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    • 专利摘要:
    reinforcement cord to reinforce rubber product and rubber product that uses the same. the present invention relates to a reinforcement cord comprising at least one thread. the yarn comprises a bundle of filaments that are bundled together and twisted mutually in one direction, and a coating layer that is formed at least on the bundle surface. the bundle essentially consists of carbon fiber filaments. the coating layer is formed of an aqueous treatment agent containing a rubber latex and a crosslinking agent as essential components and a filler as an optional component. in the aqueous treatment agent, the total mass of the crosslinking agent and the filler mass is in a range of 1 to 50% of the rubber mass in the rubber latex.
    公开号:BR112013031328B1
    申请号:R112013031328-5
    申请日:2012-06-08
    公开日:2021-03-30
    发明作者:Masamori Furusawa
    申请人:Nippon Sheet Glass Company, Limited；
    IPC主号:
    专利说明:

    TECHNICAL FIELD
    [001] The present invention relates to a reinforcement cord to reinforce a rubber product and to a rubber product that includes the reinforcement cord. BACKGROUND OF THE TECHNIQUE
    [002] A rubber belt or chain is used to drive a camshaft in an automobile's internal combustion engine, which drives an auxiliary unit, such as an injection pump, or a power transmission in an industrial machine. In general, a rubber belt includes a rubber portion and a reinforcement cord embedded in the rubber portion. Since the strength of the rubber belt depends on the strength of the reinforcement cord, the reinforcement cord is an important component that determines the duration of the rubber belt. Typically, the reinforcement cord includes reinforcement fibers and a coating layer formed on the surface of the fibers. As examples of such a reinforcement cord, rubber belts in which carbon fibers are used as reinforcement fibers have been proposed (for example, JP 2004-225178 A and JP 2010-024564 A).
    [003] A reinforcement cord using carbon fibers has the disadvantage that the cord's tensile strength decreases as the belt moves. One of the causes may be that the fibers in the reinforcement cord are locally broken due to the high concentration of local tension on them during use, therefore decreasing the strength of the cord. Another cause may be the deterioration of the lining layer of the reinforcement cord. As the coating layer deteriorates, the effect of protecting the fibers decreases, and the integrity, flexibility, etc. of the cord decrease accordingly.
    [004] The elongation at break of many of the fiberglass strands used as reinforcement strands is about 4%. On the other hand, the elongation at break of carbon fiber strands as high modulus fiber strands is as low as about 2%. Therefore, the fact that fragile and high modulus fibers, such as carbon fibers, have a low elongation at break should be kept in mind when using them in a reinforcement cord. That is, when the reinforcement cord is subjected to a certain flexural deformation, it must be protected from the overload that would result in the rupture of carbon fibers. If the coating layer formed on the reinforcement fibers is rigid, the load on the reinforcement fibers may increase when the reinforcement cord is subjected to bending deformation.
    [005] On the other hand, as one of the techniques for obtaining a carbon fiber strand that is flexible for flexion deformation, it may be possible to increase the number of strands in the strand. However, since the elastic modulus of the cord will decrease, if the number of twists is increased, that cord cannot be used for applications that require high modulus belts. LIST OF CITATIONS Patent Literature
    [006] Patent Literature 1: JP 2004-225178 A
    [007] Patent Literature 2: JP 2010-024564 A SUMMARY OF THE INVENTION Technical problem
    [008] Not only the resistance to flexion fatigue, but also the adhesion to a matrix rubber is an important factor for the reinforcement cord. Therefore, it is necessary to improve treatment agents to form a coating layer on the surface of reinforcing fibers. A coating layer having a high content of components (such as a crosslinking agent and a resin), other than a latex, tends to have better adhesion, although the coating layer becomes harder. Therefore, it is difficult to obtain a carbon fiber cord that is flexible for flexion deformation, presenting a high modulus, and exhibiting good adhesion to a matrix rubber.
    [009] Under certain circumstances, one of the objectives of the present invention is to provide a reinforcement cord that uses carbon fibers and that has a good resistance to flexing fatigue and a good adhesion to a matrix rubber. Solution to the Problem
    [0010] The reinforcement cord of the present invention is a reinforcement cord to reinforce a rubber product, including at least one thread. In this reinforcement cord, the yarn includes a bundle of filaments that are bundled together and twisted mutually in one direction, and a coating layer that is formed on at least one surface of the bundle. The bundle essentially consists of carbon fiber filaments. The coating layer is a coating layer that is formed from an aqueous treatment agent that contains a rubber latex and a crosslinking agent as essential components and a filler as an optional component. In the aqueous treatment agent, a total of one mass of the crosslinking agent and one mass of the filler is in a range of 1 to 50% of a rubber mass in the rubber latex.
