WO2022123869A1 - Rubber composition, rubber/metal composite, hose, conveyor belt, rubber crawler, and tire - Google Patents

Rubber composition, rubber/metal composite, hose, conveyor belt, rubber crawler, and tire Download PDF

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Publication number
WO2022123869A1
WO2022123869A1 PCT/JP2021/035954 JP2021035954W WO2022123869A1 WO 2022123869 A1 WO2022123869 A1 WO 2022123869A1 JP 2021035954 W JP2021035954 W JP 2021035954W WO 2022123869 A1 WO2022123869 A1 WO 2022123869A1
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WO
WIPO (PCT)
Prior art keywords
rubber
metal
acid
rubber composition
aliphatic carboxylic
Prior art date
Application number
PCT/JP2021/035954
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French (fr)
Japanese (ja)
Inventor
尚史 鉄谷
祐和 高橋
Original Assignee
株式会社ブリヂストン
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Publication of WO2022123869A1 publication Critical patent/WO2022123869A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B62—LAND VEHICLES FOR TRAVELLING OTHERWISE THAN ON RAILS
    • B62D—MOTOR VEHICLES; TRAILERS
    • B62D55/00—Endless track vehicles
    • B62D55/08—Endless track units; Parts thereof
    • B62D55/18—Tracks
    • B62D55/26—Ground engaging parts or elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65G—TRANSPORT OR STORAGE DEVICES, e.g. CONVEYORS FOR LOADING OR TIPPING, SHOP CONVEYOR SYSTEMS OR PNEUMATIC TUBE CONVEYORS
    • B65G15/00—Conveyors having endless load-conveying surfaces, i.e. belts and like continuous members, to which tractive effort is transmitted by means other than endless driving elements of similar configuration
    • B65G15/30—Belts or like endless load-carriers
    • B65G15/32—Belts or like endless load-carriers made of rubber or plastics
    • B65G15/34—Belts or like endless load-carriers made of rubber or plastics with reinforcing layers, e.g. of fabric
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • 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
    • C08K5/55—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/10—Copolymers of styrene with conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L11/00—Hoses, i.e. flexible pipes
    • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
    • F16L11/08—Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall

Definitions

  • the present invention relates to rubber compositions, rubber-metal composites, hoses, conveyor belts, rubber crawlers and tires.
  • reinforcing materials such as brass-plated steel cords are coated with a rubber composition containing natural rubber, synthetic rubber, and the like.
  • a rubber-metal composite is used.
  • an adhesion promoter is contained in the rubber composition in order to improve the adhesive force between the above-mentioned reinforcing material and the coated rubber (rubber composition).
  • an organic acid cobalt salt for example, cobalt stearate, cobalt versatic acid, cobalt naphthenate, etc.
  • an organic acid cobalt salt for example, cobalt stearate, cobalt versatic acid, cobalt naphthenate, etc.
  • Patent Document 1 describes an adhesion promoter capable of exerting a high adhesive force between a rubber and a metal without containing cobalt, and a rubber composition and a tire containing the adhesive promoter.
  • the technology related to is disclosed.
  • the rubber composition containing the adhesion promoter described in Patent Document 1 is not always sufficiently adhered to a metal member, and even if it does not contain an organic acid cobalt salt, it is a metal. There is a demand for a rubber composition having further improved adhesiveness to a member.
  • the present invention comprises a rubber-metal composite having excellent adhesiveness between a rubber and a metal member using such a rubber composition, and further comprising such a rubber-metal composite to provide excellent durability. It is a further task to provide a hose, a conveyor belt, a rubber crawler and a tire having the hose, a conveyor belt, and a rubber crawler.
  • the gist structure of the present invention that solves the above problems is as follows.
  • the rubber composition of the present invention contains a rubber component and With modified polymers Contains rubber-metal adhesion promoters, The content of the modified polymer is 50 parts by mass or less with respect to 100 parts by mass of the rubber component.
  • the rubber-metal adhesion accelerator is represented by a metal salt (1) of an aliphatic carboxylic acid (excluding zinc dimethacrylate) and a general formula (A): [ ( RCOO) x MO] 3Z. Contains one or more selected from the group consisting of compound (2).
  • the aliphatic carboxylic acid of the metal salt (1) of the aliphatic carboxylic acid has 2 to 25 carbon atoms.
  • the metal of the metal salt (1) of the aliphatic carboxylic acid is bismuth, zinc, copper, antimony, silver, niobium or zirconium.
  • (RCOO) is a residue of an aliphatic carboxylic acid having 2 to 25 carbon atoms
  • M is bismuth, zinc, copper, antimony, silver, niobium or zirconium
  • x is. It is an integer of 1 or more and (valence of M-1), and Z is characterized by having a structure selected from the following formulas (z-1) to (z-4).
  • the rubber-metal composite of the present invention is characterized by comprising the above-mentioned rubber composition and a metal member.
  • the hose of the present invention is characterized by having the above-mentioned rubber-metal composite.
  • the conveyor belt of the present invention is characterized by including the above-mentioned rubber-metal composite.
  • the rubber crawler of the present invention is characterized by including the above-mentioned rubber-metal complex.
  • the tire of the present invention is characterized by having the above-mentioned rubber-metal composite.
  • a rubber composition having excellent adhesiveness to a metal member without containing an organic acid cobalt salt.
  • a rubber-metal composite having excellent adhesion between rubber and a metal member, and further, a hose, a conveyor belt, a rubber crawler and a tire having excellent durability. Can be done.
  • the rubber composition of the present invention contains a rubber component, a modified polymer, and a rubber-metal adhesion promoter.
  • the content of the modified polymer is 50 parts by mass or less with respect to 100 parts by mass of the rubber component.
  • the rubber-metal adhesion accelerator is represented by a metal salt (1) of an aliphatic carboxylic acid (excluding zinc dimethacrylate) and a general formula (A): [ ( RCOO) x MO] 3Z. Contains one or more selected from the group consisting of compound (2).
  • the aliphatic carboxylic acid of the metal salt of the aliphatic carboxylic acid (1) has 2 to 25 carbon atoms, and the metal of the metal salt of the aliphatic carboxylic acid (1) is bismuth, zinc, copper, antimonate, and the like.
  • Silver, niobium or zirconium In the general formula (A), (RCOO) is a residue of an aliphatic carboxylic acid having 2 to 25 carbon atoms, M is bismuth, zinc, copper, antimony, silver, niobium or zirconium, and x is. It is an integer of 1 or more and (valence of M-1), and Z is characterized by having a structure selected from the following formulas (z-1) to (z-4).
  • a rubber-metal bond containing at least one selected from the group consisting of a metal salt of an aliphatic carboxylic acid (1) and a compound (2) represented by the general formula (A).
  • the accelerator contributes to the improvement of the adhesiveness with the metal member.
  • the adhesion of the rubber composition to the metal member is sufficient only by containing the rubber-metal adhesion promoter.
  • the rubber composition of the present invention by containing the modified polymer in addition to the rubber-metal adhesion promoter, the rubber is produced by the synergistic effect of the rubber-metal adhesion promoter and the modified polymer.
  • the adhesiveness of the composition to the metal member can be significantly improved. Therefore, the rubber composition of the present invention is excellent in adhesiveness to metal members even if it does not contain an organic acid cobalt salt.
  • the rubber composition of the present invention contains a rubber component.
  • the rubber component is not particularly limited, and a rubber component conventionally used in a rubber composition can be used.
  • the rubber components include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), styrene-isoprene rubber (SIR), and styrene-isoprene-butadiene rubber (SIBR).
  • NR natural rubber
  • IR isoprene rubber
  • BR butadiene rubber
  • SBR styrene-butadiene rubber
  • SIR styrene-isoprene rubber
  • SIBR styrene-isoprene-butadiene rubber
  • EPDM Ethylene-propylene-diene rubber
  • NBR acrylonitrile-butadiene rubber
  • CR chloroprene rubber
  • IIR modified rubbers thereof
  • the rubber component of the rubber composition of the present invention preferably contains at least one selected from the group consisting of natural rubber and styrene-butadiene rubber. Natural rubber is easily stretched and crystallized and has excellent fracture properties. Styrene-butadiene rubber also has excellent fracture properties. Therefore, when the rubber component contains natural rubber and / or styrene-butadiene rubber, the breaking property of the rubber composition is improved. When the rubber component contains natural rubber and styrene-butadiene rubber, the processability can be improved in addition to the destructive properties of the rubber composition.
  • the total content of the natural rubber and the styrene-butadiene rubber in the rubber component is not particularly limited, but is preferably 10% by mass or more, more preferably 20% by mass or more, and 100% by mass. There may be.
  • the rubber composition of the present invention comprises a modified polymer.
  • the adhesiveness of the rubber composition to the metal member can be improved.
  • the modified polymer does not exhibit rubber elasticity at room temperature (25 ° C.) and is different from the above-mentioned rubber component. Further, the modified polymer is preferably liquid at room temperature (25 ° C.).
  • the modified polymer contains, in its molecule, one or more functional groups selected from the group consisting of -COOH, -OH and -COOR (where R is a monovalent hydrocarbon group). Is preferable.
  • R is a monovalent hydrocarbon group.
  • the monovalent hydrocarbon group as R include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.
  • Examples of the aliphatic hydrocarbon group include an alkyl group and an alkenyl group
  • examples of the alicyclic hydrocarbon group include a cycloalkyl group and a cycloalkenyl group
  • examples of the aromatic hydrocarbon group include aryl.
  • Groups, arylene groups and the like can be mentioned.
  • the carbon number of the monovalent hydrocarbon group is preferably in the range of 1 to 20, more preferably in the range of 1 to 10, and even more preferably in the range of 1 to 4.
  • the backbone of the modified polymer is not particularly limited and may contain various monomer units.
  • Examples of the raw material monomer constituting the main chain of the modified polymer include isoprene and butadiene. Of these, isoprene is preferred.
  • the modified polymer can be synthesized by modifying the polymer chain with maleic acid, maleic anhydride or the like, or a commercially available product can also be used.
  • the modified polymer preferably has a lower molecular weight than the above-mentioned rubber component, and has a polystyrene-equivalent number average molecular weight (Mn) of 1,000 to 100,000, preferably 5,000 to 80,000. It is more preferably 10,000 to 50,000, and even more preferably 10,000 to 50,000.
  • Mn polystyrene-equivalent number average molecular weight
  • the content of the modified polymer is 50 parts by mass or less, preferably 1 to 50 parts by mass, and 3 to 30 parts by mass with respect to 100 parts by mass of the rubber component from the viewpoint of improving the adhesiveness to the metal member.
  • the range of parts is more preferable.
  • the rubber composition of the present invention contains a rubber-metal adhesion promoter.
  • the rubber-metal adhesion accelerator is represented by a metal salt (1) of an aliphatic carboxylic acid (excluding zinc dimethacrylate) and a general formula (A): [ ( RCOO) x MO] 3Z. Contains one or more selected from the group consisting of the compound (2).
  • the rubber composition contains, as a rubber-metal adhesion promoter, a metal salt (1) of an aliphatic carboxylic acid and / or a compound (2) represented by the general formula (A), thereby adhering to a metal member. It is possible to improve the sex.
  • metal salt (1) of the aliphatic carboxylic acid has 2 to 25 carbon atoms, and the metal species of the metal salt are bismuth (Bi), zinc (Zn), and copper (Cu). ), Antimony (Sb), silver (Ag), niobium (Nb) or zirconium (Zr).
  • the metal salt (1) of the aliphatic carboxylic acid has 2 to 25 carbon atoms, and the metal species of the metal salt are bismuth (Bi), zinc (Zn), and copper (Cu). ), Antimony (Sb), silver (Ag), niobium (Nb) or zirconium (Zr).
  • zinc dimethacrylate is excluded from the metal salt (1) of the aliphatic carboxylic acid.
  • the compatibility of the metal salt (1) of the aliphatic carboxylic acid with the rubber component is improved, and as a result, the metal member and the metal member The adhesive strength with the rubber composition is improved.
  • the synthesis of the metal salt (1) of the aliphatic carboxylic acid is easy.
  • the carbon number of the aliphatic carboxylic acid means the number including the number of carbon atoms of the carboxyl group.
  • the metal of the metal salt (1) of the aliphatic carboxylic acid is preferably bismuth.
  • the rubber composition contains a bismuth salt of an aliphatic carboxylic acid, the adhesiveness between the rubber composition and the metal member is further improved.
  • the aliphatic carboxylic acid of the metal salt (1) of the aliphatic carboxylic acid is preferably an aliphatic monocarboxylic acid or an aliphatic dicarboxylic acid.
  • the rubber composition contains a metal salt of an aliphatic monocarboxylic acid or an aliphatic dicarboxylic acid, the adhesiveness between the rubber composition and the metal member is further improved.
  • Examples of the aliphatic monocarboxylic acid include saturated aliphatic monocarboxylic acids and unsaturated aliphatic monocarboxylic acids.
  • Examples of the saturated aliphatic monocarboxylic acid include ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexanic acid, 2-ethylhexanoic acid, heptanic acid, octanoic acid, nonanoic acid, isononanoic acid, decanoic acid and neodecane.
  • Examples thereof include acids, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, eicosanoic acid, docosanoic acid, tetracosanoic acid, naphthenic acid and the like.
  • Examples of the unsaturated aliphatic monocarboxylic acid include 9-hexadecenoic acid, cis-9-octadecenoic acid, 11-octadecenoic acid, cis, cis-9,12-octadecadienoic acid, 9,12, 15-Octadecatorienic acid, 6,9,12-octadecatorienic acid, 9,11,13-octadecatrienoic acid, Eikosanoic acid, 8,11-Eikosadienoic acid, 5,8,11-Eicosatrioenic acid, 5,8,11,14-Eikosatetraenoic acid, tung oil fatty acid, linseed fatty oil acid, soybean oil fatty acid, tall oil fatty acid, resin acid, loginic acid, avietic acid, neoavietic acid, palastolic acid, pimalic acid, dehydro Examples include avietic acid.
  • Examples of the aliphatic dicarboxylic acid include saturated aliphatic dicarboxylic acid and unsaturated aliphatic dicarboxylic acid.
  • Examples of the saturated aliphatic dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid and the like.
  • Examples of the unsaturated aliphatic dicarboxylic acid include fumaric acid and maleic acid.
  • aliphatic carboxylic acids a cured rubber product that does not easily affect the sulfur cross-linking of the rubber component, is suitable for use in conveyor belts, hoses, rubber crawlers, tires, etc., and has little adverse effect on rubber physical properties can be obtained. Therefore, a saturated aliphatic monocarboxylic acid is preferable.
  • saturated aliphatic monocarboxylic acids having 2 to 20 carbon atoms are preferable, 2-ethylhexanoic acid, neodecanoic acid, hexadecanoic acid and octadecanoic acid are more preferable, and 2-ethylhexane Acids are particularly preferred.
  • the adhesiveness between the rubber composition and the metal member is further improved. improves.
  • the saturated aliphatic monocarboxylic acid is 2-ethylhexanoic acid, neodecanoic acid, hexadecanoic acid or octadecanoic acid, the adhesiveness between the rubber composition and the metal member is further improved.
  • Examples of the metal salt (1) of the aliphatic carboxylic acid include bismuth 2-ethylhexanoate, zinc 2-ethylhexanate, copper 2-ethylhexanoate, antimony 2-ethylhexanoate, silver 2-ethylhexanoate, and 2 -Niob ethylhexanoate, zirconium 2-ethylhexanoate, bismuth neodecanoate, zinc neodecanoate, copper neodecanoate, antimone neodecanoate, silver neodecanoate, niobium neodecanoate, zirconium neodecanoate, bismuth hexadecanoate, zinc hexadecanoate, hexadecane Examples thereof include copper acid, antimonate hexadecanoate, silver hexadecanoate, ni
  • the metal salt (1) of the aliphatic carboxylic acid may be used alone or in combination of two or more.
  • the metal salt (1) of the aliphatic carboxylic acid is, for example, an aliphatic carboxylic acid (a) having 2 to 25 carbon atoms and a metal (bismuth, zinc, copper) as described in International Publication No. 2016/039375.
  • the compound (2) is represented by the general formula (A): [ ( RCOO) x MO] 3Z.
  • (RCOO) in the above general formula (A) is a residue of an aliphatic carboxylic acid having 2 to 25 carbon atoms.
  • the compatibility of the compound (2) with the rubber component is improved, and as a result, the adhesive force between the metal member and the rubber composition is improved. ..
  • the dispersibility of the compound (2) in the rubber component and the compound (2) is improved, and the effect of improving the adhesive force between the metal member and the rubber composition is increased.
