WO2020045454A1 - Rubber composition, metal-rubber composite molded body and method for producing metal-rubber composite molded body - Google Patents

Rubber composition, metal-rubber composite molded body and method for producing metal-rubber composite molded body Download PDF

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Publication number
WO2020045454A1
WO2020045454A1 PCT/JP2019/033569 JP2019033569W WO2020045454A1 WO 2020045454 A1 WO2020045454 A1 WO 2020045454A1 JP 2019033569 W JP2019033569 W JP 2019033569W WO 2020045454 A1 WO2020045454 A1 WO 2020045454A1
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rubber
acid
ethylene
rubber composition
group
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PCT/JP2019/033569
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French (fr)
Japanese (ja)
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貴史 酒井
中野　貞之
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住友化学株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/06—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of natural rubber or synthetic rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers

Definitions

  • the present invention relates to a rubber composition, a metal-rubber composite molded article, and a method for producing a metal-rubber composite molded article.
  • Ethylene- ⁇ -olefin-non-conjugated polyene copolymer rubber is excellent in various functions such as weather resistance, heat resistance and chemical resistance, and is widely used for applications such as automobile parts, electric / electronic parts, and OA equipment parts. Have been.
  • ethylene- ⁇ -olefin copolymer rubbers have low unsaturation and do not have polar groups or functional groups in the molecular structure, and therefore themselves have poor adhesion to metals. Therefore, conventionally, when bonding a rubber molded body and a metal member, a method of applying an adhesive to the metal member in advance and vulcanizing and molding unvulcanized rubber on the adhesive in order to increase the bonding strength, By vulcanizing the unvulcanized rubber containing sulfur on the surface of the brass-plated metal member, the unvulcanized rubber is vulcanized, and at the same time copper sulfide is formed on the surface of the metal member. (For example, Non-Patent Document 1) or the like is employed.
  • one aspect of the present invention provides a rubber composition that can directly adhere to a metal member with good adhesiveness without using an adhesive and can form a rubber molded body having sufficient durability.
  • the purpose is to do.
  • One aspect of the present invention is (A) an ethylene- ⁇ -olefin-non-conjugated polyene copolymer rubber containing an ethylene unit, an ⁇ -olefin unit having 3 or more carbon atoms and a non-conjugated polyene unit; (B) an organic sulfur compound; (C) a crosslinking agent; And a rubber composition comprising: The organic sulfur compound has a mercapto group or a polysulfide bond, and an acidic functional group or an acid-derived group derived from the acidic functional group.
  • ⁇ ⁇ Another aspect of the present invention provides a metal-rubber composite molded article including a metal member and a rubber molded article directly adhered to the metal member and containing a vulcanized product of the rubber composition.
  • Still another aspect of the present invention is to form a rubber molded body directly adhered to the metal member by forming the rubber composition in contact with a metal member, and to apply the rubber composition. And vulcanizing the metal-rubber composite molded article.
  • FIG. 1 is a cross-sectional view illustrating an embodiment of a metal-rubber composite molded article.
  • Rubber Composition includes an ethylene- ⁇ -olefin-non-conjugated polyene copolymer rubber as a component (A), an organic sulfur compound as a component (B), and a crosslinking agent as a component (C). And
  • (A) Ethylene- ⁇ -olefin-non-conjugated polyene copolymer rubber The ethylene- ⁇ -olefin-non-conjugated polyene copolymer rubber of the component (A) according to one embodiment has an ethylene unit and ⁇ of 3 or more carbon atoms. -Contains olefin units and non-conjugated polyene units as the main monomer units. The ⁇ -olefin unit may have 3 to 20 carbon atoms.
  • the total content of ethylene units and ⁇ -olefin units in the ethylene- ⁇ -olefin-non-conjugated polyene copolymer rubber is 60% based on the total mass of the ethylene- ⁇ -olefin-non-conjugated polyene copolymer rubber. It may be at least 80% by mass, or at least 80% by mass.
  • the term “monomer name + unit” such as “ethylene unit”, “ ⁇ -olefin unit”, and “non-conjugated polyene unit” means “monomer unit derived from the monomer”.
  • ⁇ -olefin constituting the ethylene- ⁇ -olefin-non-conjugated polyene copolymer rubber examples include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene And a linear olefin such as 1-decene; a branched olefin such as 3-methyl-1-butene, 3-methyl-1-pentene and 4-methyl-1-pentene; and a cyclic olefin such as vinylcyclohexane.
  • a linear olefin such as 1-decene
  • branched olefin such as 3-methyl-1-butene, 3-methyl-1-pentene and 4-methyl-1-pentene
  • a cyclic olefin such as vinylcyclohexane.
  • the ⁇ -olefin contained as a monomer unit in the ethylene- ⁇ -olefin-non-conjugated polyene copolymer rubber may be at least one of propylene and 1-butene, and may be propylene.
  • the mass ratio of ethylene units / ⁇ -olefin units in the ethylene- ⁇ -olefin-non-conjugated polyene copolymer rubber is not particularly limited, but is 90/10 to 30/70 with the total mass of both as 100. Or 85/15 to 45/55.
  • the content of the non-conjugated polyene unit in the ethylene- ⁇ -olefin-non-conjugated polyene copolymer rubber is 0 or more in terms of iodine value (unit: g / 100 g ethylene- ⁇ -olefin-non-conjugated polyene copolymer rubber). It may be 40 or less. When the content of the non-conjugated polyene unit is 40 or less in terms of iodine value, the weather resistance of the rubber molded article can be further improved. From the same viewpoint, the content of the non-conjugated polyene unit may be from 0 to 35 or from 0 to 30 in terms of iodine value.
  • the non-conjugated polyene constituting the ethylene- ⁇ -olefin-non-conjugated polyene copolymer rubber may have 3 to 20 carbon atoms.
  • Specific examples of non-conjugated polyenes include: Linear non-conjugated dienes such as 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, and 7-methyl-1,6-octadiene; Cyclohexadiene, dicyclopentadiene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- (3-butenyl) -2-norbornene, 5- (4-pentenyl) ) -2-norbornene, 5- (5-hexenyl) -2-norbornene, 5- (6-hepteny
  • the ethylene- ⁇ -olefin-non-conjugated polyene copolymer rubber may contain 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinylnorbornene or a combination thereof as a monomer unit.
  • the total content of ethylene units, ⁇ -olefin units, and non-conjugated polyene units in the ethylene- ⁇ -olefin-non-conjugated polyene copolymer rubber is defined as the total mass of the ethylene- ⁇ -olefin-non-conjugated polyene copolymer rubber. May be 60% by mass or more and 100% by mass or less, or 80% by mass or more and 100% by mass or less.
  • ethylene- ⁇ -olefin-non-conjugated polyene copolymer rubber examples include ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber, ethylene-propylene-dicyclopentadiene copolymer rubber, and ethylene-propylene- 1,4-hexadiene copolymer rubber, ethylene-propylene-1,6-octadiene copolymer rubber, ethylene-propylene-2-methyl-1,5-hexadiene copolymer rubber, ethylene-propylene-6-methyl- 1,5-heptadiene copolymer rubber, ethylene-propylene-7-methyl-1,6-octadiene copolymer rubber, ethylene-propylene-cyclohexadiene copolymer rubber, ethylene-propylene-5-vinylnorbornene copolymer Rubber, ethylene-propylene-5- (2-propenyl) 2-norborn
  • the rubber composition includes ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber, ethylene-propylene-dicyclopentadiene copolymer rubber, and ethylene- ⁇ -olefin-non-conjugated polyene copolymer rubber. It may contain a propylene-5-vinylnorbornene copolymer rubber or a combination thereof, or may contain an ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber.
  • the rubber composition contains two or more ethylene- ⁇ -olefin-non-conjugated polyene copolymer rubbers
  • the above-mentioned mass ratio of ethylene units / ⁇ -olefin units and the iodine value are determined by the two or more ethylene- ⁇ -olefin units. It is a value for the whole including the ⁇ -olefin-non-conjugated polyene copolymer rubber.
  • the ethylene- ⁇ -olefin-non-conjugated polyene copolymer rubber may have a Mooney viscosity at 100 ° C (ML1 + 4, 100 ° C) of 10 to 350, or 30 to 300. If the Mooney viscosity is too low, the mechanical strength of the rubber molded article may decrease, and if the Mooney viscosity is too high, the kneading processability tends to decrease.