    [0011] The rubber product of the present invention is reinforced by the reinforcement cord of the present invention. Advantageous Effects of the Invention
    [0012] In the reinforcing strand of the present invention, the total amount of the crossover and filler in the treatment agent to form the coating layer is limited within a predetermined range, and thus both flexibility and adhesion can be obtained of the coating layer. Thus, according to the present invention, it is possible to obtain a reinforcement cord using carbon fibers and having a good resistance to flexion fatigue and an adhesion to a rubber matrix. BRIEF DESCRIPTION OF THE DRAWINGS
    [0013] FIG. 1 is a partial cross-sectional perspective view showing an example of a rubber product that includes a reinforcement cord of the present invention.
    [0014] FIG. 2 is a diagram that schematically shows a bending test performed in the examples. DESCRIPTION OF THE ACCOMPLISHMENTS
    [0015] Embodiments of the present invention are described below. In the following description, embodiments of the present invention will be described by way of examples, but the present invention is not limited to the examples described above. In the description below, specific numerical values and materials can be used, as long as the effects of the present invention are obtained. In addition, the compounds described below can be used alone or in combination with one or more of them, unless otherwise specified. Reinforcement Cord
    [0016] The reinforcement cord of the present invention is a cord for reinforcing a rubber product. This reinforcement cord includes at least one wire. The yarn includes a bundle of filaments that are bundled together and twisted mutually in one direction, and a coating layer that is formed on at least one surface of the bundle. The bundle essentially consists of carbon fiber filaments. The coating layer is a coating layer that is formed from an aqueous treatment agent containing a rubber latex and a crosslinking agent as essential components and a filler as an optional component. That is, the aqueous treatment agent contains a rubber latex and a crosslinking agent, and may or may not additionally contain a filler. In the aqueous treatment agent, the total mass of the crossover agent and the mass of the filler is in a range of 1 to 50% of the rubber mass in the rubber latex. Hereinafter, the aqueous treatment agent used to form the coating layer can be referred to as "aqueous treatment agent (A)".
    [0017] Filling is an optional component. Therefore, in another aspect, the aqueous treatment agent (A) is a treatment agent in which the mass of the crosslinking agent is in a range of 1 to 50% of the mass of the rubber in the rubber latex. If the aqueous treatment agent (A) contains a filler, in this aqueous treatment agent (A), the total mass of the crosslinking agent and the mass of the filler is in a range of 1 to 50% of the rubber mass in rubber latex.
    [0018] The number of wires in the reinforcement cord is not limited. It can be one, or it can be two or more. If the reinforcement cord includes one or more wires, they can finally be twisted. The filament bundle may be a bundle of two or more bundles of filaments. In this case, each of the filament bundles may or may not be twisted.
    [0019] The aqueous treatment agent (A) contains a rubber latex as a main component. As used herein, the main component refers to a component whose solids content is 50% by weight or more of the solids content of the aqueous treatment agent. Preferably, the aqueous treatment agent (A) contains, as a main component, a latex of at least one rubber selected from the group consisting of nitrile rubber, hydrogenated nitrile rubber, carboxyl modified nitrile rubber, and carboxyl modified hydrogenated nitrile rubber. . The aqueous treatment agent (A) can contain only one of these rubber latexes, or it can contain two or more of these latexes. These rubber latexes are preferred because they are less susceptible to swelling in oil and have a high resistance to oil. In this description, the term "nitrile rubber" refers to a nitrile rubber (acrylonitrile-butadiene copolymer rubber) that is neither hydrogenated nor modified with carboxyl, unless otherwise specified.
    [0020] The iodine value of hydrogenated nitrile rubber is normally 120 or less, and can be 100 or less, for example. The iodine value of hydrogenated nitrile rubber as an example is in a range of 0 to 50.
    [0021] The aqueous treatment agent (a) may contain another rubber latex in addition to the rubber latex mentioned above. Examples of another rubber latex include a butadiene-styrene copolymer latex, a dicarboxylated butadiene-styrene copolymer latex, a vinylpriridine-butadiene-styrene terpolymer latex, a chloroprene latex, a butadiene latex, and a chlorosulfonated polyethylene latex. The aqueous treatment agent (A) can contain two or more of these rubber latexes.
    [0022] Preferably, the ratio of rubber to latex - solids content of the aqueous treatment agent (A) is 60% by weight or more. This ratio can be in a range of 50 to 99% by mass or in a range of 75 to 97% by mass. The coating layer having a higher latex content becomes more flexible, while the adhesion of the coating layer decreases. Therefore, it is preferable to determine the ratio of the rubber to the aqueous treatment agent (A) taking into account the compatibility with the matrix rubber and the ease of adhesion to it. When the ratio of rubber to solids content (A) is less than 50% by mass, the flexibility of the reinforcement cord will decrease, which may result in a decrease in the life of the resulting rubber product (for example, a belt rubber).