  • the carbon number of (RCOO) means the number including the number of carbon atoms of the carboxyl group.
  • the residue of the aliphatic monocarboxylic acid having 2 to 25 carbon atoms is preferable.
  • the residue of the aliphatic monocarboxylic acid the residue derived from the aliphatic monocarboxylic acid can be preferably exemplified.
  • the compound (2) does not cross-link the rubber component and further promotes the dispersion of the compound (2) in the vicinity of the metal or the adsorption of the compound (2) on the metal surface, thereby causing the metal.
  • Saturated aliphatic monocarboxylic acid residues are preferred because they can more exert the effect of promoting adhesion between the member and the rubber composition.
  • the residues of saturated aliphatic monocarboxylic acid the residue of saturated aliphatic monocarboxylic acid having 2 to 20 carbon atoms is preferable, the residue of 2-ethylhexanoic acid, the residue of neodecanoic acid, and hexadecane.
  • Acid residues and octadecanoic acid residues are more preferred.
  • (RCOO) is a residue of a saturated aliphatic monocarboxylic acid having 2 to 20 carbon atoms
  • the adhesiveness between the rubber composition and the metal member is further improved.
  • the saturated aliphatic monocarboxylic acid is 2-ethylhexanoic acid, neodecanoic acid, hexadecanoic acid or octadecanoic acid
  • the adhesiveness between the rubber composition and the metal member is further improved.
  • M in the above general formula (A) is a metal species, and specifically, bismuth (Bi), zinc (Zn), copper (Cu), antimony (Sb), silver (Ag), niobium (Nb). Or zirconium (Zr).
  • bismuth is particularly preferable as M from the viewpoint of good adhesion between the metal member and the rubber composition.
  • x in the above general formula (A) is an integer of 1 or more and (valence of M-1).
  • Z in the general formula (A) is the following formula (z-1) to formula (z-4) :. It is a structure selected from. Among the above structures, the structure represented by the above formula (z-1) is preferable because the adhesive force (adhesiveness) between the metal member and the rubber composition is further increased.
  • Examples of the compound (2) include boron 2-ethylhexanoate bismuth, boron 2-ethylhexanoate zinc, boron 2-ethylhexanoate copper, boron 2-ethylhexanoate antimony, boron 2-ethylhexanoate silver, and boron 2.
  • the compound (2) represented by the general formula (A) is, for example, an aliphatic carboxylic acid (a) having 2 to 25 carbon atoms and 1 to 1 carbon atoms as described in International Publication No. 2016/039375.
  • the content of the rubber-metal adhesion promoter is not particularly limited, but is 0.1 part by mass or more with respect to 100 parts by mass of the rubber component from the viewpoint of obtaining better adhesion to the metal member. It is preferably 1.5 parts by mass or more, more preferably 6 parts by mass or more, and particularly preferably 6 parts by mass or more. Further, from the viewpoint of suppressing deterioration of the rubber composition, the content of the rubber-metal adhesion accelerator is preferably 25 parts by mass or less, and 16 parts by mass or less with respect to 100 parts by mass of the rubber component. Is more preferable, and 10 parts by mass or less is particularly preferable.
  • the content of the rubber-metal adhesion promoter as a metal element is preferably 0.05 parts by mass or more, more preferably 1 part by mass or more, and 5 parts by mass with respect to 100 parts by mass of the rubber component. The following is preferable, and 3 parts by mass or less is more preferable.
  • the content of the rubber-metal adhesion promoter as a metal element is 0.05 parts by mass or more, the adhesiveness between the rubber composition and the metal member is further improved, and when it is 5 parts by mass or less, the adhesiveness is further improved. The effect of the rubber component on the cross-linking reaction is small, and the rubber composition does not easily deteriorate.
  • the total content of the metal salt (1) of the aliphatic carboxylic acid and the compound (2) represented by the general formula (A) in the rubber-metal adhesion promoter is preferably 50% by mass or more, preferably 80% by mass. The above is more preferable, and it may be 100% by mass.
  • the unreacted product (carbon number) of the raw material used for the synthesis of the metal salt (1) of the aliphatic carboxylic acid and the compound (2) represented by the general formula (A) is contained. 2 to 25 aliphatic carboxylic acids (a) and the like) may remain.
  • the rubber composition of the present invention preferably contains silica.
  • silica By blending silica with the rubber composition, the adhesiveness of the rubber composition to the metal member can be improved even after deterioration due to moist heat.
  • silica is not particularly limited.
  • wet silica hydrous silicic acid
  • dry silica anhydrous silicic acid
  • calcium silicate aluminum silicate and the like
  • wet silica it is preferable to use wet silica.
  • the BET specific surface area (measured based on ISO 5794/1) of the silica is preferably 40 to 350 m 2 / g.
  • Silica having a BET specific surface area in this range has an advantage that it can achieve both rubber reinforcing properties and dispersibility in rubber components. From these viewpoints, silica having a BET specific surface area of 80 to 300 m 2 / g is more preferable.
  • commercially available products such as "Nipsil AQ" and “Nipsil KQ" manufactured by Tosoh Silica Co., Ltd. and "Ultrasil VN3" manufactured by Evonik Industries can be used.
  • the silica may be used alone or in combination of two or more.
  • the content of the silica is preferably 5 parts by mass or more, more preferably 7 parts by mass or more, still more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, based on 100 parts by mass of the rubber component.
  • the content of the silica is 5 parts by mass or more with respect to 100 parts by mass of the rubber component, the effect of improving the adhesiveness (moisture heat resistance deterioration resistance) of the rubber composition to the metal member after moist heat deterioration becomes large. ..
  • the rubber composition of the present invention may contain a filler other than the silica.
  • carbon black is preferable from the viewpoint of reinforcing property of the rubber composition.
  • the type of carbon black is not particularly limited.
  • any hard carbon produced by the oil furnace method can be used.
  • the type of carbon black is not particularly limited, and for example, one or more carbon blacks such as GPF, FEF, SRF, HAF, ISAF, IISAF, and SAF grade can be used.
  • the content of the carbon black is not particularly limited, but is preferably 20 to 100 parts by mass, more preferably 30 to 90 parts by mass, and 40 to 80 parts by mass with respect to 100 parts by mass of the rubber component. Is particularly preferable.
  • the reinforcing property of the rubber composition is further improved, and the content of the carbon black is 100 parts by mass of the rubber component.
  • the content of the carbon black is 100 parts by mass of the rubber component.
  • deterioration of low heat generation and deterioration of grip force can be suppressed.
  • at least one of them can be selected from GPF, FEF, and SRF, and the other can be selected from HAF, ISAF, IISAF, and SAF.
  • fillers other than the silica and carbon black include aluminum hydroxide, clay, alumina, talc, mica, kaolin, glass balloon, glass beads, calcium carbonate, magnesium carbonate, magnesium hydroxide, magnesium oxide, and oxidation.
  • examples thereof include titanium, potassium titanate, and barium sulfate.
  • a known additive to be blended in the rubber composition is appropriately blended.
  • additives include resins, curing agents, naphthols, vulcanization agents (crosslinking agents), vulcanization accelerators, vulcanization retarders, antiaging agents, reinforcing agents, vulcanization aids, and colorants.
  • the resin is not particularly limited, and various natural resins and synthetic resins can be used.
  • the resin is at least selected from the group consisting of petroleum-based resins, coal-based resins, phenol-based resins, rosin-based resins, and terpene-based resins from the viewpoint of further improving the adhesiveness of the rubber composition to the metal member. It is preferable to use one kind, and it is more preferable to use a phenolic resin. In addition, these resins may be modified.
  • phenolic resin alkylphenols such as phenol, naphthol, cresol, xylenol, p-tert-butylphenol, p-octylphenol, and p-nonylphenol can be used. These compounds having a hydroxyl group may be used alone or in combination of two or more.
  • the content of the resin is preferably in the range of 0.5 to 10 parts by mass, more preferably in the range of 1 to 5 parts by mass with respect to 100 parts by mass of the rubber component.
  • the curing agent for example, hexamethylol melamine, hexamethoxymethyl melamine, pentamethoxymethylol melamine, hexaethoxymethyl melamine, hexakiss- (methoxymethyl) melamine, N, N', N "-trimethyl-N, N', N" -trimethylol melamine, N, N', N "-trimethylol melamine, N-methylol melamine, N, N'-(methoxymethyl) melamine, N, N', Further, melamine derivatives such as N "-tributyl-N, N', N" -trimethylolmelamine can be further used.
  • HMMM hexamethoxymethylmelamine
  • the content of the curing agent is preferably in the range of 1 to 10 parts by mass, more preferably in the range of 3 to 7 parts by mass with respect to 100 parts by mass of the rubber component.
  • the naphthol examples include ⁇ -naphthol and the like.
  • the adhesiveness between the rubber composition and the metal member can be further improved.
  • the content of naphthol is preferably in the range of 0.5 to 5 parts by mass, more preferably in the range of 1 to 3 parts by mass with respect to 100 parts by mass of the rubber component.
  • Sulfur is preferable as the vulcanizing agent (crosslinking agent).
  • the sulfur is not particularly limited, and examples thereof include powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and oil-treated sulfur.
  • the content of the vulcanizing agent (crosslinking agent) is preferably in the range of 0.01 to 10 parts by mass, more preferably in the range of 1 to 10 parts by mass, and 2 to 8 parts by mass with respect to 100 parts by mass of the rubber component. The range is even more preferred.
  • vulcanization accelerator examples include a sulfenamide-based vulcanization accelerator, a thiazole-based vulcanization accelerator, and the like.
  • sulfenamide sulfide accelerating agent examples include N-cyclohexyl-2-benzothiazolesulfenamide (CZ, CBS), N-tert-butyl-2-benzothiazolesulfenamide (NS, BBS), N.
  • thiazole-based vulcanization accelerator 2-mercaptobenzothiazole (M) and the like can be mentioned.
  • the content of the vulcanization accelerator is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 8 parts by mass, and even more preferably 0.3 to 6 parts by mass with respect to 100 parts by mass of the rubber component. preferable.
  • the rubber composition of the present invention does not contain cobalt from the viewpoint of complying with environmentally friendly regulations, specifically, the content of the cobalt compound is 100 parts by mass of the rubber component. It is preferably 0.01 part by mass or less, and more preferably does not contain a cobalt compound except for unavoidable impurities.
  • the method for preparing the rubber composition of the present invention is not particularly limited, and a known method can be used.
  • a rubber component, a modified polymer, a rubber-metal adhesion promoter, and other optional components may be added simultaneously or in any order to form a kneader such as a Banbury mixer, a roll, or an internal mixer. Obtained by using and kneading.
  • the use of the rubber composition according to the present invention is not particularly limited, and can be used for any rubber article such as a hose, a conveyor belt, a rubber crawler, a tire, an electric wire, and a vibration-proof material.
  • the rubber-metal complex of the present invention is characterized by comprising the above-mentioned rubber composition of the present invention and a metal member.
  • the rubber-metal composite of the present invention has excellent adhesiveness between a rubber (rubber composition) and a metal member.
  • the rubber-metal composite of the present invention may be in contact with the above-mentioned rubber composition of the present invention and a metal member.
  • a part or all of a metal wire which is a metal member is covered with the rubber composition.
  • It may be an embodiment in which a rubber layer made of a rubber composition is laminated on at least one surface side of a layer made of a metal wire.
  • the metal member is a part made of metal, for example, a metal wire, a metal cord made by twisting a plurality of the metal wires (metal steel wires), or a metal made of a single wire of the metal wire. It can have various forms such as a cord, a metal spring, a metal plate, a metal ring, and the like.
  • the metal type of the metal member is not particularly limited, and can be appropriately selected depending on the intended use, such as steel, iron, copper, and gold.
  • the metal member may or may not be plated.
  • the type of plating is not particularly limited, and known plating such as brass plating, zinc plating, chrome plating, and nickel plating can be appropriately adopted.
  • the metal member is a metal wire, it is preferable that one or more types of plating selected from the group consisting of brass plating and zinc plating are performed.
  • the method for producing the rubber-metal complex of the present invention is not particularly limited, and a known method can be appropriately adopted.
  • the composite in a composite in which a metal wire is coated with a rubber composition, the composite can be obtained by vulcanizing the rubber composition in a state where the metal wire is coated with the rubber composition.
  • the composite in a composite in which a rubber layer made of a rubber composition is laminated on at least one surface side of a layer made of a metal wire, for example, the composite is manufactured by the method for producing a laminated body described in International Publication No. 2017/056414. Can be obtained.
  • the hose of the present invention is characterized by comprising the rubber-metal complex described above.
  • the hose of the present invention has excellent durability because it has a rubber-metal adhesiveness equal to or higher than that when a rubber composition containing a cobalt salt is used.
  • the hose of the present invention is not particularly limited except that the rubber-metal composite is used, and a known hose configuration and manufacturing method can be adopted.
  • the hose is a metal located between an inner rubber layer (inner tube rubber) located on the inner side in the radial direction, an outer surface rubber layer located on the outer side in the radial direction, and the inner surface rubber layer and the outer surface rubber layer. It has a reinforcing layer (metal member). Then, in one embodiment, the above-mentioned rubber composition can be used for at least one of the inner surface rubber layer and the outer surface rubber layer.
  • the conveyor belt of the present invention is characterized by comprising the above-mentioned rubber-metal composite.
  • the conveyor belt of the present invention has excellent durability because it has a rubber-metal adhesiveness equal to or higher than that when a rubber composition containing a cobalt salt is used.
  • the conveyor belt of the present invention is not particularly limited except that the rubber-metal composite is used, and a known conveyor belt configuration and manufacturing method can be adopted.
  • the rubber-metal composite of the present invention is used on a conveyor belt, at least under a metal reinforcing material (metal member) made of a steel cord or the like, such as a drive pulley, a driven pulley, and a shape-retaining rotor. It can be used for the surface rubber (bottom cover rubber) on the inner peripheral side that comes into contact with the metal reinforcing material, and can also be used for the surface rubber (top cover rubber) on the outer peripheral side that comes into contact with the transported article on the upper side of the metal reinforcing material.
  • a metal reinforcing material is sandwiched between rubber sheets made of the above rubber composition, and the rubber sheet is heat-pressed and vulcanized and bonded to bond rubber to the metal reinforcing material. Covering is mentioned.
  • the rubber crawler of the present invention is characterized by comprising the above-mentioned rubber-metal complex.
  • the rubber crawler of the present invention has excellent durability because it has a rubber-metal adhesiveness equal to or higher than that when a rubber composition containing a cobalt salt is used.
  • the rubber crawler of the present invention is not particularly limited except that the rubber-metal composite is used, and a known rubber crawler configuration and manufacturing method can be adopted.
  • the rubber crawler includes a steel cord (metal member), an intermediate rubber layer covering the steel cord, a core metal (metal member) arranged on the intermediate rubber layer, and the intermediate rubber layer. It is provided with a main body rubber layer surrounding the main body and the core metal, and further has a plurality of lugs on the ground contact surface side of the main body rubber layer.
  • the above-mentioned rubber composition may be used for any part of the rubber crawler.
  • the tire of the present invention is characterized by comprising the above-mentioned rubber-metal complex.
  • the tire of the present invention has excellent durability because it has a rubber-metal adhesiveness equal to or higher than that when a rubber composition containing a cobalt salt is used.
  • the tire of the present invention is not particularly limited except that the rubber-metal composite of the present invention described above is used, and a known tire configuration and manufacturing method can be adopted.
  • the application site of the rubber-metal complex of the present invention in a tire is not particularly limited and may be appropriately selected depending on the intended purpose, and examples thereof include carcass, belts and bead cores.
  • a method for manufacturing the tire a conventional method can be used. For example, on a tire forming drum, a member used for normal tire manufacturing such as a carcass and a belt (rubber-metal composite) made of an unvulcanized rubber composition and a metal cord, a tread made of an unvulcanized rubber composition, etc. Stack them one after another and remove the drums to make green tires. Then, by heating and vulcanizing this green tire according to a conventional method, a desired tire (for example, a pneumatic tire) can be manufactured.
  • the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.
  • the blending amount means parts by mass unless otherwise specified.
  • Examples 1 to 6 Comparative Examples 1 to 4
  • the compounding components were kneaded using a normal Banbury mixer to obtain each sample of the rubber composition.
  • test piece A galvanized steel cord having a diameter of 0.39 mm is sandwiched with a rubber sheet having a thickness of 1 mm and made of a rubber composition obtained by the formulation shown in Table 1, and pressed at 155 ° C. for 30 minutes. Vulcanization was performed to prepare a test piece.
  • Silica "Nipsil AQ” manufactured by Tosoh Silica Co., Ltd. * 7 Oil: A / O MIX, manufactured by Sankyo Yuka Kogyo Co., Ltd.
