WO2017145866A1 - Rubber composition for adhesives, bonding method for rubbers, and conveyor belt - Google Patents

Rubber composition for adhesives, bonding method for rubbers, and conveyor belt Download PDF

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Publication number
WO2017145866A1
WO2017145866A1 PCT/JP2017/005315 JP2017005315W WO2017145866A1 WO 2017145866 A1 WO2017145866 A1 WO 2017145866A1 JP 2017005315 W JP2017005315 W JP 2017005315W WO 2017145866 A1 WO2017145866 A1 WO 2017145866A1
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Prior art keywords
rubber
copolymer
rubber composition
adhesive
conveyor belt
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PCT/JP2017/005315
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French (fr)
Japanese (ja)
Inventor
英博 笹熊
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横浜ゴム株式会社
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Application filed by 横浜ゴム株式会社 filed Critical 横浜ゴム株式会社
Priority to CN201780012239.2A priority Critical patent/CN108699413B/en
Priority to JP2018501607A priority patent/JP6897662B2/en
Publication of WO2017145866A1 publication Critical patent/WO2017145866A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene

Definitions

  • the present invention relates to a rubber composition for an adhesive, a rubber bonding method, and a conveyor belt.
  • Patent Document 1 has been proposed as a rubber bonding method that can be applied to large rubber products such as conveyor belts, rubber crawlers, and large rubber gaskets.
  • Patent Document 1 discloses that adherend rubbers made of a rubber composition containing a diene rubber and an organic sulfur-containing compound are bonded to an unvulcanized rubber made of a rubber composition containing a diene rubber and an organic sulfur-containing compound.
  • the present invention relates to a bonding method in which a bonding rubber is used for bonding at a bonding interface.
  • a process of joining the rubber sheets may be required in order to make the size of the rolled rubber sheet correspond to the large rubber product.
  • a conveyor belt for example, there is a heat-resistant conveyor belt that conveys a transported object having a temperature exceeding 100 ° C.
  • a heat-resistant conveyor belt is required to have high heat resistance.
  • a rubber composition containing an ethylene / ⁇ -olefin copolymer and an organic peroxide that does not contain an unsaturated bond is generally used for the heat-resistant conveyor belt.
  • Patent Document 1 to adhere adherend rubbers made of a rubber composition containing an ethylene / ⁇ -olefin copolymer to each other with the same rubber composition as the adherend rubber.
  • an object of this invention is to provide the rubber composition for adhesive agents excellent in adhesiveness.
  • Another object of the present invention is to provide a rubber bonding method and a conveyor belt.
  • the present inventor contains a polymer containing at least a copolymer of ethylene, ⁇ -olefin and diene, an organic peroxide, and carbon black, and has a diene content.
  • the inventors have found that a predetermined effect can be obtained when the content is 0.01% by mass or more based on the total amount of the polymer, and have reached the present invention.
  • the present invention is based on the above knowledge and the like, and specifically, solves the above problems by the following configuration.
  • a rubber composition for an adhesive which is used for bonding a rubber formed of a rubber composition containing a copolymer of ethylene and ⁇ -olefin, an organic peroxide, and carbon black.
  • Adhering method of rubber 7).
  • the rubber composition for an adhesive of the present invention is excellent in adhesiveness.
  • the present invention can also provide a rubber bonding method and a conveyor belt.
  • FIG. 1 shows a workpiece (conveyor) in which the ends of two rubbers (two rubber layers) are vertically laminated and two rubbers (two rubber layers) are bonded with the rubber composition for an adhesive of the present invention.
  • 1 is a front view schematically showing a belt.
  • FIG. 2 schematically shows a work piece (conveyor belt) in which two rubbers (two rubber layers) are arranged side by side and two rubbers (two rubber layers) are bonded with the rubber composition for an adhesive of the present invention.
  • FIG. 1 shows a workpiece (conveyor) in which the ends of two rubbers (two rubber layers) are vertically laminated and two rubbers (two rubber layers) are bonded with the rubber composition for an adhesive of the present invention.
  • 1 is a front view schematically showing a belt.
  • FIG. 2 schematically shows a work piece (conveyor belt) in which two rubbers (two rubber layers) are arranged side by side and two rubbers (two rubber layers) are bonded with the rubber composition
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • specific examples of each component can be used alone or in combination of two or more.
  • content of a component means content of the sum total of 2 or more types of substances.
  • the rubber composition for adhesives of the present invention (the composition of the present invention) A polymer containing at least an ethylene, ⁇ -olefin and diene copolymer A1, an organic peroxide, and carbon black; The diene content is 0.01% by mass or more based on the total amount of the polymer, A rubber composition for an adhesive used for bonding a rubber formed of a rubber composition containing an ethylene / ⁇ -olefin copolymer, an organic peroxide, and carbon black.
  • the composition of the present invention contains a copolymer A1 of ethylene, ⁇ -olefin and diene and an organic peroxide.
  • the copolymer A1 can be crosslinked by heating, for example, in the presence of an organic peroxide.
  • the crosslinking reaction is performed not only inside the composition of the present invention but also the composition of the present invention and the rubber composition. It also happens between things.
  • the adhesiveness can be improved by using the composition of the present invention containing the copolymer A1 having the part. It is considered excellent.
  • each component contained in the composition of this invention is explained in full detail.
  • the polymer contains at least a copolymer A1 of ethylene, ⁇ -olefin and diene. A part or all of the polymer can be used as the copolymer A1.
  • the composition of this invention is excellent in adhesiveness by containing the copolymer A1.
  • the copolymer A1 is a copolymer of ethylene, ⁇ -olefin and diene.
  • the copolymer A1 is not particularly limited as long as it is a copolymer formed using ethylene, ⁇ -olefin and diene.
  • the ⁇ -olefin constituting the copolymer A1 is not particularly limited as long as it is an aliphatic hydrocarbon compound having one double bond at the terminal. Examples thereof include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene.
  • the diene constituting the copolymer A1 is not particularly limited as long as it is a hydrocarbon compound having two double bonds.
  • One preferred embodiment is that the diene is a non-conjugated diene.
  • dienes include chain or branched chains such as 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 2,5-dimethyl-1,5-hexadiene, and 1,4-octadiene.
  • Aliphatic hydrocarbon compounds 1,4-cyclohexadiene, cyclooctadiene, dicyclopentadiene; 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 2-methallyl-5-norbornene, 2-isopropenyl- Examples thereof include alkenyl norbornene such as 5-norbornene.
  • the method for producing the copolymer A1 is not particularly limited. For example, a conventionally well-known thing is mentioned.
  • the diene content of the copolymer A1 is 0.01% by mass or more based on the total amount of the polymer.
  • the content of the diene of the copolymer A1 is preferably 2.0% by mass or less based on the total amount of the polymer from the viewpoint of excellent adhesiveness and excellent local fatigue resistance (for example, crack resistance, the same applies hereinafter). 1.5% by mass or less is more preferable, and 0.1 to 1.0% by mass is even more preferable.
  • the content of diene in the copolymer A1 is preferably 0.5 to 10.0% by mass with respect to the copolymer A1, from the viewpoints of better adhesion and excellent local fatigue resistance. 0 to 10.0% by mass is more preferable, and 2.0 to 9.5% by mass is even more preferable.
  • the diene content of the copolymer A1 can be evaluated according to ASTM D 6047.
  • the content of the copolymer A1 is preferably 1.0 to 20.0 parts by mass with respect to 100 parts by mass of the polymer, and preferably 2.0 to 15 with respect to 100 parts by mass of the polymer, from the viewpoint of excellent adhesion and excellent local fatigue resistance 0.0 part by mass is more preferable, and 4.0 to 10.0 parts by mass is still more preferable.
  • the polymer further contains a copolymer A2 of ethylene and ⁇ -olefin.
  • the copolymer A2 does not include the copolymer A1.
  • the copolymer A2 is not particularly limited as long as it is a copolymer formed using ethylene and ⁇ -olefin.
  • the ⁇ -olefin constituting the copolymer A2 is the same as the ⁇ -olefin constituting the copolymer A1.
  • the mass ratio of the copolymer A2 to the copolymer A1 is superior in adhesiveness and excellent in local fatigue resistance. Therefore, 4.0 to 49.0 is preferable, and 9.0 to 24.0 is more preferable.
  • Organic peroxide contained in the composition of the present invention is not particularly limited as long as it is a compound having a peroxy group (—O—O—).
  • a conventionally well-known thing is mentioned.
  • Specific examples of the organic peroxide include dicumyl peroxide, di-t-butyl peroxide, 1,3-bis (t-butylperoxyisopropyl) benzene, and 4,4′-di (t -Butylperoxy) valeric acid n-butyl, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane and the like.
  • organic peroxide examples thereof include 1,3-bis (t-butylperoxyisopropyl) benzene (trade name “Perkadox 14-40”, manufactured by Kayaku Akzo Corporation. ) And the like.
  • the content of the peroxy group in the organic peroxide is preferably 0.01 to 0.03 molar equivalent with respect to 100 parts by mass of the polymer, from the viewpoint of excellent adhesion and excellent local fatigue resistance. 0.15-0.25 molar equivalent is more preferred.
  • the carbon black contained in the composition of the present invention is not particularly limited.
  • a conventionally well-known thing is mentioned.
  • Specific examples of carbon black include furnace carbon blacks such as SAF, ISAF, HAF, FEF, GPE, and SRF.
  • the content of carbon black is preferably 30 to 60 parts by mass, and more preferably 35 to 55 parts by mass with respect to 100 parts by mass of the polymer, from the viewpoint of excellent adhesion and excellent local fatigue resistance.
  • the composition of the present invention may contain a filler other than carbon black (for example, silica), an anti-aging agent, an antioxidant, a pigment (dye), a plasticizer, a softener, Flame retardants, crosslinking accelerators, waxes, antistatic agents, processing aids, and crosslinking agents such as magnesium dimethacrylate can be included as additives.
  • a filler other than carbon black for example, silica
  • an anti-aging agent for example, an antioxidant, a pigment (dye), a plasticizer, a softener, Flame retardants, crosslinking accelerators, waxes, antistatic agents, processing aids, and crosslinking agents such as magnesium dimethacrylate can be included as additives.
  • a filler other than carbon black for example, silica
  • an anti-aging agent for example, an antioxidant, a pigment (dye), a plasticizer, a softener, Flame retardants, crosslinking accelerators, waxes, antistatic agents, processing aids,
  • the above-described components can be kneaded with a Banbury mixer or the like.
  • the composition of the present invention can be processed into a sheet by, for example, rolling.
  • the composition of the present invention can be crosslinked, for example, under conditions of 150 to 170 ° C.
  • the composition of the present invention can be, for example, an adhesive layer after crosslinking.