    [0023] The aqueous treatment agent (A) contains a crosslinking agent. The use of this crosslinking agent improves adhesion to the matrix rubber. Examples of the crosslinking agent contained in the aqueous treatment agent (A) include: quinoline dioxima crosslinking agents, such as p-quinone dioxima; methacrylate cross-linking agents, such as lauryl methacrylate and methyl methacrylate; allyl crosslinking agents, such as diallyl fumarate (DAF), dithail phthalate (DAP), trialyl cyanide (TAC), and trialyl isocyanide (TAIC); maleimide crosslinking agents, such as bis-maleimide, phenyl-maleimide, and N, N'-m-phenylene-dimaleimide; aromatic or aliphatic organic diisocyanate; polyisocyanate; blocked isocyanate; blocked polyisocyanate; aromatic nitrous compounds; sulfur; and peroxides. These crosslinking agents can be used alone or in combination with two or more of them. These crosslinking agents are selected in view of the type of latex rubber contained in the aqueous treatment agent, the type of matrix rubber in which the reinforcement cord must be embedded, etc. It is preferable to use these crosslinking agents in the form of an aqueous dispersion in order to allow them to be homogeneously present in the aqueous treatment agent. The crosslinking agent can be at least one agent selected from the group consisting of maleimide crosslinking agents, organic diisocyanates, and aromatic nitrous compounds.
    [0024] Among the cross-linking agents mentioned above, it is preferable to use at least one agent selected from the group consisting of maleimide and polyisocyanate cross-linking agents. Among maleimide crosslinking agents, 4,4'-diphenylmethane-bismaleimide is suitably used because it will be stable, when dispersed in water, will have a high crosslinking effect, and will have a high resistance to heat after crosslinking. When each maleimide crosslinking agent or polyisocyanate is used in combination with a latex rubber, the maleimide crosslinking agent and polyisocyanate may each specifically enhance the adhesion between the strand. reinforcement and matrix rubber. In particular, a combination of a latex of a hydrogenated nitrile rubber modified with carboxyl and a maleimide crosslinking agent is preferred because it can additionally enhance adhesion.
    [0025] In the aqueous treatment agent (A), the mass of the crosslinking agent is preferably in a range of 1 to 50% (for example, in a range of 1 to 40%), more preferably in a range of 1 to 30%, even more preferably in a range of 1 to 25%, and particularly preferably in a range of 1 to 20%, respectively, with respect to the mass of the rubber in the rubber latex. The mass of the crosslinking agent can be in the range of 1 to 10%. It is possible to form a coating layer showing both adhesion and flexibility, when the mass of the crosslinking agent is in the above range.
    [0026] Preferably, the aqueous treatment agent (A) contains a filler. The filling contained in the aqueous treatment agent (A) is not particularly limited. Examples of the filler include fine particles of covalently bonded compounds, such as silica and carbon black, fine particles of insoluble salts, fine particles of metal oxides, fine particles of metal hydroxides, and fine particles of composite metal oxide salts, such as talc . Among these, at least one selected from the group consisting of silica and carbon black is preferred.
    [0027] The average silica particle diameter is preferably in the range of 5 to 200 nm, and, for example, in the range of 7 to 100 nm. It is most preferably in a range of 7 to 30 nm. The average carbon black particle diameter is preferably in the range of 5 to 300 nm, and, for example, in the range of 100 to 200 nm. It is most preferably in a range of 130 to 170 nm. As used here, the term "average particle diameter" refers to a value obtained by measuring the particle diameters of 50 or more particles using a transmission electron microscope and dividing the total particle diameters by the number of the particles measures. When the particles are not spherical, the average of the longest and shortest diameter of each particle will be determined as the particle diameter of the particle.
    [0028] The presence of the dispersed filler in the rubber has the effect of improving the properties, such as the tensile strength, the tear resistance, etc., of the coating layer. In addition to these effects, the filling also has the effect of increasing the cohesion of the adhesive components between the fibers and the coating layer and between the coating layer and the matrix rubber and thus increasing the adhesive strength between them. These effects are significantly affected by the particle diameter and the content of the fill.
    [0029] In the aqueous treatment agent (A), the filler mass is preferably in a range of 1 to 20%, more preferably in a range of 1 to 10%, and most preferably still in a range of 1 to 5% , respectively with respect to the mass of the rubber in the rubber latex. When the filler mass is in this range, it will be possible to achieve the effect of increasing the adhesive strength between the reinforcement cord and the matrix rubber while suppressing an increase in the hardness of the coating layer. When the filler mass exceeds 20% of the rubber mass in the rubber latex, the flexural fatigue strength of the reinforcement cord is likely to decrease.