  • Anti-aging agent N-phenyl-N'-(1,3-dimethylbutyl) -p-phenylenediamine, Ouchi Shinko Kagaku Kogyo ( Made by Co., Ltd., trade name "Nocrack 6C” * 9 Zinc Oxide: Made by Hakusui Tech Co., Ltd., Product name "No. 3 Zinc Oxide” * 10 Zinc dimethacrylate: Product name "Actor ZMA" manufactured by Kawaguchi Chemical Industry Co., Ltd.
  • the samples (rubber-metal composite) of Examples 3 to 6 in which the steel cord was coated with the rubber composition containing the modified polymer, the rubber-metal adhesion promoter, and silica were moisture resistant. It can be seen that the thermal deterioration property is also significantly improved.
  • the rubber composition of the present invention can be used for a rubber-metal composite, and the rubber-metal composite of the present invention can be used for hoses, conveyor belts, rubber crawlers, tires and the like.

Abstract

The present invention addresses the problem of providing a rubber composition having excellent adhesiveness to metallic members. The rubber composition comprises a rubber component, a modified polymer, and a rubber-metal adhesion promoter, wherein the modified polymer is contained in an amount of 50 parts by mass or less per 100 parts by mass of the rubber component and the rubber-metal adhesion promoter comprises one or more compounds selected from the group consisting of aliphatic carboxylic acid/metal salts (1) (excluding zinc dimethacrylate) and compounds (2) represented by formula (A): [(RCOO)xMO]3Z, the aliphatic carboxylic acids of the metal salts (1) each having 2-25 carbon atoms, the metals of the metal salts (1) each being Bi, Zn, Cu, Sb, Ag, Nb, or Zr. In the formula (A), (RCOO) is a residue of an aliphatic carboxylic acid having 2-25 carbon atoms, M is Bi, Zn, Cu, Sb, Ag, Nb, or Zr, x is an integer of 1 to [(valence of M)-1], and Z is a structure selected from among formulae (z-1) to (z-4).

Description

ゴム組成物、ゴム－金属複合体、ホース、コンベヤベルト、ゴムクローラ及びタイヤRubber compositions, rubber-metal composites, hoses, conveyor belts, rubber crawlers and tires
　本発明は、ゴム組成物、ゴム－金属複合体、ホース、コンベヤベルト、ゴムクローラ及びタイヤに関するものである。 The present invention relates to rubber compositions, rubber-metal composites, hoses, conveyor belts, rubber crawlers and tires.
　従来、ホース、コンベヤベルト、ゴムクローラ、タイヤ等のゴム製品の性能を高めるために、例えば、真鍮でメッキされたスチールコード等の補強材を、天然ゴムや合成ゴム等を含むゴム組成物で被覆したゴム－金属複合体を使用している。また、上述した補強材と、被覆ゴム（ゴム組成物）との接着力を向上させるため、ゴム組成物中に接着促進剤を含有させることが知られている。該接着促進剤としては、スチールコード等の金属部材と、被覆ゴムとの接着性を向上できる点から、有機酸コバルト塩（例えば、ステアリン酸コバルト、バーサチック酸コバルト、ナフテン酸コバルト等）等が一般的に使用されている。 Conventionally, in order to improve the performance of rubber products such as hoses, conveyor belts, rubber crawlers, and tires, for example, reinforcing materials such as brass-plated steel cords are coated with a rubber composition containing natural rubber, synthetic rubber, and the like. A rubber-metal composite is used. Further, it is known that an adhesion promoter is contained in the rubber composition in order to improve the adhesive force between the above-mentioned reinforcing material and the coated rubber (rubber composition). As the adhesion accelerator, an organic acid cobalt salt (for example, cobalt stearate, cobalt versatic acid, cobalt naphthenate, etc.) is generally used from the viewpoint of improving the adhesiveness between a metal member such as a steel cord and a coated rubber. Is used for.
　しかしながら、近年、欧州の「化学物質の登録、評価、認可および制限」に関する規則（ＲＥＡＣＨ規則）のように、環境規制の動きがあり、上述した接着促進剤として使用されている有機酸コバルト塩についても、ＲＥＡＣＨ規則等の規制の候補に挙がっている。そのため、非コバルト系の接着促進剤の開発が望まれている。 However, in recent years, there have been movements in environmental regulations such as the European Regulation on "Registration, Evaluation, Authorization and Restriction of Chemical Substances" (REACH Regulation), and organic acid cobalt salts used as the above-mentioned adhesion promoters have been introduced. Is also listed as a candidate for regulations such as the REACH regulation. Therefore, the development of a non-cobalt-based adhesion promoter is desired.
　これに対して、例えば、下記特許文献１には、コバルトを含有せずとも、ゴム－金属間に高い接着力を奏することができる接着促進剤や、該接着促進剤を含むゴム組成物及びタイヤに関する技術が開示されている。 On the other hand, for example, the following Patent Document 1 describes an adhesion promoter capable of exerting a high adhesive force between a rubber and a metal without containing cobalt, and a rubber composition and a tire containing the adhesive promoter. The technology related to is disclosed.
国際公開第２０１６／０３９３７５号International Publication No. 2016/039375
　しかしながら、本発明者らが検討したところ、上記特許文献１に記載の接着促進剤を含むゴム組成物は、金属部材に対する接着が必ずしも十分でなく、有機酸コバルト塩を含有しなくても、金属部材に対する接着性を更に向上させたゴム組成物が求められている。 However, as a result of studies by the present inventors, the rubber composition containing the adhesion promoter described in Patent Document 1 is not always sufficiently adhered to a metal member, and even if it does not contain an organic acid cobalt salt, it is a metal. There is a demand for a rubber composition having further improved adhesiveness to a member.
　そこで、本発明は、上記従来技術の問題を解決し、有機酸コバルト塩を含有しなくても、金属部材に対する接着性に優れるゴム組成物を提供することを課題とする。
　また、本発明は、かかるゴム組成物を用いた、ゴムと金属部材との間の接着性に優れたゴム－金属複合体、更には、かかるゴム－金属複合体を具え、優れた耐久性を有する、ホース、コンベヤベルト、ゴムクローラ及びタイヤを提供することを更なる課題とする。 Therefore, it is an object of the present invention to solve the above-mentioned problems of the prior art and to provide a rubber composition having excellent adhesiveness to a metal member even if it does not contain an organic acid cobalt salt.
Further, the present invention comprises a rubber-metal composite having excellent adhesiveness between a rubber and a metal member using such a rubber composition, and further comprising such a rubber-metal composite to provide excellent durability. It is a further task to provide a hose, a conveyor belt, a rubber crawler and a tire having the hose, a conveyor belt, and a rubber crawler.
　上記課題を解決する本発明の要旨構成は、以下の通りである。 The gist structure of the present invention that solves the above problems is as follows.
　本発明のゴム組成物は、ゴム成分と、
　変性ポリマーと、
　ゴム－金属間接着促進剤と、を含み、
　前記変性ポリマーの含有量は、前記ゴム成分１００質量部に対し、５０質量部以下であり、
　前記ゴム－金属間接着促進剤は、脂肪族カルボン酸の金属塩（１）（但し、ジメタクリル酸亜鉛を除く。）及び一般式（Ａ）：［（ＲＣＯＯ）ｘＭＯ］３Ｚで表される化合物（２）からなる群より選択される１種以上を含み、
　前記脂肪族カルボン酸の金属塩（１）の脂肪族カルボン酸は、炭素数が２～２５であり、
　前記脂肪族カルボン酸の金属塩（１）の金属は、ビスマス、亜鉛、銅、アンチモン、銀、ニオブ又はジルコニウムであり、
　前記一般式（Ａ）中、（ＲＣＯＯ）は、炭素数２～２５の脂肪族カルボン酸の残基であり、Ｍは、ビスマス、亜鉛、銅、アンチモン、銀、ニオブ又はジルコニウムであり、ｘは、１以上かつ（Ｍの価数－１）の整数であり、Ｚは、下記式（ｚ－１）～（ｚ－４）から選択される構造であることを特徴とする。
Figure JPOXMLDOC01-appb-C000002
 The rubber composition of the present invention contains a rubber component and
With modified polymers
Contains rubber-metal adhesion promoters,
The content of the modified polymer is 50 parts by mass or less with respect to 100 parts by mass of the rubber component.
The rubber-metal adhesion accelerator is represented by a metal salt (1) of an aliphatic carboxylic acid (excluding zinc dimethacrylate) and a general formula (A): [ ( RCOO) x MO] 3Z. Contains one or more selected from the group consisting of compound (2).
The aliphatic carboxylic acid of the metal salt (1) of the aliphatic carboxylic acid has 2 to 25 carbon atoms.
The metal of the metal salt (1) of the aliphatic carboxylic acid is bismuth, zinc, copper, antimony, silver, niobium or zirconium.
In the general formula (A), (RCOO) is a residue of an aliphatic carboxylic acid having 2 to 25 carbon atoms, M is bismuth, zinc, copper, antimony, silver, niobium or zirconium, and x is. It is an integer of 1 or more and (valence of M-1), and Z is characterized by having a structure selected from the following formulas (z-1) to (z-4).
Figure JPOXMLDOC01-appb-C000002
　また、本発明のゴム－金属複合体は、上記のゴム組成物と、金属部材と、を具えることを特徴とする。 Further, the rubber-metal composite of the present invention is characterized by comprising the above-mentioned rubber composition and a metal member.
　また、本発明のホースは、上記のゴム－金属複合体を具えることを特徴とする。 Further, the hose of the present invention is characterized by having the above-mentioned rubber-metal composite.
　また、本発明のコンベヤベルトは、上記のゴム－金属複合体を具えることを特徴とする。 Further, the conveyor belt of the present invention is characterized by including the above-mentioned rubber-metal composite.
　また、本発明のゴムクローラは、上記のゴム－金属複合体を具えることを特徴とする。 Further, the rubber crawler of the present invention is characterized by including the above-mentioned rubber-metal complex.
　また、本発明のタイヤは、上記のゴム－金属複合体を具えることを特徴とする。 Further, the tire of the present invention is characterized by having the above-mentioned rubber-metal composite.
　本発明によれば、有機酸コバルト塩を含有しなくても、金属部材に対する接着性に優れるゴム組成物を提供することができる。
　また、本発明によれば、ゴムと金属部材との間の接着性に優れたゴム－金属複合体、更には、優れた耐久性を有する、ホース、コンベヤベルト、ゴムクローラ及びタイヤを提供することができる。 According to the present invention, it is possible to provide a rubber composition having excellent adhesiveness to a metal member without containing an organic acid cobalt salt.
Further, according to the present invention, there is provided a rubber-metal composite having excellent adhesion between rubber and a metal member, and further, a hose, a conveyor belt, a rubber crawler and a tire having excellent durability. Can be done.
　以下に、本発明のゴム組成物、ゴム－金属複合体、ホース、コンベヤベルト、ゴムクローラ及びタイヤを、その実施形態に基づき、詳細に例示説明する。 Hereinafter, the rubber composition, rubber-metal composite, hose, conveyor belt, rubber crawler, and tire of the present invention will be illustrated in detail based on the embodiments thereof.
＜ゴム組成物＞
　本発明のゴム組成物は、ゴム成分と、変性ポリマーと、ゴム－金属間接着促進剤と、を含む。ここで、前記変性ポリマーの含有量は、前記ゴム成分１００質量部に対し、５０質量部以下であり、
　前記ゴム－金属間接着促進剤は、脂肪族カルボン酸の金属塩（１）（但し、ジメタクリル酸亜鉛を除く。）及び一般式（Ａ）：［（ＲＣＯＯ）ｘＭＯ］３Ｚで表される化合物（２）からなる群より選択される１種以上を含み、
　前記脂肪族カルボン酸の金属塩（１）の脂肪族カルボン酸は、炭素数が２～２５であり、前記脂肪族カルボン酸の金属塩（１）の金属は、ビスマス、亜鉛、銅、アンチモン、銀、ニオブ又はジルコニウムであり、
　前記一般式（Ａ）中、（ＲＣＯＯ）は、炭素数２～２５の脂肪族カルボン酸の残基であり、Ｍは、ビスマス、亜鉛、銅、アンチモン、銀、ニオブ又はジルコニウムであり、ｘは、１以上かつ（Ｍの価数－１）の整数であり、Ｚは、下記式（ｚ－１）～（ｚ－４）から選択される構造であることを特徴とする。
Figure JPOXMLDOC01-appb-C000003
 <Rubber composition>
The rubber composition of the present invention contains a rubber component, a modified polymer, and a rubber-metal adhesion promoter. Here, the content of the modified polymer is 50 parts by mass or less with respect to 100 parts by mass of the rubber component.
The rubber-metal adhesion accelerator is represented by a metal salt (1) of an aliphatic carboxylic acid (excluding zinc dimethacrylate) and a general formula (A): [ ( RCOO) x MO] 3Z. Contains one or more selected from the group consisting of compound (2).
The aliphatic carboxylic acid of the metal salt of the aliphatic carboxylic acid (1) has 2 to 25 carbon atoms, and the metal of the metal salt of the aliphatic carboxylic acid (1) is bismuth, zinc, copper, antimonate, and the like. Silver, niobium or zirconium,
In the general formula (A), (RCOO) is a residue of an aliphatic carboxylic acid having 2 to 25 carbon atoms, M is bismuth, zinc, copper, antimony, silver, niobium or zirconium, and x is. It is an integer of 1 or more and (valence of M-1), and Z is characterized by having a structure selected from the following formulas (z-1) to (z-4).
Figure JPOXMLDOC01-appb-C000003
　本発明のゴム組成物においては、脂肪族カルボン酸の金属塩（１）及び一般式（Ａ）で表される化合物（２）からなる群より選択される１種以上を含むゴム－金属間接着促進剤が、金属部材との接着性の向上に寄与する。但し、上述のように、該ゴム－金属間接着促進剤を含むだけでは、ゴム組成物の金属部材に対する接着は、十分とは言えない。
　これに対して、本発明のゴム組成物においては、前記ゴム－金属間接着促進剤に加えて、変性ポリマーを含むことで、ゴム－金属間接着促進剤と変性ポリマーとの相乗効果により、ゴム組成物の金属部材に対する接着性を大幅に向上させることができる。
　従って、本発明のゴム組成物は、有機酸コバルト塩を含有しなくても、金属部材に対する接着性に優れる。 In the rubber composition of the present invention, a rubber-metal bond containing at least one selected from the group consisting of a metal salt of an aliphatic carboxylic acid (1) and a compound (2) represented by the general formula (A). The accelerator contributes to the improvement of the adhesiveness with the metal member. However, as described above, it cannot be said that the adhesion of the rubber composition to the metal member is sufficient only by containing the rubber-metal adhesion promoter.
On the other hand, in the rubber composition of the present invention, by containing the modified polymer in addition to the rubber-metal adhesion promoter, the rubber is produced by the synergistic effect of the rubber-metal adhesion promoter and the modified polymer. The adhesiveness of the composition to the metal member can be significantly improved.
Therefore, the rubber composition of the present invention is excellent in adhesiveness to metal members even if it does not contain an organic acid cobalt salt.
（ゴム成分）
　本発明のゴム組成物は、ゴム成分を含む。該ゴム成分については、特に限定されず、従来ゴム組成物において用いられるゴム成分を用いることができる。例えば、前記ゴム成分としては、天然ゴム（ＮＲ）、イソプレンゴム（ＩＲ）、ブタジエンゴム（ＢＲ）、スチレン－ブタジエンゴム（ＳＢＲ）、スチレン－イソプレンゴム（ＳＩＲ）、スチレン－イソプレン－ブタジエンゴム（ＳＩＢＲ）、エチレン－プロピレン－ジエンゴム（ＥＰＤＭ）、アクリロニトリル－ブタジエンゴム（ＮＢＲ）、クロロプレンゴム（ＣＲ）、ブチルゴム（ＩＩＲ）、これらの変性ゴム等を用いることができる。これらゴム成分は、１種単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 (Rubber component)
The rubber composition of the present invention contains a rubber component. The rubber component is not particularly limited, and a rubber component conventionally used in a rubber composition can be used. For example, the rubber components include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), styrene-isoprene rubber (SIR), and styrene-isoprene-butadiene rubber (SIBR). ), Ethylene-propylene-diene rubber (EPDM), acrylonitrile-butadiene rubber (NBR), chloroprene rubber (CR), butyl rubber (IIR), modified rubbers thereof and the like can be used. These rubber components may be used alone or in combination of two or more.