  • the composition of the present invention is a rubber composition containing a copolymer of ethylene and ⁇ -olefin, an organic peroxide, and carbon black (hereinafter, this rubber composition is referred to as “rubber composition for adherend”). Can be used as an adhesive for adhering the rubber (adhered body) formed by the above method.
  • copolymer B As the copolymer of ethylene and ⁇ -olefin (hereinafter, this copolymer may be referred to as “copolymer B”) contained in the rubber composition for adherend, ethylene and ⁇ -olefin are used.
  • the copolymer is not particularly limited as long as it is a copolymer formed.
  • Copolymer B can be the same as copolymer A2.
  • One preferred embodiment of the copolymer B is that it does not contain the copolymer A1.
  • the rubber composition for adherends is excellent in heat resistance by containing the copolymer B.
  • the organic peroxide, carbon black, and additives that can be further contained as necessary are the same as those of the composition of the present invention, which are contained in the adherend rubber composition.
  • the method for producing the rubber composition for adherend and the crosslinking are not particularly limited. For example, a conventionally well-known method is mentioned.
  • the rubber bonding method of the present invention includes a rubber containing an ethylene / ⁇ -olefin copolymer, an organic peroxide, and carbon black using the rubber composition for an adhesive of the present invention.
  • the rubber composition for an adhesive used in the method of the present invention is not particularly limited as long as it is the composition of the present invention.
  • the rubber composition used in the method of the present invention is not particularly limited as long as it is the above-described rubber composition for adherends.
  • an adhesive rubber composition and an adherend rubber composition are placed adjacent to each other and heated, whereby an adhesive layer and a rubber (adherent) are heated. Can be adhered.
  • a rubber composition for an adhesive for example, a plurality of rubbers can be bonded to make the rubber larger or longer.
  • the rubber composition for an adhesive for example, at least two ends of one rubber are bonded to each other to form the one rubber as a ring (ring shape, ring shape). be able to.
  • the one rubber may be one in which a plurality of rubbers are connected in advance. Further, the one rubber may be obtained by previously bonding a plurality of rubbers with the rubber composition for an adhesive. Examples of the rubber formed in a ring include an endless conveyor belt.
  • an adhesive rubber composition layer is disposed between adjacent adhering rubber compositions and heated to thereby form an adhesive layer and A plurality of rubbers can be bonded.
  • the processed product obtained after bonding can have a laminated portion or a bonded portion in which the first rubber, the adhesive layer, and the second rubber are bonded by the adhesive layer.
  • attach with an adhesive bond layer the kind as a some rubber
  • the members to be connected using the rubber composition for adhesive of the present invention can be, for example, upper surface cover rubbers or lower surface cover rubbers.
  • the materials of the plurality of rubbers may be the same or different.
  • a ring is formed in the same manner as in the case where the plurality of rubbers are bonded with an adhesive rubber composition. At least two ends can be bonded together.
  • FIG. 1 is a front view schematically showing a processed product in which end portions of two rubbers are vertically laminated and two rubbers are bonded with the rubber composition for an adhesive of the present invention.
  • the workpiece 10 includes a first rubber 12, a second rubber 14, and an adhesive layer 16. The first rubber 12 and the second rubber 14 are connected so that the workpiece 10 becomes longer in the lateral direction.
  • the workpiece 10 also has a laminated portion 18.
  • an adhesive layer 16 is disposed between the lower surface of the right end of the first rubber 12 and the upper surface of the left end of the second rubber 14, and the first rubber 12 and the second rubber 12.
  • the rubber 14 is bonded with an adhesive layer 16.
  • the right end portion of the first rubber 12 and the left end portion of the second rubber 14 are vertically laminated via the adhesive layer 16.
  • the thickness 17 of the adhesive layer 16 can be set to 0.10 to 50.0 mm.
  • the width of the adhesive layer 16 is not particularly limited.
  • FIG. 2 is a front view schematically showing a processed product obtained by bonding two rubbers side by side with the rubber composition for an adhesive of the present invention.
  • the workpiece 20 includes a first rubber 22, a second rubber 24, and an adhesive layer 26.
  • the first rubber 22 and the second rubber 24 are connected so that the workpiece 20 becomes longer in the lateral direction.
  • the workpiece 20 has a joint portion 28.
  • an adhesive layer 26 is disposed between the side surface (cut end surface) of the right end portion of the first rubber 22 and the side surface (cut end surface) of the left end portion of the second rubber 24. 22 and the second rubber 24 are bonded by an adhesive layer 26.
  • the width 27 of the adhesive layer 26 can be set to 0.10 to 50.0 mm.
  • the workpiece having two rubbers bonded thereto has been described with reference to FIGS. 1 and 2, but when at least two ends of one rubber are bonded to each other to form a ring of the one rubber, Similar to FIG. 1 or FIG. 2, the at least two ends can be bonded to each other.
  • the heating temperature for bonding is preferably 150 to 170 ° C. When heating, you may pressurize together.
  • the rubber composition for adherends is used as a rubber sheet.
  • the rubber composition for adherends may be unvulcanized (or uncrosslinked) or after vulcanization (or after crosslinking), but is not vulcanized (or uncrosslinked) from the viewpoint of better adhesion. It is preferable that The same applies to the rubber composition for adhesive.
  • the rubber sheet of the adherend rubber composition can be bonded, for example, between surfaces or ends. Since the composition of this invention is excellent in adhesiveness, it can be made to adhere
  • the rubber obtained by the method of the present invention can be used for, for example, a conveyor belt.
  • the conveyor belt of the present invention is An adhesive layer formed of the rubber composition for an adhesive of the present invention;
  • the rubber composition for adhesives used for the conveyor belt of this invention is a rubber composition of this invention, it will not restrict
  • a plurality of rubber layers can be bonded by the adhesive layer, and the rubber layer can be enlarged or lengthened. Further, according to the present invention, for example, at least two ends of one rubber layer can be bonded to each other by the adhesive layer, and the one rubber layer can be formed into a ring (ring shape, ring shape). .
  • the one rubber layer may be one in which a plurality of rubber layers are connected in advance. The one rubber layer may be obtained by previously bonding a plurality of rubber layers with the rubber composition for an adhesive.
  • An example of the rubber layer in a ring is an endless conveyor belt.
  • a conveyor belt of the present invention for example, it is mentioned as one of preferred embodiments that a plurality of rubber layers are provided and adjacent rubber layers are bonded via an adhesive layer.
  • the conveyor belt in this case can have a laminated part or a joining part in which the first rubber layer, the adhesive layer and the second rubber layer are bonded.
  • One or both of the first rubber layer and the second rubber layer are formed of a rubber composition containing a copolymer of ethylene and ⁇ -olefin, an organic peroxide, and carbon black. It can be a layer.
  • the kind as a member of a some rubber layer can be made the same.
  • the rubber layers to be connected using the rubber composition for an adhesive of the present invention can be, for example, upper surface cover rubbers and lower surface cover rubbers.
  • the rubber layers to be connected using the rubber composition for an adhesive of the present invention can be, for example, upper surface cover rubbers and lower surface cover rubbers.
  • at least two ends of one rubber layer are bonded to each other with an adhesive layer to form an endless conveyor belt
  • at least the above-mentioned at least two rubber layers are bonded to each other with the adhesive layer. Two ends can be bonded together.
  • FIG. 1 is a front view schematically showing a conveyor belt in which the ends of two rubber layers are vertically laminated and the two rubber layers are bonded with the rubber composition for an adhesive of the present invention.
  • the conveyor belt 10 has a first rubber layer 12, a second rubber layer 14, and an adhesive layer 16.
  • the first rubber 12 layer and the second rubber layer 14 are connected so that the conveyor belt 10 becomes longer in the lateral direction.
  • the conveyor belt 10 also has a laminated portion 18.
  • an adhesive layer 16 is disposed between the lower surface of the right end portion of the first rubber layer 12 and the upper surface of the left end portion of the second rubber layer 14, and the first rubber layer 12
  • the second rubber layer 14 is bonded with an adhesive layer 16.
  • the right end portion of the first rubber layer 12 and the left end portion of the second rubber layer 14 are laminated vertically via the adhesive layer 16.
  • the thickness 17 of the adhesive layer 16 can be set to 0.10 to 10.0 mm.
  • the width of the adhesive layer 16 is not particularly limited.
  • FIG. 2 is a front view schematically showing a conveyor belt in which two rubber layers are arranged side by side and the two rubber layers are bonded with the rubber composition for an adhesive of the present invention.
  • the conveyor belt 20 has a first rubber layer 22, a second rubber layer 24, and an adhesive layer 26.
  • the first rubber layer 22 and the second rubber layer 24 are connected so that the conveyor belt 20 becomes longer in the lateral direction.
  • the conveyor belt 20 has a joint portion 28.
  • the adhesive layer 26 is disposed between the side surface (cut end surface) of the right end portion of the first rubber layer 22 and the side surface (cut end surface) of the left end portion of the second rubber layer 24.
  • the rubber layer 22 and the second rubber layer 24 are bonded with an adhesive layer 26.
  • the first rubber layer 22, the adhesive layer 26, and the second rubber layer 24 are joined side by side.
  • the width 27 of the adhesive layer 26 can be set to 0.10 to 10.0 mm.
  • the conveyor belt having two rubber layers bonded is described above with reference to FIGS. 1 and 2, but at least two ends of one rubber layer are bonded to each other so that the one rubber layer is an endless conveyor belt.
  • the at least two ends can be bonded to each other in the same manner as in FIG. 1 or FIG.
  • the conveyor belt of the present invention includes, for example, a conveyor belt having an upper cover rubber layer and a lower cover rubber layer.
  • the rubber layer may be bonded with an adhesive layer.
  • the conveyor belt of the present invention is a heat-resistant conveyor belt, it is mentioned as one of preferable embodiments that the rubber layer is bonded with an adhesive layer at least on the upper surface cover.
  • (Modulus) -Modulus evaluation sample Each composition produced as described above was heated and pressed at 160 ° C for 60 minutes, and a No. 3 dumbbell-shaped test piece was punched out from the resulting rubber sheet to obtain a 2 mm thick sample for modulus evaluation. (Initial modulus sample) was prepared.
  • Heat resistance test A heat resistance test was performed in which the initial modulus sample was placed at 180 ° C. for 168 hours, and a modulus sample after heat aging (modulus sample after heat aging) was produced.
  • Copolymer A2-1 Ethylene / propylene copolymer (KEP-110, manufactured by KUMHO POLYCHEM)
  • Copolymer A2-2 Ethylene / 1-butene copolymer [Enge HM7487, manufactured by Dow Chemical Co., Ltd.]