    [0030] When the aqueous treatment agent (A) contains the crosslinking agent and the filler, it will be preferable that, in the aqueous treatment agent (A), the mass of the crosslinking agent is in a range of 1 to 30%, the mass of the filler is in a range of 1 to 20%, and the total mass of the crosslinking agent and the filler is in a range of 2 to 50%, with respect to the mass of the rubber in the rubber latex. It is more preferable that, in the aqueous treatment agent (A), the mass of the crosslinking agent is in a range of 1 to 30%, the mass of the filler is in a range of 1 to 10%, and the total mass of the agent of crosslinking and filling is in a range of 2 to 40%, with respect to the mass of the rubber in the rubber latex. It is additionally preferable that, in the aqueous treatment agent (A), the mass of the crosslinking agent is in a range of 1 to 20%, the mass of the filler is in a range of 1 to 10%, and the total mass of the agent of crosslinking and filling is in a range of 2 to 30%, with respect to the mass of the rubber in the rubber latex. It is particularly preferable that, in the aqueous treatment agent (A), the mass of the crosslinking agent is in a range of 1 to 10%, the mass of the filler is in a range of 1 to 5%, and the total mass of the agent of crosslinking and filling is in a range of 2 to 15%, with respect to the mass of the rubber in the rubber latex. In the aqueous treatment agent (A), as an example, the mass of the crosslinking agent is in a range of 2 to 40%, the mass of the filler is in a range of 1 to 5%, and the total mass of the crosslinking agent crosslinking and filling is in a range of 3 to 45%, with respect to the mass of the rubber in the rubber latex.
    [0031] Preferably, the aqueous treatment agent (A) is free of a resorcinol-formaldehyde condensation product. In that case, there is no need to use substances that have a major environmental impact, such as formaldehyde and ammonia, during the manufacture of the reinforcement cord, and therefore there is no need for environmental measures for workers. It should be noted, however, that the aqueous treatment agent (A) may contain a resorcinal-formaldehyde condensation product.
    [0032] In a preferred example, the reinforcing strand of the present invention is formed by applying the aqueous treatment agent (A) to a filament bundle and then twisting the bundle in one direction.
    [0033] The constituent components (components other than a solvent) of the aqueous treatment agent (A) are dispersed or dissolved in the solvent. The solvent in the aqueous treatment agent (A) is an aqueous solvent containing 50% by weight or more of water. The water content in the aqueous solvent can be 80% by weight or more, 90% by weight or more, or 100% by weight. Like the aqueous solvent, water is used appropriately because water is easy to handle, makes it easier to control the concentrations of constituent components, and is much more environmentally friendly than organic solvents. The aqueous solvent may contain a lower alcohol or the like. Examples of the lower alcohol include alcohols having 4 or less or 3 or less carbon atoms (for example, methanol, ethanol, and propanol). Preferably, the aqueous solvent is free of an organic solvent other than the lower alcohol.
    [0034] The aqueous treatment agent (A) may contain components other than rubber latex, the crosslinking agent and the filler. For example, the aqueous treatment agent (A) can contain a resin, a plasticizer, an antioxidant, a stabilizer, a metal oxide that does not serve as a filler, etc. The aqueous treatment agent (A) can be a resin-free treatment agent.
    [0035] In order to increase adhesion to the matrix rubber, the reinforcement cord of the present invention may include a second coating layer formed in the above described coating layer (first coating layer). The treatment agent to form the second coating layer can be the same as the aqueous treatment agent (A) or can be different from it. For example, the second coating layer can be formed from a treatment agent whose components and solvent are different from those in the aqueous treatment agent (A). The second layer of coating can increase the effect of preventing water or oil from penetrating the reinforcement cord. Therefore, the second coating layer is particularly preferably formed on the reinforcement cord used in an environment where the rubber product is exposed to water or oil.
    [0036] The number of twists of the filament bundle, that is, the number of twists given to the filament bundle can be in a range of 20 to 160 times per meter, in a range of 30 to 100 times per meter, or in a range of 40 to 80 times per meter. The direction of the twists is not limited. It can be the S direction or the Z direction.
    [0037] In the reinforcement cord of the present invention, the filament bundle consists essentially of carbon fiber filaments. As used herein, the term "consisting essentially of" indicates that the filament bundle may include filaments other than carbon fiber filaments, unless they have a major influence on the effects of the present invention.