  • the molecular weight distribution (Mw / Mn) of the ethylene- ⁇ -olefin-non-conjugated polyene copolymer rubber may be 1.5 or more and 10 or less. When the molecular weight distribution is 1.5 or more, good roll processability of the rubber composition is easily obtained. When the molecular weight distribution is 10 or less, the mechanical properties of the rubber molded article tend to be improved. From the same viewpoint, the molecular weight distribution of the ethylene- ⁇ -olefin-non-conjugated polyene copolymer rubber may be 2.0 or more and 7.0 or less. The molecular weight distribution can be adjusted by changing the polymerization conditions.
  • the molecular weight distribution in the present specification is a ratio (Mw / Mn) calculated from a weight average molecular weight (Mw) and a number average molecular weight (Mn) in terms of standard polystyrene measured using gel permeation chromatography (GPC method). is there.
  • the conditions for measuring the weight average molecular weight and the number average molecular weight by the GPC method are as follows, for example.
  • ⁇ GPC device manufactured by Tosoh Corporation, trade name: HLC-8121GPC / HT -Column: TSKgel GMHHR-H (S) HT, manufactured by Tosoh Corporation -Molecular weight standard substance: polystyrene having a molecular weight of 500 or more and 20,000,000 or less-Elution solvent flow rate: 1.0 mL / min -Sample concentration: 1 mg / mL ⁇ Measurement temperature: 140 ° C ⁇ Eluent solvent: ortho-dichlorobenzene ⁇ Injection volume: 500 ⁇ L ⁇ Detector: Differential refractometer
  • the content of the ethylene- ⁇ -olefin-non-conjugated polyene copolymer rubber in the rubber composition may be 20% by mass or more, or 35% by mass or more based on the mass of the rubber composition.
  • the content of the component (A) ethylene- ⁇ -olefin-non-conjugated polyene copolymer rubber is 75% by mass. % Or 85% by mass or more.
  • the method for producing the ethylene- ⁇ -olefin-non-conjugated polyene copolymer rubber is not particularly limited.
  • ethylene, ⁇ -olefin, ethylene- ⁇ -olefin, or so-called Ziegler-Natta catalyst or metallocene catalyst may be used.
  • An ethylene- ⁇ -olefin-nonconjugated polyene copolymer rubber can be produced by a method including a step of copolymerizing a monomer mixture containing a nonconjugated polyene and, if necessary, a monomer mixture.
  • a catalyst formed from a vanadium compound represented by the following formula (1) and an organoaluminum compound represented by the following formula (2) VO (OR) m X 3-m (1)
  • R represents a linear hydrocarbon group having 1 to 8 carbon atoms
  • X represents a halogen atom
  • m represents a number satisfying 0 ⁇ m ⁇ 3.
  • R " j AlX" 3-j (2)
  • R ′′ represents a hydrocarbon group
  • X ′′ represents a halogen atom
  • j represents a number satisfying 0 ⁇ j ⁇ 3.
  • R in the formula (1) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group.
  • a linear alkyl group having 1 to 3 carbon atoms is preferable.
  • X includes a fluorine atom, a chlorine atom and the like.
  • m is a number that preferably satisfies 1 ⁇ m ⁇ 2.
  • vanadium compound represented by the formula (1) examples include VO (OCH 3 ) Cl 2 , VO (OC 2 H 5 ) Cl 2 , VO (O (nC 3 H 7 )) Cl 2 , VO (O (nC 4 H 9 )) Cl 2 , VO (O (nC 5 H 11 )) Cl 2 , VO (O (nC 6 H 13 )) Cl 2 , VO (O (n ⁇ C 7 H 15)) Cl 2 , VO (O (n-C 8 H 17)) Cl 2, VO (OCH 3) 0.5 Cl 2.5, VO (OC 2 H 5) 0.5 Cl 2.
  • VO (O (nC 6 H 13 )) 1.8 Cl 1.2 VO (O (nC 7 H 15 )) 1.8 Cl 1.2
  • VO (OC 2 H 5 ) Cl 2 VO (OC 2 H 5 ) 0.5 Cl 2.5 , VO (OC 2 H 5 ) 1.5 Cl 1.5 , VO (OC 2 H 5) ) 0.8 Cl 2.2 and VO (OC 2 H 5 ) 1.8 Cl 1.2 are particularly preferred. These may be used alone or in combination.
  • the vanadium compound represented by the formula (1) is obtained, for example, by a method in which VOX 3 and ROH are reacted at a predetermined molar ratio.
  • the reaction between VOCl 3 and C 2 H 5 OH is represented by the following equation.
  • VOX 3 and ROH may be supplied to a polymerization tank to generate a vanadium compound of the formula (1) in the polymerization tank.
  • R ′′ in the formula (2) may be an alkyl group having 1 to 10 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, Examples include an iso-butyl group, a pentyl group, and a hexyl group.
  • X ′′ includes a fluorine atom, a chlorine atom, and the like.
  • j is preferably a number satisfying 0 ⁇ j ⁇ 2.
  • organoaluminum compound represented by the formula (2) As specific examples of the organoaluminum compound represented by the formula (2), (C 2 H 5 ) 2 AlCl, (nC 4 H 9 ) 2 AlCl, (iso-C 4 H 9 ) 2 AlCl, (n- C 6 H 13 ) 2 AlCl, (C 2 H 5 ) 1.5 AlCl 1.5 , (nC 4 H 9 ) 1.5 AlCl 1.5 , (iso-C 4 H 9 ) 1.5 AlCl 1.5 , (nC 6 H 13 ) 1.5 AlCl 1.5 , C 2 H 5 AlCl 2 , (nC 4 H 9 ) AlCl 2 , (iso-C 4 H 9 ) AlCl 2 , and (NC 6 H 13 ) AlCl 2 .
  • (C 2 H 5 ) 2 AlCl, (C 2 H 5 ) 1.5 AlCl 1.5 and C 2 H 5 AlCl 2 are particularly preferred. These may be used alone or in combination.
  • the molar ratio of the amount of the organoaluminum compound of the formula (2) to the amount of the vanadium compound of the formula (1) (mol of the organoaluminum compound / mol of the vanadium compound) is preferably 0.1 or more and 50 or less. It is more preferably 30 or more, more preferably 2 or more and 15 or less, particularly preferably 3 or more and 10 or less.
  • the viscosity, Mw / Mn, etc. of the ethylene- ⁇ -olefin-non-conjugated polyene copolymer rubber can be adjusted. For example, when the molar ratio is large, the viscosity of the ethylene- ⁇ -olefin-non-conjugated polyene copolymer rubber tends to increase, and Mw / Mn tends to decrease.
  • the polymerization reaction can be performed by, for example, a method of performing polymerization using one polymerization tank, or using two polymerization tanks connected in series.
  • a monomer, a catalyst and, if necessary, other components are supplied to the polymerization tank, and the monomer can be polymerized in the polymerization tank.
  • the polymerization reaction is usually performed in a solvent.
  • the solvent used for the polymerization include inert solvents such as aliphatic hydrocarbons such as propane, butane, isobutane, pentane, hexane, heptane, and octane; and alicyclic hydrocarbons such as cyclopentane and cyclohexane. These may be used alone or in combination. Of these, aliphatic hydrocarbons are preferred.
  • the polymerization temperature may be generally from 0 ° C to 200 ° C, preferably from 20 ° C to 150 ° C, and more preferably from 30 ° C to 120 ° C.
  • the polymerization pressure may be generally from 0.1 MPa to 10 MPa, preferably from 0.1 MPa to 5 MPa, more preferably from 0.1 MPa to 3 MPa.
  • hydrogen may be supplied to the polymerization tank as a molecular weight regulator if necessary.
  • the amount of hydrogen supplied to the polymerization tank is preferably 0.001 to 0.1 NL, more preferably 0.005 to 0.05 NL, and still more preferably 0 to 0.05 NL per kg of the solvent supplied to the polymerization tank. .01 to 0.04 NL.
  • the supply amount of hydrogen By adjusting the supply amount of hydrogen, the Mw / Mn, viscosity, and the like of the ethylene- ⁇ -olefin copolymer can be adjusted. For example, when the supply amount of hydrogen is large, Mw / Mn tends to decrease. When the supply amount of hydrogen is small, the viscosity tends to increase.
  • the amount of the vanadium compound supplied to the polymerization tank is preferably 0.002 parts by mass or more and 0.2 parts by mass or less, more preferably 0.003 parts by mass or more, per 100 parts by mass of the solvent supplied to the polymerization tank. 0.1 parts by mass or less.
  • the organosulfur compound of the component (B) has one or more mercapto groups (—SH) or one or more polysulfide bonds (—S n —, n is an integer of 2 or more) in the molecule.
  • the organic sulfur compound has one or two mercapto groups or one or two polysulfide bonds, and one or two acidic functional groups or one or two acid-derived groups. It may be.
