produce an uncrosslinked rubber sheet.

[0240] Furthermore, an uncrosslinked rubber sheet (thickness 0.5 mm) was produced using a rubber composition having the composition shown in Table 1 as the uncrosslinked rubber sheet C for forming the intermediate layer of the second aspect.

[0241] [Lamination of Intermediate Layer Precursor] (Examples 1 to 14) A zinc methacrylate-containing solution was prepared by dissolving zinc methacrylate (R-20S, manufactured by Asada Chemical Industries, Ltd., 85% purity by mass) in toluene. The resulting solution was then applied with a brush to the entire surface of the uncrosslinked rubber sheet A (the surface that will be joined to the uncrosslinked rubber sheet B) to form the second rubber layer, and dried to produce an uncrosslinked rubber sheet A with an intermediate layer precursor laminated on top. In Example 1, the amount of zinc methacrylate attached was 70 g / m². 2 In Example 2, the concentration was 100 g / m². 2 In Example 3, the concentration was 150 g / m². 2 In Example 4, the amount was 200 g / m². 2 In Examples 5-14, the concentration was 100 g / m². 2 The amount applied was adjusted to achieve this result.

[0242] (Examples 15-28) Using the prepared uncrosslinked rubber sheet C as an intermediate layer precursor, the uncrosslinked rubber sheet C was layered on the surface of the uncrosslinked rubber sheet A (the surface that joins with the uncrosslinked rubber sheet B) to produce an uncrosslinked rubber sheet A in which the intermediate layer precursor was laminated. The zinc methacrylate content in the rubber composition in which the uncrosslinked rubber sheet C was formed was 5 parts by mass in Example 15 (R2), 10 parts by mass in Example 16 (R3), 15 parts by mass in Example 17 (R4), 25 parts by mass in Example 18 (R5), and 15 parts by mass in Examples 19 to 28 (R4).

[0243] (Examples 29-42) The prepared intermediate fabric precursor (adhesive-treated intermediate fabric) was used as an intermediate layer precursor, and the intermediate fabric precursor was layered on the surface of the uncrosslinked rubber sheet A (the surface that joins with the uncrosslinked rubber sheet B) to produce an uncrosslinked rubber sheet A in which the intermediate layer precursor was laminated. The zinc methacrylate content in the rubber adhesive (rubber composition) to which this intermediate fabric was adhesive-treated was 5 parts by mass in Example 29 (R9), 10 parts by mass in Example 30 (R10), 15 parts by mass in Example 31 (R11), 25 parts by mass in Example 32 (R12), and 15 parts by mass in Examples 33 to 42 (R11).

[0244] [Adhesion (peel strength) test on test specimens] A reinforcing cloth, an uncrosslinked rubber sheet for the first rubber layer (an uncrosslinked silicone rubber sheet, which is uncrosslinked rubber sheet B, with a thickness of 2 mm, a width of 30 mm, and a length of 150 mm), an uncrosslinked rubber sheet for the second rubber layer (an uncrosslinked HNBR sheet, which is uncrosslinked rubber sheet A, with a thickness of 2 mm, a width of 30 mm, and a length of 150 mm) with an intermediate layer precursor pre-laminated on top, and a reinforcing cloth were stacked in that order (Comparative Example 1 did not have an intermediate layer precursor), and crosslinking molding was performed in a press die (surface pressure of 2 MPa, 165°C) for 30 minutes to produce a laminate (crosslinked molded body) 16 in which the reinforcing cloth 11, silicone rubber sheet 12, intermediate layer 13, HNBR sheet 14, and reinforcing cloth 15 were joined together to form an integrated structure, as shown in Figure 3.

[0245] In this laminate 16, the interface between the silicone rubber sheet 12 and the HNBR sheet 14 is joined over a length of 120 mm via an intermediate layer 13. One end of each uncrosslinked rubber sheet was not joined, as shown in Figure 3, in order to be used as gripping portions A and B (30 mm in length each) for the tensile force measurement described later. The resulting laminate 16 was cut to a width of 25 mm to produce a sample with a width of 25 mm, a length of 150 mm (joining length 120 mm), and a thickness of 4 mm.

[0246] The Autograph (Shimadzu Corporation, "AGS-J10kN") was used to grip section A (a laminate of reinforcing fabric 11 and silicone rubber sheet 12) with its upper grip and grip section B (a laminate of intermediate layer 13, HNBR sheet 14, and reinforcing fabric 15) with its lower grip. The upper grip was raised at a speed of 50 mm / min according to JIS K 6256 (2013) to separate the bonding interface, and the tensile strength (tensile force) at that time was recorded as the peel strength (peel force). The measurement time was set to 2 minutes so that the movement distance of the upper grip and the peeled area were approximately 100 mm. The test temperature (ambient temperature) was 23°C, and the sample was measured after being left at the test temperature for 16 hours or more. The tensile force showed a wavy curve, and its average value was calculated according to Method E of JIS K 6274 (2018). In other words, ignoring the initial upward curve at the start of the test, we calculated the average of the maximum and minimum values ​​among all the peaks of the wave curve.

[0247] Then, based on the obtained peel strength (peeling force), the bonding strength (adhesion) between the first rubber layer (silicone rubber composition) and the intermediate layer was determined according to the following criteria.