  • Copolymer A1-1 Ethylene / propylene / 5-ethylidene-2-norbornene copolymer (Esprene 505A, manufactured by Sumitomo Chemical Co., Ltd., diene content: 9.5% by mass)
  • Copolymer A1-2 ethylene / propylene / 5-ethylidene-2-norbornene copolymer (Mitsui EPT4021, manufactured by Mitsui Chemicals, diene content 8.1% by mass)
  • Copolymer A1-3 ethylene / propylene / 5-ethylidene-2-norbornene copolymer (Mitsui EPT3091, Mitsui Chemicals, diene content 5.4% by mass)
  • Copolymer A1-4 ethylene / propylene / 5-ethylidene-2-norbornene copolymer (JSR EP24, manufactured by JSR, diene content: 4.5% by mass)
  • Carbon black Show black N220 [ISAF carbon black, manufactured by Cabot Japan Co., Ltd.]
  • Zinc oxide 3 types of zinc oxide [manufactured by Shodo Chemical Industry Co., Ltd.]
  • Stearic acid Stearic acid 50S [Chiba Fatty Acid Co., Ltd.]
  • Organic peroxide 1,3-bis (t-butylperoxyisopropyl) benzene (Perkadox 14-40, manufactured by Kayaku Akzo)
  • Comparative Example 1 containing no copolymer A1 had low adhesiveness.
  • the composition of this invention was excellent in adhesiveness. Moreover, the adhesive layer by the composition of this invention was excellent in the balance of rigidity with a rubber layer. From the results of Examples 1, 4 and 7, when the diene content with respect to the total amount of the polymer is 1% by mass or less (Examples 1 and 4), after the heat aging, more than 1% by mass (Example 7).
  • the index of 300% modulus in was in a suitable range, and was excellent in the balance of rigidity between the rubber layer and the adhesive layer after heat aging.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Belt Conveyors (AREA)

Abstract

The purpose of the present invention is to provide: a rubber composition for adhesives, which exhibits excellent adhesiveness; a bonding method for rubbers; and a conveyor belt. The present invention provides: a rubber composition for adhesives, which is used for the purpose of bonding rubbers that are formed from rubber compositions containing a copolymer of ethylene and an α-olefin, an organic peroxide and carbon black, and which contains a polymer that contains at least a copolymer A1 of ethylene, an α-olefin and a diene, an organic peroxide and carbon black, and wherein the content of the diene is 0.01% by mass or more relative to the total amount of the polymer; a bonding method for rubbers; and a conveyor belt.

Description

接着剤用ゴム組成物、ゴムの接着方法及びコンベヤベルトRubber composition for adhesive, rubber bonding method and conveyor belt
　本発明は接着剤用ゴム組成物、ゴムの接着方法及びコンベヤベルトに関する。 The present invention relates to a rubber composition for an adhesive, a rubber bonding method, and a conveyor belt.
　従来、コンベヤベルト、ゴムクローラ、ゴム製大型ガスケットのような大型ゴム製品に適用することができるゴムの接着方法として、例えば、特許文献１が提案されている。
　特許文献１は、ジエン系ゴムと有機含硫黄化合物とを含有するゴム組成物からなる被着体ゴム同士を、ジエン系ゴムと有機含硫黄化合物とを含有するゴム組成物からなる未加硫の接着用ゴムを接着界面に使用して接着させる接着方法に関する。 Conventionally, for example, Patent Document 1 has been proposed as a rubber bonding method that can be applied to large rubber products such as conveyor belts, rubber crawlers, and large rubber gaskets.
Patent Document 1 discloses that adherend rubbers made of a rubber composition containing a diene rubber and an organic sulfur-containing compound are bonded to an unvulcanized rubber made of a rubber composition containing a diene rubber and an organic sulfur-containing compound. The present invention relates to a bonding method in which a bonding rubber is used for bonding at a bonding interface.
特許第５１２５１７９号公報Japanese Patent No. 5125179
　上記のような大型ゴム製品を製造する過程では、圧延されたゴムシートの大きさを大型ゴム製品に対応させるため、ゴムシートを繋ぎ合わせる工程が必要となる場合がある。 In the process of manufacturing a large rubber product as described above, a process of joining the rubber sheets may be required in order to make the size of the rolled rubber sheet correspond to the large rubber product.
　また、コンベヤベルトとしては、例えば１００℃を超える温度の運搬物を搬送する耐熱コンベヤベルトがある。耐熱コンベヤベルトには高い耐熱性が要求される。このため、耐熱コンベヤベルトには、不飽和結合を含まない、エチレン／α－オレフィン共重合体と有機過酸化物とを配合するゴム組成物が一般的に使用される。 Also, as a conveyor belt, for example, there is a heat-resistant conveyor belt that conveys a transported object having a temperature exceeding 100 ° C. A heat-resistant conveyor belt is required to have high heat resistance. For this reason, a rubber composition containing an ethylene / α-olefin copolymer and an organic peroxide that does not contain an unsaturated bond is generally used for the heat-resistant conveyor belt.
　このようななか、発明者は特許文献１を参考にして、エチレン／α－オレフィン共重合体を含有するゴム組成物による被着体ゴム同士を、被着体ゴムと同種のゴム組成物で接着させたところ、接着が不十分となる場合があることが明らかとなった。
　そこで、本発明は接着性に優れる接着剤用ゴム組成物を提供することを目的とする。
　また、本発明は、ゴムの接着方法、および、コンベヤベルトを提供することも目的とする。 Under these circumstances, the inventor refers to Patent Document 1 to adhere adherend rubbers made of a rubber composition containing an ethylene / α-olefin copolymer to each other with the same rubber composition as the adherend rubber. As a result, it became clear that the adhesion might be insufficient.
Then, an object of this invention is to provide the rubber composition for adhesive agents excellent in adhesiveness.
Another object of the present invention is to provide a rubber bonding method and a conveyor belt.
　本発明者は、上記課題を解決すべく鋭意研究した結果、エチレン、α－オレフィン及びジエンの共重合体を少なくとも含む重合体と有機過酸化物とカーボンブラックとを含有し、ジエンの含有量が重合体全量に対して０．０１質量％以上であることによって所定の効果が得られることを見出し、本発明に至った。
　本発明は上記知見等に基づくものであり、具体的には以下の構成により上記課題を解決するものである。 As a result of diligent research to solve the above-mentioned problems, the present inventor contains a polymer containing at least a copolymer of ethylene, α-olefin and diene, an organic peroxide, and carbon black, and has a diene content. The inventors have found that a predetermined effect can be obtained when the content is 0.01% by mass or more based on the total amount of the polymer, and have reached the present invention.
The present invention is based on the above knowledge and the like, and specifically, solves the above problems by the following configuration.
　１．　エチレン、α－オレフィン及びジエンの共重合体Ａ１を少なくとも含む重合体と、有機過酸化物と、カーボンブラックとを含有し、
　上記ジエンの含有量が、上記重合体全量に対して、０．０１質量％以上であり、
　エチレン及びα－オレフィンの共重合体と有機過酸化物とカーボンブラックとを含有するゴム組成物で形成されるゴムを接着させるために使用される、接着剤用ゴム組成物。
　２．　上記重合体が、更に、エチレン及びα－オレフィンの共重合体Ａ２を含む、上記１に記載の接着剤用ゴム組成物。
　３．　上記ジエンの含有量が、上記重合体全量に対して、２．０質量％以下である、上記１又は２に記載の接着剤用ゴム組成物。
　４．　上記共重合体Ａ１の含有量が、上記重合体１００質量部に対して、１～２０質量部である、上記１～３のいずれかに記載の接着剤用ゴム組成物。
　５．　上記ジエンの含有量が、上記共重合体Ａ１に対して、０．５～１０．０質量％である、上記１～４のいずれかに記載の接着剤用ゴム組成物。
　６．　上記１～５のいずれかに記載の接着剤用ゴム組成物を用いて、エチレン及びα－オレフィンの共重合体と有機過酸化物とカーボンブラックとを含有するゴム組成物で形成されるゴムを接着させる、ゴムの接着方法。
　７．　上記１～５のいずれかに記載の接着剤用ゴム組成物で形成された接着剤層と、
　エチレン及びα－オレフィンの共重合体と有機過酸化物とカーボンブラックとを含有するゴム組成物で形成されたゴム層とを有し、上記接着剤層と上記ゴム層とが接着する、コンベヤベルト。
　８．　複数の上記ゴム層を有し、隣接する上記ゴム層が上記接着剤層を介して接着する、上記７に記載のコンベヤベルト。 1. A polymer containing at least an ethylene, α-olefin and diene copolymer A1, an organic peroxide, and carbon black;
The diene content is 0.01% by mass or more based on the total amount of the polymer,
A rubber composition for an adhesive, which is used for bonding a rubber formed of a rubber composition containing a copolymer of ethylene and α-olefin, an organic peroxide, and carbon black.
2. 2. The rubber composition for adhesives according to 1 above, wherein the polymer further contains a copolymer A2 of ethylene and α-olefin.
3. The rubber composition for an adhesive according to 1 or 2 above, wherein the content of the diene is 2.0% by mass or less based on the total amount of the polymer.
4). 4. The rubber composition for an adhesive according to any one of 1 to 3, wherein the content of the copolymer A1 is 1 to 20 parts by mass with respect to 100 parts by mass of the polymer.
5. 5. The rubber composition for an adhesive according to any one of 1 to 4, wherein the content of the diene is 0.5 to 10.0% by mass with respect to the copolymer A1.
6). A rubber formed from a rubber composition containing an ethylene / α-olefin copolymer, an organic peroxide, and carbon black, using the rubber composition for an adhesive according to any one of 1 to 5 above. Adhering method of rubber.
7). An adhesive layer formed of the rubber composition for an adhesive according to any one of 1 to 5 above,
A conveyor belt having a rubber layer formed of a rubber composition containing a copolymer of ethylene and α-olefin, an organic peroxide, and carbon black, and the adhesive layer and the rubber layer are bonded to each other. .
8). 8. The conveyor belt according to 7, wherein the conveyor belt has a plurality of the rubber layers, and the adjacent rubber layers are bonded via the adhesive layer.
　本発明の接着剤用ゴム組成物は接着性に優れる。
　また、本発明は、ゴムの接着方法、および、コンベヤベルトを提供することもできる。 The rubber composition for an adhesive of the present invention is excellent in adhesiveness.
The present invention can also provide a rubber bonding method and a conveyor belt.
図１は、２つのゴム（２つのゴム層）の端部を縦に積層させて、本発明の接着剤用ゴム組成物で２つのゴム（２つのゴム層）を接着させた加工物（コンベヤベルト）を模式的に表す正面図である。FIG. 1 shows a workpiece (conveyor) in which the ends of two rubbers (two rubber layers) are vertically laminated and two rubbers (two rubber layers) are bonded with the rubber composition for an adhesive of the present invention. 1 is a front view schematically showing a belt. 図２は、２つのゴム（２つのゴム層）を横並びにして、本発明の接着剤用ゴム組成物で２つのゴム（２つのゴム層）を接着させた加工物（コンベヤベルト）を模式的に表す正面図である。FIG. 2 schematically shows a work piece (conveyor belt) in which two rubbers (two rubber layers) are arranged side by side and two rubbers (two rubber layers) are bonded with the rubber composition for an adhesive of the present invention. FIG.