  • the organic sulfur compound may have an acidic functional group and an acid-derived group.
  • the rubber composition may include one or more organic sulfur compounds.
  • the type of the acidic functional group is not particularly limited as long as it is a functional group exhibiting acidity.
  • the organic sulfur compound of the component (B) may have one or more acidic functional groups selected from these.
  • the acidic functional group may be a carboxyl group, a sulfo group, a sulfeno group, or may be a carboxyl group.
  • the diacid-derived group is not particularly limited, but may be, for example, a metal salt, an amine salt (eg, an ammonium salt), an acid anhydride, an acid halide, or an ester, or may be a metal salt.
  • a metal salt is a functional group formed by an anion formed by dissociation of hydrogen from an acidic functional group and a metal cation. Two molecules of the organic sulfur compound may form a metal salt with one metal cation. Examples of metal salts include potassium, calcium, sodium, magnesium, aluminum, and zinc salts.
  • the acid-derived group may in particular be a metal carboxylate.
  • the rubber composition may be prepared by mixing an organic sulfur compound having a metal salt with the component (A), or an organic sulfur compound having an acidic functional group and a metal oxide may be mixed with the component (A), and The metal salt may be formed by allowing the neutralization reaction to proceed.
  • Examples of the organic sulfur compound having a mercapto group and an acidic functional group include 3-mercaptopropionic acid, mercaptosuccinic acid, 2-mercaptopropionic acid, thioglycolic acid, mercaptobutanoic acid, mercaptovaleric acid, and amino-4-mercaptobutyric acid Oxo-4-mercaptobutyric acid, 4-mercapto-4-oxobutanoic acid, tetranordihydrolipoic acid, 3- (dithiocarboxy) propionic acid, (1-mercaptomethylcyclopropyl) acetic acid, 3- (mercaptomethyl) -4 -Aminobutanoic acid, dimercaptoacetic acid, 2-mercaptopropanoic acid, mercaptoacrylic acid, mercaptocaproic acid, mercaptoheptanoic acid, mercaptooctanoic acid, mercaptononanoic acid, mercaptode
  • organic sulfur compound having a polysulfide bond and an acidic functional group examples include 3,3′-dithiodipropionic acid, dithioglycolic acid, 1,2-dithiane-4-carboxylic acid, 4,4′-dithiobisbutyric acid, bis [3-carboxy-1-iminopropyl] persulfide, 1,2-dithiane-3,6-dicarboxylic acid, 2,2′-dithiobispropionic acid, 2,2′-dithiobisglycine, sawtrabispropionate Sulfide, dithiobisformic acid, dithiobiscaproic acid, dithiobisheptanoic acid, dithiobisoctanoic acid, dithiobisnonanoic acid, dithiobismercaptodecanoic acid, dithiobismercaptododecanoic acid, dithiobisdodecanoic acid, dithiobistetradecanoic acid, dithiobi
  • Examples of the organic sulfur compound having a mercapto group and an acid-derived group include methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, propyl 3-mercaptopropionate, butyl 3-mercaptopropionate, and potassium 3-mercaptopropionate.
  • Examples of the organic sulfur compound having a polysulfide bond and an acid-derived group include dimethyl 3,3′-dithiodipropionate, diethyl 3,3′-dithiodipropionate, dipropyl 3,3′-dithiodipropionate, Dibutyl 3,3'-dithiodipropionate, potassium 3,3'-dithiodipropionate, calcium 3,3'-dithiodipropionate, sodium 3,3'-dithiodipropionate, 3,3 ' -Magnesium dithiodipropionate, aluminum 3,3'-dithiodipropionate, and zinc 3,3'-dithiodipropionate.
  • the rubber composition may contain one or more selected from the compounds exemplified above as the component (B).
  • the content of the organic sulfur compound (B) in the rubber composition is large, the adhesion of the rubber molded body to the metal member tends to be further improved.
  • the content of the organic sulfur compound (B) is 1 part by mass or more, 2.5 parts by mass or more, and 3 parts by mass with respect to 100 parts by mass of the ethylene- ⁇ -olefin-non-conjugated polyene copolymer rubber. Or more than 5 parts by mass.
  • the upper limit of the content of the organic sulfur compound (B) is not particularly limited, but may be 100 parts by mass or less.
  • the organic sulfur compound when (B) the organic sulfur compound is a compound having an acid-derived group, the acid-derived group of the compound having the same substance amount as that of the compound having the acid-derived group is replaced with this.
  • the amount of the compound replaced by the deriving acidic functional group is regarded as the content of the organic sulfur compound (B).
  • R-COO ⁇ M + R represents a mercapto group or a monovalent organic group containing a polysulfide bond, in which the organic sulfur compound has a carboxylate metal salt formed from a carbochelate group and a metal cation.
  • M + represents a metal cation.
  • the amount is converted to the amount of a compound represented by R-COOH in which -COO ⁇ M + of the compound is replaced with -COOH.
  • the amount of the compound represented by R-COOH which is the same as the amount of the compound represented by R-COO - M + , contained in the rubber composition is (B) the content of the organic sulfur compound Considered as quantity.
  • the amount of an organic sulfur compound having a carboxylic acid amine salt, a carboxylic acid anhydride, a carboxylic acid halide, or a carboxylic acid ester is converted to the amount of a compound in which these acid-derived groups have been replaced with carboxyl groups.
  • the crosslinking agent is not particularly limited, and can be selected from compounds commonly used for crosslinking or vulcanizing rubber.
  • the cross-linking agent may include, for example, an organic peroxide, sulfur, a sulfur compound, an oxime compound, a nitroso compound, a polyamine compound, an alkylphenol-formaldehyde condensate, or a combination of two or more selected from these.
  • a sulfur compound as a crosslinking agent means a compound other than the above-mentioned (B) organic sulfur compound.
  • the crosslinker may include an organic peroxide.
  • organic peroxide examples include ketone peroxide, diacyl peroxide, hydroperoxide, dialkyl peroxide, peroxyketal, alkyl perester, percarbonate, peroxydicarbonate, and peroxyester.
  • organic peroxide examples include dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and 2,5-dimethyl-2,5-di (t-butylperoxide).
  • a single compound or two or more compounds may be used as the
  • the rubber composition of the present embodiment may further contain other components in addition to the components described above, as long as the effects of the present invention are not significantly impaired.
  • other components include a reinforcing agent, a softening agent, a crosslinking aid, a processing aid, and rubber components other than the ethylene- ⁇ -olefin-non-conjugated polyene copolymer rubber.
  • the reinforcing agent examples include various carbon blacks such as SRF, GPF, FEF, MAF, ISAF, SAF, FT, and MT, dry silica, wet silica, synthetic silicate silica, colloidal silica, calcium carbonate, mica, Examples include magnesium silicate, aluminum silicate, lignin, aluminum hydroxide, and magnesium hydroxide. These are used alone or in combination of two or more.
  • the content of the reinforcing agent in the rubber composition may be 200 parts by mass or less, or 150 parts by mass or less based on 100 parts by mass of the ethylene- ⁇ -olefin-nonconjugated polyene copolymer rubber.
  • softeners examples include process oils, lubricating oils, paraffins, paraffinic oils such as liquid paraffin, naphthenic oils, petroleum asphalt, petrolatum, coal tar pitch, castor oil, linseed oil, sub, beeswax, and ricinoleic acid. Is mentioned. These are used alone or in combination of two or more.
  • the content of the softener in the rubber composition may be 150 parts by mass or less, or 100 parts by mass or less based on 100 parts by mass of the ethylene- ⁇ -olefin-non-conjugated polyene copolymer rubber.
  • the crosslinking aid may include a compound having two or more double bonds in the molecule.
  • the crosslinking assistant include N, N′-m-phenylenebismaleimide, toluylenebismaleimide, triallyl isocyanurate, triallyl cyanurate, p-quinonedioxime, nitrobenzene, diphenylguanidine, divinylbenzene, ethylene glycol diethylene Examples include methacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, and allyl methacrylate. These may be used alone or in combination of two or more.
  • the content of the crosslinking aid in the rubber composition is 0.05 to 20 parts by mass, or 0.1 or more parts by mass based on 100 parts by mass of the ethylene- ⁇ -olefin-non-conjugated polyene copolymer rubber. It may be 8 parts by mass or less.
  • processing aid examples include fatty acids such as oleic acid, palmitic acid and stearic acid; metal salts of fatty acids such as zinc laurate, zinc stearate, barium stearate and calcium stearate; fatty acid esters; Glycol. These can be used alone or in combination.