[0248] (Judgment criteria) a: Peel strength (peeling force) of 100N or more per 25mm width b: Peel strength (peel force) per 25 mm width is 50 N or more and less than 100 N c: Peel strength (peel force) per 25mm width is less than 50N

[0249] As shown in Figure 3, this test involves delamination at the interface between the silicone rubber sheet and the intermediate layer. This interface is more prone to delamination than the interface between the HNBR sheet and the intermediate layer and is the weakest point, making it a dominant factor in the belt's durability and lifespan.

[0250] [Manufacturing of toothed belts] In Comparative Examples 1-2 and Examples 1-42, an uncrosslinked rubber sheet formed from a rubber composition having the composition shown in Table 1 was used as the uncrosslinked rubber sheet A for forming the tooth rubber layer and the second rubber layer, and an uncrosslinked rubber sheet formed from a rubber composition having the composition shown in Table 2 was used as the uncrosslinked rubber sheet B for forming the first rubber layer. A toothed belt with a tooth profile G8M, tooth height (including tooth cloth) 3.35 mm, tooth pitch 8 mm, number of teeth 100, core wire pitch 1.45 mm, and circumference 800 mm was manufactured using the first manufacturing method described in the section [Modes for Carrying Out the Invention], which does not go through (a) pre-forming. The width of the toothed belt used for measuring bonding strength (peel strength) was 36.0 mm, and the width of the toothed belt used for the durability running test was 15.0 mm.

[0251] (Comparative Example 1) Uncrosslinked rubber composition R1 was used as uncrosslinked rubber sheet A, and uncrosslinked rubber composition R7 was used as uncrosslinked rubber sheet B. In the molding process, an uncrosslinked belt molded body (uncrosslinked molded body) was formed without using an intermediate layer precursor. This was crosslinked to form a sleeve-shaped crosslinked molded body (crosslinked belt sleeve), and a toothed belt was produced by cutting it to a predetermined width. The back hardness of the first rubber layer was A50, the average thickness of the first rubber layer was 2.9 mm, the average thickness of the second rubber layer was 1.2 mm, and the thickness ratio of the first rubber layer to the outer rubber layer was 70.7%.

[0252] (Comparative Example 2) A toothed belt was fabricated in the same manner as in Comparative Example 1, except that uncrosslinked rubber sheet A and uncrosslinked rubber sheet B were bonded together with an epoxy resin adhesive. The back hardness of the first rubber layer was A50, the average thickness of the first rubber layer was 2.9 mm, the average thickness of the second rubber layer was 1.2 mm, and the thickness ratio of the first rubber layer to the outer rubber layer was 70.7%.

[0253] (Examples 1-4) A toothed belt was manufactured in the same manner as in Comparative Example 1, except that the laminated sheet described in the section [Lamination of Intermediate Layer Precursors] (uncrosslinked rubber sheet A with intermediate layer precursors laminated) was used as the uncrosslinked rubber sheet A. The back hardness of the first rubber layer was A50, the average thickness of the first rubber layer was 2.9 mm, the average thickness of the second rubber layer was 1.2 mm, and the thickness ratio of the first rubber layer to the outer rubber layer was 70.7%.

[0254] (Example 5) A toothed belt was manufactured in the same manner as in Example 2, except that an uncrosslinked rubber composition R6 was used as the uncrosslinked rubber sheet A. The back hardness of the first rubber layer was A50, the average thickness of the first rubber layer was 2.9 mm, the average thickness of the second rubber layer was 1.2 mm, and the thickness ratio of the first rubber layer to the outer rubber layer was 70.7%.

[0255] (Example 6) A toothed belt was produced in the same manner as in Example 2, except that the unvulcanized rubber composition R8 was used as the unvulcanized rubber sheet B. The Shore hardness of the back surface of the first rubber layer was A60, the average thickness of the first rubber layer was 2.9 mm, the average thickness of the second rubber layer was 1.2 mm, and the thickness ratio of the first rubber layer to the outer peripheral rubber layer was 70.7%.

[0256] (Example 7) A toothed belt was produced in the same manner as in Example 2, except that the unvulcanized rubber composition R6 was used as the unvulcanized rubber sheet A and the unvulcanized rubber composition R8 was used as the unvulcanized rubber sheet B. The Shore hardness of the back surface of the first rubber layer was A60, the average thickness of the first rubber layer was 2.9 mm, the average thickness of the second rubber layer was 1.2 mm, and the thickness ratio of the first rubber layer to the outer peripheral rubber layer was 70.7%.

[0257] (Examples 8 to 14) A toothed belt was produced in the same manner as in Example 2, except that the average thicknesses of the first rubber layer and the second rubber layer (and accordingly, the thickness ratio of the first rubber layer to the outer peripheral rubber layer) were adjusted to the values shown in Table 7.

[0258] (Examples 15 to 18) A toothed belt was produced in the same manner as in Comparative Example 1, except that the laminated sheet (the unvulcanized rubber sheet A laminated with the unvulcanized rubber sheet C as the intermediate layer precursor) described in the section [Lamination of Intermediate Layer Precursors] was used as the unvulcanized rubber sheet A. The average thickness of the first rubber layer was 2.9 mm, the thickness of the intermediate layer was 0.4 mm, the average thickness of the second rubber layer was 1.2 mm, and the thickness ratio of the first rubber layer to the outer peripheral rubber layer was 64.4%.