　本発明について以下詳細に説明する。
　なお、本明細書において、「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値および上限値として含む範囲を意味する。
　本明細書において特に断りのない限り、各成分はその具体例をそれぞれ単独でまたは２種以上を組み合わせて使用することができる。
　本明細書において、成分が２種以上の物質を含む場合、成分の含有量は、２種以上の物質の合計の含有量を意味する。 The present invention will be described in detail below.
In this specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the present specification, unless otherwise specified, specific examples of each component can be used alone or in combination of two or more.
In this specification, when a component contains 2 or more types of substances, content of a component means content of the sum total of 2 or more types of substances.
［接着剤用ゴム組成物］
　本発明の接着剤用ゴム組成物（本発明の組成物）は、
　エチレン、α－オレフィン及びジエンの共重合体Ａ１を少なくとも含む重合体と、有機過酸化物と、カーボンブラックとを含有し、
　上記ジエンの含有量が、上記重合体全量に対して、０．０１質量％以上であり、
　エチレン及びα－オレフィンの共重合体と有機過酸化物とカーボンブラックとを含有するゴム組成物で形成されるゴムを接着させるために使用される、接着剤用ゴム組成物である。 [Rubber composition for adhesive]
The rubber composition for adhesives of the present invention (the composition of the present invention)
A polymer containing at least an ethylene, α-olefin and diene copolymer A1, an organic peroxide, and carbon black;
The diene content is 0.01% by mass or more based on the total amount of the polymer,
A rubber composition for an adhesive used for bonding a rubber formed of a rubber composition containing an ethylene / α-olefin copolymer, an organic peroxide, and carbon black.
　本発明の組成物はこのような構成をとるため、所望の効果が得られるものと考えられる。その理由は明らかではないが、およそ以下のとおりと推測される。
　本発明の組成物は、エチレン、α－オレフィン及びジエンの共重合体Ａ１及び有機過酸化物を含有する。上記共重合体Ａ１は有機過酸化物の存在下において例えば加熱によって架橋することができる。架橋反応は、本発明の組成物がエチレン及びα－オレフィンの共重合体を含有するゴム組成物に隣接する場合、本発明の組成物の内部のみならず、本発明の組成物と上記ゴム組成物との間でも起こる。すなわち、上記共重合体Ａ１中ジエンによって形成される部分は有機過酸化物との反応性が高いことから、上記部分を有する共重合体Ａ１を含む本発明の組成物を用いることで接着性に優れると考えられる。
　以下、本発明の組成物に含有される各成分について詳述する。 Since the composition of this invention takes such a structure, it is thought that a desired effect is acquired. The reason is not clear, but it is presumed that it is as follows.
The composition of the present invention contains a copolymer A1 of ethylene, α-olefin and diene and an organic peroxide. The copolymer A1 can be crosslinked by heating, for example, in the presence of an organic peroxide. When the composition of the present invention is adjacent to a rubber composition containing a copolymer of ethylene and an α-olefin, the crosslinking reaction is performed not only inside the composition of the present invention but also the composition of the present invention and the rubber composition. It also happens between things. That is, since the part formed by the diene in the copolymer A1 has high reactivity with the organic peroxide, the adhesiveness can be improved by using the composition of the present invention containing the copolymer A1 having the part. It is considered excellent.
Hereinafter, each component contained in the composition of this invention is explained in full detail.
＜重合体＞
　本発明において、重合体は、エチレン、α－オレフィン及びジエンの共重合体Ａ１を少なくとも含む。重合体の一部又は全部を共重合体Ａ１とすることができる。
　本発明の組成物は共重合体Ａ１を含有することによって接着性に優れる。 <Polymer>
In the present invention, the polymer contains at least a copolymer A1 of ethylene, α-olefin and diene. A part or all of the polymer can be used as the copolymer A1.
The composition of this invention is excellent in adhesiveness by containing the copolymer A1.
＜共重合体Ａ１＞
　本発明において、共重合体Ａ１は、エチレン、α－オレフィン及びジエンの共重合体である。共重合体Ａ１は、エチレン、α－オレフィン及びジエンを用いて形成される共重合体であれば特に制限されない。 <Copolymer A1>
In the present invention, the copolymer A1 is a copolymer of ethylene, α-olefin and diene. The copolymer A1 is not particularly limited as long as it is a copolymer formed using ethylene, α-olefin and diene.
　共重合体Ａ１を構成するα－オレフィンは末端に二重結合を１個有する脂肪族炭化水素化合物であれば特に制限されない。例えば、プロピレン、１－ブテン、１－ペンテン、１－ヘキセン、１－ヘプテン、１－オクテンが挙げられる。 The α-olefin constituting the copolymer A1 is not particularly limited as long as it is an aliphatic hydrocarbon compound having one double bond at the terminal. Examples thereof include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene.
　共重合体Ａ１を構成するジエンは、二重結合を２個有する炭化水素化合物であれば特に制限されない。
　ジエンは非共役ジエンであることが好ましい態様の１つとして挙げられる。 The diene constituting the copolymer A1 is not particularly limited as long as it is a hydrocarbon compound having two double bonds.
One preferred embodiment is that the diene is a non-conjugated diene.
　ジエンとしては、例えば、１，４－ペンタジエン、１，４－ヘキサジエン、１，５－ヘキサジエン、２，５－ジメチル－１，５－ヘキサジエン、１，４－オクタジエンのような鎖状又は分岐状の脂肪族炭化水素化合物；１，４－シクロヘキサジエン、シクロオクタジエン、ジシクロペンタジエン；５－エチリデン－２－ノルボルネン、５－ブチリデン－２－ノルボルネン、２－メタリル－５－ノルボルネン、２－イソプロペニル－５－ノルボルネンのようなアルケニルノルボルネン等が挙げられる。 Examples of dienes include chain or branched chains such as 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 2,5-dimethyl-1,5-hexadiene, and 1,4-octadiene. Aliphatic hydrocarbon compounds; 1,4-cyclohexadiene, cyclooctadiene, dicyclopentadiene; 5-ethylidene-2-norbornene, 5-butylidene-2-norbornene, 2-methallyl-5-norbornene, 2-isopropenyl- Examples thereof include alkenyl norbornene such as 5-norbornene.
　共重合体Ａ１の製造方法は特に制限されない。例えば、従来公知のものが挙げられる。 The method for producing the copolymer A1 is not particularly limited. For example, a conventionally well-known thing is mentioned.
　本発明において、共重合体Ａ１のジエンの含有量は、重合体全量に対して、０．０１質量％以上である。共重合体Ａ１のジエンの含有量は、接着性により優れ、耐局所疲労性（例えば耐クラック性。以下同様）に優れるという観点から、重合体全量に対して、２．０質量％以下が好ましく、１．５質量％以下がより好ましく、０．１～１．０質量％が更に好ましい。 In the present invention, the diene content of the copolymer A1 is 0.01% by mass or more based on the total amount of the polymer. The content of the diene of the copolymer A1 is preferably 2.0% by mass or less based on the total amount of the polymer from the viewpoint of excellent adhesiveness and excellent local fatigue resistance (for example, crack resistance, the same applies hereinafter). 1.5% by mass or less is more preferable, and 0.1 to 1.0% by mass is even more preferable.
　また、共重合体Ａ１のジエンの含有量は、接着性により優れ、耐局所疲労性に優れるという観点から、共重合体Ａ１に対して、０．５～１０．０質量％が好ましく、１．０～１０．０質量％がより好ましく、２．０～９．５質量％が更に好ましい。
　共重合体Ａ１のジエンの含有量は、ＡＳＴＭ　Ｄ　６０４７に準じて評価できる。 In addition, the content of diene in the copolymer A1 is preferably 0.5 to 10.0% by mass with respect to the copolymer A1, from the viewpoints of better adhesion and excellent local fatigue resistance. 0 to 10.0% by mass is more preferable, and 2.0 to 9.5% by mass is even more preferable.
The diene content of the copolymer A1 can be evaluated according to ASTM D 6047.
　共重合体Ａ１の含有量は、接着性により優れ、耐局所疲労性に優れるという観点から、重合体１００質量部に対して、１．０～２０．０質量部が好ましく、２．０～１５．０質量部がより好ましく、４．０～１０．０質量部が更に好ましい。 The content of the copolymer A1 is preferably 1.0 to 20.0 parts by mass with respect to 100 parts by mass of the polymer, and preferably 2.0 to 15 with respect to 100 parts by mass of the polymer, from the viewpoint of excellent adhesion and excellent local fatigue resistance 0.0 part by mass is more preferable, and 4.0 to 10.0 parts by mass is still more preferable.
（共重合体Ａ２）
　重合体は、接着性により優れ、耐局所疲労性に優れるという観点から、更に、エチレン及びα－オレフィンの共重合体Ａ２を含むことが好ましい態様の１つとして挙げられる。なお本発明において共重合体Ａ２は共重合体Ａ１を含まない。 (Copolymer A2)
From the viewpoint that the polymer is more excellent in adhesiveness and excellent in local fatigue resistance, one preferred embodiment is that the polymer further contains a copolymer A2 of ethylene and α-olefin. In the present invention, the copolymer A2 does not include the copolymer A1.
　共重合体Ａ２は、エチレン及びα－オレフィンを用いて形成される共重合体であれば特に制限されない。
　共重合体Ａ２を構成するα－オレフィンは、共重合体Ａ１を構成するα－オレフィンと同様である。 The copolymer A2 is not particularly limited as long as it is a copolymer formed using ethylene and α-olefin.
The α-olefin constituting the copolymer A2 is the same as the α-olefin constituting the copolymer A1.
　重合体が更に共重合体Ａ２を含む場合、共重合体Ａ１に対する共重合体Ａ２の質量比（共重合体Ａ２／共重合体Ａ１）は、接着性により優れ、耐局所疲労性に優れるという観点から、４.０～４９.０が好ましく、９．０～２４.０がより好ましい。 In the case where the polymer further contains a copolymer A2, the mass ratio of the copolymer A2 to the copolymer A1 (copolymer A2 / copolymer A1) is superior in adhesiveness and excellent in local fatigue resistance. Therefore, 4.0 to 49.0 is preferable, and 9.0 to 24.0 is more preferable.
＜有機過酸化物＞
　本発明の組成物に含有される有機過酸化物はペルオキシ基（－Ｏ－Ｏ－）を有する化合物であれば特に限定されない。例えば、従来公知のものが挙げられる。
　有機過酸化物としては、具体的には、例えば、ジクミルパーオキサイド、ジ－ｔ－ブチルパーオキサイド、１，３－ビス（ｔ－ブチルパーオキシイソプロピル）ベンゼン、４，４´－ジ（ｔ－ブチルパーオキシ）バレリック酸ｎ－ブチル、２，５－ジメチル－２，５－ビス（ｔ－ブチルパーオキシ）ヘキサン等が挙げられる。 <Organic peroxide>
The organic peroxide contained in the composition of the present invention is not particularly limited as long as it is a compound having a peroxy group (—O—O—). For example, a conventionally well-known thing is mentioned.