  • the content of the processing aid in the rubber composition is 0.2 parts by mass or more and 10 parts by mass or less, or 0.3 parts by mass or more based on 100 parts by mass of the ethylene- ⁇ -olefin-nonconjugated polyene copolymer rubber. It may be 8 parts by mass or less.
  • ⁇ Rubber components other than ethylene- ⁇ -olefin-non-conjugated polyene copolymer rubber include, for example, natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, and butyl rubber.
  • the content of the rubber component other than the system copolymer rubber in the rubber composition is from 10 parts by mass to 40 parts by mass, or 15 parts by mass, based on 100 parts by mass of the ethylene- ⁇ -olefin-nonconjugated polyene copolymer rubber. To 30 parts by mass.
  • the rubber composition can be obtained, for example, by kneading a mixture containing an ethylene- ⁇ -olefin-non-conjugated polyene copolymer rubber and other components.
  • the kneading can be performed using a closed kneader such as a mixer, a kneader, and a twin-screw extruder. Kneading can be performed until the components are uniformly mixed.
  • the kneading time may be 1 minute or more and 60 minutes or less.
  • the kneading temperature may be 40 ° C or more and 200 ° C or less.
  • An oil-extended rubber obtained by mixing an ethylene- ⁇ -olefin-non-conjugated polyene copolymer rubber with a process oil such as a paraffinic oil and a naphthenic oil may be used for the production of the rubber composition.
  • FIG. 1 is a cross-sectional view showing one embodiment of a metal-rubber composite molded product.
  • the metal-rubber composite molded body 5 shown in FIG. 1 includes a metal member 1 and a rubber molded body 3 directly adhered to the metal member 1.
  • the rubber molded body 3 includes a vulcanized product of the rubber composition according to the above-described embodiment. In other words, the rubber molded body 3 is made of a vulcanized rubber composition.
  • the rubber molded body 3 is directly bonded to the surface of the metal member 1 without using an adhesive.
  • the rubber molded body 3 is formed, for example, by molding the rubber composition in a mold in contact with the metal member, thereby forming the rubber molded body 3 directly adhered to the metal member 1; And vulcanizing the product.
  • the rubber composition may be vulcanized while the rubber molded body 3 is formed by heating, or after the rubber molded body 3 is formed, the rubber composition forming the rubber molded body 3 may be vulcanized.
  • the rubber composition is molded in a mold while being heated to 100 ° C. or more and 250 ° C. or less, or 120 ° C. or more and 230 ° C. or less using a molding machine such as an injection molding machine, a compression molding machine, or a hot air vulcanizing device. Thereby, it is possible to form a vulcanized rubber molded body that is bonded to the metal member.
  • the molding time is, for example, 1 minute or more and 60 minutes or less.
  • the metal constituting the metal member is not particularly limited, and can be selected from a wide range of metals.
  • the metal member is, for example, magnesium, calcium, barium, titanium, zirconium, iron, cobalt, beryllium, aluminum, chromium, manganese, nickel, copper, zinc, tin, cadmium, silver, platinum, gold, lead, or a combination thereof.
  • a molded article of an alloy containing The metal member may be a formed body of iron, aluminum, copper, or an alloy containing any of these.
  • the metal member may be a steel compact.
  • the metal member may be a molded body having a plated surface.
  • the plating process is a process other than the brass plating process, and may be, for example, a chrome plating process.
  • the metal-rubber composite molded article can be used for various members such as a rubber roll, an anti-vibration rubber for an automobile, and a seismic isolation rubber for a building.
  • the shapes of the metal member and the rubber molded body are not particularly limited, and are designed according to the application.
  • Iodine value Each of three types of ethylene-propylene-5-ethylidene-2-norbornene copolymer rubbers having different known iodine values based on “JIS K0070-1992 6. Iodine value” was hot-pressed. To form a film having a thickness of about 0.2 mm. The infrared absorption spectrum of each film was measured with an infrared spectrophotometer (IR-700 manufactured by JASCO Corporation).
  • the transmittance of the peak derived from 5-ethylidene-2-norbornene (the absorption peak at 1686 cm -1 ) and the base peak (the absorption peak at 1664 to 1674 cm -1 ) of each film were determined.
  • the IR index was calculated according to the formula (I).
  • A is the transmittance of the base peak
  • B is the transmittance of the peak derived from 5-ethylidene-2-norbornene
  • D (mm) is the thickness of the film.
  • ⁇ GPC device manufactured by Tosoh Corporation, trade name: HLC-8121GPC / HT -Column: TSKgel GMHHR-H (S) HT, manufactured by Tosoh Corporation -Molecular weight standard substance: polystyrene having a molecular weight of 500 or more and 20,000,000 or less-Elution solvent flow rate: 1.0 mL / min -Sample concentration: 1 mg / mL ⁇ Measurement temperature: 140 ° C ⁇ Eluent solvent: ortho-dichlorobenzene ⁇ Injection volume: 500 ⁇ L ⁇ Detector: Differential refractometer
  • Stearic acid 50S (trade name), Shin-Nippon Rikasha -Malic acid: Reagent special grade, manufactured by Fujifilm Wako Pure Chemical Co., Ltd.-4-Aminobenzenethiol: Reagent special grade, manufactured by Fujifilm Wako Pure Chemical Co., Ltd.-Methionine: Reagent special grade, manufactured by Fujifilm Wako Pure Chemical Co., Ltd.-Zinc oxide: 2 Seed (trade name), manufactured by Shodo Chemical Co., Ltd. ⁇ Calcium oxide: VESTA-PP (trade name), manufactured by Inoue Lime Industry Co.
  • Example 2 to 6 Comparative Examples 1 to 8 A rubber composition was prepared in the same manner as in Example 1 except that the type and the mixing ratio of each component were changed as shown in Table 1 or Table 2.
  • the mixing ratio shown in each table is parts by mass.
  • the types and mixing ratios of the components not specified in the table are common to all Examples and Comparative Examples.
  • Comparative Examples 3 to 8 zinc acrylate, 1-heptanol, stearic acid, malic acid, 4-aminobenzenethiol, or methionine was used in place of mercaptosuccinic acid during kneading using a Banbury mixer.
  • a metal-rubber composite member (total thickness: 8 mm) consisting of a steel sheet and a sheet-like rubber molded body (length 125 mm, width 25 mm, thickness: 6 mm) directly vulcanized and bonded to the surface of the steel sheet was formed. .
  • a Teflon (registered trademark) sheet between the press surface of the press and the rubber composition, adhesion of the rubber to the press surface of the press was prevented.
  • the adhesiveness of the rubber molded product to a steel plate was measured in accordance with JIS K 6256-2.
  • the constant elongation fatigue test was performed using a dumbbell-shaped No. 3 test piece (thickness: 2 mm) in accordance with JIS K 6270 under the conditions of an elongation ratio of 50%, a frequency of 5 Hz, and 23 ° C. Four specimens were tested and 50% elongation was repeated 20,000 times. The average value of the number of elongations at the time when each of the four test pieces broke was recorded.
  • the rubber molded article formed from the rubber composition of the example exhibited high adhesiveness to a steel sheet without using an adhesive.
  • the rubber molded articles of the examples exhibited excellent durability such that they did not break until the number of elongations reached 20,000 in a durability test.
  • the rubber composition of Comparative Example 3 containing zinc acrylate was excellent in adhesion to a steel sheet, but was insufficient in durability.
  • the rubber compositions of the other comparative examples were excellent in durability, but had low adhesion to steel plates. Note that the rubber composition of Comparative Example 2 containing no crosslinking agent could not form a test piece for evaluation of adhesive strength and durability because crosslinking did not proceed sufficiently.
  • Examples 12 to 14 At the time of kneading using a Banbury mixer, instead of mercaptosuccinic acid, calcium mercaptoacetate trihydrate, 3,3'-dithiopropionic acid, or 3-mercaptopropionic acid was used. A rubber composition was prepared in the same manner as in Example 5, except that the parts were changed to parts by mass shown in No. 3.
  • Table 3 the numerical values in parentheses of the blending ratio of calcium mercaptoacetate trihydrate are the blending ratios converted to the amount of mercaptoacetic acid having the same substance amount as the calcium mercaptoacetate trianhydride used.
  • Example 15 to 17 Using the rubber composition of Example 8, a metal-rubber composite molded body was produced using a stainless steel plate, an aluminum plate copper plate, a cold-rolled steel plate, an aluminum alloy plate, or a hard chromium-plated steel plate instead of a steel plate, The adhesive strength was evaluated.