　本発明のゴム組成物のゴム成分は、天然ゴム及びスチレン－ブタジエンゴムからなる群より選択される１種以上を含むことが好ましい。天然ゴムは、伸長結晶化し易く、破壊特性に優れる。また、スチレン－ブタジエンゴムも、破壊特性に優れる。そのため、ゴム成分が、天然ゴム及び／又はスチレン－ブタジエンゴムを含むことで、ゴム組成物の破壊特性が向上する。また、ゴム成分が天然ゴム及びスチレン－ブタジエンゴムを含む場合、ゴム組成物の破壊特性に加えて、加工性も向上させることができる。
　ゴム成分中の天然ゴム及びスチレン－ブタジエンゴムの合計含有率は、特に限定はされないが、１０質量％以上であることが好ましく、２０質量％以上であることがより好ましく、また、１００質量％であってもよい。 The rubber component of the rubber composition of the present invention preferably contains at least one selected from the group consisting of natural rubber and styrene-butadiene rubber. Natural rubber is easily stretched and crystallized and has excellent fracture properties. Styrene-butadiene rubber also has excellent fracture properties. Therefore, when the rubber component contains natural rubber and / or styrene-butadiene rubber, the breaking property of the rubber composition is improved. When the rubber component contains natural rubber and styrene-butadiene rubber, the processability can be improved in addition to the destructive properties of the rubber composition.
The total content of the natural rubber and the styrene-butadiene rubber in the rubber component is not particularly limited, but is preferably 10% by mass or more, more preferably 20% by mass or more, and 100% by mass. There may be.
（変性ポリマー）
　本発明のゴム組成物は、変性ポリマーを含む。ゴム組成物が変性ポリマーを含むことで、ゴム組成物の金属部材に対する接着性を向上させることができる。
　なお、該変性ポリマーは、室温（２５℃）でゴム弾性を示さず、上述のゴム成分とは異なる。また、該変性ポリマーは、好ましくは、室温（２５℃）において、液状である。 (Denatured polymer)
The rubber composition of the present invention comprises a modified polymer. When the rubber composition contains the modified polymer, the adhesiveness of the rubber composition to the metal member can be improved.
The modified polymer does not exhibit rubber elasticity at room temperature (25 ° C.) and is different from the above-mentioned rubber component. Further, the modified polymer is preferably liquid at room temperature (25 ° C.).
　前記変性ポリマーは、分子内に、－ＣＯＯＨ、－ＯＨ及び－ＣＯＯＲ（ここで、Ｒは、一価の炭化水素基である。）からなる群より選択される１種以上の官能基を含むことが好ましい。分子内に、－ＣＯＯＨ、－ＯＨ及び－ＣＯＯＲを有する変性ポリマーをゴム組成物に配合することで、ゴム組成物と金属部材との間の接着性を更に向上させることができる。
　なお、前記Ｒとしての一価の炭化水素基としては、脂肪族炭化水素基、脂環式炭化水素基、芳香族炭化水素基等が挙げられる。また、脂肪族炭化水素基としては、アルキル基、アルケニル基等が挙げられ、脂環式炭化水素基としては、シクロアルキル基、シクロアルケニル基等が挙げられ、芳香族炭化水素基としては、アリール基、アリーレン基等が挙げられる。
　また、前記一価の炭化水素基の炭素数は、１～２０の範囲が好ましく、１～１０の範囲が更に好ましく、１～４の範囲がより一層好ましい。 The modified polymer contains, in its molecule, one or more functional groups selected from the group consisting of -COOH, -OH and -COOR (where R is a monovalent hydrocarbon group). Is preferable. By blending a modified polymer having —COOH, —OH and —COOR in the molecule into the rubber composition, the adhesiveness between the rubber composition and the metal member can be further improved.
Examples of the monovalent hydrocarbon group as R include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Examples of the aliphatic hydrocarbon group include an alkyl group and an alkenyl group, examples of the alicyclic hydrocarbon group include a cycloalkyl group and a cycloalkenyl group, and examples of the aromatic hydrocarbon group include aryl. Groups, arylene groups and the like can be mentioned.
The carbon number of the monovalent hydrocarbon group is preferably in the range of 1 to 20, more preferably in the range of 1 to 10, and even more preferably in the range of 1 to 4.
　前記変性ポリマーの主鎖は、特に限定されず、種々のモノマー単位を含むことができる。該変性ポリマーの主鎖を構成する原料モノマーとしては、イソプレン、ブタジエン等が挙げられる。これらの中でも、イソプレンが好ましい。
　前記変性ポリマーは、ポリマー鎖を、マレイン酸、無水マレイン酸等で変性することで合成することができ、また、市販品を利用することもできる。 The backbone of the modified polymer is not particularly limited and may contain various monomer units. Examples of the raw material monomer constituting the main chain of the modified polymer include isoprene and butadiene. Of these, isoprene is preferred.
The modified polymer can be synthesized by modifying the polymer chain with maleic acid, maleic anhydride or the like, or a commercially available product can also be used.
　前記変性ポリマーは、上述のゴム成分よりも分子量が低いことが好ましく、ポリスチレン換算の数平均分子量（Ｍｎ）が１，０００～１００，０００であることが好ましく、５，０００～８０，０００であることが更に好ましく、１０，０００～５０，０００であることがより一層好ましい。 The modified polymer preferably has a lower molecular weight than the above-mentioned rubber component, and has a polystyrene-equivalent number average molecular weight (Mn) of 1,000 to 100,000, preferably 5,000 to 80,000. It is more preferably 10,000 to 50,000, and even more preferably 10,000 to 50,000.
　前記変性ポリマーの含有量は、金属部材に対する接着性を向上させる観点から、前記ゴム成分１００質量部に対して、５０質量部以下であり、１～５０質量部の範囲が好ましく、３～３０質量部の範囲が更に好ましい。 The content of the modified polymer is 50 parts by mass or less, preferably 1 to 50 parts by mass, and 3 to 30 parts by mass with respect to 100 parts by mass of the rubber component from the viewpoint of improving the adhesiveness to the metal member. The range of parts is more preferable.
（ゴム－金属間接着促進剤）
　本発明のゴム組成物は、ゴム－金属間接着促進剤を含む。該ゴム－金属間接着促進剤は、脂肪族カルボン酸の金属塩（１）（但し、ジメタクリル酸亜鉛を除く。）及び一般式（Ａ）：［（ＲＣＯＯ）ｘＭＯ］３Ｚで表される化合物（２）からなる群より選択される１種以上を含む。ゴム組成物が、ゴム－金属間接着促進剤として、脂肪族カルボン酸の金属塩（１）及び／又は一般式（Ａ）で表される化合物（２）を含むことで、金属部材との接着性を向上させることができる。 (Rubber-metal adhesion promoter)
The rubber composition of the present invention contains a rubber-metal adhesion promoter. The rubber-metal adhesion accelerator is represented by a metal salt (1) of an aliphatic carboxylic acid (excluding zinc dimethacrylate) and a general formula (A): [ ( RCOO) x MO] 3Z. Contains one or more selected from the group consisting of the compound (2). The rubber composition contains, as a rubber-metal adhesion promoter, a metal salt (1) of an aliphatic carboxylic acid and / or a compound (2) represented by the general formula (A), thereby adhering to a metal member. It is possible to improve the sex.
－－脂肪族カルボン酸の金属塩（１）－－
　前記脂肪族カルボン酸の金属塩（１）において、脂肪族カルボン酸は、炭素数が２～２５であり、また、金属塩の金属種は、ビスマス（Ｂｉ）、亜鉛（Ｚｎ）、銅（Ｃｕ）、アンチモン（Ｓｂ）、銀（Ａｇ）、ニオブ（Ｎｂ）又はジルコニウム（Ｚｒ）である。但し、本発明において、前記脂肪族カルボン酸の金属塩（１）からは、ジメタクリル酸亜鉛を除く。 --Metal salt of aliphatic carboxylic acid (1) ---
In the metal salt (1) of the aliphatic carboxylic acid, the aliphatic carboxylic acid has 2 to 25 carbon atoms, and the metal species of the metal salt are bismuth (Bi), zinc (Zn), and copper (Cu). ), Antimony (Sb), silver (Ag), niobium (Nb) or zirconium (Zr). However, in the present invention, zinc dimethacrylate is excluded from the metal salt (1) of the aliphatic carboxylic acid.
　前記脂肪族カルボン酸として、炭素数が２以上の脂肪族カルボン酸を用いた場合、脂肪族カルボン酸の金属塩（１）のゴム成分との相溶性が向上し、その結果として、金属部材とゴム組成物との間の接着力が向上する。また、脂肪族カルボン酸として、炭素数が２５以下の脂肪族カルボン酸を用いた場合、脂肪族カルボン酸の金属塩（１）の合成が容易である。ここで、脂肪族カルボン酸の炭素数とは、カルボキシル基の炭素原子数を含めた数を言う。 When an aliphatic carboxylic acid having 2 or more carbon atoms is used as the aliphatic carboxylic acid, the compatibility of the metal salt (1) of the aliphatic carboxylic acid with the rubber component is improved, and as a result, the metal member and the metal member The adhesive strength with the rubber composition is improved. Further, when an aliphatic carboxylic acid having 25 or less carbon atoms is used as the aliphatic carboxylic acid, the synthesis of the metal salt (1) of the aliphatic carboxylic acid is easy. Here, the carbon number of the aliphatic carboxylic acid means the number including the number of carbon atoms of the carboxyl group.
　前記脂肪族カルボン酸の金属塩（１）の金属は、ビスマスであることが好ましい。ゴム組成物が、脂肪族カルボン酸のビスマス塩を含む場合、ゴム組成物と金属部材との間の接着性が更に向上する。 The metal of the metal salt (1) of the aliphatic carboxylic acid is preferably bismuth. When the rubber composition contains a bismuth salt of an aliphatic carboxylic acid, the adhesiveness between the rubber composition and the metal member is further improved.
　前記脂肪族カルボン酸の金属塩（１）の脂肪族カルボン酸は、脂肪族モノカルボン酸又は脂肪族ジカルボン酸であることが好ましい。ゴム組成物が、脂肪族モノカルボン酸又は脂肪族ジカルボン酸の金属塩を含む場合、ゴム組成物と金属部材との間の接着性が更に向上する。 The aliphatic carboxylic acid of the metal salt (1) of the aliphatic carboxylic acid is preferably an aliphatic monocarboxylic acid or an aliphatic dicarboxylic acid. When the rubber composition contains a metal salt of an aliphatic monocarboxylic acid or an aliphatic dicarboxylic acid, the adhesiveness between the rubber composition and the metal member is further improved.
　前記脂肪族モノカルボン酸としては、例えば、飽和の脂肪族モノカルボン酸、不飽和の脂肪族モノカルボン酸等が挙げられる。
　前記飽和の脂肪族モノカルボン酸としては、例えば、エタン酸、プロパン酸、ブタン酸、ペンタン酸、ヘキサン酸、２－エチルヘキサン酸、ヘプタン酸、オクタン酸、ノナン酸、イソノナン酸、デカン酸、ネオデカン酸、ドデカン酸、テトラデカン酸、ヘキサデカン酸、ヘプタデカン酸、オクタデカン酸、エイコサン酸、ドコサン酸、テトラコサン酸、ナフテン酸等が挙げられる。
　また、前記不飽和の脂肪族モノカルボン酸としては、例えば、９－ヘキサデセン酸、ｃｉｓ－９－オクタデセン酸、１１－オクタデセン酸、ｃｉｓ，ｃｉｓ－９，１２－オクタデカジエン酸、９，１２，１５－オクタデカトリエン酸、６，９，１２－オクタデカトリエン酸、９，１１，１３－オクタデカトリエン酸、エイコサン酸、８，１１－エイコサジエン酸、５，８，１１－エイコサトリエン酸、５，８，１１，１４－エイコサテトラエン酸、桐油脂肪酸、アマニ脂肪油酸、大豆油脂肪酸、トール油脂肪酸、樹脂酸、ロジン酸、アビエチン酸、ネオアビエチン酸、パラストリン酸、ピマール酸、デヒドロアビエチン酸等が挙げられる。 Examples of the aliphatic monocarboxylic acid include saturated aliphatic monocarboxylic acids and unsaturated aliphatic monocarboxylic acids.
Examples of the saturated aliphatic monocarboxylic acid include ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexanic acid, 2-ethylhexanoic acid, heptanic acid, octanoic acid, nonanoic acid, isononanoic acid, decanoic acid and neodecane. Examples thereof include acids, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, eicosanoic acid, docosanoic acid, tetracosanoic acid, naphthenic acid and the like.
Examples of the unsaturated aliphatic monocarboxylic acid include 9-hexadecenoic acid, cis-9-octadecenoic acid, 11-octadecenoic acid, cis, cis-9,12-octadecadienoic acid, 9,12, 15-Octadecatorienic acid, 6,9,12-octadecatorienic acid, 9,11,13-octadecatrienoic acid, Eikosanoic acid, 8,11-Eikosadienoic acid, 5,8,11-Eicosatrioenic acid, 5,8,11,14-Eikosatetraenoic acid, tung oil fatty acid, linseed fatty oil acid, soybean oil fatty acid, tall oil fatty acid, resin acid, loginic acid, avietic acid, neoavietic acid, palastolic acid, pimalic acid, dehydro Examples include avietic acid.
　前記脂肪族ジカルボン酸としては、例えば、飽和の脂肪族ジカルボン酸、不飽和の脂肪族ジカルボン酸等が挙げられる。
　前記飽和の脂肪族ジカルボン酸としては、例えば、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸等が挙げられる。
　また、前記不飽和の脂肪族ジカルボン酸としては、例えば、フマル酸、マレイン酸等が挙げられる。 Examples of the aliphatic dicarboxylic acid include saturated aliphatic dicarboxylic acid and unsaturated aliphatic dicarboxylic acid.
Examples of the saturated aliphatic dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid and the like.
Examples of the unsaturated aliphatic dicarboxylic acid include fumaric acid and maleic acid.
　前記脂肪族カルボン酸の中でも、ゴム成分の硫黄架橋に影響を及ぼし難く、コンベヤベルト、ホース、ゴムクローラ、タイヤ等に使用するのに適した、ゴム物性への悪影響が少ないゴム硬化物が得られることから、飽和の脂肪族モノカルボン酸が好ましい。また、飽和の脂肪族モノカルボン酸の中でも、炭素数２～２０の飽和の脂肪族モノカルボン酸が好ましく、２－エチルヘキサン酸、ネオデカン酸、ヘキサデカン酸及びオクタデカン酸がより好ましく、２－エチルヘキサン酸が特に好ましい。
　また、前記脂肪族カルボン酸の金属塩（１）の脂肪族カルボン酸が、炭素数２～２０の飽和脂肪族モノカルボン酸である場合、ゴム組成物と金属部材との間の接着性が更に向上する。
　また、前記飽和脂肪族モノカルボン酸が、２－エチルヘキサン酸、ネオデカン酸、ヘキサデカン酸又はオクタデカン酸である場合、ゴム組成物と金属部材との間の接着性がより一層向上する。 Among the aliphatic carboxylic acids, a cured rubber product that does not easily affect the sulfur cross-linking of the rubber component, is suitable for use in conveyor belts, hoses, rubber crawlers, tires, etc., and has little adverse effect on rubber physical properties can be obtained. Therefore, a saturated aliphatic monocarboxylic acid is preferable. Among the saturated aliphatic monocarboxylic acids, saturated aliphatic monocarboxylic acids having 2 to 20 carbon atoms are preferable, 2-ethylhexanoic acid, neodecanoic acid, hexadecanoic acid and octadecanoic acid are more preferable, and 2-ethylhexane Acids are particularly preferred.
Further, when the aliphatic carboxylic acid of the metal salt (1) of the aliphatic carboxylic acid is a saturated aliphatic monocarboxylic acid having 2 to 20 carbon atoms, the adhesiveness between the rubber composition and the metal member is further improved. improves.
Further, when the saturated aliphatic monocarboxylic acid is 2-ethylhexanoic acid, neodecanoic acid, hexadecanoic acid or octadecanoic acid, the adhesiveness between the rubber composition and the metal member is further improved.