Specific examples of the organic peroxide include dicumyl peroxide, di-t-butyl peroxide, 1,3-bis (t-butylperoxyisopropyl) benzene, and 4,4′-di (t -Butylperoxy) valeric acid n-butyl, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane and the like.
　上記有機過酸化物として市販品を用いることができ、その具体例としては、１，３－ビス（ｔ－ブチルパーオキシイソプロピル）ベンゼン（商品名「パーカドックス１４－４０」、化薬アクゾ社製）等が挙げられる。 Commercially available products can be used as the organic peroxide, and specific examples thereof include 1,3-bis (t-butylperoxyisopropyl) benzene (trade name “Perkadox 14-40”, manufactured by Kayaku Akzo Corporation. ) And the like.
　有機過酸化物が有するペルオキシ基の含有量は、接着性により優れ、耐局所疲労性に優れるという観点から、上記重合体１００質量部に対して、０．０１～０．０３モル当量が好ましく、０．１５～０．２５モル当量がより好ましい。 The content of the peroxy group in the organic peroxide is preferably 0.01 to 0.03 molar equivalent with respect to 100 parts by mass of the polymer, from the viewpoint of excellent adhesion and excellent local fatigue resistance. 0.15-0.25 molar equivalent is more preferred.
＜カーボンブラック＞
　本発明の組成物に含有されるカーボンブラックは特に限定されない。例えば、従来公知のものが挙げられる。
　カーボンブラックとしては、具体的には、例えば、ＳＡＦ、ＩＳＡＦ、ＨＡＦ、ＦＥＦ、ＧＰＥ、ＳＲＦ等のファーネスカーボンブラックが挙げられる。 <Carbon black>
The carbon black contained in the composition of the present invention is not particularly limited. For example, a conventionally well-known thing is mentioned.
Specific examples of carbon black include furnace carbon blacks such as SAF, ISAF, HAF, FEF, GPE, and SRF.
　カーボンブラックの含有量は、接着性により優れ、耐局所疲労性に優れるという観点から、上記重合体１００質量部に対して、３０～６０質量部が好ましく、３５～５５質量部がより好ましい。 The content of carbon black is preferably 30 to 60 parts by mass, and more preferably 35 to 55 parts by mass with respect to 100 parts by mass of the polymer, from the viewpoint of excellent adhesion and excellent local fatigue resistance.
（添加剤）
　本発明の組成物は、上述した成分以外に、必要に応じて、カーボンブラック以外の充填剤（例えば、シリカ等）、老化防止剤、酸化防止剤、顔料（染料）、可塑剤、軟化剤、難燃剤、架橋促進剤、ワックス、帯電防止剤、加工助剤、マグネシウムジメタクリレートのような架橋剤を添加剤として含有することができる。
　本発明の組成物は加硫剤として実質的に硫黄を含有しないことが好ましい態様の１つとして挙げられる。本発明において、硫黄を実質的に含有しないとは、硫黄の含有量が上記重合体１００質量部に対して、０～０．１質量部であることを意味する。 (Additive)
In addition to the above-described components, the composition of the present invention may contain a filler other than carbon black (for example, silica), an anti-aging agent, an antioxidant, a pigment (dye), a plasticizer, a softener, Flame retardants, crosslinking accelerators, waxes, antistatic agents, processing aids, and crosslinking agents such as magnesium dimethacrylate can be included as additives.
It is mentioned as one of the preferable aspects that the composition of this invention does not contain sulfur substantially as a vulcanizing agent. In the present invention, “substantially not containing sulfur” means that the sulfur content is 0 to 0.1 parts by mass with respect to 100 parts by mass of the polymer.
　本発明の組成物の製造方法としては、例えば、上述した各成分をバンバリーミキサー等で混練して行うことができる。
　本発明の組成物は、例えば圧延などによって、シート状に加工することができる。
　本発明の組成物は、例えば、１５０～１７０℃の条件下で架橋することができる。本発明の組成物は、架橋後、例えば、接着剤層となることができる。 As a method for producing the composition of the present invention, for example, the above-described components can be kneaded with a Banbury mixer or the like.
The composition of the present invention can be processed into a sheet by, for example, rolling.
The composition of the present invention can be crosslinked, for example, under conditions of 150 to 170 ° C. The composition of the present invention can be, for example, an adhesive layer after crosslinking.
＜ゴム組成物（被着体用ゴム組成物）＞
　本発明の組成物は、エチレン及びα－オレフィンの共重合体と有機過酸化物とカーボンブラックとを含有するゴム組成物（以下このゴム組成物を「被着体用ゴム組成物」と称することがある。）で形成されるゴム（被着体）を接着させるための接着剤として使用することができる。 <Rubber composition (rubber composition for adherend)>
The composition of the present invention is a rubber composition containing a copolymer of ethylene and α-olefin, an organic peroxide, and carbon black (hereinafter, this rubber composition is referred to as “rubber composition for adherend”). Can be used as an adhesive for adhering the rubber (adhered body) formed by the above method.
　被着体用ゴム組成物に含有される、エチレン及びα－オレフィンの共重合体（以下この共重合体を「共重合体Ｂ」と称することがある。）は、エチレン及びα－オレフィンを用いて形成される共重合体であれば特に制限されない。共重合体Ｂは共重合体Ａ２と同様とすることができる。共重合体Ｂは共重合体Ａ１を含まないことが好ましい態様の１つとして挙げられる。被着体用ゴム組成物は共重合体Ｂを含有することによって耐熱性に優れる。
　被着体用ゴム組成物に含有される、有機過酸化物、カーボンブラック、及び必要に応じて更に含有することができる添加剤は、それぞれ、本発明の組成物と同様である。
　被着体用ゴム組成物の製造方法及び架橋は特に制限されない。例えば、従来公知の方法が挙げられる。 As the copolymer of ethylene and α-olefin (hereinafter, this copolymer may be referred to as “copolymer B”) contained in the rubber composition for adherend, ethylene and α-olefin are used. The copolymer is not particularly limited as long as it is a copolymer formed. Copolymer B can be the same as copolymer A2. One preferred embodiment of the copolymer B is that it does not contain the copolymer A1. The rubber composition for adherends is excellent in heat resistance by containing the copolymer B.
The organic peroxide, carbon black, and additives that can be further contained as necessary are the same as those of the composition of the present invention, which are contained in the adherend rubber composition.
The method for producing the rubber composition for adherend and the crosslinking are not particularly limited. For example, a conventionally well-known method is mentioned.
［ゴムの接着方法］
　本発明のゴムの接着方法（本発明の方法）は、本発明の接着剤用ゴム組成物を用いて、エチレン及びα－オレフィンの共重合体と有機過酸化物とカーボンブラックとを含有するゴム組成物で形成されるゴムを接着させる、ゴムの接着方法である。 [Rubber bonding method]
The rubber bonding method of the present invention (the method of the present invention) includes a rubber containing an ethylene / α-olefin copolymer, an organic peroxide, and carbon black using the rubber composition for an adhesive of the present invention. A method for adhering rubber, in which rubber formed by a composition is adhered.
　本発明の方法に使用される接着剤用ゴム組成物は本発明の組成物であれば特に制限されない。
　本発明の方法に使用されるゴム組成物は、上記の被着体用ゴム組成物であれば特に制限されない。 The rubber composition for an adhesive used in the method of the present invention is not particularly limited as long as it is the composition of the present invention.
The rubber composition used in the method of the present invention is not particularly limited as long as it is the above-described rubber composition for adherends.
　本発明の方法としては、具体的には例えば、接着剤用ゴム組成物と被着体用ゴム組成物とを隣接させ、これを加熱することによって、接着剤層とゴム（被着体）とを接着させることができる。
　本発明の方法によれば、接着剤用ゴム組成物で、例えば、複数のゴムを接着させて、ゴムを大きく又は長くすることができる。
　また、本発明の方法によれば、接着剤用ゴム組成物で、例えば、１つのゴムにおける少なくとも２つの端部同士を接着させて、上記１つのゴムを輪（輪状、輪の形）とすることができる。上記１つのゴムは、複数のゴムが予め連結されたものであってもよい。また、上記１つのゴムは、複数のゴムを上記接着剤用ゴム組成物で予め接着させたものであってもよい。輪になったゴムとしては、例えば、エンドレスのコンベヤベルトが挙げられる。 Specifically, as the method of the present invention, for example, an adhesive rubber composition and an adherend rubber composition are placed adjacent to each other and heated, whereby an adhesive layer and a rubber (adherent) are heated. Can be adhered.
According to the method of the present invention, with a rubber composition for an adhesive, for example, a plurality of rubbers can be bonded to make the rubber larger or longer.
Further, according to the method of the present invention, with the rubber composition for an adhesive, for example, at least two ends of one rubber are bonded to each other to form the one rubber as a ring (ring shape, ring shape). be able to. The one rubber may be one in which a plurality of rubbers are connected in advance. Further, the one rubber may be obtained by previously bonding a plurality of rubbers with the rubber composition for an adhesive. Examples of the rubber formed in a ring include an endless conveyor belt.
　複数のゴムを接着剤用ゴム組成物で接着させる場合、隣接する被着体用ゴム組成物の間に接着剤用ゴム組成物層を配置して、これを加熱することによって、接着剤層と複数のゴムとを接着させることができる。この場合、接着後に得られる加工物は、第１のゴムと接着剤層と第２のゴムとが接着剤層で接着した、積層部分又は接合部分を有することができる。
　また、複数のゴム（部材）を接着剤層と接着させる場合、複数のゴムの部材としての種類を、同じとすることができる。例えば、上記加工物がコンベヤベルトである場合、本発明の接着剤用ゴム組成物を用いて接続させる部材を、例えば、上面カバーゴム同士、下面カバーゴム同士とすることができる。
　また、複数のゴムを接着剤層と接着させる場合、複数のゴムの材質は、同じであっても異なってもよい。
　なお、１つのゴムにおける少なくとも２つの端部同士を接着剤用ゴム組成物で接着させて輪とする場合も、上記複数のゴムを接着剤用ゴム組成物で接着させる場合と同様にして、上記少なくとも２つの端部同士を接着できる。 When adhering a plurality of rubbers with an adhesive rubber composition, an adhesive rubber composition layer is disposed between adjacent adhering rubber compositions and heated to thereby form an adhesive layer and A plurality of rubbers can be bonded. In this case, the processed product obtained after bonding can have a laminated portion or a bonded portion in which the first rubber, the adhesive layer, and the second rubber are bonded by the adhesive layer.