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Abstract

The present invention discloses a rubber composition which contains (A) an ethylene/α-olefin/non-conjugated polyene copolymer rubber that contains an ethylene unit, an α-olefin unit having 3 or more carbon atoms and a non-conjugated polyene unit, (B) an organic sulfur compound and (C) a crosslinking agent. The organic sulfur compound has: a mercapto group or a polysulfide bond; and an acidic functional group or an acid derivative group derived from an acidic functional group.

Description

ゴム組成物、金属－ゴム複合成形体、及び、金属－ゴム複合成形体の製造方法Rubber composition, metal-rubber composite molded article, and method for producing metal-rubber composite molded article
　本発明は、ゴム組成物、金属－ゴム複合成形体、及び、金属－ゴム複合成形体の製造方法に関する。 The present invention relates to a rubber composition, a metal-rubber composite molded article, and a method for producing a metal-rubber composite molded article.
　エチレン－α－オレフィン－非共役ポリエン共重合体ゴムは、耐候性、耐熱性、耐薬品性等の諸機能に優れており、自動車部品、電気・電子部品、ＯＡ機器部品などの用途に広く使用されている。 Ethylene-α-olefin-non-conjugated polyene copolymer rubber is excellent in various functions such as weather resistance, heat resistance and chemical resistance, and is widely used for applications such as automobile parts, electric / electronic parts, and OA equipment parts. Have been.
　一般に、エチレン－α－オレフィン系共重合体ゴムは低不飽和度でかつ、分子構造中に極性基又は官能基を有しないため、それ自体は金属との接着性が乏しい。そこで、従来、ゴム成形体と金属部材とを接着する場合、接着強度を高めるために、金属部材に予め接着剤を塗布しておき、接着剤上に未加硫ゴムを加硫成形する方法、黄銅（ブラス）メッキした金属部材の表面上に硫黄を含む未加硫ゴムを加硫成形することで、未加硫ゴムを加硫すると同時に金属部材の表面に硫化銅を形成させ、硫黄を介してゴム成形体と金属部材を接着する方法（例えば非特許文献１）などが採用される。 エ チ レ ン Generally, ethylene-α-olefin copolymer rubbers have low unsaturation and do not have polar groups or functional groups in the molecular structure, and therefore themselves have poor adhesion to metals. Therefore, conventionally, when bonding a rubber molded body and a metal member, a method of applying an adhesive to the metal member in advance and vulcanizing and molding unvulcanized rubber on the adhesive in order to increase the bonding strength, By vulcanizing the unvulcanized rubber containing sulfur on the surface of the brass-plated metal member, the unvulcanized rubber is vulcanized, and at the same time copper sulfide is formed on the surface of the metal member. (For example, Non-Patent Document 1) or the like is employed.
　接着剤を使用せずに金属部材とゴムとを直接接着する方法として、特許文献１のようにアクリル酸亜鉛を配合したゴムと金属とを直接加硫接着させる方法が報告されている。 と し て As a method of directly bonding a metal member and rubber without using an adhesive, a method of directly vulcanizing and bonding a rubber containing zinc acrylate and a metal as in Patent Document 1 has been reported.
特開平５－３１１００８号公報JP-A-5-311008
　しかし、アクリル酸亜鉛をゴム組成物に添加すると、直接加硫接着によって金属部材との良好な接着性を有するゴム成形体を形成できるものの、加硫後のゴム成形体の耐久性が不足するという問題があった。 However, when zinc acrylate is added to a rubber composition, a rubber molded body having good adhesion to a metal member can be formed by direct vulcanization bonding, but the durability of the rubber molded body after vulcanization is insufficient. There was a problem.
　そこで、本発明の一側面は、接着剤を介さなくても良好な接着性で金属部材と直接接着し、かつ十分な耐久性を有するゴム成形体を形成することができる、ゴム組成物を提供することを目的とする。 Therefore, one aspect of the present invention provides a rubber composition that can directly adhere to a metal member with good adhesiveness without using an adhesive and can form a rubber molded body having sufficient durability. The purpose is to do.
　本発明の一側面は、
　（Ａ）エチレン単位、炭素数３以上のα－オレフィン単位及び非共役ポリエン単位を含むエチレン－α－オレフィン－非共役ポリエン共重合体ゴムと、
　（Ｂ）有機硫黄化合物と、
　（Ｃ）架橋剤と、
を含有する、ゴム組成物を提供する。前記有機硫黄化合物が、メルカプト基又はポリスルフィド結合と、酸性官能基、又は、酸性官能基から誘導される酸誘導基と、を有する。 One aspect of the present invention is
(A) an ethylene-α-olefin-non-conjugated polyene copolymer rubber containing an ethylene unit, an α-olefin unit having 3 or more carbon atoms and a non-conjugated polyene unit;
(B) an organic sulfur compound;
(C) a crosslinking agent;
And a rubber composition comprising: The organic sulfur compound has a mercapto group or a polysulfide bond, and an acidic functional group or an acid-derived group derived from the acidic functional group.
　本発明の別の一側面は、金属部材と、前記金属部材に直接接着し上記ゴム組成物の加硫物を含むゴム成形体と、を備える金属－ゴム複合成形体を提供する。 の 一 Another aspect of the present invention provides a metal-rubber composite molded article including a metal member and a rubber molded article directly adhered to the metal member and containing a vulcanized product of the rubber composition.
　本発明の更に別の一側面は、上記ゴム組成物を金属部材と接触させた状態で成形することで、前記金属部材に直接接着したゴム成形体を形成させることと、前記ゴム組成物を加硫することとを含む、金属－ゴム複合成形体の製造方法を提供する。 Still another aspect of the present invention is to form a rubber molded body directly adhered to the metal member by forming the rubber composition in contact with a metal member, and to apply the rubber composition. And vulcanizing the metal-rubber composite molded article.
　本発明の一側面によれば、接着剤を介さずに良好な接着性で金属部材に接着し、しかも十分な耐久性を有するゴム成形体、及びこれを有する金属－ゴム複合成形体を得ることができる。 According to one aspect of the present invention, it is possible to obtain a rubber molded article which adheres to a metal member with good adhesiveness without using an adhesive and has sufficient durability, and a metal-rubber composite molded article having the same. Can be.
金属－ゴム複合成形体の一実施形態を示す断面図である。FIG. 1 is a cross-sectional view illustrating an embodiment of a metal-rubber composite molded article.
　以下、本発明のいくつかの実施形態について詳細に説明する。ただし、本発明は以下の実施形態に限定されるものではない。 Hereinafter, some embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.
ゴム組成物
　一実施形態に係るゴム組成物は、成分（Ａ）としてエチレン－α－オレフィン－非共役ポリエン共重合体ゴムと、成分（Ｂ）として有機硫黄化合物と、成分（Ｃ）として架橋剤とを含有する。 Rubber Composition A rubber composition according to one embodiment includes an ethylene-α-olefin-non-conjugated polyene copolymer rubber as a component (A), an organic sulfur compound as a component (B), and a crosslinking agent as a component (C). And
（Ａ）エチレン－α－オレフィン－非共役ポリエン共重合体ゴム
　一実施形態に係る成分（Ａ）のエチレン－α－オレフィン－非共役ポリエン共重合体ゴムは、エチレン単位及び炭素数３以上のα－オレフィン単位及び非共役ポリエン単位を主な単量体単位として含む。α－オレフィン単位の炭素数は３以上２０以下であってもよい。エチレン－α－オレフィン－非共役ポリエン共重合体ゴムにおける、エチレン単位とα－オレフィン単位の合計の含有量は、エチレン－α－オレフィン－非共役ポリエン共重合体ゴムの全体質量に対して、６０質量％以上、又は８０質量％以上であってもよい。本明細書において、「エチレン単位」、「α－オレフィン単位」、「非共役ポリエン単位」のような「モノマー名＋単位」という用語は、「該モノマーに由来するモノマー単位」を意味する。 (A) Ethylene-α-olefin-non-conjugated polyene copolymer rubber The ethylene-α-olefin-non-conjugated polyene copolymer rubber of the component (A) according to one embodiment has an ethylene unit and α of 3 or more carbon atoms. -Contains olefin units and non-conjugated polyene units as the main monomer units. The α-olefin unit may have 3 to 20 carbon atoms. The total content of ethylene units and α-olefin units in the ethylene-α-olefin-non-conjugated polyene copolymer rubber is 60% based on the total mass of the ethylene-α-olefin-non-conjugated polyene copolymer rubber. It may be at least 80% by mass, or at least 80% by mass. As used herein, the term “monomer name + unit” such as “ethylene unit”, “α-olefin unit”, and “non-conjugated polyene unit” means “monomer unit derived from the monomer”.