[0259] (Example 19) A toothed belt was produced in the same manner as in Example 17, except that the unvulcanized rubber composition R6 was used as the unvulcanized rubber sheet A. The Shore hardness of the back surface of the first rubber layer was A50, the average thickness of the first rubber layer was 2.9 mm, the thickness of the intermediate layer was 0.4 mm, the average thickness of the second rubber layer was 1.2 mm, and the thickness ratio of the first rubber layer to the outer peripheral rubber layer was 64.4%.

[0260] (Example 20) A toothed belt was manufactured in the same manner as in Example 17, except that an uncrosslinked rubber composition R8 was used as the uncrosslinked rubber sheet B. The back hardness of the first rubber layer was A60, the average thickness of the first rubber layer was 2.9 mm, the thickness of the intermediate layer was 0.4 mm, the average thickness of the second rubber layer was 1.2 mm, and the thickness ratio of the first rubber layer to the outer rubber layer was 64.4%.

[0261] (Example 21) A toothed belt was manufactured in the same manner as in Example 17, except that uncrosslinked rubber composition R6 was used as uncrosslinked rubber sheet A and uncrosslinked rubber composition R8 was used as uncrosslinked rubber sheet B. The back hardness of the first rubber layer was A60, the average thickness of the first rubber layer was 2.9 mm, the thickness of the intermediate layer was 0.4 mm, the average thickness of the second rubber layer was 1.2 mm, and the thickness ratio of the first rubber layer to the outer rubber layer was 64.4%.

[0262] (Examples 22-28) A toothed belt was manufactured in the same manner as in Example 17, except that the average thickness of the first and second rubber layers (and consequently the thickness ratio of the first rubber layer to the outer rubber layer) was adjusted to the values ​​shown in Table 9.

[0263] (Examples 29-32) A toothed belt was manufactured in the same manner as in Comparative Example 1, except that the laminated sheet described in the section on [Lamination of Intermediate Layer Precursors] (an uncrosslinked rubber sheet A with an intermediate fabric precursor laminated as an intermediate layer precursor) was used as the uncrosslinked rubber sheet A. The back hardness of the first rubber layer was A50, the average thickness of the first rubber layer was 2.9 mm, the thickness of the intermediate layer was 0.2 mm, the average thickness of the second rubber layer was 1.2 mm, and the thickness ratio of the first rubber layer to the outer rubber layer was 67.4%.

[0264] (Example 33) A toothed belt was manufactured in the same manner as in Example 31, except that an uncrosslinked rubber composition R6 was used as the uncrosslinked rubber sheet A. The back hardness of the first rubber layer was A50, the average thickness of the first rubber layer was 2.9 mm, the thickness of the intermediate layer was 0.2 mm, the average thickness of the second rubber layer was 1.2 mm, and the thickness ratio of the first rubber layer to the outer rubber layer was 67.4%.

[0265] (Example 34) A toothed belt was manufactured in the same manner as in Example 31, except that an uncrosslinked rubber composition R8 was used as the uncrosslinked rubber sheet B. The back hardness of the first rubber layer was A60, the average thickness of the first rubber layer was 2.9 mm, the thickness of the intermediate layer was 0.2 mm, the average thickness of the second rubber layer was 1.2 mm, and the thickness ratio of the first rubber layer to the outer rubber layer was 67.4%.

[0266] (Example 35) A toothed belt was manufactured in the same manner as in Example 31, except that uncrosslinked rubber composition R6 was used as uncrosslinked rubber sheet A and uncrosslinked rubber composition R8 was used as uncrosslinked rubber sheet B. The back hardness of the first rubber layer was A60, the average thickness of the first rubber layer was 2.9 mm, the thickness of the intermediate layer was 0.2 mm, the average thickness of the second rubber layer was 1.2 mm, and the thickness ratio of the first rubber layer to the outer rubber layer was 67.4%.

[0267] (Examples 36-42) A toothed belt was manufactured in the same manner as in Example 31, except that the average thickness of the first and second rubber layers (and consequently the thickness ratio of the first rubber layer to the outer rubber layer) was adjusted to the values ​​shown in Table 11.

[0268] [Measurement of bonding strength (peel strength) in toothed belts] A 15cm section was cut from the fabricated endless toothed belt in the length direction to obtain a sample for measurement, representing the belt in its unrunned state. Similarly, a sample was also taken from the endless toothed belt after it had been run, representing the belt in its runned state. A two-axis running test machine consisting of a drive (Dr.) pulley with a diameter of 56.02mm and a driven (Dn.) pulley with a diameter of 56.02mm was used to run the toothed belt. On the two-axis running test machine, a toothed belt with a width of 36.0mm was mounted on each pulley, the shaft load was set to 128N, the drive pulley rotation speed to 3600rpm, and the driven pulley load to 4.86N·m. The belt was run for 720 hours at an ambient temperature of 100°C.