　前記脂肪族カルボン酸の金属塩（１）としては、２－エチルヘキサン酸ビスマス、２－エチルヘキサン酸亜鉛、２－エチルヘキサン酸銅、２－エチルヘキサン酸アンチモン、２－エチルヘキサン酸銀、２－エチルヘキサン酸ニオブ、２－エチルヘキサン酸ジルコニウム、ネオデカン酸ビスマス、ネオデカン酸亜鉛、ネオデカン酸銅、ネオデカン酸アンチモン、ネオデカン酸銀、ネオデカン酸ニオブ、ネオデカン酸ジルコニウム、ヘキサデカン酸ビスマス、ヘキサデカン酸亜鉛、ヘキサデカン酸銅、ヘキサデカン酸アンチモン、ヘキサデカン酸銀、ヘキサデカン酸ニオブ、ヘキサデカン酸ジルコニウム、オクタデカン酸ビスマス、オクタデカン酸亜鉛、オクタデカン酸銅、オクタデカン酸アンチモン、オクタデカン酸銀、オクタデカン酸ニオブ、オクタデカン酸ジルコニウム等が挙げられ、これらの中でも、２－エチルヘキサン酸ビスマス、ネオデカン酸ビスマス、ヘキサデカン酸ビスマス、オクタデカン酸ビスマスが好ましい。前記脂肪族カルボン酸の金属塩（１）は、１種単独で使用してもよいし、２種以上を組み合わせて使用してもよい。 Examples of the metal salt (1) of the aliphatic carboxylic acid include bismuth 2-ethylhexanoate, zinc 2-ethylhexanate, copper 2-ethylhexanoate, antimony 2-ethylhexanoate, silver 2-ethylhexanoate, and 2 -Niob ethylhexanoate, zirconium 2-ethylhexanoate, bismuth neodecanoate, zinc neodecanoate, copper neodecanoate, antimone neodecanoate, silver neodecanoate, niobium neodecanoate, zirconium neodecanoate, bismuth hexadecanoate, zinc hexadecanoate, hexadecane Examples thereof include copper acid, antimonate hexadecanoate, silver hexadecanoate, niobium hexadecanoate, zirconium hexadecanoate, bismuth octadecanoate, zinc octadecanoate, copper octadecanoate, antimonate octadecanoate, silver octadecanoate, niobium octadecanoate, zirconium octadecanoate and the like. Among these, bismuth 2-ethylhexanoate, bismuth neodecanoate, bismuth hexadecanoate, and bismuth octadecanoate are preferable. The metal salt (1) of the aliphatic carboxylic acid may be used alone or in combination of two or more.
　前記脂肪族カルボン酸の金属塩（１）は、例えば、国際公開第２０１６／０３９３７５号に記載のような、炭素数２～２５の脂肪族カルボン酸（ａ）と、金属（ビスマス、亜鉛、銅、アンチモン、銀、ニオブ、ジルコニウム）の酸化物（ｂ－１）、金属（ビスマス、亜鉛、銅、アンチモン、銀、ニオブ、ジルコニウム）の水酸化物（ｂ－２）及び金属（ビスマス、亜鉛、銅、アンチモン、銀、ニオブ、ジルコニウム）の炭酸塩（ｂ－３）から選ばれる一種以上と、を直接反応させて製造する方法（直接法）や、炭素数２～２５の脂肪族カルボン酸（ａ）と水酸化ナトリウムを水の存在下で反応させて脂肪族カルボン酸のナトリウム塩を得た後、該脂肪族カルボン酸のナトリウム塩と、金属（ビスマス、亜鉛、銅、アンチモン、銀、ニオブ、ジルコニウムの金属塩）の硫酸塩（ｃ－１）、金属（ビスマス、亜鉛、銅、アンチモン、銀、ニオブ、ジルコニウム）の塩化物（ｃ－２）及び金属（ビスマス、亜鉛、銅、アンチモン、銀、ニオブ、ジルコニウム）の硝酸塩（ｃ－３）から選ばれる一種以上と、を反応させて製造する方法（複分解法）により得ることができる。 The metal salt (1) of the aliphatic carboxylic acid is, for example, an aliphatic carboxylic acid (a) having 2 to 25 carbon atoms and a metal (bismuth, zinc, copper) as described in International Publication No. 2016/039375. , Antimonate, silver, niobium, zirconium oxide (b-1), metal (bismuth, zinc, copper, antimony, silver, niobium, zirconium) hydroxide (b-2) and metal (bismuth, zinc, A method for producing by directly reacting one or more selected from carbonates (b-3) of copper, antimony, silver, niobium, zirconium (direct method), and aliphatic carboxylic acids having 2 to 25 carbon atoms (direct method). After a) and sodium hydroxide are reacted in the presence of water to obtain a sodium salt of an aliphatic carboxylic acid, the sodium salt of the aliphatic carboxylic acid and a metal (bismuth, zinc, copper, antimony, silver, niobium) are obtained. , Sulfate (c-1) of (metal salt of zirconium), chloride (c-2) of metal (bismuth, zinc, copper, antimonate, silver, niobium, zirconium) and metal (bismuth, zinc, copper, antimony, It can be obtained by a method (multi-decomposition method) produced by reacting one or more selected from nitrates (c-3) of silver, niobium, and zirconium with one or more.
－－化合物（２）－－
　前記化合物（２）は、一般式（Ａ）：［（ＲＣＯＯ）ｘＭＯ］３Ｚで表される。 --Compound (2) ---
The compound (2) is represented by the general formula (A): [ ( RCOO) x MO] 3Z.
　上記一般式（Ａ）中の（ＲＣＯＯ）は、炭素数２～２５の脂肪族カルボン酸の残基である。炭素数が２以上の脂肪族カルボン酸の残基の場合、化合物（２）のゴム成分との相溶性が向上し、その結果として、金属部材とゴム組成物との間の接着力が向上する。また、炭素数が２５以下の脂肪族カルボン酸の残基の場合、化合物（２）の合成が容易であることに加えて、化合物（２）のゴム成分中での分散性や化合物（２）の金属部材表面への吸着性が向上して、金属部材とゴム組成物との間の接着力を向上させる効果が大きくなる。ここで、（ＲＣＯＯ）の炭素数とは、カルボキシル基の炭素原子数を含めた数を言う。 (RCOO) in the above general formula (A) is a residue of an aliphatic carboxylic acid having 2 to 25 carbon atoms. In the case of a residue of an aliphatic carboxylic acid having 2 or more carbon atoms, the compatibility of the compound (2) with the rubber component is improved, and as a result, the adhesive force between the metal member and the rubber composition is improved. .. Further, in the case of a residue of an aliphatic carboxylic acid having 25 or less carbon atoms, in addition to the ease of synthesizing the compound (2), the dispersibility of the compound (2) in the rubber component and the compound (2) The adsorptivity to the surface of the metal member is improved, and the effect of improving the adhesive force between the metal member and the rubber composition is increased. Here, the carbon number of (RCOO) means the number including the number of carbon atoms of the carboxyl group.
　前記炭素数２～２５の脂肪族モノカルボン酸の残基としては、脂肪族モノカルボン酸の残基が好ましい。該脂肪族モノカルボン酸の残基としては、前記の脂肪族モノカルボン酸由来の残基を好ましく例示できる。 As the residue of the aliphatic monocarboxylic acid having 2 to 25 carbon atoms, the residue of the aliphatic monocarboxylic acid is preferable. As the residue of the aliphatic monocarboxylic acid, the residue derived from the aliphatic monocarboxylic acid can be preferably exemplified.
　前記脂肪族カルボン酸の残基の中でも、化合物（２）がゴム成分を架橋せず、金属近傍への化合物（２）の分散又は金属表面への化合物（２）の吸着をより進行させ、金属部材とゴム組成物との接着を促進する効果をより発現できることから、飽和の脂肪族モノカルボン酸の残基が好ましい。また、飽和の脂肪族モノカルボン酸の残基の中でも、炭素数２～２０の飽和の脂肪族モノカルボン酸の残基が好ましく、２－エチルヘキサン酸の残基、ネオデカン酸の残基、ヘキサデカン酸の残基及びオクタデカン酸の残基がより好ましい。
　また、前記一般式（Ａ）中、（ＲＣＯＯ）が、炭素数２～２０の飽和脂肪族モノカルボン酸の残基である場合、ゴム組成物と金属部材との間の接着性が更に向上する。また、前記飽和脂肪族モノカルボン酸が、２－エチルヘキサン酸、ネオデカン酸、ヘキサデカン酸又はオクタデカン酸である場合、ゴム組成物と金属部材との間の接着性がより一層向上する。 Among the residues of the aliphatic carboxylic acid, the compound (2) does not cross-link the rubber component and further promotes the dispersion of the compound (2) in the vicinity of the metal or the adsorption of the compound (2) on the metal surface, thereby causing the metal. Saturated aliphatic monocarboxylic acid residues are preferred because they can more exert the effect of promoting adhesion between the member and the rubber composition. Among the residues of saturated aliphatic monocarboxylic acid, the residue of saturated aliphatic monocarboxylic acid having 2 to 20 carbon atoms is preferable, the residue of 2-ethylhexanoic acid, the residue of neodecanoic acid, and hexadecane. Acid residues and octadecanoic acid residues are more preferred.
Further, in the general formula (A), when (RCOO) is a residue of a saturated aliphatic monocarboxylic acid having 2 to 20 carbon atoms, the adhesiveness between the rubber composition and the metal member is further improved. .. Further, when the saturated aliphatic monocarboxylic acid is 2-ethylhexanoic acid, neodecanoic acid, hexadecanoic acid or octadecanoic acid, the adhesiveness between the rubber composition and the metal member is further improved.
　上記一般式（Ａ）中のＭは、金属種であり、具体的には、ビスマス（Ｂｉ）、亜鉛（Ｚｎ）、銅（Ｃｕ）、アンチモン（Ｓｂ）、銀（Ａｇ）、ニオブ（Ｎｂ）又はジルコニウム（Ｚｒ）である。これら金属種の中でも、金属部材とゴム組成物との接着が良好となる観点から、Ｍとしては、ビスマスが特に好ましい。 M in the above general formula (A) is a metal species, and specifically, bismuth (Bi), zinc (Zn), copper (Cu), antimony (Sb), silver (Ag), niobium (Nb). Or zirconium (Zr). Among these metal species, bismuth is particularly preferable as M from the viewpoint of good adhesion between the metal member and the rubber composition.
　また、上記一般式（Ａ）中のｘは、１以上かつ（Ｍの価数－１）の整数である。 Further, x in the above general formula (A) is an integer of 1 or more and (valence of M-1).
　また、上記一般式（Ａ）中のＺは、下記式（ｚ－１）～式（ｚ－４）：
Figure JPOXMLDOC01-appb-C000004
 から選ばれる構造である。上記構造の中でも、金属部材とゴム組成物との間の接着力（接着性）が更に高くなることから、上記式（ｚ－１）で表される構造が好ましい。 Further, Z in the general formula (A) is the following formula (z-1) to formula (z-4) :.
Figure JPOXMLDOC01-appb-C000004
 It is a structure selected from. Among the above structures, the structure represented by the above formula (z-1) is preferable because the adhesive force (adhesiveness) between the metal member and the rubber composition is further increased.
　前記化合物（２）としては、ホウ素２－エチルヘキサン酸ビスマス、ホウ素２－エチルヘキサン酸亜鉛、ホウ素２－エチルヘキサン酸銅、ホウ素２－エチルヘキサン酸アンチモン、ホウ素２－エチルヘキサン酸銀、ホウ素２－エチルヘキサン酸ニオブ、ホウ素２－エチルヘキサン酸ジルコニウム、ホウ素ネオデカン酸ビスマス、ホウ素ネオデカン酸亜鉛、ホウ素ネオデカン酸銅、ホウ素ネオデカン酸アンチモン、ホウ素ネオデカン酸銀、ホウ素ネオデカン酸ニオブ、ホウ素ネオデカン酸ジルコニウム、ホウ素ヘキサデカン酸ビスマス、ホウ素ヘキサデカン酸亜鉛、ホウ素ヘキサデカン酸銅、ホウ素ヘキサデカン酸アンチモン、ホウ素ヘキサデカン酸銀、ホウ素ヘキサデカン酸ニオブ、ホウ素ヘキサデカン酸ジルコニウム、ホウ素オクタデカン酸ビスマス、ホウ素オクタデカン酸亜鉛、ホウ素オクタデカン酸銅、ホウ素オクタデカン酸アンチモン、ホウ素オクタデカン酸銀、ホウ素オクタデカン酸ニオブ、ホウ素オクタデカン酸ジルコニウム等が挙げられ、これらの中でも、ホウ素２－エチルヘキサン酸ビスマス、ホウ素ネオデカン酸ビスマス、ホウ素ヘキサデカン酸ビスマス、ホウ素オクタデカン酸ビスマスが好ましい。前記化合物（２）は、１種単独で使用してもよいし、２種以上を組み合わせて使用してもよい。 Examples of the compound (2) include boron 2-ethylhexanoate bismuth, boron 2-ethylhexanoate zinc, boron 2-ethylhexanoate copper, boron 2-ethylhexanoate antimony, boron 2-ethylhexanoate silver, and boron 2. -Niob ethylhexanoate, zirconium 2-ethylhexanate, boron neodecanoate bismuth, boron neodecanoate zinc, boron neodecanoate copper, boron neodecanoate antimony, boron neodecanoate silver, boron neodecanoate niobium, boron neodecanoate zirconium, boron Bismus hexadecanoate, zinc boron hexadecanoate, copper boron hexadecanoate, antimony boron hexadecanoate, silver boron hexadecanoate, niobium hexadecanoate, zirconium boron hexadecanoate, bismuth boron octadecanoate, zinc boron octadecanoate, copper octadecanoate, boron Antimon octadecanoate, silver boron octadecanoate, niobium octadecanoate boron, zirconium octadecanoate boron, etc. are mentioned. preferable. The compound (2) may be used alone or in combination of two or more.
　上記一般式（Ａ）で表される化合物（２）は、例えば、国際公開第２０１６／０３９３７５号に記載のような、炭素数２～２５の脂肪族カルボン酸（ａ）と、炭素数１～５の低級アルコールのホウ酸エステル（ｄ－１）、炭素数１～５の低級アルコールのメタホウ酸エステル（ｄ－２）、炭素数１～５の低級アルコールのリン酸エステル（ｄ－３）又は炭素数１～５の低級アルコールの亜リン酸エステル（ｄ－４）と、該エステル（ｄ－１）～（ｄ－４）中に存在している炭素数１～５の低級アルコール残基との揮発性エステルを生成可能な酸（ｅ）と、金属源である金属化合物Ｍ（ｆ）と、を混合、加熱し、得られる揮発性エステルを除去する方法により製造することができる。 The compound (2) represented by the general formula (A) is, for example, an aliphatic carboxylic acid (a) having 2 to 25 carbon atoms and 1 to 1 carbon atoms as described in International Publication No. 2016/039375. A borate ester of a lower alcohol of 5 (d-1), a metaboric acid ester of a lower alcohol having 1 to 5 carbon atoms (d-2), a phosphoric acid ester of a lower alcohol having 1 to 5 carbon atoms (d-3) or A subphosphate ester (d-4) of a lower alcohol having 1 to 5 carbon atoms and a lower alcohol residue having 1 to 5 carbon atoms present in the esters (d-1) to (d-4). It can be produced by a method of mixing and heating an acid (e) capable of producing the volatile ester of the above and a metal compound M (f) as a metal source to remove the obtained volatile ester.
　前記ゴム－金属間接着促進剤の含有量は、特に限定されないが、金属部材とのより優れた接着性を得る点からは、前記ゴム成分１００質量部に対して０．１質量部以上であることが好ましく、１．５質量部以上であることがより好ましく、６質量部以上であることが特に好ましい。また、ゴム組成物の劣化を抑制する観点からは、前記ゴム－金属間接着促進剤の含有量は、前記ゴム成分１００質量部に対して２５質量部以下であることが好ましく、１６質量部以下であることがより好ましく、１０質量部以下であることが特に好ましい。
　また、前記ゴム－金属間接着促進剤の金属元素としての含有量は、前記ゴム成分１００質量部に対して０．０５質量部以上が好ましく、１質量部以上がより好ましく、また、５質量部以下が好ましく、３質量部以下がより好ましい。ゴム－金属間接着促進剤の金属元素として含有量が、０．０５質量部以上の場合、ゴム組成物と金属部材との間の接着性が更に向上し、また、５質量部以下の場合、ゴム成分の架橋反応への影響が小さく、ゴム組成物が劣化し難い。
　前記ゴム－金属間接着促進剤中の脂肪族カルボン酸の金属塩（１）及び一般式（Ａ）で表される化合物（２）の総含有率は、５０質量％以上が好ましく、８０質量％以上が更に好ましく、１００質量％であってもよい。ゴム－金属間接着促進剤中には、脂肪族カルボン酸の金属塩（１）や、一般式（Ａ）で表される化合物（２）の合成に用いた原料の未反応物（炭素数が２～２５の脂肪族カルボン酸（ａ）等）が残存していてもよい。 The content of the rubber-metal adhesion promoter is not particularly limited, but is 0.1 part by mass or more with respect to 100 parts by mass of the rubber component from the viewpoint of obtaining better adhesion to the metal member. It is preferably 1.5 parts by mass or more, more preferably 6 parts by mass or more, and particularly preferably 6 parts by mass or more. Further, from the viewpoint of suppressing deterioration of the rubber composition, the content of the rubber-metal adhesion accelerator is preferably 25 parts by mass or less, and 16 parts by mass or less with respect to 100 parts by mass of the rubber component. Is more preferable, and 10 parts by mass or less is particularly preferable.