    [0038] Typically, the filament bundle (ie, a yarn) consists of carbon fiber filaments. However, the filament bundle (the yarn) may contain filaments (reinforcement fiber filaments) other than carbon fiber filaments, as long as the effects of the present invention can be obtained. For example, the filament bundle may contain filaments other than carbon fiber filaments in 10% or less (for example, 5% or less or 1% or less) of the cross-sectional area of the bundle. Filaments other than carbon fiber filaments are not particularly limited, and the filaments of fibers commonly used as reinforcement fibers can be used.
    [0039] The number of carbon fiber filaments in the yarn (the filament bundle) can be in a range of 500 to 48000, in a range of 1000 to 24000, or in a range of 1000 to 12000. The number of filaments carbon fiber in the wire can be 500, 1000, 3000, 6000, 12000, 24000 or 48000.
    [0040] The surface of the carbon fiber filament contained in the bundle described above can be treated with a glue agent. That is, the surface of the carbon fiber filament can be subjected to a pre-treatment commonly called "glue". A preferred example of the glue agent contains at least one agent selected from the group consisting of an epoxy group and an amine group. Examples of sizing agent include aminosilanes, epoxylsilanes, epoxy resins like novolak, epoxy resins like bisphenol A, epoxy resins from bisphenol F, epoxy resins from brominated, epoxy resins from bisphenol AD, and epoxy resins from glycidylamine . Specific examples thereof include the Denacol series manufactured by Nagase ChemteX Corporation, the Epiclon series manufactured by DIC Corporation, and the Epicoat series manufactured by Mitsubishi Chemical Corporation. The use of carbon fiber filament whose surface is treated with a glue agent increases the adhesion between the matrix rubber and the reinforcement cord.
    [0041] As the method for depositing a glue agent on carbon fiber filaments, for example, there is a method of immersing carbon fiber filaments in a liquid in which the glue agent is dispersed or dissolved, followed by drying to remove a solvent. The amount of adhesive agent deposited is desirably from 0.1 to 3% by weight of the carbon fiber filaments. If the amount of the bonding agent deposited is less than 0.1% by mass, the effect of improving adhesion will be reduced. If the amount of the bonding agent deposited is greater than 3% by mass, the resistance to flexion fatigue may decrease.
    [0042] The mass of the coating layer can be in a range of 7 to 30% (for example, in a range of 10 to 25% or in a range of 15 to 20%) of the mass of the filament bundle. The strand containing a greater amount of the coating layer is more flexible and therefore has an improved bending property. However, if the amount of the coating layer is too large, the cord may be more affected by oil or the dimensional stability in the resulting rubber product may decrease. On the other hand, if the amount of the coating layer is too small, the reinforcement fibers cannot be sufficiently protected, and as a result, the life of the resulting rubber product can be reduced.
    [0043] The type of carbon fiber filaments is not particularly limited. The diameter of the carbon fiber filaments is not particularly limited. The diameter of the carbon fiber filaments is preferably in the range of 4 μm to 12 μm, more preferably in the range of 5 μm to 8 μm, and even more preferably in the range of 5 μm to 7 μm. In another aspect, the average diameter of the carbon fiber filaments is preferably in the range of 4 μm to 12 μm, more preferably in the range of 5 μm to 8 μm, and most preferably in the range of 5 μm to 7 μm .
    [0044] In a preferred example, the filament bundle includes 1000 to 24000 carbon fiber filaments (with a diameter of 4 μm to 12 μm, for example, 6000 to 12000 carbon fiber filaments (with a diameter of 5 μm to 8 μm). Rubber Product
    [0045] The rubber product of the present invention is a rubber product reinforced by the reinforcement cord of the present invention. The rubber product is not particularly limited. Examples of the rubber product of the present invention include tires for automobiles and bicycles, and transmission belts. Examples of transmission belts include synchronous transmission belts and friction transmission belts. Examples of synchronous transmission belts include toothed belts typified by a toothed belt for an automobile. Examples of friction drive belts include flat belts, round belts, V-belts, and V-ribbed belts. That is, the rubber product of the present invention can be a toothed belt, a flat belt, a round belt, a V-belt, or a V-ribbed belt.
    [0046] The rubber product of the present invention is formed by embedding the reinforcing cord of the present invention in a rubber composition (or a matrix rubber). The method for embedding the reinforcement cord in the rubber matrix is not particularly limited, and any known method can be employed. The reinforcement cord of the present invention is embedded in the rubber product of the present invention (for example, a rubber belt). Therefore, the rubber product of the present invention has a high resistance to high flexural fatigue. Consequently, the rubber product of the present invention is particularly suitable for use as a vehicle toothed belt for a vehicle engine.