[0269] The peel strength of each sample was measured as follows: On the end face of a sample taken from an endless belt, an incision was made with a cutting tool at the interface between the first rubber layer and the intermediate layer to create gripping portions A and B. Then, gripping portion A (first rubber layer) was gripped with the upper grip of an Autograph (Shimadzu Corporation "AGS-J10kN"), and gripping portion B (laminated structure of intermediate layer, second rubber layer, and teeth) was gripped with the lower grip. In the same manner as in the "Measurement of bonding strength (peel strength) using a test piece" described above, gripping portion A and gripping portion B were pulled apart (peel angle of 180°, i.e., gripping portion A was folded back 180° relative to gripping portion B), and the tensile strength (tensile force) when the interface was peeled was recorded as the peel strength (peel force). The peel strength was calculated by converting the measured tensile force to a value per 25 mm width.

[0270] Based on the obtained peel strength (peel force), the bonding strength (adhesion) between the first rubber layer (silicone rubber composition) and the intermediate layer was determined according to the following criteria.

[0271] (Judgment criteria) a: Peel strength (peeling force) of 40N or more per 25mm width b: Peel strength (peel force) per 25mm width is 30N or more and less than 40N c: Peel strength (peel force) per 25mm width is 10N or more and less than 30N d: Peeling strength (peeling force) per 25mm width is less than 10N, or peeling occurs during driving.

[0272] [Endurance driving test] To verify the conveying performance on the back, we evaluated its superiority or inferiority using the belt's durability and running life as an indicator. Specifically, since conveying performance is lost due to failures caused by durable running (cracks on the back, delamination of the back layer), we used the durability and running life (running time until failure occurs) as an indicator of "sustainability of conveying performance" to determine its superiority or inferiority.

[0273] The durability running test was conducted using the same two-axis running test machine used for measuring joint strength (peel strength). A toothed belt with a width of 15.0 mm was used, and the machine was run with an axle load of 442 N, a drive pulley rotation speed of 3600 rpm, a driven pulley load of 10.33 N·m, and an ambient temperature of 100°C. The running time until failure occurred in the toothed belt was measured as the running life.

[0274] The travel time until this failure occurs (hereinafter referred to as "travel time") is shown as a relative value, with the travel time of Comparative Example 1 set to 1.0. If this relative value is greater than 1.0, it indicates a longer travel life than the toothed belt of Comparative Example 1 (i.e., superior sustained transport performance), and if it is 1.0 or less, it indicates that it is equivalent to or less than the toothed belt of Comparative Example 1.

[0275] (Criteria for judging endurance driving tests) a: Driving time until breakdown (relative value) is 18 or more b: Driving time until breakdown (relative value) is 10 or more, but less than 18. c: Driving time until failure (relative value) is greater than 1.0 and less than 10. d: Driving time until failure (relative value) is 1.0 or less

[0276] [Overall assessment] Considering three factors for toothed belts—bonding strength in the non-running state (bonding strength between the first and second rubber layers), bonding strength after running (maintainability from the non-running state), and durable running life (maintenance of conveying performance)—a comprehensive evaluation (ranking) was conducted according to the following criteria. From the perspective of product practicality, ranks A, B, and C were deemed acceptable, while rank D was deemed unacceptable.

[0277] (Criteria for overall evaluation) A Rank: All three of the above criteria have been judged as A. Rank B: Includes a 'b' rating in the above three criteria (but does not include 'c' or 'd' ratings). Rank C: Includes a "c" rating in the above three criteria (but does not include a "d" rating). Rank D: Includes a 'd' rating in the evaluation of the above three items.

[0278] The evaluation results for Comparative Examples 1-2 and Examples 1-42 are shown in Tables 6-11.

[0279] [Table 6]

[0280] [Table 7]

[0281] [Table 8]

[0282] [Table 9]

[0283] [Table 10]

[0284] [Table 11]

[0285] <Verification results in Table 6> (Comparative Examples 1 and 2) Comparative Example 1 is an example of a toothed belt in which a first rubber layer (R7) that does not contain zinc methacrylate and a second rubber layer (R1) that does not contain zinc methacrylate are joined together. Comparative Example 2 is an example of a toothed belt in which the first rubber layer (R7) and the second rubber layer (R1) of Comparative Example 1 are joined together with an epoxy resin adhesive.

[0286] In all cases, the bonding strength between the first and second rubber layers was low in the undriven belt (rating c), and because the first and second rubber layers separated during driving, the bonding strength after driving could not be measured (rating d). It was confirmed that sufficient bonding strength could not be obtained without using zinc methacrylate.

[0287] Furthermore, in the durability driving test, the driving life (driving time until failure (relative value)) was also low (rated D) due to delamination between the first and second rubber layers at an early stage, resulting in an overall rating of D (fail).

[0288] (Examples 1-4) Examples 1-4 are examples of toothed belts in which zinc methacrylate is sprayed at the bonding interface between the first and second rubber layers to perform crosslinking, thereby bonding the first and second rubber layers. The amount of zinc methacrylate sprayed at the bonding interface was 70 g / m². 2 (Example 1), 100g / m 2 (Example 2), 150g / m 2 (Example 3), 200g / m 2 As a result of the variation in (Example 4), the bonding strength between the first and second rubber layers of the belt in its unused state improved to a passing level (rating B) in Example 1 and to a passing level (rating A) in Examples 2-4. Furthermore, this bonding strength was maintained even after use.