　エチレン－α－オレフィン－非共役ポリエン共重合体ゴムを構成するα－オレフィンの具体例としては、プロピレン、１－ブテン、１－ペンテン、１－ヘキセン、１－ヘプテン、１－オクテン、１－ノネン、及び１－デセン等の直鎖状オレフィン；３－メチル－１－ブテン、３－メチル－１－ペンテン、及び４－メチル－１－ペンテン等の分岐鎖状オレフィン；ビニルシクロヘキサン等の環状オレフィンが挙げられる。これらは単独で又は２種以上組み合わせでエチレン－α－オレフィン－非共役ポリエン共重合体ゴムを構成することができる。エチレン－α－オレフィン－非共役ポリエン共重合体ゴムにモノマー単位として含まれるα－オレフィンは、プロピレン又は１－ブテンのうち少なくともいずれか一方であってもよく、プロピレンであってもよい。 Specific examples of the α-olefin constituting the ethylene-α-olefin-non-conjugated polyene copolymer rubber include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene And a linear olefin such as 1-decene; a branched olefin such as 3-methyl-1-butene, 3-methyl-1-pentene and 4-methyl-1-pentene; and a cyclic olefin such as vinylcyclohexane. No. These can be used alone or in combination of two or more to constitute an ethylene-α-olefin-non-conjugated polyene copolymer rubber. The α-olefin contained as a monomer unit in the ethylene-α-olefin-non-conjugated polyene copolymer rubber may be at least one of propylene and 1-butene, and may be propylene.
　エチレン－α－オレフィン－非共役ポリエン共重合体ゴムにおけるエチレン単位／α－オレフィン単位の質量比は、特に制限されることはないが、両者の合計質量を１００として、９０／１０～３０／７０、又は８５／１５～４５／５５であってもよい。 The mass ratio of ethylene units / α-olefin units in the ethylene-α-olefin-non-conjugated polyene copolymer rubber is not particularly limited, but is 90/10 to 30/70 with the total mass of both as 100. Or 85/15 to 45/55.
　エチレン－α－オレフィン－非共役ポリエン共重合体ゴムにおける非共役ポリエン単位の含有量は、ヨウ素価換算（単位：ｇ／１００ｇエチレン－α－オレフィン－非共役ポリエン共重合体ゴム）で、０以上４０以下であってもよい。非共役ポリエン単位の含有量がヨウ素価換算で４０以下であることによって、ゴム成形体の耐候性がより向上し得る。同様の観点から、非共役ポリエン単位の含有量は、ヨウ素価換算で、０以上３５以下であってもよく、０以上３０以下であってもよい。 The content of the non-conjugated polyene unit in the ethylene-α-olefin-non-conjugated polyene copolymer rubber is 0 or more in terms of iodine value (unit: g / 100 g ethylene-α-olefin-non-conjugated polyene copolymer rubber). It may be 40 or less. When the content of the non-conjugated polyene unit is 40 or less in terms of iodine value, the weather resistance of the rubber molded article can be further improved. From the same viewpoint, the content of the non-conjugated polyene unit may be from 0 to 35 or from 0 to 30 in terms of iodine value.
　エチレン－α－オレフィン－非共役ポリエン共重合体ゴムを構成する非共役ポリエンの炭素数は、３以上２０以下であってもよい。非共役ポリエンの具体例としては、
１，４－ヘキサジエン、１，６－オクタジエン、２－メチル－１，５－ヘキサジエン、６－メチル－１，５－ヘプタジエン、及び７－メチル－１，６－オクタジエン等の鎖状非共役ジエン；
シクロヘキサジエン、ジシクロペンタジエン、５－ビニルノルボルネン、５－エチリデン－２－ノルボルネン、５－（２－プロペニル）－２－ノルボルネン、５－（３－ブテニル）－２－ノルボルネン、５－（４－ペンテニル）－２－ノルボルネン、５－（５－ヘキセニル）－２－ノルボルネン、５－（６－ヘプテニル）－２－ノルボルネン、５－（７－オクテニル）－２－ノルボルネン、５－メチレン－２－ノルボルネン、及び６－クロロメチル－５－イソプロペニル－２－ノルボルネン等の環状非共役ジエン；並びに、
４－エチリデン－８－メチル－１，７－ノナジエン、５，９，１３－トリメチル－１，４，８，１２－テトラデカジエン、４－エチリデン－１２－メチル－１，１１－ペンタデカジエン、２，３－ジイソプロピリデン－５－ノルボルネン、２－エチリデン－３－イソプロピリデン－５－ノルボルネン、２－プロペニル－２，２－ノルボルナジエン、１，３，７－オクタトリエン、６，１０－ジメチル－１，５，９－ウンデカトリエン、５，９－ジメチル－１，４，８－デカトリエン、１３－エチル－９－メチル－１，９，１２－ペンタデカトリエン、５，９，８，１４，１６－ペンタメチル－１，７，１４－ヘキサデカトリエン、及び１，４，９－デカトリエン等のトリエンが挙げられる。これらは単独で又は２種以上の組み合わせでエチレン－α－オレフィン－非共役ポリエン共重合体ゴムを構成することができる。これらのうち、５－エチリデン－２－ノルボルネン、ジシクロペンタジエン、５－ビニルノルボルネン又はこれらの組合せをモノマー単位としてエチレン－α－オレフィン－非共役ポリエン共重合体ゴムが含んでいてもよい。 The non-conjugated polyene constituting the ethylene-α-olefin-non-conjugated polyene copolymer rubber may have 3 to 20 carbon atoms. Specific examples of non-conjugated polyenes include:
Linear non-conjugated dienes such as 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, and 7-methyl-1,6-octadiene;
Cyclohexadiene, dicyclopentadiene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- (3-butenyl) -2-norbornene, 5- (4-pentenyl) ) -2-norbornene, 5- (5-hexenyl) -2-norbornene, 5- (6-heptenyl) -2-norbornene, 5- (7-octenyl) -2-norbornene, 5-methylene-2-norbornene, And a cyclic non-conjugated diene such as 6-chloromethyl-5-isopropenyl-2-norbornene; and
4-ethylidene-8-methyl-1,7-nonadiene, 5,9,13-trimethyl-1,4,8,12-tetradecadiene, 4-ethylidene-12-methyl-1,11-pentadecadiene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, 1,3,7-octatriene, 6,10-dimethyl- 1,5,9-undecatriene, 5,9-dimethyl-1,4,8-decatriene, 13-ethyl-9-methyl-1,9,12-pentadecatriene, 5,9,8,14, Trienes such as 16-pentamethyl-1,7,14-hexadecatriene and 1,4,9-decatriene are mentioned. These can be used alone or in combination of two or more to constitute an ethylene-α-olefin-non-conjugated polyene copolymer rubber. Among these, the ethylene-α-olefin-non-conjugated polyene copolymer rubber may contain 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinylnorbornene or a combination thereof as a monomer unit.
　エチレン－α－オレフィン－非共役ポリエン共重合体ゴムにおける、エチレン単位、α－オレフィン単位及び非共役ポリエン単位の合計の含有量は、エチレン－α－オレフィン－非共役ポリエン共重合体ゴムの全体質量に対して、６０質量％以上１００質量％以下、又は８０質量％以上１００質量％以下であってもよい。 The total content of ethylene units, α-olefin units, and non-conjugated polyene units in the ethylene-α-olefin-non-conjugated polyene copolymer rubber is defined as the total mass of the ethylene-α-olefin-non-conjugated polyene copolymer rubber. May be 60% by mass or more and 100% by mass or less, or 80% by mass or more and 100% by mass or less.