    [0047] The rubber of the rubber composition in which the reinforcing cord of the present invention is to be embedded is not particularly limited. The rubber may be chloroprene rubber, chlorosulfonated polyethylene rubber, ethylene propylene rubber, hydrogenated nitrile rubber, or the like. The hydrogenated nitrile rubber can be a hydrogenated nitrile rubber containing a derivative of zinc acrylate (for example, zinc methacrylate) dispersed therein. At least one rubber selected from hydrogenated nitrile rubber and hydrogenated nitrile rubber containing a zinc acrylate derivative dispersed in it is preferred from the point of view of water resistance and oil resistance. The matrix rubber may additionally contain hydrogenated nitrile rubber modified with carboxyl. From the point of view of adhesion, it is preferable that the coating layer of the reinforcement cord and the rubber composition of the rubber product contain the same type of rubber or consist of the same type of rubber.
    [0048] FIG. 1 shows a toothed belt as an example of the rubber product. A toothed belt 10 shown in FIG. 1 includes a toothed belt 11 and a plurality of reinforcement strands 12. The belt body 11 includes a belt portion 13 and a plurality of tooth portions 14 that protrude from the belt portion 13 at regular intervals. The reinforcement strands 12 are embedded in the belt portion 13 so that they are parallel to the longitudinal direction of the belt portion 13. The reinforcement strands 12 are each the reinforcement cord of the present invention. Method to Produce Reinforcement Cord
    [0049] An example of the method for producing the reinforcement cord of the present invention is described below. Since the description of the reinforcement cord of the present invention can be applied to the following production method, the description of overlap can be omitted. The following description of the production method can be applied to the reinforcement cord of the present invention. An example of this production method includes the following steps.
    [0050] First, a plurality of filaments are grouped together in bundle. An aqueous treatment agent (A) is applied to the beam surface. Then, a solvent in the aqueous treatment agent (A) is removed. Specifically, first, a plurality of filaments are aligned with the filaments with each other and mutually in a bundle. The aqueous treatment agent (A) is applied to the surface of the resulting beam. Then, the solvent in the aqueous treatment agent (A) is removed. The filament bundle consists essentially of carbon fiber filaments.
    [0051] A coating layer is formed by the steps above. The method for applying the aqueous treatment agent (A) is not limited, and, for example, the bundle of filaments can be immersed in the aqueous treatment agent (A). The method for removing the solvent is not limited, for example, the solvent can be removed using a drying oven. The drying conditions for removing the solvent are not particularly limited. For example, the solvent can be removed by drying the beam in an atmosphere of 80 ° C to 300 ° C for 0.1 to 2 minutes.
    [0052] The bundle of filaments coated with the coating layer is usually twisted in one direction. The bundle can be twisted in the S or Z direction. Since the number of filaments and the number of twists are as described above, their description is omitted. The reinforcement cord of the present invention is produced in this way. Two or more bundles of filaments coated with the coating layer can be bundled together to finally twist the resulting bundle. The direction of the final twist can be the same or different from the twist direction of the filament bundle (the direction of the main twist). Alternatively, two or more untwisted bundles of filaments coated with the sheath layer can be bundled together and twisted together on a wire.
    [0053] The coating layer can be formed after the filament bundle is twisted. The type of filaments, the number of filaments, and the number of twists are as described above.
    [0054] In the event that another coating layer (a second coating layer) is formed on the above coating layer (a first coating layer), the second coating layer can be formed by applying a treatment agent to the first coating layer and the removal of a solvent in the treatment agent. EXAMPLES
    [0055] Hereinafter, the present invention is described in more detail by way of examples. Examples 1 to 11
    [0056] First, 12000 carbon fiber filaments were bundled together to obtain a filament bundle. Carbon fiber filaments with an average diameter of 7 μm were used.
    [0057] The resulting beam was immersed in an aqueous treatment agent (A) having a composition shown in Table 1 below, and then dried at 200 ° C for 2 minutes. In this way, a carbon fiber cord was obtained with the first coating layer. This carbon fiber cord was twisted at a rate of 60 times per meter in one direction. The composition ratio of each component shown in Table 1 is the composition ratio of the component's solid content.

    [0058] In Table 1, hardness is the measured hardness value of an aqueous treatment agent film (A). The film of the aqueous treatment agent (A) was formed by placing the aqueous treatment agent (A) in a tray, removing water using a dryer, and then pressing it (at 160 ° C for 30 minutes). minutes). The thickness of the film was 1 mm. The hardness of the film was measured by a type A durometer according to the hardness test based on JIS K 6253.
    [0059] Then, in order to improve adhesion to the matrix rubber, the second coating layer was formed on the first coating layer described above with the application of a treatment agent having a composition shown in Table 2 below on the first layer of coating. In this way, a reinforcement cord from Example 1 was obtained. Table 2
    (* 1) Manufactured by Lord Far East Incorporated
    The reinforcement strands of Examples 2 to 11 were produced under the same conditions as those of Example 1, except that the composition of the aqueous treatment agent (A) to form the first coating layer has been changed. The aqueous treatment agent compositions (A) used in Examples 2 to 11 are shown in Table 1.