[0289] Furthermore, regarding the running life, in Example 1, the belt failed (reached the end of its lifespan) due to delamination between the first and second rubber layers at a running time (relative value) of 14 (rating b). In other words, it can run 14 times longer than Comparative Example 1 (conveying performance is maintained). In Examples 2 to 4, the running time (relative value) until failure was 20, when tooth chipping occurred and the belt failed (reached the end of its lifespan) without delamination between the first and second rubber layers during running (rating a). In the overall evaluation, the toothed belt in Example 1 was rated C (pass), and the toothed belts in Examples 2 to 4 were rated A (pass).

[0290] From these results, it was confirmed that spraying zinc methacrylate on the bonding interface improves the bonding strength between the first and second rubber layers (making delamination between the first and second rubber layers less likely) and improves the durability and lifespan of the toothed belt (improving the sustainability of conveying performance).

[0291] (Examples 5-7) Example 5 is an example of a toothed belt in which the type of HNBR in the second rubber layer was changed (composition changed from R1 to R6) compared to the configuration of Example 2. Example 6 is an example of a toothed belt in which the type of silicone rubber in the first rubber layer was changed (composition changed from R7 to R8) compared to the configuration of Example 2. Example 7 is an example of a toothed belt in which the type of HNBR in the second rubber layer was changed (composition changed from R1 to R6) and the type of silicone rubber in the first rubber layer was changed (composition changed from R7 to R8) compared to the configuration of Example 2. In all of the toothed belts, the bonding strength between the first rubber layer and the second rubber layer, and the durable running life (maintenance of conveying function) were equivalent to that of Example 2, and the overall evaluation was A rank (pass).

[0292] <Verification results in Table 7> (Examples 8-11) Examples 8 to 11 are based on the configuration of Example 2, but with the total belt thickness (and back thickness of 4.1 mm) kept constant. By changing the ratio of the thickness of the second rubber layer (HNBR composition) to the first rubber layer (silicone rubber composition), the "thickness ratio of the first rubber layer to the total thickness of the outer rubber layer (back rubber layer)" was varied. Specifically, the thickness ratio of the first rubber layer to the outer rubber layer was varied to 39.0% (Example 8), 53.7% (Example 9), 70.7% (Example 2), 78.0% (Example 10), and 82.9% (Example 11). In all cases, the bonding strength between the first and second rubber layers was equivalent to that of Example 2. Regarding durability and running life (maintenance of conveying function), in Example 8, where the thickness ratio of the first rubber layer was small (the first rubber layer was thin), the high proportion of HNBR composition in the outer rubber layer increased rigidity and made it difficult to bend, resulting in a crack on the back surface and failure (end of life) after a running time (relative value) of 14 (rating b). On the other hand, in Example 11, where the thickness ratio of the first rubber layer was large (the first rubber layer was thick), the high proportion of silicone rubber composition in the outer rubber layer reduced rigidity near the teeth, resulting in tooth chipping and failure (end of life) after a running time (relative value) of 16 (rating b). In Examples 9 and 10, no delamination between the first and second rubber layers or back surface cracking occurred during running, but tooth chipping occurred and failure (end of life) occurred (rating a). The overall rating was B rank (pass) for the toothed belts in Examples 8 and 11, and A rank (pass) for the toothed belts in Examples 9 and 10.

[0293] (Examples 12-14) Examples 12 to 14 are based on the configuration of Example 2, but vary the thickness of the first rubber layer (silicone rubber composition) laminated onto a second rubber layer (HNBR composition) of a constant thickness (1.2 mm), thereby varying the "ratio of the thickness of the first rubber layer to the total thickness of the outer rubber layer (back rubber layer)". Specifically, the ratio of the thickness of the first rubber layer to the outer rubber layer was varied to 62.5% (Example 12), 70.7% (Example 2), 78.9% (Example 13), and 82.1% (Example 14). In all cases, the bonding strength between the first and second rubber layers was equivalent to that of Example 2. Regarding durable running life (maintenance of conveying function), as the thickness ratio of the first rubber layer increased, the total belt thickness (and back thickness) increased, making it more difficult for the outer rubber layer to bend, which tended to decrease the durable running life. In Examples 12 and 13, tooth breakage occurred during running without delamination between the first and second rubber layers or cracks on the back surface (rating a), but in Example 14, which had the largest total belt thickness, cracks occurred on the back surface after a running time (relative value) of 16, resulting in failure (rating b). The overall rating was B rank (pass) for the toothed belt in Example 14, and A rank (pass) for the toothed belts in Examples 12 and 13.

[0294] Based on these results, it can be said that the preferred range for the "ratio of the thickness of the first rubber layer to the total thickness of the outer rubber layer (back rubber layer)" is 50-80%.

[0295] <Verification results in Table 8> (Examples 15-18) Examples 15-18 are examples of toothed belts in which an uncrosslinked rubber sheet containing zinc methacrylate was interposed at the interface between the first and second rubber layers, and the two layers were joined by crosslinking. By varying the amount of zinc methacrylate added to the uncrosslinked rubber sheet (5 parts by mass (Example 15), 10 parts by mass (Example 16), 15 parts by mass (Example 17), and 25 parts by mass (Example 18)), the bonding strength between the first and second rubber layers in the un-running belt improved to a passing level (grade C) in Example 15 and to a passing level (grade A) in Examples 16-18. Furthermore, this bonding strength was maintained even after running.