　エチレン－α－オレフィン－非共役ポリエン共重合体ゴムの具体例として、エチレン－プロピレン－５－エチリデン－２－ノルボルネン共重合体ゴム、エチレン－プロピレン－ジシクロペンタジエン共重合体ゴム、エチレン－プロピレン－１，４－ヘキサジエン共重合体ゴム、エチレン－プロピレン－１，６－オクタジエン共重合体ゴム、エチレン－プロピレン－２－メチル－１，５－ヘキサジエン共重合体ゴム、エチレン－プロピレン－６－メチル－１，５－ヘプタジエン共重合体ゴム、エチレン－プロピレン－７－メチル－１，６－オクタジエン共重合体ゴム、エチレン－プロピレン－シクロヘキサジエン共重合体ゴム、エチレン－プロピレン－５－ビニルノルボルネン共重合体ゴム、エチレン－プロピレン－５－（２－プロペニル）－２－ノルボルネン共重合体ゴム、エチレン－プロピレン－５－（３－ブテニル）－２－ノルボルネン共重合体ゴム、エチレン－プロピレン－５－（４－ペンテニル）－２－ノルボルネン共重合体ゴム、エチレン－プロピレン－５－（５－ヘキセニル）－２－ノルボルネン共重合体ゴム、エチレン－プロピレン－５－（６－ヘプテニル）－２－ノルボルネン共重合体ゴム、エチレン－プロピレン－５－（７－オクテニル）－２－ノルボルネン共重合体ゴム、エチレン－プロピレン－５－メチレン－２－ノルボルネン共重合体ゴム、エチレン－プロピレン－４－エチリデン－８－メチル－１，７－ノナジエン共重合体ゴム、エチレン－プロピレン－５，９，１３－トリメチル－１，４，８，１２－テトラデカジエン共重合体ゴム、エチレン－プロピレン－４－エチリデン－１２－メチル－１，１１－ペンタデカジエン共重合体ゴム、エチレン－プロピレン－６－クロロメチル－５－イソプロペニル－２－ノルボルネン共重合体ゴム、エチレン－プロピレン－２，３－ジイソプロピリデン－５－ノルボルネン共重合体ゴム、エチレン－プロピレン－２－エチリデン－３－イソプロピリデン－５－ノルボルネン共重合体ゴム、エチレン－プロピレン－２－プロペニル－２，２－ノルボルナジエン共重合体ゴム、エチレン－プロピレン－１，３，７－オクタトリエン共重合体ゴム、エチレン－プロピレン－６，１０－ジメチル－１，５，９－ウンデカトリエン共重合体ゴム、エチレン－プロピレン－５，９－ジメチル－１，４，８－デカトリエン共重合体ゴム、エチレン－プロピレン－１３－エチル－９－メチル－１，９，１２－ペンタデカトリエン共重合体ゴム、エチレン－プロピレン－５，９，８，１４，１６－ペンタメチル－１，７，１４－ヘキサデカトリエン共重合体ゴム、及びエチレン－プロピレン－１，４，９－デカトリエン共重合体ゴムが挙げられる。これらは単独で又は２種以上を組み合わせて用いられる。 Specific examples of the ethylene-α-olefin-non-conjugated polyene copolymer rubber include ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber, ethylene-propylene-dicyclopentadiene copolymer rubber, and ethylene-propylene- 1,4-hexadiene copolymer rubber, ethylene-propylene-1,6-octadiene copolymer rubber, ethylene-propylene-2-methyl-1,5-hexadiene copolymer rubber, ethylene-propylene-6-methyl- 1,5-heptadiene copolymer rubber, ethylene-propylene-7-methyl-1,6-octadiene copolymer rubber, ethylene-propylene-cyclohexadiene copolymer rubber, ethylene-propylene-5-vinylnorbornene copolymer Rubber, ethylene-propylene-5- (2-propenyl) 2-norbornene copolymer rubber, ethylene-propylene-5- (3-butenyl) -2-norbornene copolymer rubber, ethylene-propylene-5- (4-pentenyl) -2-norbornene copolymer rubber, ethylene- Propylene-5- (5-hexenyl) -2-norbornene copolymer rubber, ethylene-propylene-5- (6-heptenyl) -2-norbornene copolymer rubber, ethylene-propylene-5- (7-octenyl)- 2-norbornene copolymer rubber, ethylene-propylene-5-methylene-2-norbornene copolymer rubber, ethylene-propylene-4-ethylidene-8-methyl-1,7-nonadiene copolymer rubber, ethylene-propylene- 5,9,13-trimethyl-1,4,8,12-tetradecadiene copolymer rubber, ethylene-pro Pyrene-4-ethylidene-12-methyl-1,11-pentadecadiene copolymer rubber, ethylene-propylene-6-chloromethyl-5-isopropenyl-2-norbornene copolymer rubber, ethylene-propylene-2, 3-diisopropylidene-5-norbornene copolymer rubber, ethylene-propylene-2-ethylidene-3-isopropylidene-5-norbornene copolymer rubber, ethylene-propylene-2-propenyl-2,2-norbornadiene copolymer Copolymer rubber, ethylene-propylene-1,3,7-octatriene copolymer rubber, ethylene-propylene-6,10-dimethyl-1,5,9-undecatriene copolymer rubber, ethylene-propylene-5 9-dimethyl-1,4,8-decatriene copolymer rubber, ethylene-propylene-13 Tyl-9-methyl-1,9,12-pentadecatriene copolymer rubber, ethylene-propylene-5,9,8,14,16-pentamethyl-1,7,14-hexadecatriene copolymer rubber, And ethylene-propylene-1,4,9-decatriene copolymer rubber. These are used alone or in combination of two or more.
　ゴム組成物は、エチレン－α－オレフィン－非共役ポリエン共重合体ゴムとして、エチレン－プロピレン－５－エチリデン－２－ノルボルネン共重合体ゴム、エチレン－プロピレン－ジシクロペンタジエン共重合体ゴム、エチレン－プロピレン－５－ビニルノルボルネン共重合体ゴム又はこれらの組み合わせを含んでいてもよいし、エチレン－プロピレン－５－エチリデン－２－ノルボルネン共重合体ゴムを含んでいてもよい。 The rubber composition includes ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber, ethylene-propylene-dicyclopentadiene copolymer rubber, and ethylene-α-olefin-non-conjugated polyene copolymer rubber. It may contain a propylene-5-vinylnorbornene copolymer rubber or a combination thereof, or may contain an ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber.
　ゴム組成物が２種以上のエチレン－α－オレフィン－非共役ポリエン共重合体ゴムを含む場合、上述のエチレン単位／α－オレフィン単位の質量比、及びヨウ素価は、それら２種以上のエチレン－α－オレフィン－非共役ポリエン共重合体ゴムを含む全体における値である。 When the rubber composition contains two or more ethylene-α-olefin-non-conjugated polyene copolymer rubbers, the above-mentioned mass ratio of ethylene units / α-olefin units and the iodine value are determined by the two or more ethylene-α-olefin units. It is a value for the whole including the α-olefin-non-conjugated polyene copolymer rubber.
　エチレン－α－オレフィン－非共役ポリエン共重合体ゴムの１００℃におけるムーニー粘度（ＭＬ１＋４、１００℃）は、１０～３５０、又は３０～３００であってもよい。ムーニー粘度が過小であるとゴム成形体の機械的強度が低下することがあり、ムーニー粘度が過大であると混練加工性が低下する傾向がある。 ム ー The ethylene-α-olefin-non-conjugated polyene copolymer rubber may have a Mooney viscosity at 100 ° C (ML1 + 4, 100 ° C) of 10 to 350, or 30 to 300. If the Mooney viscosity is too low, the mechanical strength of the rubber molded article may decrease, and if the Mooney viscosity is too high, the kneading processability tends to decrease.
　エチレン－α－オレフィン－非共役ポリエン共重合体ゴムの分子量分布（Ｍｗ／Ｍｎ）は、１．５以上１０以下であってもよい。分子量分布が１．５以上であると、ゴム組成物の良好なロール加工性が得られ易い。分子量分布が１０以下であると、ゴム成形体の機械的物性が向上する傾向がある。同様の観点から、エチレン－α－オレフィン－非共役ポリエン共重合体ゴムの分子量分布は２．０以上７．０以下であってもよい。分子量分布は重合条件を変更することで調節することが可能である。 The molecular weight distribution (Mw / Mn) of the ethylene-α-olefin-non-conjugated polyene copolymer rubber may be 1.5 or more and 10 or less. When the molecular weight distribution is 1.5 or more, good roll processability of the rubber composition is easily obtained. When the molecular weight distribution is 10 or less, the mechanical properties of the rubber molded article tend to be improved. From the same viewpoint, the molecular weight distribution of the ethylene-α-olefin-non-conjugated polyene copolymer rubber may be 2.0 or more and 7.0 or less. The molecular weight distribution can be adjusted by changing the polymerization conditions.
　本明細書における分子量分布は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ法）を用いて測定した標準ポリスチレン換算の重量平均分子量（Ｍｗ）及び数平均分子量（Ｍｎ）から算出された比（Ｍｗ／Ｍｎ）である。ＧＰＣ法による重量平均分子量と数平均分子量の測定条件としては、例えば以下のとおりである。
・ＧＰＣ装置：東ソー株式会社製、商品名ＨＬＣ－８１２１ＧＰＣ／ＨＴ
・カラム：東ソー株式会社製、商品名ＴＳＫｇｅｌ　ＧＭＨＨＲ－Ｈ（Ｓ）ＨＴ
・分子量標準物質：分子量５００以上２０，０００，０００以下のポリスチレン
・溶出溶媒流速：１．０ｍＬ／ｍｉｎ
・試料濃度：１ｍｇ／ｍＬ
・測定温度：１４０℃
・溶出溶媒：オルトジクロロベンゼン
・注入量：５００μＬ
・検出器：示差屈折計 The molecular weight distribution in the present specification is a ratio (Mw / Mn) calculated from a weight average molecular weight (Mw) and a number average molecular weight (Mn) in terms of standard polystyrene measured using gel permeation chromatography (GPC method). is there. The conditions for measuring the weight average molecular weight and the number average molecular weight by the GPC method are as follows, for example.