    [0061] All aqueous treatment agents (A) used to form the reinforcing strands of Examples 1 to 3, 10 and 11 were free of a filler (silica or carbon black). In each of the aqueous treatment agents (A), the total mass of the crosslinking agents and fillers is in a range of 10 to 20% of the mass of the rubber in the rubber latex.
    [0062] All aqueous treatment agents (A) used to form the reinforcing strands of Examples 4 to 9 contain fillers. In each of the aqueous treatment agents (A), the total mass of the crosslinking agents and fillers is in a range of 3 to 45% of the mass of the rubber in the rubber latex. Comparative Examples 1 to 6
    [0063] Reinforcing strands of Comparative Examples 1 to 6 were produced under the same conditions as those of Example 1, except that the composition of the aqueous treatment agent (A) to form the first coating layer has been changed. The aqueous treatment agent compositions (A) used in Comparative Examples 1 to 6 are shown in Table 3. The composition ratio of each component shown in Table 3 is the composition ratio of the component's solids content. Two different types of rubber latex shown in Table 3 are the same as those shown in Table 1.
    [0064] In each of the aqueous treatment agents (A) used to form the reinforcing cords of Comparative Examples 1 to 6, the total mass of the crosslinking agents and fillers is in a range of 60 to 105% of the mass of the rubber on rubber latex.


    [0065] In Examples 1 to 11 and Comparative Examples 1 to 6, the mass of the first coating layer was 20% of the total mass of the filaments.
    [0066] Next, each of the reinforcing cords of Examples 1 to 11 and Comparative Examples 1 to 6 was embedded in the rubber showing a composition shown in Table 4 below to produce a specimen (size: 300 mm x 10 mm x 3 mm) for a flexion test. Table 4
    (* 1) Zetpol 2020 (manufactured by Zeon Corporal ion) (* 2) Zetpol 2000L (manufactured by Zeon Corporation
    [0067] Then, each specimen was subjected to a flexion test in which the specimen was folded 100,000 times. The flexion test was performed using a flexion tester 20 shown in FIG. 2. For each specimen, tensile strengths were measured before and after the flexion test. Here, tensile strength refers to the tensile strength obtained by performing a tensile test using a commonly used test apparatus and a commonly used lanyard grip. The unit of tensile strength is N / strand.
    [0068] The bending tester 20 includes a flat pulley 21 with a diameter of 10 mm, a motor (not shown), and four guide pulleys 22. First, a specimen produced 23 was hung on the five pulleys. Then, a weight was attached at one end 23a of specimen 23 to apply a 10 N load to specimen 23. In that state, the other end 23b of specimen 23 was alternated 10000 times in a direction indicated by an arrow in FIG. 2, so that specimen 23 was folded repeatedly on the flat pulley 21. The flexion test was performed at room temperature. After the flexion test of specimen 23 was performed in this way, the tensile strength was measured after the flexion test.
    [0069] Then, for each specimen, the tensile strength ratio was obtained after the flexion test - tensile strength (100%) before the flexion test, that is, the strength retention (%). The higher the retention value of the tensile strength, the greater the resistance to flexion fatigue. Table 1 and Table 3 show the results of Examples 1 to 11 and Comparative Examples 1 to 6. Since the reinforcement of Comparative Example 6 was broken during the bending test, the retention of the resistance of the same is shown as 0%.
    [0070] As shown in Tables 1 and 3, the hardness of the first coating layers formed in Examples 1 to 11 was low. As a result, the strands of Examples 1 to 11 were more flexible and exhibited greater resistance to flexion fatigue than those of Comparative Examples 1 to 6.
    [0071] Additionally, the reinforcement cords of Examples 1 to 11 were subjected to an adhesion test to assess adhesion to the matrix rubber. Specifically, first, a canvas, a reinforcement cord, and a matrix rubber sheet were stacked in that order, and the resulting stack was pressed under the conditions of 160 ° C and 30 minutes. In this way, a specimen was produced for the adhesion test. The specimen was 25 mm wide, 150 mm long and 3 mm wide. The matrix rubber containing hydrogenated nitrile rubber was used as a main component. For this test, first, the reinforcement cord and the matrix rubber were attached to an upper chuck and a lower chuck of a tensile tester respectively. Then, the cord was removed from the matrix rubber, and it was observed how the specimen was broken. In all specimens in which the reinforcement cords of Examples 1 to 11 were used, rubber fracture was observed. Rubber fracture refers to a fracture that occurs due to cracks formed in the matrix rubber. Consequently, this adhesion test revealed that each of the reinforcing strands of Examples 1 to 11 and the matrix rubber were adhered to each other with sufficient adhesive strength.