[0296] Furthermore, regarding the running life, in Example 15, the belt failed (reached the end of its lifespan) due to delamination between the first and second rubber layers at a running time (relative value) of 14 (rating b). In other words, Example 15 could run 14 times longer than Comparative Example 1 (conveying performance was maintained). In Examples 16-18, the running time (relative value) until failure was 20 minutes, during which tooth chipping occurred and the belt failed (reached the end of its lifespan) without delamination between the first and second rubber layers during running (rating a). In the overall evaluation, the toothed belt in Example 15 was rated C (pass), while the toothed belts in Examples 16-18 were rated A (pass).

[0297] From these results, it was confirmed that by placing a crosslinked rubber composition containing zinc methacrylate at the bonding interface, the bonding strength between the first rubber layer and the second rubber layer is improved (delamination between the first and second rubber layers becomes less likely), and the durability life of the toothed belt is improved (the sustainability of conveying performance is improved).

[0298] (Examples 19-21) Example 19 is an example of a toothed belt in which the type of HNBR in the second rubber layer was changed (composition changed from R1 to R6) compared to the configuration of Example 17. Example 20 is an example of a toothed belt in which the type of silicone rubber in the first rubber layer was changed (composition changed from R7 to R8) compared to the configuration of Example 17. Example 21 is an example of a toothed belt in which the type of HNBR in the second rubber layer was changed (composition changed from R1 to R6) and the type of silicone rubber in the first rubber layer was changed (composition changed from R7 to R8) compared to the configuration of Example 17. The bonding strength between the first rubber layer and the second rubber layer, and the durable running life (maintenance of conveying function) were equivalent to that of Example 17, and the overall evaluation was A rank (pass).

[0299] <Verification results in Table 9> (Examples 22-25) Examples 22 to 25 are based on the configuration of Example 17, but with the total belt thickness (and back thickness of 4.5 mm) kept constant. By changing the ratio of the thickness of the second rubber layer (HNBR composition) to the first rubber layer (silicone rubber composition), the "thickness ratio of the first rubber layer to the total thickness of the outer rubber layer (back rubber layer)" was varied. Specifically, the thickness ratio of the first rubber layer to the outer rubber layer was varied to 35.6% (Example 22), 51.1% (Example 23), 64.4% (Example 17), 71.1% (Example 24), and 82.2% (Example 25). In all cases, the bonding strength between the first and second rubber layers was equivalent to that of Example 17. Regarding durability and running life (maintenance of conveying function), in Example 22, where the thickness ratio of the first rubber layer was small (the first rubber layer was thin), the high proportion of HNBR composition in the outer rubber layer increased rigidity and made it difficult to bend, resulting in a crack on the back surface and failure (end of life) after a running time (relative value) of 14 (rating b). On the other hand, in Example 25, where the thickness ratio of the first rubber layer was large (the first rubber layer was thick), the high proportion of silicone rubber composition in the outer rubber layer reduced rigidity near the teeth, resulting in tooth chipping and failure (end of life) after a running time (relative value) of 14 (rating b). In Examples 23 and 24, no delamination between the first and second rubber layers or cracking on the back surface occurred during running, but tooth chipping occurred and failure (end of life) occurred (rating a). The overall rating was B rank (pass) for the toothed belts in Examples 22 and 25, and A rank (pass) for the toothed belts in Examples 23 and 24.

[0300] (Examples 26-28) Examples 26 to 28 are based on the configuration of Example 17, but vary the thickness of the first rubber layer (silicone rubber composition) laminated onto a second rubber layer (HNBR composition) of a constant thickness (1.2 mm), thereby varying the "ratio of the thickness of the first rubber layer to the total thickness of the outer rubber layer (back rubber layer)". Specifically, the ratio of the thickness of the first rubber layer to the outer rubber layer was varied to 55.6% (Example 26), 64.4% (Example 17), 77.5% (Example 27), and 81.4% (Example 28). In all cases, the bonding strength between the first and second rubber layers was equivalent to that of Example 17. Regarding durable running life (maintenance of conveying function), as the thickness ratio of the first rubber layer increased, the total belt thickness (and back thickness) increased, making it more difficult for the outer rubber layer to bend, which tended to decrease the durable running life. In Examples 26 and 27, no delamination between the first and second rubber layers or back cracks occurred during running, but tooth chipping occurred, resulting in failure (end of life) (rating a). However, in Example 28, which had the largest total belt thickness, cracks occurred on the back after a running time (relative value) of 14, resulting in failure (end of life) (rating b). The overall rating was B rank (pass) for the toothed belt in Example 28, and A rank (pass) for the toothed belts in Examples 26 and 27.

[0301] Based on these results, it can be said that the preferred range for the "ratio of the thickness of the first rubber layer to the total thickness of the outer rubber layer (back rubber layer)" is 50-80%.