Moreover, when making a some rubber | gum (member) adhere | attach with an adhesive bond layer, the kind as a some rubber | gum member can be made the same. For example, when the workpiece is a conveyor belt, the members to be connected using the rubber composition for adhesive of the present invention can be, for example, upper surface cover rubbers or lower surface cover rubbers.
Further, when a plurality of rubbers are bonded to the adhesive layer, the materials of the plurality of rubbers may be the same or different.
In the case where at least two ends of one rubber are bonded to each other with an adhesive rubber composition, a ring is formed in the same manner as in the case where the plurality of rubbers are bonded with an adhesive rubber composition. At least two ends can be bonded together.
　本発明の接着剤用ゴム組成物を用いて、２つのゴムを接着させた加工物について、添付の図面を用いて以下に説明する。本発明は添付の図面に制限されない。
　図１は、２つのゴムの端部を縦に積層させて、本発明の接着剤用ゴム組成物で２つのゴムを接着させた加工物を模式的に表す正面図である。
　図１において、加工物１０は第１のゴム１２と第２のゴム１４と接着剤層１６とを有する。
　第１のゴム１２と第２のゴム１４とは、加工物１０が横方向に長くなるように連結されている。
　また、加工物１０は積層部分１８を有する。積層部分１８において、第１のゴム１２の右端部の下側表面と第２のゴム１４の左端部の上側表面との間に接着剤層１６が配置され、第１のゴム１２と第２のゴム１４とは接着剤層１６で接着されている。積層部分１８において、第１のゴム１２の右端部と第２のゴム１４の左端部が接着剤層１６を介して縦に積層している。
　接着剤層１６の厚さ１７を、０．１０～５０．０ｍｍとすることができる。
　接着剤層１６の幅は特に制限されない。 A workpiece obtained by bonding two rubbers using the rubber composition for an adhesive of the present invention will be described below with reference to the accompanying drawings. The present invention is not limited to the attached drawings.
FIG. 1 is a front view schematically showing a processed product in which end portions of two rubbers are vertically laminated and two rubbers are bonded with the rubber composition for an adhesive of the present invention.
In FIG. 1, the workpiece 10 includes a first rubber 12, a second rubber 14, and an adhesive layer 16.
The first rubber 12 and the second rubber 14 are connected so that the workpiece 10 becomes longer in the lateral direction.
The workpiece 10 also has a laminated portion 18. In the laminated portion 18, an adhesive layer 16 is disposed between the lower surface of the right end of the first rubber 12 and the upper surface of the left end of the second rubber 14, and the first rubber 12 and the second rubber 12. The rubber 14 is bonded with an adhesive layer 16. In the laminated portion 18, the right end portion of the first rubber 12 and the left end portion of the second rubber 14 are vertically laminated via the adhesive layer 16.
The thickness 17 of the adhesive layer 16 can be set to 0.10 to 50.0 mm.
The width of the adhesive layer 16 is not particularly limited.
　図２は、２つのゴムを横並びにして、本発明の接着剤用ゴム組成物で２つのゴムを接着させた加工物を模式的に表す正面図である。
　図２において、加工物２０は、第１のゴム２２と第２のゴム２４と接着剤層２６とを有する。
　第１のゴム２２と第２のゴム２４とは、加工物２０が横方向に長くなるように連結されている。
　また、加工物２０は、接合部分２８を有する。接合部分２８において、第１のゴム２２の右端部の側面（切断端面）と第２のゴム２４の左端部の側面（切断端面）との間に接着剤層２６が配置され、第１のゴム２２と第２のゴム２４とは接着剤層２６で接着されている。接合部分２８において、第１のゴム２２、接着剤層２６、第２のゴム２４は横並びに接合している。
　接着剤層２６の幅２７を、０．１０～５０．０ｍｍとすることができる。 FIG. 2 is a front view schematically showing a processed product obtained by bonding two rubbers side by side with the rubber composition for an adhesive of the present invention.
In FIG. 2, the workpiece 20 includes a first rubber 22, a second rubber 24, and an adhesive layer 26.
The first rubber 22 and the second rubber 24 are connected so that the workpiece 20 becomes longer in the lateral direction.
Further, the workpiece 20 has a joint portion 28. In the joint portion 28, an adhesive layer 26 is disposed between the side surface (cut end surface) of the right end portion of the first rubber 22 and the side surface (cut end surface) of the left end portion of the second rubber 24. 22 and the second rubber 24 are bonded by an adhesive layer 26. In the joint portion 28, the first rubber 22, the adhesive layer 26, and the second rubber 24 are joined side by side.
The width 27 of the adhesive layer 26 can be set to 0.10 to 50.0 mm.
　以上のとおり、２つのゴムを接着させた加工物について図１、２に用いて説明したが、１つのゴムにおける少なくとも２つの端部同士を接着させて上記１つのゴムを輪にする場合も、図１又は図２と同様にして、上記少なくとも２つの端部同士を接着させることができる。 As described above, the workpiece having two rubbers bonded thereto has been described with reference to FIGS. 1 and 2, but when at least two ends of one rubber are bonded to each other to form a ring of the one rubber, Similar to FIG. 1 or FIG. 2, the at least two ends can be bonded to each other.
　接着させる際の加熱温度は１５０～１７０℃が好ましい。加熱する際、合わせて加圧をしてもよい。 The heating temperature for bonding is preferably 150 to 170 ° C. When heating, you may pressurize together.
　被着体用ゴム組成物はゴムシートとして使用されることが好ましい態様の１つとして挙げられる。
　被着体用ゴム組成物は未加硫（又は未架橋）であっても加硫後（又は架橋後）であってもよいが、接着性により優れるという観点から未加硫（又は未架橋）であることが好ましい。接着剤用ゴム組成物も同様である。 One preferred embodiment is that the rubber composition for adherends is used as a rubber sheet.
The rubber composition for adherends may be unvulcanized (or uncrosslinked) or after vulcanization (or after crosslinking), but is not vulcanized (or uncrosslinked) from the viewpoint of better adhesion. It is preferable that The same applies to the rubber composition for adhesive.
　本発明の方法によれば、被着体用ゴム組成物のゴムシートを、例えば、面同士で、又は、端部同士で接着させることができる。本発明の組成物は接着性に優れるため、ゴムシートの端部同士で接着させることができる。
　また、本発明の方法によれば、被着体用ゴム組成物のゴムシートの大きさ（例えば、幅、長さ）を大きくすることができる。また被着体用ゴム組成物をエンドレス加工することができる。 According to the method of the present invention, the rubber sheet of the adherend rubber composition can be bonded, for example, between surfaces or ends. Since the composition of this invention is excellent in adhesiveness, it can be made to adhere | attach between the edge parts of a rubber sheet.
Moreover, according to the method of this invention, the magnitude | size (for example, width | variety, length) of the rubber sheet of the rubber composition for adherends can be enlarged. Moreover, the rubber composition for adherends can be processed endlessly.
　本発明の方法によって得られたゴムを、例えば、コンベヤベルトに使用することができる。 The rubber obtained by the method of the present invention can be used for, for example, a conveyor belt.
［コンベヤベルト］
　本発明のコンベヤベルトは、
　本発明の接着剤用ゴム組成物で形成された接着剤層と、
　エチレン及びα－オレフィンの共重合体と有機過酸化物とカーボンブラックとを含有するゴム組成物で形成されたゴム層とを有し、上記接着剤層と上記ゴム層とが接着する、コンベヤベルトである。 [Conveyor belt]
The conveyor belt of the present invention is
An adhesive layer formed of the rubber composition for an adhesive of the present invention;
A conveyor belt having a rubber layer formed of a rubber composition containing a copolymer of ethylene and α-olefin, an organic peroxide, and carbon black, and the adhesive layer and the rubber layer are bonded to each other. It is.
　本発明のコンベヤベルトに使用される接着剤用ゴム組成物は本発明のゴム組成物であれば特に制限されない。
　本発明のコンベヤベルトに使用されるゴム組成物は、上記の被着体用ゴム組成物であれば特に制限されない。
　本発明によれば、接着剤層によって、例えば、複数のゴム層を接着させて、ゴム層を大きく又は長くすることができる。
　また、本発明によれば、接着剤層によって、例えば、１つのゴム層における少なくとも２つの端部同士を接着させて、上記１つのゴム層を輪（輪状、輪の形）とすることができる。上記１つのゴム層は、複数のゴム層が予め連結されたものであってもよい。また、上記１つのゴム層は、複数のゴム層を上記接着剤用ゴム組成物で予め接着させたものであってもよい。輪になったゴム層としては、例えば、エンドレスのコンベヤベルトが挙げられる。 If the rubber composition for adhesives used for the conveyor belt of this invention is a rubber composition of this invention, it will not restrict | limit in particular.
If the rubber composition used for the conveyor belt of this invention is said rubber composition for adherends, it will not restrict | limit in particular.
According to the present invention, for example, a plurality of rubber layers can be bonded by the adhesive layer, and the rubber layer can be enlarged or lengthened.
Further, according to the present invention, for example, at least two ends of one rubber layer can be bonded to each other by the adhesive layer, and the one rubber layer can be formed into a ring (ring shape, ring shape). . The one rubber layer may be one in which a plurality of rubber layers are connected in advance. The one rubber layer may be obtained by previously bonding a plurality of rubber layers with the rubber composition for an adhesive. An example of the rubber layer in a ring is an endless conveyor belt.
　本発明のコンベヤベルトとしては、例えば、複数のゴム層を有し、隣接するゴム層が接着剤層を介して接着することが好ましい態様の１つとして挙げられる。この場合のコンベヤベルトは、第１のゴム層と接着剤層と第２のゴム層とが接着した、積層部分又は接合部分を有することができる。
　第１のゴム層及び第２のゴム層のうちのいずれか一方又は両方を、エチレン及びα－オレフィンの共重合体と有機過酸化物とカーボンブラックとを含有するゴム組成物で形成されたゴム層とすることができる。
　また、複数のゴム層を接着剤層と接着させる場合、複数のゴム層の部材としての種類を、同じとすることができる。例えば、本発明の接着剤用ゴム組成物を用いて接続させるゴム層を、例えば、上面カバーゴム同士、下面カバーゴム同士とすることができる。
　なお、１つのゴム層における少なくとも２つの端部同士を接着剤層で接着させてエンドレスのコンベヤベルトとする場合も、上記複数のゴム層を接着剤層で接着させる場合と同様にして、上記少なくとも２つの端部同士を接着できる。 As a conveyor belt of the present invention, for example, it is mentioned as one of preferred embodiments that a plurality of rubber layers are provided and adjacent rubber layers are bonded via an adhesive layer. The conveyor belt in this case can have a laminated part or a joining part in which the first rubber layer, the adhesive layer and the second rubber layer are bonded.
One or both of the first rubber layer and the second rubber layer are formed of a rubber composition containing a copolymer of ethylene and α-olefin, an organic peroxide, and carbon black. It can be a layer.