The content of the rubber-metal adhesion promoter as a metal element is preferably 0.05 parts by mass or more, more preferably 1 part by mass or more, and 5 parts by mass with respect to 100 parts by mass of the rubber component. The following is preferable, and 3 parts by mass or less is more preferable. When the content of the rubber-metal adhesion promoter as a metal element is 0.05 parts by mass or more, the adhesiveness between the rubber composition and the metal member is further improved, and when it is 5 parts by mass or less, the adhesiveness is further improved. The effect of the rubber component on the cross-linking reaction is small, and the rubber composition does not easily deteriorate.
The total content of the metal salt (1) of the aliphatic carboxylic acid and the compound (2) represented by the general formula (A) in the rubber-metal adhesion promoter is preferably 50% by mass or more, preferably 80% by mass. The above is more preferable, and it may be 100% by mass. In the rubber-metal adhesion accelerator, the unreacted product (carbon number) of the raw material used for the synthesis of the metal salt (1) of the aliphatic carboxylic acid and the compound (2) represented by the general formula (A) is contained. 2 to 25 aliphatic carboxylic acids (a) and the like) may remain.
（シリカ）
　本発明のゴム組成物は、シリカを含むことが好ましい。ゴム組成物にシリカを配合することで、湿熱劣化後においても、ゴム組成物の金属部材に対する接着性を向上させることができる。 (silica)
The rubber composition of the present invention preferably contains silica. By blending silica with the rubber composition, the adhesiveness of the rubber composition to the metal member can be improved even after deterioration due to moist heat.
　前記シリカの種類については、特に限定はされない。例えば、湿式シリカ（含水ケイ酸）、乾式シリカ（無水ケイ酸）、ケイ酸カルシウム、ケイ酸アルミニウム等を用いることができる。これらの中でも、湿式シリカを用いることが好ましい。 The type of silica is not particularly limited. For example, wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate and the like can be used. Among these, it is preferable to use wet silica.
　前記シリカのＢＥＴ比表面積（ＩＳＯ　５７９４／１に基づき測定する）は、４０～３５０ｍ２／ｇであることが好ましい。ＢＥＴ比表面積がこの範囲であるシリカは、ゴム補強性とゴム成分中への分散性とを両立できるという利点がある。これらの観点から、ＢＥＴ比表面積が８０～３００ｍ２／ｇであるシリカがより好ましい。このようなシリカとして、例えば、東ソー・シリカ（株）社製「Ｎｉｐｓｉｌ　ＡＱ」、「Ｎｉｐｓｉｌ　ＫＱ」、エボニック社製「Ｕｌｔｒａｓｉｌ　ＶＮ３」等の市販品を用いることもできる。なお、前記シリカは、一種類を用いてもよく、二種類以上を組み合わせて用いてもよい。 The BET specific surface area (measured based on ISO 5794/1) of the silica is preferably 40 to 350 m 2 / g. Silica having a BET specific surface area in this range has an advantage that it can achieve both rubber reinforcing properties and dispersibility in rubber components. From these viewpoints, silica having a BET specific surface area of 80 to 300 m 2 / g is more preferable. As such silica, for example, commercially available products such as "Nipsil AQ" and "Nipsil KQ" manufactured by Tosoh Silica Co., Ltd. and "Ultrasil VN3" manufactured by Evonik Industries can be used. The silica may be used alone or in combination of two or more.
　前記シリカの含有量は、前記ゴム成分１００質量部に対して、５質量部以上が好ましく、７質量部以上が更に好ましく、また、３０質量部以下が好ましく、２０質量部以下が更に好ましい。前記シリカの含有量が、ゴム成分１００質量部に対して５質量部以上であると、湿熱劣化後における、ゴム組成物の金属部材に対する接着性（耐湿熱劣化性）を向上させる効果が大きくなる。 The content of the silica is preferably 5 parts by mass or more, more preferably 7 parts by mass or more, still more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, based on 100 parts by mass of the rubber component. When the content of the silica is 5 parts by mass or more with respect to 100 parts by mass of the rubber component, the effect of improving the adhesiveness (moisture heat resistance deterioration resistance) of the rubber composition to the metal member after moist heat deterioration becomes large. ..
（他の充填剤）
　本発明のゴム組成物は、前記シリカ以外の充填剤を含んでもよい。該シリカ以外の充填剤としては、ゴム組成物の補強性の観点から、カーボンブラックが好ましい。
　前記カーボンブラックの種類については、特に限定はされない。例えば、オイルファーネス法により製造された任意のハードカーボンを用いることができる。カーボンブラックの種類については、特に限定はされず、例えば、ＧＰＦ、ＦＥＦ、ＳＲＦ、ＨＡＦ、ＩＳＡＦ、ＩＩＳＡＦ、ＳＡＦグレード等のカーボンブラックを、一種以上用いることができる。
　前記カーボンブラックの含有量は、特に限定されないが、前記ゴム成分１００質量部に対して２０～１００質量部であることが好ましく、３０～９０質量部であることがより好ましく、４０～８０質量部であることが特に好ましい。前記カーボンブラックの含有量を前記ゴム成分１００質量部に対して、２０質量部以上とすることで、ゴム組成物の補強性が更に向上し、前記カーボンブラックの含有量が前記ゴム成分１００質量部に対して、１００質量部以下の場合には、低発熱性の悪化や、グリップ力の低下を抑えることができる。
　なお、カーボンブラックを二種以上配合する際は、その少なくとも一種をＧＰＦ、ＦＥＦ、ＳＲＦから選択し、もう一種をＨＡＦ、ＩＳＡＦ、ＩＩＳＡＦ、ＳＡＦから選択することもできる。 (Other fillers)
The rubber composition of the present invention may contain a filler other than the silica. As the filler other than silica, carbon black is preferable from the viewpoint of reinforcing property of the rubber composition.
The type of carbon black is not particularly limited. For example, any hard carbon produced by the oil furnace method can be used. The type of carbon black is not particularly limited, and for example, one or more carbon blacks such as GPF, FEF, SRF, HAF, ISAF, IISAF, and SAF grade can be used.
The content of the carbon black is not particularly limited, but is preferably 20 to 100 parts by mass, more preferably 30 to 90 parts by mass, and 40 to 80 parts by mass with respect to 100 parts by mass of the rubber component. Is particularly preferable. By setting the content of the carbon black to 20 parts by mass or more with respect to 100 parts by mass of the rubber component, the reinforcing property of the rubber composition is further improved, and the content of the carbon black is 100 parts by mass of the rubber component. On the other hand, in the case of 100 parts by mass or less, deterioration of low heat generation and deterioration of grip force can be suppressed.
When two or more types of carbon black are blended, at least one of them can be selected from GPF, FEF, and SRF, and the other can be selected from HAF, ISAF, IISAF, and SAF.
　また、前記シリカ及びカーボンブラック以外の充填剤としては、例えば、水酸化アルミニウム、クレー、アルミナ、タルク、マイカ、カオリン、ガラスバルーン、ガラスビーズ、炭酸カルシウム、炭酸マグネシウム、水酸化マグネシウム、酸化マグネシウム、酸化チタン、チタン酸カリウム、硫酸バリウム等が挙げられる。 Examples of fillers other than the silica and carbon black include aluminum hydroxide, clay, alumina, talc, mica, kaolin, glass balloon, glass beads, calcium carbonate, magnesium carbonate, magnesium hydroxide, magnesium oxide, and oxidation. Examples thereof include titanium, potassium titanate, and barium sulfate.
（その他の成分）
　本発明に係るゴム組成物には、上述した、ゴム成分、変性ポリマー、ゴム－金属間接着促進剤、シリカ等の充填剤に加えて、ゴム組成物に配合される公知の添加剤を適宜配合してもよい。このような添加剤としては、例えば、樹脂、硬化剤、ナフトール、加硫剤（架橋剤）、加硫促進剤、加硫遅延剤、老化防止剤、補強剤、加硫助剤、着色剤、難燃剤、滑剤、発泡剤、可塑剤、加工助剤、酸化防止剤、スコーチ防止剤、紫外線防止剤、帯電防止剤、着色防止剤、オイル等が挙げられる。これらは、それぞれ、一種単独で、または二種以上を組み合わせて用いてもよい。 (Other ingredients)
In the rubber composition according to the present invention, in addition to the above-mentioned fillers such as a rubber component, a modified polymer, a rubber-metal adhesion promoter, and silica, a known additive to be blended in the rubber composition is appropriately blended. You may. Examples of such additives include resins, curing agents, naphthols, vulcanization agents (crosslinking agents), vulcanization accelerators, vulcanization retarders, antiaging agents, reinforcing agents, vulcanization aids, and colorants. Examples thereof include flame retardants, lubricants, foaming agents, plasticizers, processing aids, antioxidants, scorch inhibitors, ultraviolet inhibitors, antistatic agents, anticoloring agents, oils and the like. These may be used alone or in combination of two or more, respectively.
　前記ゴム組成物が前記樹脂を含むことによって、ゴムの柔軟性を高めることができ、ゴム組成物の金属部材との接着性をより向上させることができる。前記樹脂については、特に限定はされず、種々の天然樹脂及び合成樹脂を使用することができる。
　前記樹脂としては、ゴム組成物の金属部材との接着性をより向上できる点からは、石油系樹脂、石炭系樹脂、フェノール系樹脂、ロジン系樹脂及びテルペン系樹脂からなる群より選択される少なくとも一種を用いることが好ましく、フェノール系樹脂を用いることがより好ましい。なお、これら樹脂は、変性されていてもよい。
　前記フェノール系樹脂については、フェノール、ナフトール、クレゾール、キシレノール、ｐ－ｔｅｒｔ－ブチルフェノール、ｐ－オクチルフェノール、ｐ－ノニルフェノール等のアルキルフェノール類を使用できる。これらの水酸基を有する化合物は、単独で用いてもよく、二種以上を併用してもよい。
　前記樹脂の含有量は、前記ゴム成分１００質量部に対して０．５～１０質量部の範囲が好ましく、１～５質量部の範囲が更に好ましい。 When the rubber composition contains the resin, the flexibility of the rubber can be enhanced, and the adhesiveness of the rubber composition to the metal member can be further improved. The resin is not particularly limited, and various natural resins and synthetic resins can be used.
The resin is at least selected from the group consisting of petroleum-based resins, coal-based resins, phenol-based resins, rosin-based resins, and terpene-based resins from the viewpoint of further improving the adhesiveness of the rubber composition to the metal member. It is preferable to use one kind, and it is more preferable to use a phenolic resin. In addition, these resins may be modified.
As the phenolic resin, alkylphenols such as phenol, naphthol, cresol, xylenol, p-tert-butylphenol, p-octylphenol, and p-nonylphenol can be used. These compounds having a hydroxyl group may be used alone or in combination of two or more.
The content of the resin is preferably in the range of 0.5 to 10 parts by mass, more preferably in the range of 1 to 5 parts by mass with respect to 100 parts by mass of the rubber component.
　また、前記フェノール系樹脂を用いる場合には、硬化剤として、例えば、ヘキサメチロールメラミン、ヘキサメトキシメチルメラミン、ペンタメトキシメチロールメラミン、ヘキサエトキシメチルメラミン、ヘキサキス－（メトキシメチル）メラミン、Ｎ，Ｎ’，Ｎ”－トリメチル－Ｎ，Ｎ’，Ｎ”－トリメチロールメラミン、Ｎ，Ｎ’，Ｎ”－トリメチロールメラミン、Ｎ－メチロールメラミン、Ｎ，Ｎ’－（メトキシメチル）メラミン、Ｎ，Ｎ’，Ｎ”－トリブチル－Ｎ，Ｎ’，Ｎ”－トリメチロールメラミン等のメラミン誘導体を更に用いることができる。これらのメラミン誘導体の中でも、ヘキサメトキシメチルメラミン（ＨＭＭＭ）を用いることが好ましい。
　前記硬化剤の含有量は、前記ゴム成分１００質量部に対して１～１０質量部の範囲が好ましく、３～７質量部の範囲が更に好ましい。 When the phenolic resin is used, as the curing agent, for example, hexamethylol melamine, hexamethoxymethyl melamine, pentamethoxymethylol melamine, hexaethoxymethyl melamine, hexakiss- (methoxymethyl) melamine, N, N', N "-trimethyl-N, N', N" -trimethylol melamine, N, N', N "-trimethylol melamine, N-methylol melamine, N, N'-(methoxymethyl) melamine, N, N', Further, melamine derivatives such as N "-tributyl-N, N', N" -trimethylolmelamine can be further used. Among these melamine derivatives, hexamethoxymethylmelamine (HMMM) is preferably used.
The content of the curing agent is preferably in the range of 1 to 10 parts by mass, more preferably in the range of 3 to 7 parts by mass with respect to 100 parts by mass of the rubber component.
　前記ナフトールとしては、β－ナフトール等が挙げられる。ナフトールを含むことで、ゴム組成物と金属部材との間の接着性をより向上させることができる。ここで、接着性の観点から、ナフトールの含有量は、前記ゴム成分１００質量部に対して０．５～５質量部の範囲が好ましく、１～３質量部の範囲が更に好ましい。 Examples of the naphthol include β-naphthol and the like. By including naphthol, the adhesiveness between the rubber composition and the metal member can be further improved. Here, from the viewpoint of adhesiveness, the content of naphthol is preferably in the range of 0.5 to 5 parts by mass, more preferably in the range of 1 to 3 parts by mass with respect to 100 parts by mass of the rubber component.
　前記加硫剤（架橋剤）としては、硫黄が好ましい。該硫黄としては、特に限定されるものではないが、粉末硫黄、沈降硫黄、コロイド硫黄、不溶性硫黄、オイル処理硫黄等が挙げられる。加硫剤（架橋剤）の含有量は、前記ゴム成分１００質量部に対して０．０１～１０質量部の範囲が好ましく、１～１０質量部の範囲が更に好ましく、２～８質量部の範囲がより一層好ましい。 Sulfur is preferable as the vulcanizing agent (crosslinking agent). The sulfur is not particularly limited, and examples thereof include powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and oil-treated sulfur. The content of the vulcanizing agent (crosslinking agent) is preferably in the range of 0.01 to 10 parts by mass, more preferably in the range of 1 to 10 parts by mass, and 2 to 8 parts by mass with respect to 100 parts by mass of the rubber component. The range is even more preferred.
　前記加硫促進剤としては、例えば、スルフェンアミド系加硫促進剤、チアゾール系加硫促進剤等が挙げられる。該スルフェンアミド加硫促進剤としては、例えば、Ｎ－シクロヘキシル－２－ベンゾチアゾールスルフェンアミド（ＣＺ、ＣＢＳ）、Ｎ－ｔｅｒｔ－ブチル－２－ベンゾチアゾールスルフェンアミド（ＮＳ、ＢＢＳ）、Ｎ－オキシジエチレン－２－ベンゾチアゾールスルフェンアミド（ＯＢＳ）、Ｎ，Ｎ－ジイソプロピル－２－ベンゾチアゾールスルフェンアミド（ＤＰＢＳ）、Ｎ，Ｎ－ジシクロヘキシル－２－ベンゾチアゾールスルフェンアミド（ＤＺ、ＤＣＢＳ）等が挙げられる。また、前記チアゾール系加硫促進剤としては、２－メルカプトベンゾチアゾール（Ｍ）等が挙げられる。
　前記加硫促進剤の含有量は、ゴム成分１００質量部に対して、０．０１～１０質量部が好ましく、０．１～８質量部がより好ましく、０．３～６質量部がより一層好ましい。 Examples of the vulcanization accelerator include a sulfenamide-based vulcanization accelerator, a thiazole-based vulcanization accelerator, and the like. Examples of the sulfenamide sulfide accelerating agent include N-cyclohexyl-2-benzothiazolesulfenamide (CZ, CBS), N-tert-butyl-2-benzothiazolesulfenamide (NS, BBS), N. -Oxydiethylene-2-benzothiazolesulfenamide (OBS), N, N-diisopropyl-2-benzothiazolesulfenamide (DPBS), N, N-dicyclohexyl-2-benzothiazolesulfenamide (DZ, DCBS) And so on. Moreover, as the thiazole-based vulcanization accelerator, 2-mercaptobenzothiazole (M) and the like can be mentioned.