[0302] <Verification results in Table 10> (Examples 29-32) Examples 29 to 32 are examples of toothed belts in which the first and second rubber layers are joined by cross-linking a cross-linking process with an intermediate fabric containing zinc methacrylate interposed at the bonding interface between the first and second rubber layers. By varying the zinc methacrylate content in the rubber adhesive used to bond the intermediate fabric (5 parts by mass (Example 29), 10 parts by mass (Example 30), 15 parts by mass (Example 31), and 25 parts by mass (Example 32)), the bonding strength between the first and second rubber layers in an undriven belt state improved to an acceptable level (C rating in Example 29, B rating in Example 30, and A rating in Examples 31 and 32). Furthermore, this bonding strength was maintained even after driving.

[0303] Furthermore, regarding the running life, in Examples 29 and 30, the point at which delamination between the first and second rubber layers occurred and failure (end of life) was 14 running times (relative value) (grade b). In other words, Examples 29 and 30 can run 14 times longer than Comparative Example 1 (conveying performance is maintained). In Examples 31 and 32, the running time (relative value) until failure was 20 running times when tooth chipping occurred and failure (end of life) occurred without delamination between the first and second rubber layers during running (grade a). In the overall evaluation, the toothed belts in Examples 29 and 30 were graded C (pass), and the toothed belts in Examples 31 and 32 were graded A (pass).

[0304] From these results, it was confirmed that by placing an intermediate cloth with zinc methacrylate attached at the bonding interface, the bonding strength between the first rubber layer and the second rubber layer is improved (delamination between the first and second rubber layers becomes less likely), and the durability life of the toothed belt is improved (the sustainability of conveying performance is improved).

[0305] (Examples 33-35) Example 33 is an example of a toothed belt in which the type of HNBR in the second rubber layer was changed (the composition was changed from R1 to R6) compared to the configuration of Example 31. Example 34 is an example of a toothed belt in which the type of silicone rubber in the first rubber layer was changed (the composition was changed from R7 to R8) compared to the configuration of Example 31. Example 35 is an example of a toothed belt in which the type of HNBR in the second rubber layer was changed (the composition was changed from R1 to R6) and the type of silicone rubber in the first rubber layer was changed (the composition was changed from R7 to R8) compared to the configuration of Example 31. The bonding strength between the first rubber layer and the second rubber layer, and the durable running life (maintenance of conveying function) were equivalent to that of Example 31, and the overall evaluation was A rank (pass).

[0306] <Verification results in Table 11> (Examples 36-39) Examples 36 to 39 are based on the configuration of Example 31, but with the total belt thickness (and back thickness of 4.3 mm) kept constant. By changing the ratio of the thickness of the second rubber layer (HNBR composition) to the first rubber layer (silicone rubber composition), the "thickness ratio of the first rubber layer to the total thickness of the outer rubber layer (back rubber layer)" was varied. Specifically, the thickness ratio of the first rubber layer to the outer rubber layer was varied to 37.2% (Example 36), 53.5% (Example 37), 67.4% (Example 31), 74.4% (Example 38), and 86.0% (Example 39). In all cases, the bonding strength between the first and second rubber layers was equivalent to that of Example 31. Regarding durability and running life (maintenance of conveying function), in Example 36, where the thickness ratio of the first rubber layer was small (the first rubber layer was thin), the high proportion of HNBR composition in the outer rubber layer increased rigidity and made it difficult to bend, resulting in a crack on the back surface and failure (end of life) after a running time (relative value) of 14 (rating b). On the other hand, in Example 39, where the thickness ratio of the first rubber layer was large (the first rubber layer was thick), the high proportion of silicone rubber composition in the outer rubber layer reduced rigidity near the teeth, resulting in tooth chipping and failure (end of life) after a running time (relative value) of 16 (rating b). In Examples 37 and 38, no delamination between the first and second rubber layers or back surface cracking occurred during running, but tooth chipping occurred and failure (end of life) occurred (rating a). The overall rating was B rank (pass) for the toothed belts in Examples 36 and 39, and A rank (pass) for the toothed belts in Examples 37 and 38.

[0307] (Examples 40-42) Examples 40 to 42 are based on the configuration of Example 31, but vary the thickness of the first rubber layer (silicone rubber composition) laminated onto a second rubber layer (HNBR composition) of a constant thickness (1.2 mm), thereby varying the "ratio of the thickness of the first rubber layer to the total thickness of the outer rubber layer (back rubber layer)". Specifically, the ratio of the thickness of the first rubber layer to the outer rubber layer was varied to 58.8% (Example 40), 67.4% (Example 31), 79.7% (Example 41), and 83.3% (Example 42). In all cases, the bonding strength between the first and second rubber layers was equivalent to that of Example 31. Regarding durable running life (maintenance of conveying function), as the thickness ratio of the first rubber layer increased, the total belt thickness (and back thickness) increased, making it more difficult for the outer rubber layer to bend, which tended to decrease the durable running life. In Examples 40 and 41, no delamination between the first and second rubber layers or back cracks occurred during running, but tooth chipping occurred, resulting in failure (end of life) (rating a). However, in Example 42, which had the largest total belt thickness, cracks occurred on the back after a running time (relative value) of 14, resulting in failure (end of life) (rating b). The overall rating was B rank (pass) for the toothed belt in Example 42, and A rank (pass) for the toothed belts in Examples 40 and 41.

[0308] Based on these results, it can be said that the preferred range for the "ratio of the thickness of the first rubber layer to the total thickness of the outer rubber layer (back rubber layer)" is 50-80%.