Moreover, when bonding a some rubber layer with an adhesive bond layer, the kind as a member of a some rubber layer can be made the same. For example, the rubber layers to be connected using the rubber composition for an adhesive of the present invention can be, for example, upper surface cover rubbers and lower surface cover rubbers.
In the case where at least two ends of one rubber layer are bonded to each other with an adhesive layer to form an endless conveyor belt, at least the above-mentioned at least two rubber layers are bonded to each other with the adhesive layer. Two ends can be bonded together.
　本発明のコンベヤベルトについて、添付の図面を用いて以下に説明する。本発明は添付の図面に制限されない。
　図１は、２つのゴム層の端部を縦に積層させて、本発明の接着剤用ゴム組成物で２つのゴム層を接着させたコンベヤベルトを模式的に表す正面図である。
　図１において、コンベヤベルト１０は第１のゴム層１２と第２のゴム層１４と接着剤層１６とを有する。
　第１のゴム１２層と第２のゴム層１４とは、コンベヤベルト１０が横方向に長くなるように連結されている。
　また、コンベヤベルト１０は積層部分１８を有する。積層部分１８において、第１のゴム層１２の右端部の下側表面と第２のゴム層１４の左端部の上側表面との間に接着剤層１６が配置され、第１のゴム層１２と第２のゴム層１４とは接着剤層１６で接着されている。積層部分１８において、第１のゴム層１２の右端部と第２のゴム層１４の左端部が接着剤層１６を介して縦に積層している。
　接着剤層１６の厚さ１７を、０．１０～１０．０ｍｍとすることができる。
　接着剤層１６の幅は特に制限されない。 The conveyor belt of this invention is demonstrated below using attached drawing. The present invention is not limited to the attached drawings.
FIG. 1 is a front view schematically showing a conveyor belt in which the ends of two rubber layers are vertically laminated and the two rubber layers are bonded with the rubber composition for an adhesive of the present invention.
In FIG. 1, the conveyor belt 10 has a first rubber layer 12, a second rubber layer 14, and an adhesive layer 16.
The first rubber 12 layer and the second rubber layer 14 are connected so that the conveyor belt 10 becomes longer in the lateral direction.
The conveyor belt 10 also has a laminated portion 18. In the laminated portion 18, an adhesive layer 16 is disposed between the lower surface of the right end portion of the first rubber layer 12 and the upper surface of the left end portion of the second rubber layer 14, and the first rubber layer 12 The second rubber layer 14 is bonded with an adhesive layer 16. In the laminated portion 18, the right end portion of the first rubber layer 12 and the left end portion of the second rubber layer 14 are laminated vertically via the adhesive layer 16.
The thickness 17 of the adhesive layer 16 can be set to 0.10 to 10.0 mm.
The width of the adhesive layer 16 is not particularly limited.
　図２は、２つのゴム層を横並びにして、本発明の接着剤用ゴム組成物で２つのゴム層を接着させたコンベヤベルトを模式的に表す正面図である。
　図２において、コンベヤベルト２０は、第１のゴム層２２と第２のゴム層２４と接着剤層２６とを有する。
　第１のゴム層２２と第２のゴム層２４とは、コンベヤベルト２０が横方向に長くなるように連結されている。
　また、コンベヤベルト２０は、接合部分２８を有する。接合部分２８において、第１のゴム層２２の右端部の側面（切断端面）と第２のゴム層２４の左端部の側面（切断端面）との間に接着剤層２６が配置され、第１のゴム層２２と第２のゴム層２４とは接着剤層２６で接着されている。接合部分２８において、第１のゴム層２２、接着剤層２６、第２のゴム層２４は横並びに接合している。
　接着剤層２６の幅２７を、０．１０～１０．０ｍｍとすることができる。 FIG. 2 is a front view schematically showing a conveyor belt in which two rubber layers are arranged side by side and the two rubber layers are bonded with the rubber composition for an adhesive of the present invention.
In FIG. 2, the conveyor belt 20 has a first rubber layer 22, a second rubber layer 24, and an adhesive layer 26.
The first rubber layer 22 and the second rubber layer 24 are connected so that the conveyor belt 20 becomes longer in the lateral direction.
Further, the conveyor belt 20 has a joint portion 28. In the joint portion 28, the adhesive layer 26 is disposed between the side surface (cut end surface) of the right end portion of the first rubber layer 22 and the side surface (cut end surface) of the left end portion of the second rubber layer 24. The rubber layer 22 and the second rubber layer 24 are bonded with an adhesive layer 26. In the joint portion 28, the first rubber layer 22, the adhesive layer 26, and the second rubber layer 24 are joined side by side.
The width 27 of the adhesive layer 26 can be set to 0.10 to 10.0 mm.
　２つのゴム層を接着させたコンベヤベルトについて図１、２に用いて以上のとおり説明したが、１つのゴム層における少なくとも２つの端部同士を接着させて上記１つのゴム層をエンドレスのコンベヤベルトとする場合も、図１又は図２と同様にして、上記少なくとも２つの端部同士を接着できる。 The conveyor belt having two rubber layers bonded is described above with reference to FIGS. 1 and 2, but at least two ends of one rubber layer are bonded to each other so that the one rubber layer is an endless conveyor belt. In this case, the at least two ends can be bonded to each other in the same manner as in FIG. 1 or FIG.
　本発明のコンベヤベルトは、例えば、上面カバーゴム層及び下面カバーゴム層を有するコンベアベルトが挙げられる。上面カバー及び下面カバーのうちの一方又は両方において、ゴム層が接着剤層で接着されているものとすることができる。本発明のコンベヤベルトが耐熱コンベヤベルトである場合、少なくとも上面カバーにおいて、ゴム層が接着剤層で接着されていることが好ましい態様の１つとして挙げられる。 The conveyor belt of the present invention includes, for example, a conveyor belt having an upper cover rubber layer and a lower cover rubber layer. In one or both of the upper surface cover and the lower surface cover, the rubber layer may be bonded with an adhesive layer. When the conveyor belt of the present invention is a heat-resistant conveyor belt, it is mentioned as one of preferable embodiments that the rubber layer is bonded with an adhesive layer at least on the upper surface cover.
　以下に実施例を示して本発明を具体的に説明する。ただし本発明はこれらに限定されない。
＜組成物の製造＞
　下記第１表の各成分を同表に示す組成（質量部）で用い、有機過酸化物以外の成分を予め撹拌機で混合し、これに有機過酸化物を加えて更に混合して、組成物を製造した。
　第１表において、ジエン含有量は、重合体全量に対する質量％である。
　また、第１表の「有機過酸化物（モル当量）」は、重合体１００質量部に対する、上記有機過酸化物が有するペルオキシ基の含有量（モル当量）である。 The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these.
<Production of composition>
Each component of the following Table 1 is used in the composition (part by mass) shown in the same table, components other than the organic peroxide are mixed in advance with a stirrer, the organic peroxide is added to this, and further mixed, the composition The thing was manufactured.
In Table 1, the diene content is mass% relative to the total amount of the polymer.
Further, “Organic peroxide (molar equivalent)” in Table 1 is the content (molar equivalent) of the peroxy group of the organic peroxide with respect to 100 parts by mass of the polymer.
＜評価＞
　上記のとおり製造された各組成物を用いて以下の評価を行った。結果を第１表に示す。
　なお、初期モジュラス及び初期の接着力を第１表において「ブランク物性」欄に示す。熱老化後モジュラス及び熱老化後の接着力を第１表において「老化後物性」欄に示す。 <Evaluation>
The following evaluation was performed using each composition manufactured as mentioned above. The results are shown in Table 1.
The initial modulus and initial adhesive strength are shown in the “Blank physical properties” column in Table 1. The modulus after heat aging and the adhesive strength after heat aging are shown in the "Physical properties after aging" column in Table 1.
（モジュラス）
・モジュラス評価用サンプル
　上記のとおり製造された各組成物を１６０℃で６０分間、加熱プレスし、得られたゴムシートから３号ダンベル状の試験片を打ち抜いて、厚さ２ｍｍのモジュラス評価用サンプル（初期モジュラスサンプル）を作製した。 (Modulus)
-Modulus evaluation sample Each composition produced as described above was heated and pressed at 160 ° C for 60 minutes, and a No. 3 dumbbell-shaped test piece was punched out from the resulting rubber sheet to obtain a 2 mm thick sample for modulus evaluation. (Initial modulus sample) was prepared.
・耐熱試験
　上記初期モジュラスサンプルを１８０℃の条件下に１６８時間置く耐熱試験を行い、熱老化後のモジュラスサンプル（熱老化後モジュラスサンプル）を作製した。 Heat resistance test A heat resistance test was performed in which the initial modulus sample was placed at 180 ° C. for 168 hours, and a modulus sample after heat aging (modulus sample after heat aging) was produced.
・引張試験
　上記初期モジュラスサンプル又は熱老化後モジュラスサンプルを用いて、引張速度５００ｍｍ／分、室温の条件下で引張試験をＪＩＳ　Ｋ６２５１に準拠して行い、３００％モジュラスを測定した。
　初期モジュラスの結果は、比較例１の初期モジュラスを１００とする指数で表した。
　熱老化後モジュラスの結果は、比較例１の熱老化後モジュラスを１００とする指数で表した。
　モジュラスの結果が１００±１５である場合、ゴム層と接着剤層との剛性のバランスに優れる。剛性のバランスに優れると耐局所疲労性に優れると考えられる。 -Tensile test Using the initial modulus sample or the modulus sample after heat aging, a tensile test was performed in accordance with JIS K6251 under the conditions of a tensile speed of 500 mm / min and room temperature, and a 300% modulus was measured.
The result of the initial modulus was expressed as an index with the initial modulus of Comparative Example 1 as 100.
The result of the modulus after heat aging was expressed as an index with the modulus after heat aging of Comparative Example 1 as 100.
When the modulus result is 100 ± 15, the rigidity balance between the rubber layer and the adhesive layer is excellent. If the balance of rigidity is excellent, it is considered that the local fatigue resistance is excellent.
（接着力）
・接着性評価用サンプル
　上記のとおり製造された比較例１の組成物を厚さ５ｍｍに圧延して、被着体ゴムシートを作製した。次に、上記のとおり製造された各組成物を厚さ５ｍｍに圧延して、接着剤用ゴムシートを作製した。上記被着体ゴムシート１枚と上記接着剤用ゴムシート１枚とを貼り合わせた後に、これを１６０℃で６０分間、加熱プレスすることによって接着性評価用サンプル（初期接着性サンプル）を作製した。接着性評価用サンプルの形状は、ＪＩＳ　Ｋ６２５６－１：２００６の「布とのはく離強さ」に準じた。
　なお、比較例１において、被着体ゴムと接着剤用ゴムとは同じである。 (Adhesive strength)
-Adhesive evaluation sample The composition of Comparative Example 1 produced as described above was rolled to a thickness of 5 mm to produce an adherend rubber sheet. Next, each composition produced as described above was rolled to a thickness of 5 mm to produce an adhesive rubber sheet. After bonding the above-mentioned adherend rubber sheet and the above-mentioned adhesive rubber sheet, a sample for evaluating adhesiveness (initial adhesive sample) is produced by heating and pressing this at 60 ° C. for 60 minutes. did. The shape of the sample for evaluating adhesiveness was in accordance with “peel strength against cloth” of JIS K6256-1: 2006.