The content of the vulcanization accelerator is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 8 parts by mass, and even more preferably 0.3 to 6 parts by mass with respect to 100 parts by mass of the rubber component. preferable.
　なお、本発明のゴム組成物は、環境に配慮した規制に対応する点から、コバルトが添加されていないこと、具体的には、コバルト化合物の含有量が、前記ゴム成分１００質量部に対して０．０１質量部以下であることが好ましく、不可避不純物を除いて、コバルト化合物を含まないことがより好ましい。 In addition, the rubber composition of the present invention does not contain cobalt from the viewpoint of complying with environmentally friendly regulations, specifically, the content of the cobalt compound is 100 parts by mass of the rubber component. It is preferably 0.01 part by mass or less, and more preferably does not contain a cobalt compound except for unavoidable impurities.
（ゴム組成物の製法）
　本発明のゴム組成物の調製方法は特に限定されず、公知の方法を用いることができる。
　例えば、ゴム成分と、変性ポリマーと、ゴム－金属間接着促進剤と、その他の任意成分とを、同時にまたは任意の順序で添加して、バンバリーミキサー、ロール又はインターナルミキサー等の混練り機を用いて混練りすることによって得られる。 (Manufacturing method of rubber composition)
The method for preparing the rubber composition of the present invention is not particularly limited, and a known method can be used.
For example, a rubber component, a modified polymer, a rubber-metal adhesion promoter, and other optional components may be added simultaneously or in any order to form a kneader such as a Banbury mixer, a roll, or an internal mixer. Obtained by using and kneading.
（ゴム組成物の用途）
　本発明に係るゴム組成物の用途は、特に限定されず、例えば、ホース、コンベヤベルト、ゴムクローラ、タイヤ、電線、防振材等、任意のゴム物品に用いることができる。 (Use of rubber composition)
The use of the rubber composition according to the present invention is not particularly limited, and can be used for any rubber article such as a hose, a conveyor belt, a rubber crawler, a tire, an electric wire, and a vibration-proof material.
＜ゴム－金属複合体＞
　本発明のゴム－金属複合体は、上述した本発明のゴム組成物と、金属部材と、を具えることを特徴とする。かかる本発明のゴム－金属複合体は、ゴム（ゴム組成物）と、金属部材との間の接着性に優れる。 <Rubber-metal complex>
The rubber-metal complex of the present invention is characterized by comprising the above-mentioned rubber composition of the present invention and a metal member. The rubber-metal composite of the present invention has excellent adhesiveness between a rubber (rubber composition) and a metal member.
　本発明のゴム－金属複合体は、上述した本発明のゴム組成物と金属部材とが接していればよく、例えば、金属部材である金属ワイヤーの、一部又は全部をゴム組成物によって被覆していてもよいし、金属ワイヤーからなる層の少なくとも一面側にゴム組成物からなるゴム層が積層されるような実施形態でもよい。 The rubber-metal composite of the present invention may be in contact with the above-mentioned rubber composition of the present invention and a metal member. For example, a part or all of a metal wire which is a metal member is covered with the rubber composition. It may be an embodiment in which a rubber layer made of a rubber composition is laminated on at least one surface side of a layer made of a metal wire.
　前記金属部材については、金属から構成された部品のことであり、例えば、金属ワイヤーや、該金属ワイヤー（金属鋼線）を複数本撚り合わせてなる金属コードや、該金属ワイヤーの単線からなる金属コード、更に、金属のバネ、金属の板、金属のリング等、種々の形態を有することができる。
　また、前記金属部材の金属種については、特に限定はされず、スチール、鉄、銅、金等、用途に応じて適宜選択することができる。 The metal member is a part made of metal, for example, a metal wire, a metal cord made by twisting a plurality of the metal wires (metal steel wires), or a metal made of a single wire of the metal wire. It can have various forms such as a cord, a metal spring, a metal plate, a metal ring, and the like.
The metal type of the metal member is not particularly limited, and can be appropriately selected depending on the intended use, such as steel, iron, copper, and gold.
　前記金属部材については、メッキされていてもよいし、メッキされていなくてもよい。メッキの種類は特に限定されず、ブラスメッキ、亜鉛メッキ、クロムメッキ、ニッケルメッキ等、公知のメッキを適宜採用することができる。
　前記金属部材が、金属ワイヤーである場合には、ブラスメッキ及び亜鉛メッキからなる群より選択される１種以上のメッキがされていることが好ましい。 The metal member may or may not be plated. The type of plating is not particularly limited, and known plating such as brass plating, zinc plating, chrome plating, and nickel plating can be appropriately adopted.
When the metal member is a metal wire, it is preferable that one or more types of plating selected from the group consisting of brass plating and zinc plating are performed.
　本発明のゴム－金属複合体の製造方法は、特に限定されず、公知の方法を適宜採用することができる。例えば、金属ワイヤーをゴム組成物が被覆している複合体では、金属ワイヤーをゴム組成物で被覆した状態でゴム組成物を加硫することで複合体を得ることができる。また、例えば、金属ワイヤーからなる層の少なくとも一面側にゴム組成物からなるゴム層が積層されている複合体では、例えば、国際公開第２０１７／０５６４１４号に記載の積層体の製造方法によって複合体を得ることができる。 The method for producing the rubber-metal complex of the present invention is not particularly limited, and a known method can be appropriately adopted. For example, in a composite in which a metal wire is coated with a rubber composition, the composite can be obtained by vulcanizing the rubber composition in a state where the metal wire is coated with the rubber composition. Further, for example, in a composite in which a rubber layer made of a rubber composition is laminated on at least one surface side of a layer made of a metal wire, for example, the composite is manufactured by the method for producing a laminated body described in International Publication No. 2017/056414. Can be obtained.
＜ホース＞
　本発明のホースは、上述のゴム－金属複合体を具えることを特徴とする。かかる本発明のホースは、コバルト塩を含有するゴム組成物を用いた場合と同等以上のゴム－金属間の接着性を有するため、優れた耐久性を有する。 <Hose>
The hose of the present invention is characterized by comprising the rubber-metal complex described above. The hose of the present invention has excellent durability because it has a rubber-metal adhesiveness equal to or higher than that when a rubber composition containing a cobalt salt is used.
　なお、本発明のホースは、上記ゴム－金属複合体を用いたこと以外は特に限定されず、公知のホースの構成や製造方法を採用し得る。
　一実施形態において、ホースは、径方向内側に位置する内面ゴム層（内管ゴム）と、径方向外側に位置する外面ゴム層と、上記内面ゴム層及び上記外面ゴム層の間に位置する金属補強層（金属部材）と、を具える。そして、一実施形態においては、上述のゴム組成物を、内面ゴム層及び外面ゴム層の少なくともいずれかに用いることができる。 The hose of the present invention is not particularly limited except that the rubber-metal composite is used, and a known hose configuration and manufacturing method can be adopted.
In one embodiment, the hose is a metal located between an inner rubber layer (inner tube rubber) located on the inner side in the radial direction, an outer surface rubber layer located on the outer side in the radial direction, and the inner surface rubber layer and the outer surface rubber layer. It has a reinforcing layer (metal member). Then, in one embodiment, the above-mentioned rubber composition can be used for at least one of the inner surface rubber layer and the outer surface rubber layer.
＜コンベヤベルト＞
　本発明のコンベヤベルトは、上述のゴム－金属複合体を具えることを特徴とする。かかる本発明のコンベヤベルトは、コバルト塩を含有するゴム組成物を用いた場合と同等以上のゴム－金属間の接着性を有するため、優れた耐久性を有する。 <Conveyor belt>
The conveyor belt of the present invention is characterized by comprising the above-mentioned rubber-metal composite. The conveyor belt of the present invention has excellent durability because it has a rubber-metal adhesiveness equal to or higher than that when a rubber composition containing a cobalt salt is used.
　なお、本発明のコンベヤベルトは、上記ゴム－金属複合体を用いたこと以外は特に限定されず、公知のコンベヤベルトの構成や製造方法を採用し得る。
　一実施形態においては、本発明のゴム－金属複合体を、コンベヤベルトのうち、少なくとも、スチールコード等からなる金属補強材（金属部材）の下側の、駆動プーリー、従動プーリー、保形ローター等と接触する内周側の表層ゴム（下面カバーゴム）に用いることができ、また、金属補強材の上側の、輸送物品と接触する外周側の表層ゴム（上面カバーゴム）に用いることもできる。
　前記コンベヤベルトの具体的な製造例としては、上記ゴム組成物からなるゴムシートで金属補強材を挟み込み、このゴムシートを加熱圧着して加硫接着することにより、金属補強材にゴムを接着及び被覆することが挙げられる。 The conveyor belt of the present invention is not particularly limited except that the rubber-metal composite is used, and a known conveyor belt configuration and manufacturing method can be adopted.
In one embodiment, the rubber-metal composite of the present invention is used on a conveyor belt, at least under a metal reinforcing material (metal member) made of a steel cord or the like, such as a drive pulley, a driven pulley, and a shape-retaining rotor. It can be used for the surface rubber (bottom cover rubber) on the inner peripheral side that comes into contact with the metal reinforcing material, and can also be used for the surface rubber (top cover rubber) on the outer peripheral side that comes into contact with the transported article on the upper side of the metal reinforcing material.
As a specific manufacturing example of the conveyor belt, a metal reinforcing material is sandwiched between rubber sheets made of the above rubber composition, and the rubber sheet is heat-pressed and vulcanized and bonded to bond rubber to the metal reinforcing material. Covering is mentioned.
＜ゴムクローラ＞
　本発明のゴムクローラは、上述のゴム－金属複合体を具えることを特徴とする。かかる本発明のゴムクローラは、コバルト塩を含有するゴム組成物を用いた場合と同等以上のゴム－金属間の接着性を有するため、優れた耐久性を有する。 <Rubber crawler>
The rubber crawler of the present invention is characterized by comprising the above-mentioned rubber-metal complex. The rubber crawler of the present invention has excellent durability because it has a rubber-metal adhesiveness equal to or higher than that when a rubber composition containing a cobalt salt is used.
　なお、本発明のゴムクローラは、上記ゴム－金属複合体を用いたこと以外は特に限定されず、公知のゴムクローラの構成や製造方法を採用し得る。
　一実施形態において、ゴムクローラは、スチールコード（金属部材）と、該スチールコードを被覆する中間ゴム層と、該中間ゴム層の上に配置された芯金（金属部材）と、前記中間ゴム層と芯金とを囲む本体ゴム層とを具え、更に、本体ゴム層の接地面側に複数のラグを有している。ここで、上述のゴム組成物は、ゴムクローラのいずれの部位に用いてもよい。 The rubber crawler of the present invention is not particularly limited except that the rubber-metal composite is used, and a known rubber crawler configuration and manufacturing method can be adopted.
In one embodiment, the rubber crawler includes a steel cord (metal member), an intermediate rubber layer covering the steel cord, a core metal (metal member) arranged on the intermediate rubber layer, and the intermediate rubber layer. It is provided with a main body rubber layer surrounding the main body and the core metal, and further has a plurality of lugs on the ground contact surface side of the main body rubber layer. Here, the above-mentioned rubber composition may be used for any part of the rubber crawler.
＜タイヤ＞
　本発明のタイヤは、上述のゴム－金属複合体を具えることを特徴とする。かかる本発明のタイヤはコバルト塩を含有するゴム組成物を用いた場合と同等以上のゴム－金属間の接着性を有するため、優れた耐久性を有する。 <Tire>
The tire of the present invention is characterized by comprising the above-mentioned rubber-metal complex. The tire of the present invention has excellent durability because it has a rubber-metal adhesiveness equal to or higher than that when a rubber composition containing a cobalt salt is used.
　本発明のタイヤは、上述した本発明のゴム－金属複合体を用いたこと以外は特に限定されず、公知のタイヤの構成や製造方法を採用し得る。
　タイヤにおける本発明のゴム－金属複合体の適用部位としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、カーカス、ベルト、ビードコア等が挙げられる。
　前記タイヤを製造する方法としては、慣用の方法を用いることができる。例えば、タイヤ成形用ドラム上に、未加硫ゴム組成物及び金属コードからなるカーカス及びベルト（ゴム－金属複合体）、未加硫ゴム組成物からなるトレッド等の通常タイヤ製造に用いられる部材を順次貼り重ね、ドラムを抜き去ってグリーンタイヤとする。次いで、このグリーンタイヤを常法に従って加熱加硫することにより、所望のタイヤ（例えば、空気入りタイヤ）を製造することができる。 The tire of the present invention is not particularly limited except that the rubber-metal composite of the present invention described above is used, and a known tire configuration and manufacturing method can be adopted.
The application site of the rubber-metal complex of the present invention in a tire is not particularly limited and may be appropriately selected depending on the intended purpose, and examples thereof include carcass, belts and bead cores.
As a method for manufacturing the tire, a conventional method can be used. For example, on a tire forming drum, a member used for normal tire manufacturing such as a carcass and a belt (rubber-metal composite) made of an unvulcanized rubber composition and a metal cord, a tread made of an unvulcanized rubber composition, etc. Stack them one after another and remove the drums to make green tires. Then, by heating and vulcanizing this green tire according to a conventional method, a desired tire (for example, a pneumatic tire) can be manufactured.
　以下に、実施例を挙げて本発明を更に詳しく説明するが、本発明は下記の実施例に何ら限定されるものではない。実施例において、配合量は、特に断らない限り、質量部を意味する。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples. In the examples, the blending amount means parts by mass unless otherwise specified.
（実施例１～６、比較例１～４）
　表１に示す配合に従い、通常のバンバリーミキサーを用いて配合成分を混練し、ゴム組成物の各サンプルを得た。 (Examples 1 to 6, Comparative Examples 1 to 4)
According to the formulation shown in Table 1, the compounding components were kneaded using a normal Banbury mixer to obtain each sample of the rubber composition.
（評価）
　得られたゴム組成物の各サンプルについて、以下の評価を行った。評価結果を表１に示す。 (evaluation)
The following evaluations were performed on each sample of the obtained rubber composition. The evaluation results are shown in Table 1.
（１）試験片の作製
　直径０．３９ｍｍの亜鉛メッキスチールコードを、表１に示す配合処方により得られたゴム組成物からなる厚さ１ｍｍのゴムシートでサンドイッチし、１５５℃で３０分間加圧加硫を行い、試験片を作製した。 (1) Preparation of test piece A galvanized steel cord having a diameter of 0.39 mm is sandwiched with a rubber sheet having a thickness of 1 mm and made of a rubber composition obtained by the formulation shown in Table 1, and pressed at 155 ° C. for 30 minutes. Vulcanization was performed to prepare a test piece.
（２）ゴム－金属間の接着性（引抜力、ゴム被覆率）
　上記（１）で作製した試験片から亜鉛メッキスチールコードを引き抜き、引抜力（Ｎ）とゴム被覆率（％）を測定した。なお、引抜試験の条件は、ＤＩＮ２２１３１に準拠して行った。
　ゴム被覆率は、亜鉛メッキスチールコードの表面積に対する引き抜き後のスチールコード表面に残存するゴムの被覆面積の割合（％）として算出した。評価については、比較例１のサンプル（コバルトを含有するサンプル）の引抜力、被覆率を、それぞれ１００としたときの指数値とし表示し、指数値が大きい程、引抜力、被覆率が大きく、接着力が良好なことを示す。 (2) Adhesion between rubber and metal (pulling force, rubber coverage)
The zinc-plated steel cord was pulled out from the test piece prepared in (1) above, and the pulling force (N) and the rubber coverage (%) were measured. The conditions for the withdrawal test were performed in accordance with DIN 22131.
The rubber coverage was calculated as the ratio (%) of the rubber coverage area remaining on the surface of the steel cord after extraction to the surface area of the galvanized steel cord. Regarding the evaluation, the extraction force and coverage of the sample of Comparative Example 1 (sample containing cobalt) are displayed as index values when each is set to 100, and the larger the index value, the larger the extraction force and coverage. Indicates that the adhesive strength is good.
（３）耐湿熱劣化性
　上記（１）と同様にして作製した試験片を、７０℃、９５％ＲＨの高温オーブン中に９６時間保管した。保管後の試験片に対して、上記（２）と同様にして、引抜試験を行い、引き抜き後のスチールコード表面に残存するゴムの被覆面積の割合（％）を算出し、比較例１のサンプル（コバルトを含有するサンプル）の被覆率を１００としたときの指数値で表示した。指数値が大きい程、耐湿熱劣化性が良好なことを示す。
　なお、比較例２、３、４のサンプルについては、ゴム被覆率が低いため、耐湿熱劣化性を評価できなかった。 (3) Moisture and heat deterioration resistance The test piece prepared in the same manner as in (1) above was stored in a high temperature oven at 70 ° C. and 95% RH for 96 hours. A drawing test was performed on the stored test piece in the same manner as in (2) above, and the ratio (%) of the rubber covering area remaining on the surface of the steel cord after drawing was calculated, and the sample of Comparative Example 1 was obtained. It is expressed as an exponential value when the coverage of (a sample containing cobalt) is 100. The larger the index value, the better the moisture resistance and heat deterioration resistance.