[0309] From the above, it was confirmed that the adhesion (bonding strength) between the silicone rubber layer and the HNBR layer can be improved by interposing an intermediate layer formed of a binder component containing an unsaturated carboxylic acid metal salt between the silicone rubber layer that forms the conveying surface of the transmission belt and the HNBR layer. [Industrial applicability]

[0310] The power transmission belt of the present invention is not particularly limited as long as it is a power transmission belt that transmits power and transports articles using the back surface of the belt. For example, it can be used as a friction transmission belt such as a flat belt, V-belt, or V-ribbed belt; or as a toothed transmission belt such as a toothed belt or a double-sided toothed belt. In particular, it can be suitably used as a toothed belt that transports articles using the back surface of the belt.

[0311] Preferred toothed belts include those used for transporting goods such as daily necessities, industrial products, agricultural products, and food products (for example, toothed belts for office automation (OA) equipment parts, coin handling equipment, photocopiers, and printing presses), and are particularly suitable as toothed belts for transporting paper products (paper, corrugated cardboard, etc.). [Explanation of Symbols]

[0312] 1…Toothed belt 1a...teeth part 1b...Root of the tooth 1c...back 2... Back elastic layer 2a...First rubber layer 2b…Middle layer 2c...Second rubber layer 3… Core wire 4…Tooth rubber layer 5... Toothcloth

Claims

1. A power transmission belt comprising a core wire extending along the circumferential direction of the belt, and an outer rubber layer formed on the outer circumferential side of the belt relative to the core wire, wherein the outer surface of the outer rubber layer is used to transport articles, The outer periphery rubber layer has a laminated structure including a first rubber layer that forms the transport surface which is the outer periphery, an intermediate layer laminated on the inner periphery of the first rubber layer, and a second rubber layer laminated on the inner periphery of the intermediate layer. The first rubber layer is formed of a crosslinked product of a first rubber composition containing silicone rubber, The aforementioned intermediate layer comprises a crosslinked product of a binder component containing an unsaturated carboxylic acid metal salt, A power transmission belt in which the second rubber layer is formed of a crosslinked product of a second rubber composition containing hydrogenated nitrile rubber.

2. The transmission belt according to claim 1, wherein the unsaturated carboxylic acid metal salt comprises zinc methacrylate.

3. The transmission belt according to claim 1 or 2, wherein the intermediate layer is formed of a crosslinked product of the binder component, and the binder component is the unsaturated carboxylic acid metal salt.

4. The basis weight of the aforementioned binder component is 50 g / m². ２ The transmission belt according to claim 3, as described above.

5. The transmission belt according to claim 1 or 2, wherein the intermediate layer is an intermediate layer formed of a crosslinked product of the binder component, or an intermediate layer formed of a cloth containing a crosslinked product of the binder component, and the binder component is a third rubber composition containing a rubber component and the unsaturated carboxylic acid metal salt.

6. The transmission belt according to claim 5, wherein the rubber component comprises silicone rubber and / or hydrogenated nitrile rubber.

7. The transmission belt according to claim 5, wherein the rubber component includes hydrogenated nitrile rubber, and the proportion of the unsaturated carboxylic acid metal salt is 3 parts by mass or more per 100 parts by mass of the rubber component.

8. The average thickness of the aforementioned cloth is 0.05 to 1 mm. The aforementioned fabric is formed from a woven fabric consisting of warp threads extending in the belt width direction and weft threads extending in the belt circumferential direction, and The transmission belt according to claim 5, wherein the woven fabric contains polyamide fibers, and the average diameter of the warp threads is 0.3 times or more the average diameter of the weft threads.

9. The transmission belt according to claim 1 or 2, wherein the average thickness of the first rubber layer is 50 to 80% of the average thickness of the outer rubber layer.

10. The transmission belt according to claim 1 or 2, wherein the peel strength between the first rubber layer and the intermediate layer is 30 N / 25 mm or more.

11. The transmission belt according to claim 1 or 2, which is a toothed belt.

12. A method for manufacturing a power transmission belt according to claim 1 or 2, comprising a joining step of joining the first rubber layer and the second rubber layer by crosslinking a first rubber layer precursor formed from the first rubber composition, an intermediate layer precursor containing the binder component, and a second rubber layer precursor formed from the second rubber composition in this order, thereby interposing an intermediate layer between the first rubber layer and the second rubber layer.

13. A power transmission belt comprising a core wire extending along the circumferential direction of the belt and an outer rubber layer formed on the outer circumference side of the belt relative to the core wire, wherein the outer surface of the outer rubber layer is used to transport articles, The outer periphery rubber layer has a laminated structure including a first rubber layer that forms the transport surface which is the outer periphery, an intermediate layer laminated on the inner periphery of the first rubber layer, and a second rubber layer laminated on the inner periphery of the intermediate layer. The first rubber layer is formed from a crosslinked product of a first rubber composition containing silicone rubber. The intermediate layer contains a crosslinked binder component containing an unsaturated carboxylic acid metal salt. A method for improving the adhesion between the first rubber layer and the second rubber layer by forming the second rubber layer with a crosslinked product of a second rubber composition containing hydrogenated nitrile rubber.

14. A belt transmission mechanism for transporting articles, comprising a transmission belt according to claim 1 or 2 and a pulley.

Images