In Comparative Example 1, the adherend rubber and the adhesive rubber are the same.
・耐熱試験
　上記初期接着性サンプルを１８０℃の条件下に１６８時間置く耐熱試験を行い、熱老化後の接着性評価用サンプル（熱老化後接着性サンプル）を作製した。 -Heat resistance test The heat resistance test which puts the said initial adhesiveness sample on 180 degreeC conditions for 168 hours was done, and the sample for adhesiveness evaluation after heat aging (adhesion sample after heat aging) was produced.
・はく離試験
　上記初期接着性サンプル又は熱老化後接着性サンプルを用いて、室温（ＲＴ）又は１５０℃の条件下において、ＪＩＳ　Ｋ６２５６－１：２００６の「布とのはく離強さ」に準じてはく離試験を行い、はく離力（Ｎ／ｍｍ）を測定した。
　はく離力が大きいほど接着性に優れる。
　なお、初期のはく離力を第１表において「ブランク物性　接着力」欄に示す。熱老化後のはく離力を第１表において「老化後物性　接着力」欄に示す。 ・ Peeling test Using the above initial adhesive sample or adhesive sample after heat aging, peeling in accordance with JIS K6256-1: 2006 “Peeling strength with fabric” under conditions of room temperature (RT) or 150 ° C. The test was performed and the peeling force (N / mm) was measured.
The greater the peeling force, the better the adhesion.
The initial peeling force is shown in the “Blank physical property adhesive force” column in Table 1. The peeling force after heat aging is shown in the column of “Adhesive strength after physical aging” in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　第１表に示した各成分の詳細は以下のとおりである。
　・共重合体Ａ２－１：エチレン・プロピレン共重合体〔ＫＥＰ－１１０、ＫＵＭＨＯ ＰＯＬＹＣＨＥＭ社製〕
　・共重合体Ａ２－２：エチレン・１－ブテン共重合体〔Ｅｎｇａｇｅ　ＨＭ７４８７、ダウケミカル社製〕 Details of each component shown in Table 1 are as follows.
Copolymer A2-1: Ethylene / propylene copolymer (KEP-110, manufactured by KUMHO POLYCHEM)
Copolymer A2-2: Ethylene / 1-butene copolymer [Enge HM7487, manufactured by Dow Chemical Co., Ltd.]
　・共重合体Ａ１－１：エチレン・プロピレン・５－エチリデン－２－ノルボルネン共重合体（エスプレン５０５Ａ、住友化学社製、ジエン含有量９．５質量％）
　・共重合体Ａ１－２：エチレン・プロピレン・５－エチリデン－２－ノルボルネン共重合体（三井ＥＰＴ４０２１、三井化学社製、ジエン含有量８．１質量％）
　・共重合体Ａ１－３：エチレン・プロピレン・５－エチリデン－２－ノルボルネン共重合体（三井ＥＰＴ３０９１、三井化学社製、ジエン含有量５．４質量％）
　・共重合体Ａ１－４：エチレン・プロピレン・５－エチリデン－２－ノルボルネン共重合体（ＪＳＲ　ＥＰ２４、ＪＳＲ社製、ジエン含有量４．５質量％） Copolymer A1-1: Ethylene / propylene / 5-ethylidene-2-norbornene copolymer (Esprene 505A, manufactured by Sumitomo Chemical Co., Ltd., diene content: 9.5% by mass)
Copolymer A1-2: ethylene / propylene / 5-ethylidene-2-norbornene copolymer (Mitsui EPT4021, manufactured by Mitsui Chemicals, diene content 8.1% by mass)
Copolymer A1-3: ethylene / propylene / 5-ethylidene-2-norbornene copolymer (Mitsui EPT3091, Mitsui Chemicals, diene content 5.4% by mass)
Copolymer A1-4: ethylene / propylene / 5-ethylidene-2-norbornene copolymer (JSR EP24, manufactured by JSR, diene content: 4.5% by mass)
　・カーボンブラック：ショウブラックＮ２２０〔ＩＳＡＦカーボンブラック、キャボットジャパン社製〕
　・酸化亜鉛：酸化亜鉛３種〔正同化学工業社製〕
　・ステアリン酸：ステアリン酸５０Ｓ〔千葉脂肪酸社製〕
　・有機過酸化物：１，３－ビス（ｔ－ブチルパーオキシイソプロピル）ベンゼン〔パーカドックス１４－４０、化薬アクゾ社製〕 Carbon black: Show black N220 [ISAF carbon black, manufactured by Cabot Japan Co., Ltd.]
・ Zinc oxide: 3 types of zinc oxide [manufactured by Shodo Chemical Industry Co., Ltd.]
・ Stearic acid: Stearic acid 50S [Chiba Fatty Acid Co., Ltd.]
Organic peroxide: 1,3-bis (t-butylperoxyisopropyl) benzene (Perkadox 14-40, manufactured by Kayaku Akzo)
　第１表に示す結果から明らかなように、共重合体Ａ１を含有しない比較例１は接着性が低かった。 As is clear from the results shown in Table 1, Comparative Example 1 containing no copolymer A1 had low adhesiveness.
　これに対して、本発明の組成物は接着性に優れた。
　また、本発明の組成物による接着剤層はゴム層との剛性のバランスに優れた。
　実施例１、４及び７の結果から、重合体全量に対するジエン含有量が１質量％以下である場合（実施例１、４）は１質量％を超える場合（実施例７）よりも熱老化後における３００％モジュラスの指数が好適範囲となり、熱老化後における、ゴム層と接着剤層との剛性のバランスにより優れた。 On the other hand, the composition of this invention was excellent in adhesiveness.
Moreover, the adhesive layer by the composition of this invention was excellent in the balance of rigidity with a rubber layer.
From the results of Examples 1, 4 and 7, when the diene content with respect to the total amount of the polymer is 1% by mass or less (Examples 1 and 4), after the heat aging, more than 1% by mass (Example 7). The index of 300% modulus in was in a suitable range, and was excellent in the balance of rigidity between the rubber layer and the adhesive layer after heat aging.
　１０　加工物（コンベヤベルト）
　１２　第１のゴム（第１のゴム層）
　１４　第２のゴム（第２のゴム層）
　１６　接着剤層
　１７　厚さ
　１８　積層部分
　２０　加工物（コンベヤベルト）
　２２　第１のゴム（第１のゴム層）
　２４　第２のゴム（第２のゴム層）
　２６　接着剤層
　２７　幅
　２８　接合部分 10 Workpiece (conveyor belt)
12 First rubber (first rubber layer)
14 Second rubber (second rubber layer)
16 Adhesive Layer 17 Thickness 18 Laminated Part 20 Workpiece (Conveyor Belt)
22 First rubber (first rubber layer)
24 Second rubber (second rubber layer)
26 Adhesive layer 27 Width 28 Joint part

Claims (8)

  1. 　エチレン、α－オレフィン及びジエンの共重合体Ａ１を少なくとも含む重合体と、有機過酸化物と、カーボンブラックとを含有し、
    　前記ジエンの含有量が、前記重合体全量に対して、０．０１質量％以上であり、
    　エチレン及びα－オレフィンの共重合体と有機過酸化物とカーボンブラックとを含有するゴム組成物で形成されるゴムを接着させるために使用される、接着剤用ゴム組成物。     A polymer containing at least an ethylene, α-olefin and diene copolymer A1, an organic peroxide, and carbon black;
    The diene content is 0.01% by mass or more based on the total amount of the polymer,
    A rubber composition for an adhesive, which is used for bonding a rubber formed of a rubber composition containing a copolymer of ethylene and α-olefin, an organic peroxide, and carbon black.
  2. 　前記重合体が、更に、エチレン及びα－オレフィンの共重合体Ａ２を含む、請求項１に記載の接着剤用ゴム組成物。 2. The rubber composition for an adhesive according to claim 1, wherein the polymer further contains a copolymer A2 of ethylene and α-olefin.
  3. 　前記ジエンの含有量が、前記重合体全量に対して、２．０質量％以下である、請求項１又は２に記載の接着剤用ゴム組成物。 The rubber composition for an adhesive according to claim 1 or 2, wherein the content of the diene is 2.0% by mass or less based on the total amount of the polymer.
  4. 　前記共重合体Ａ１の含有量が、前記重合体１００質量部に対して、１～２０質量部である、請求項１～３のいずれか１項に記載の接着剤用ゴム組成物。 The rubber composition for an adhesive according to any one of claims 1 to 3, wherein the content of the copolymer A1 is 1 to 20 parts by mass with respect to 100 parts by mass of the polymer.
  5. 　前記ジエンの含有量が、前記共重合体Ａ１に対して、０．５～１０．０質量％である、請求項１～４のいずれか１項に記載の接着剤用ゴム組成物。 The rubber composition for an adhesive according to any one of claims 1 to 4, wherein a content of the diene is 0.5 to 10.0 mass% with respect to the copolymer A1.
  6. 　請求項１～５のいずれか１項に記載の接着剤用ゴム組成物を用いて、エチレン及びα－オレフィンの共重合体と有機過酸化物とカーボンブラックとを含有するゴム組成物で形成されるゴムを接着させる、ゴムの接着方法。 An adhesive rubber composition according to any one of claims 1 to 5 is used to form a rubber composition containing an ethylene / α-olefin copolymer, an organic peroxide, and carbon black. This is a method of adhering rubber.
  7. 　請求項１～５のいずれか１項に記載の接着剤用ゴム組成物で形成された接着剤層と、
    　エチレン及びα－オレフィンの共重合体と有機過酸化物とカーボンブラックとを含有するゴム組成物で形成されたゴム層とを有し、前記接着剤層と前記ゴム層とが接着する、コンベヤベルト。     An adhesive layer formed of the rubber composition for an adhesive according to any one of claims 1 to 5;
    A conveyor belt having a rubber layer formed of a rubber composition containing a copolymer of ethylene and α-olefin, an organic peroxide, and carbon black, and the adhesive layer and the rubber layer are bonded to each other. .
  8. 　複数の前記ゴム層を有し、隣接する前記ゴム層が前記接着剤層を介して接着する、請求項７に記載のコンベヤベルト。 The conveyor belt according to claim 7, comprising a plurality of the rubber layers, wherein the adjacent rubber layers are bonded via the adhesive layer.
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