    [0072] In addition, as a comparative example, a reinforcement cord was produced in the same manner as in Example 1, except that the amount of crosslinking agents in the aqueous treatment agent was 0.5 parts by mass, and subjected to an adherence test. In this adhesion test for the comparative example, most of the matrix rubber was removed at the interface between the reinforcement cord and the matrix rubber. This result suggests that when the amount of crosslinking agents is reduced, the adhesive strength between the matrix rubber and the treatment agent will decrease or the adhesive resistance between the treatment agent and the carbon fiber cord will decrease. That is, this result shows that the amount of crosslinking agents in the aqueous treatment agent is preferably 1% or more of the mass of the rubber in the rubber latex.
    [0073] The 12000 carbon fiber filament bundle was used as an example to describe Examples 1 to 11. However, resistance retention tends to increase as the number of filaments in the bundle decreases. Therefore, the number of carbon fiber filaments can be, for example, 6000, 3000 or 1000. INDUSTRIAL APPLICABILITY
    [0074] The present invention is applicable to a reinforcement cord to reinforce a rubber product and to a rubber product including the reinforcement cord.
    权利要求:
    Claims (8)
    [0001]
    1. Reinforcement cord (12) to reinforce a rubber product (10), which comprises at least one wire, in which the wire comprises: a bundle of filaments that are bundled together and twisted mutually in one direction, and a layer of coating that is formed on at least one surface of the beam, the beam comprises in carbon fiber filaments in 90% or more of a cross-sectional area of the beam, the coating layer is a coating layer that is formed from of an aqueous treatment agent containing a crosslinking agent as an essential component and, as a main component, a latex of at least one rubber selected from the group consisting of nitrile rubber, hydrogenated nitrile rubber, carboxyl modified nitrile rubber, and rubber hydrogenated nitrile modified with carboxyl, and a filler as an optional component, and in the aqueous treatment agent, a total of one mass of the crosslinking agent and one mass of the filler is in a range of 1 to 50% of a rubber mass in the rubber latex, characterized by the fact that the aqueous treatment agent is free of a resorcinol-formaldehyde condensation product, and in the aqueous treatment agent, a mass of the crosslinking agent is in a range of 1 to 25% with respect to the rubber mass in the rubber latex.
    [0002]
    2. Reinforcement cord (12), according to claim 1, characterized by the fact that the number of carbon fiber filaments in the bundle is in the range of 500 to 48,000.
    [0003]
    Reinforcement cord (12) according to claim 1, characterized in that a surface of the carbon fiber filament in the bundle is treated with a glue agent, and the glue agent contains at least one selected agent of the group consisting of an epoxy group and an amine group.
    [0004]
    Reinforcement cord (12), according to claim 1, characterized by the fact that, in the aqueous treatment agent, the mass of the filler is in a range of 1 to 20% of the mass of the rubber in the rubber latex.
    [0005]
    5. Reinforcement cord (12), according to claim 1, characterized by the fact that, in the aqueous treatment agent, the mass of the crosslinking agent is in a range of 1 to 25%, the mass of the filling is in a range of 1 to 20%, and the total mass of the crosslinking agent and the mass of the filler is in a range of 3 to 45%, with respect to the mass of the rubber in the rubber latex.
    [0006]
    Reinforcement cord (12), according to claim 1, characterized by the fact that a mass of the coating layer is in a range of 7 to 30% of a mass of the filament bundle.
    [0007]
    Reinforcement cord (12) according to claim 1, characterized by the fact that the crosslinking agent contains at least one selected from the group consisting of a maleimide and polyisocyanate crosslinking agent.
    [0008]
    8. Reinforcement cord (12) according to claim 1, characterized by the fact that the filler contains at least one selected from the group consisting of silica and carbon black.
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    同族专利:
    公开号 | 公开日
    US10041194B2|2018-08-07|
    JPWO2012169207A1|2015-02-23|
    US20140093729A1|2014-04-03|
    JP6034783B2|2016-11-30|
    WO2012169207A1|2012-12-13|
    EP2719824B1|2017-02-22|
    CN103608513B|2016-11-02|
    BR112013031328A2|2016-11-29|
    EP2719824A1|2014-04-16|
    EP2719824A4|2015-04-22|
    CN103608513A|2014-02-26|
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    法律状态:
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-07-23| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-09-15| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|
    2021-02-02| B09A| Decision: intention to grant|
    2021-03-30| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 08/06/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2011130445|2011-06-10|
    JP2011-130445|2011-06-10|
    PCT/JP2012/003765|WO2012169207A1|2011-06-10|2012-06-08|Reinforcement cord for reinforcing rubber product, and rubber product using same|
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