Since the rubber coverage of the samples of Comparative Examples 2, 3 and 4 was low, the moisture resistance and heat deterioration resistance could not be evaluated.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
＊１　天然ゴム：　ＲＳＳ＃３（天然ゴム各種等級品の国際品質包装標準による分類）
＊２　スチレン－ブタジエンゴム：　ＪＳＲ（株）製、商品名「ＪＳＲ　１５００」
＊３　変性ポリマー：　（株）クラレ社製、商品名「クラプレン　ＬＩＲ－４１０」、下記式で表される繰り返し単位を有するカルボキシル化タイプの液状ポリイソプレン、数平均分子量＝３０，０００
Figure JPOXMLDOC01-appb-C000006
 * 1 Natural rubber: RSS # 3 (classification of various grades of natural rubber according to international quality packaging standards)
* 2 Styrene-butadiene rubber: Made by JSR Corporation, product name "JSR 1500"
* 3 Modified polymer: Kuraray Co., Ltd., trade name "Claprene LIR-410", carboxylated type liquid polyisoprene having a repeating unit represented by the following formula, number average molecular weight = 30,000
Figure JPOXMLDOC01-appb-C000006
＊４　カーボンブラック１：　ＧＰＦ級カーボンブラック、旭カーボン（株）製、「旭＃５５」、ＤＢＰ吸収量＝８７ｃｍ３／１００ｇ、窒素吸着比表面積＝２６ｍ２／ｇ
＊５　カーボンブラック２：　ＨＡＦ級カーボンブラック、旭カーボン（株）製、「旭＃７０Ｌ」、ＤＢＰ吸収量＝７５ｃｍ３／１００ｇ、窒素吸着比表面積＝８４ｍ２／ｇ
＊６　シリカ：　東ソー・シリカ株式会社製、「Ｎｉｐｓｉｌ　ＡＱ」
＊７　オイル：　Ａ／Ｏ　ＭＩＸ、三共油化工業（株）製
＊８　老化防止剤：　Ｎ－フェニル－Ｎ’－（１，３－ジメチルブチル）－ｐ－フェニレンジアミン、大内新興化学工業（株）製、商品名「ノクラック　６Ｃ」
＊９　亜鉛華：　ハクスイテック（株）製、商品名「３号亜鉛華」
＊１０　ジメタクリル酸亜鉛：　川口化学工業（株）製、商品名「アクターＺＭＡ」
＊１１　変性フェノール樹脂：　住友ベークライ製、商品名「スミライトレジン　ＰＲ－１２６８７」
＊１２　β－ナフトール：　三井化学ファイン（株）製、商品名「βナフトール」
＊１３　ＨＭＭＭ：　ヘキサメトキシメチルメラミン、日本サイテックインダストリー（株）製、商品名「ＣＹＲＥＺ９６４ＲＰＣ」
＊１４　有機酸コバルト：　有機酸のコバルト塩中の有機酸の一部をホウ酸で置き換えた複合塩、ＯＭ　Ｇｒｏｕｐ　Ｉｎｃ．製、商品名「マノボンドＣ２２．５」、コバルト含有量＝２２．５質量％
＊１５　有機酸ビスマス：　２－エチルヘキサン酸ビスマス、ビスマス含有量＝２７．２質量％
＊１６　有機酸亜鉛：　２－エチルヘキサン酸亜鉛、亜鉛含有量＝２２．１質量％
＊１７　加硫促進剤：　Ｎ－シクロヘキシル－２－ベンゾチアゾリルスルフェンアミド、大内新興化学工業株式会社製、商品名「ノクセラーＣＺ－Ｇ」 * 4 Carbon black 1: GPF grade carbon black, manufactured by Asahi Carbon Co., Ltd., "Asahi # 55", DBP absorption amount = 87 cm 3/100 g, nitrogen adsorption specific surface area = 26 m 2 / g
* 5 Carbon black 2: HAF grade carbon black, manufactured by Asahi Carbon Co., Ltd., "Asahi # 70L", DBP absorption amount = 75 cm 3/100 g, nitrogen adsorption specific surface area = 84 m 2 / g
* 6 Silica: "Nipsil AQ" manufactured by Tosoh Silica Co., Ltd.
* 7 Oil: A / O MIX, manufactured by Sankyo Yuka Kogyo Co., Ltd. * 8 Anti-aging agent: N-phenyl-N'-(1,3-dimethylbutyl) -p-phenylenediamine, Ouchi Shinko Kagaku Kogyo ( Made by Co., Ltd., trade name "Nocrack 6C"
* 9 Zinc Oxide: Made by Hakusui Tech Co., Ltd., Product name "No. 3 Zinc Oxide"
* 10 Zinc dimethacrylate: Product name "Actor ZMA" manufactured by Kawaguchi Chemical Industry Co., Ltd.
* 11 Modified phenolic resin: Made by Sumitomo Bakery, trade name "Sumilite Resin PR-12687"
* 12 β-naphthol: Made by Mitsui Kagaku Fine Co., Ltd., product name "β-naphthol"
* 13 HMMM: Hexamethoxymethylmelamine, manufactured by Nippon Cytec Industry Co., Ltd., trade name "CYREZ964RPC"
* 14 Cobalt organic acid: A complex salt in which a part of the organic acid in the cobalt salt of the organic acid is replaced with boric acid, OM Group Inc. Made, trade name "Manobond C22.5", cobalt content = 22.5% by mass
* 15 Bismuth organic acid: Bismuth 2-ethylhexanoate, bismuth content = 27.2% by mass
* 16 Zinc organic acid: Zinc 2-ethylhexanoate, zinc content = 22.1% by mass
* 17 Vulcanization accelerator: N-cyclohexyl-2-benzothiazolyl sulfenamide, manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd., trade name "Noxeller CZ-G"
　表１の結果から、従来、接着促進剤として用いられてきたコバルト塩を含まない場合であっても、変性ポリマーと、ゴム－金属間接着促進剤と、を配合したゴム組成物を用いてスチールコードを被覆した実施例のサンプル（ゴム－金属複合体）については、ゴム組成物中にゴム－金属間接着促進剤を含むものの、変性ポリマーを含まない比較例２及び３のサンプル（ゴム－金属複合体）や、ゴム組成物中に変性ポリマーを含むものの、ゴム－金属間接着促進剤を含まない比較例４のサンプル（ゴム－金属複合体）に比べて、スチールコード引抜後のゴム被覆率及びスチールコード引抜力のいずれについても優れていることが分かる。
　更に、変性ポリマーと、ゴム－金属間接着促進剤と、シリカと、を配合したゴム組成物を用いてスチールコードを被覆した実施例３～６のサンプル（ゴム－金属複合体）については、耐湿熱劣化性についても、大幅に向上していることが分かる。 From the results in Table 1, even when the cobalt salt conventionally used as an adhesion promoter is not contained, a rubber composition containing a modified polymer and a rubber-metal adhesion promoter is used for steel. As for the sample of the example coated with the cord (rubber-metal composite), the samples of Comparative Examples 2 and 3 (rubber-metal) containing the rubber-metal adhesion promoter in the rubber composition but not the modified polymer. Compared to the sample (rubber-metal composite) of Comparative Example 4 which contains a modified polymer in the composite) or the rubber composition but does not contain the rubber-metal adhesion promoter, the rubber coverage after drawing out the steel cord It can be seen that both the steel cord pulling force and the steel cord pulling force are excellent.
Further, the samples (rubber-metal composite) of Examples 3 to 6 in which the steel cord was coated with the rubber composition containing the modified polymer, the rubber-metal adhesion promoter, and silica were moisture resistant. It can be seen that the thermal deterioration property is also significantly improved.
　本発明のゴム組成物は、ゴム－金属複合体に利用でき、また、本発明のゴム－金属複合体は、ホース、コンベヤベルト、ゴムクローラ、タイヤ等に利用できる。 The rubber composition of the present invention can be used for a rubber-metal composite, and the rubber-metal composite of the present invention can be used for hoses, conveyor belts, rubber crawlers, tires and the like.

Claims (17)

  1. 　ゴム成分と、
    　変性ポリマーと、
    　ゴム－金属間接着促進剤と、を含み、
    　前記変性ポリマーの含有量は、前記ゴム成分１００質量部に対し、５０質量部以下であり、
    　前記ゴム－金属間接着促進剤は、脂肪族カルボン酸の金属塩（１）（但し、ジメタクリル酸亜鉛を除く。）及び一般式（Ａ）：［（ＲＣＯＯ）ｘＭＯ］３Ｚで表される化合物（２）からなる群より選択される１種以上を含み、
    　前記脂肪族カルボン酸の金属塩（１）の脂肪族カルボン酸は、炭素数が２～２５であり、
    　前記脂肪族カルボン酸の金属塩（１）の金属は、ビスマス、亜鉛、銅、アンチモン、銀、ニオブ又はジルコニウムであり、
    　前記一般式（Ａ）中、（ＲＣＯＯ）は、炭素数２～２５の脂肪族カルボン酸の残基であり、Ｍは、ビスマス、亜鉛、銅、アンチモン、銀、ニオブ又はジルコニウムであり、ｘは、１以上かつ（Ｍの価数－１）の整数であり、Ｚは、下記式（ｚ－１）～（ｚ－４）から選択される構造である、ゴム組成物。
    Figure JPOXMLDOC01-appb-C000001
         With the rubber component,
    With modified polymers
    Contains rubber-metal adhesion promoters,
    The content of the modified polymer is 50 parts by mass or less with respect to 100 parts by mass of the rubber component.
    The rubber-metal adhesion accelerator is represented by a metal salt (1) of an aliphatic carboxylic acid (excluding zinc dimethacrylate) and a general formula (A): [ ( RCOO) x MO] 3Z. Contains one or more selected from the group consisting of compound (2).
    The aliphatic carboxylic acid of the metal salt (1) of the aliphatic carboxylic acid has 2 to 25 carbon atoms.
    The metal of the metal salt (1) of the aliphatic carboxylic acid is bismuth, zinc, copper, antimony, silver, niobium or zirconium.
    In the general formula (A), (RCOO) is a residue of an aliphatic carboxylic acid having 2 to 25 carbon atoms, M is bismuth, zinc, copper, antimony, silver, niobium or zirconium, and x is. A rubber composition having a structure of 1 or more and an integer of (valence of M-1), where Z is a structure selected from the following formulas (z-1) to (z-4).
    Figure JPOXMLDOC01-appb-C000001
  2. 　前記変性ポリマーは、分子内に、－ＣＯＯＨ、－ＯＨ及び－ＣＯＯＲ（ここで、Ｒは、一価の炭化水素基である。）からなる群より選択される１種以上の官能基を含む、請求項１に記載のゴム組成物。 The modified polymer contains, within the molecule, one or more functional groups selected from the group consisting of -COOH, -OH and -COOR (where R is a monovalent hydrocarbon group). The rubber composition according to claim 1.
  3. 　前記ゴム成分が、天然ゴム及びスチレン－ブタジエンゴムからなる群より選択される１種以上を含む、請求項１又は２に記載のゴム組成物。 The rubber composition according to claim 1 or 2, wherein the rubber component contains at least one selected from the group consisting of natural rubber and styrene-butadiene rubber.
  4. 　前記ゴム－金属間接着促進剤が、前記脂肪族カルボン酸の金属塩（１）を含み、該脂肪族カルボン酸の金属塩（１）の金属が、ビスマスである、請求項１～３のいずれか一項に記載のゴム組成物。 Any of claims 1 to 3, wherein the rubber-metal adhesion accelerator contains the metal salt (1) of the aliphatic carboxylic acid, and the metal of the metal salt (1) of the aliphatic carboxylic acid is bismuth. The rubber composition according to item 1.
  5. 　前記ゴム－金属間接着促進剤が、前記脂肪族カルボン酸の金属塩（１）を含み、該脂肪族カルボン酸の金属塩（１）の脂肪族カルボン酸が、脂肪族モノカルボン酸又は脂肪族ジカルボン酸である、請求項１～４のいずれか一項に記載のゴム組成物。 The rubber-metal adhesion promoter contains the metal salt (1) of the aliphatic carboxylic acid, and the aliphatic carboxylic acid of the metal salt (1) of the aliphatic carboxylic acid is an aliphatic monocarboxylic acid or an aliphatic acid. The rubber composition according to any one of claims 1 to 4, which is a dicarboxylic acid.
  6. 　前記脂肪族カルボン酸の金属塩（１）の脂肪族カルボン酸が、炭素数２～２０の飽和脂肪族モノカルボン酸である、請求項５に記載のゴム組成物。 The rubber composition according to claim 5, wherein the aliphatic carboxylic acid of the metal salt (1) of the aliphatic carboxylic acid is a saturated aliphatic monocarboxylic acid having 2 to 20 carbon atoms.
  7. 　前記飽和脂肪族モノカルボン酸が、２－エチルヘキサン酸、ネオデカン酸、ヘキサデカン酸又はオクタデカン酸である、請求項６に記載のゴム組成物。 The rubber composition according to claim 6, wherein the saturated aliphatic monocarboxylic acid is 2-ethylhexanoic acid, neodecanoic acid, hexadecanoic acid or octadecanoic acid.
  8. 　前記ゴム－金属間接着促進剤が、前記化合物（２）を含み、前記一般式（Ａ）中、Ｍが、ビスマスである、請求項１～７のいずれか一項に記載のゴム組成物。 The rubber composition according to any one of claims 1 to 7, wherein the rubber-metal adhesion accelerator contains the compound (2), and M is bismuth in the general formula (A).
  9. 　前記ゴム－金属間接着促進剤が、前記化合物（２）を含み、前記一般式（Ａ）中、Ｚが、前記式（ｚ－１）で表される構造である、請求項１～８のいずれか一項に記載のゴム組成物。 The rubber-metal adhesion accelerator contains the compound (2), and in the general formula (A), Z has a structure represented by the formula (z-1), claim 1 to 8. The rubber composition according to any one of the above.
  10. 　前記ゴム－金属間接着促進剤が、前記化合物（２）を含み、前記一般式（Ａ）中、（ＲＣＯＯ）が、炭素数２～２０の飽和脂肪族モノカルボン酸の残基である、請求項１～９のいずれか一項に記載のゴム組成物。 The rubber-metal adhesion promoter comprises the compound (2), and in the general formula (A), (RCOO) is a residue of a saturated aliphatic monocarboxylic acid having 2 to 20 carbon atoms. Item 6. The rubber composition according to any one of Items 1 to 9.
  11. 　前記飽和脂肪族モノカルボン酸が、２－エチルヘキサン酸、ネオデカン酸、ヘキサデカン酸又はオクタデカン酸である、請求項１０に記載のゴム組成物。 The rubber composition according to claim 10, wherein the saturated aliphatic monocarboxylic acid is 2-ethylhexanoic acid, neodecanoic acid, hexadecanoic acid or octadecanoic acid.
  12. 　前記ゴム成分１００質量部に対し、更にシリカを５質量部以上含む、請求項１～１１のいずれか一項に記載のゴム組成物。 The rubber composition according to any one of claims 1 to 11, further containing 5 parts by mass or more of silica with respect to 100 parts by mass of the rubber component.
  13. 　請求項１～１２のいずれか一項に記載のゴム組成物と、金属部材と、を具える、ゴム－金属複合体。 A rubber-metal complex comprising the rubber composition according to any one of claims 1 to 12 and a metal member.
  14. 　請求項１３に記載のゴム－金属複合体を具える、ホース。 A hose comprising the rubber-metal complex according to claim 13.
  15. 　請求項１３に記載のゴム－金属複合体を具える、コンベヤベルト。 A conveyor belt comprising the rubber-metal complex according to claim 13.
  16. 　請求項１３に記載のゴム－金属複合体を具える、ゴムクローラ。 A rubber crawler comprising the rubber-metal complex according to claim 13.
  17. 　請求項１３に記載のゴム－金属複合体を具える、タイヤ。 A tire comprising the rubber-metal complex according to claim 13.
PCT/JP2021/035954 2020-12-09 2021-09-29 Rubber composition, rubber/metal composite, hose, conveyor belt, rubber crawler, and tire WO2022123869A1 (en)

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