・ GPC device: manufactured by Tosoh Corporation, trade name: HLC-8121GPC / HT
-Column: TSKgel GMHHR-H (S) HT, manufactured by Tosoh Corporation
-Molecular weight standard substance: polystyrene having a molecular weight of 500 or more and 20,000,000 or less-Elution solvent flow rate: 1.0 mL / min
-Sample concentration: 1 mg / mL
・ Measurement temperature: 140 ° C
・ Eluent solvent: ortho-dichlorobenzene ・ Injection volume: 500 μL
・ Detector: Differential refractometer
　ゴム組成物におけるエチレン－α－オレフィン－非共役ポリエン共重合体ゴムの含有量は、ゴム組成物の質量を基準として、２０質量％以上、又は３５質量％以上であってもよい。また、成分（Ａ）、成分（Ｂ）、および成分（Ｃ）の合計を１００質量％としたときの成分（Ａ）エチレン－α－オレフィン－非共役ポリエン共重合体ゴムの含有量が７５質量％以上、又は８５質量％以上であってもよい。 含有 The content of the ethylene-α-olefin-non-conjugated polyene copolymer rubber in the rubber composition may be 20% by mass or more, or 35% by mass or more based on the mass of the rubber composition. When the total of the component (A), the component (B) and the component (C) is 100% by mass, the content of the component (A) ethylene-α-olefin-non-conjugated polyene copolymer rubber is 75% by mass. % Or 85% by mass or more.
　エチレン－α－オレフィン－非共役ポリエン共重合体ゴムの製造方法は、特に限定されるものではなく、例えば、所謂チーグラーナッタ触媒、又はメタロセン触媒などの触媒の存在下で、エチレン、α－オレフィン、及び必要に応じて非共役ポリエンを含むモノマー混合物を共重合させる工程を含む方法によりエチレン－α－オレフィン－非共役ポリエン共重合体ゴムを製造することができる。 The method for producing the ethylene-α-olefin-non-conjugated polyene copolymer rubber is not particularly limited. For example, ethylene, α-olefin, ethylene-α-olefin, or so-called Ziegler-Natta catalyst or metallocene catalyst may be used. An ethylene-α-olefin-nonconjugated polyene copolymer rubber can be produced by a method including a step of copolymerizing a monomer mixture containing a nonconjugated polyene and, if necessary, a monomer mixture.
　共重合のための触媒として、下式（１）で表されるバナジウム化合物と下式（２）で表される有機アルミニウム化合物とから形成される触媒を用いることが好ましい。
ＶＯ（ＯＲ）ｍＸ３－ｍ　　　（１）
［式中、Ｒは炭素原子数が１以上８以下の直鎖状炭化水素基を表し、Ｘはハロゲン原子を表し、ｍは０＜ｍ≦３を充足する数を表す。］
Ｒ”ｊＡｌＸ”３－ｊ　　　（２）
［式中、Ｒ”は炭化水素基を表し、Ｘ”はハロゲン原子を表し、ｊは０＜ｊ≦３を充足する数を表す。］ As a catalyst for copolymerization, it is preferable to use a catalyst formed from a vanadium compound represented by the following formula (1) and an organoaluminum compound represented by the following formula (2).
VO (OR) m X 3-m (1)
[Wherein, R represents a linear hydrocarbon group having 1 to 8 carbon atoms, X represents a halogen atom, and m represents a number satisfying 0 <m ≦ 3. ]
R " j AlX" 3-j (2)
[Wherein, R ″ represents a hydrocarbon group, X ″ represents a halogen atom, and j represents a number satisfying 0 <j ≦ 3. ]
　式（１）におけるＲの具体例としては、メチル基、エチル基、ｎ－プロピル基、ｎ－ブチル基、ｎ－ペンチル基、及びｎ－ヘキシル基が挙げられる。これらのうち、炭素原子数が１以上３以下の直鎖状アルキル基が好ましい。Ｘとしては、フッ素原子、塩素原子等が挙げられる。ｍは、好ましくは１≦ｍ≦２を充足する数である。 具体 Specific examples of R in the formula (1) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group. Among these, a linear alkyl group having 1 to 3 carbon atoms is preferable. X includes a fluorine atom, a chlorine atom and the like. m is a number that preferably satisfies 1 ≦ m ≦ 2.
　式（１）で表されるバナジウム化合物の具体例としては、ＶＯ（ＯＣＨ３）Ｃｌ２、ＶＯ（ＯＣ２Ｈ５）Ｃｌ２、ＶＯ（Ｏ（ｎ－Ｃ３Ｈ７））Ｃｌ２、ＶＯ（Ｏ（ｎ－Ｃ４Ｈ９））Ｃｌ２、ＶＯ（Ｏ（ｎ－Ｃ５Ｈ１１））Ｃｌ２、ＶＯ（Ｏ（ｎ－Ｃ６Ｈ１３））Ｃｌ２、ＶＯ（Ｏ（ｎ－Ｃ７Ｈ１５））Ｃｌ２、ＶＯ（Ｏ（ｎ－Ｃ８Ｈ１７））Ｃｌ２、ＶＯ（ＯＣＨ３）０．５Ｃｌ２．５、ＶＯ（ＯＣ２Ｈ５）０．５Ｃｌ２．５、ＶＯ（Ｏ（ｎ－Ｃ３Ｈ７））０．５Ｃｌ２．５、ＶＯ（Ｏ（ｎ－Ｃ４Ｈ９））０．５Ｃｌ２．５、ＶＯ（Ｏ（ｎ－Ｃ５Ｈ１１））０．５Ｃｌ２．５、ＶＯ（Ｏ（ｎ－Ｃ６Ｈ１３））０．５Ｃｌ２．５、ＶＯ（Ｏ（ｎ－Ｃ７Ｈ１５））０．５Ｃｌ２．５、ＶＯ（Ｏ（ｎ－Ｃ８Ｈ１７））０．５Ｃｌ２．５、ＶＯ（ＯＣＨ３）１．５Ｃｌ１．５、ＶＯ（ＯＣ２Ｈ５）１．５Ｃｌ１．５、ＶＯ（Ｏ（ｎ－Ｃ３Ｈ７））１．５Ｃｌ１．５、ＶＯ（Ｏ（ｎ－Ｃ４Ｈ９））１．５Ｃｌ１．５、ＶＯ（Ｏ（ｎ－Ｃ５Ｈ１１））１．５Ｃｌ１．５、ＶＯ（Ｏ（ｎ－Ｃ６Ｈ１３））１．５Ｃｌ１．５、ＶＯ（Ｏ（ｎ－Ｃ７Ｈ１５））１．５Ｃｌ１．５、ＶＯ（Ｏ（ｎ－Ｃ８Ｈ１７））１．５Ｃｌ１．５、ＶＯ（ＯＣＨ３）０．８Ｃｌ２．２、ＶＯ（ＯＣ２Ｈ５）０．８Ｃｌ２．２、ＶＯ（Ｏ（ｎ－Ｃ３Ｈ７））０．８Ｃｌ２．２、ＶＯ（Ｏ（ｎ－Ｃ４Ｈ９））０．８Ｃｌ２．２、ＶＯ（Ｏ（ｎ－Ｃ５Ｈ１１））０．８Ｃｌ２．２、ＶＯ（Ｏ（ｎ－Ｃ６Ｈ１３））０．８Ｃｌ２．２、ＶＯ（Ｏ（ｎ－Ｃ７Ｈ１５））０．８Ｃｌ２．２、及びＶＯ（Ｏ（ｎ－Ｃ８Ｈ１７））０．８Ｃｌ２．２、ＶＯ（ＯＣＨ３）１．８Ｃｌ１．２、ＶＯ（ＯＣ２Ｈ５）１．８Ｃｌ１．２、ＶＯ（Ｏ（ｎ－Ｃ３Ｈ７））１．８Ｃｌ１．２、ＶＯ（Ｏ（ｎ－Ｃ４Ｈ９））１．８Ｃｌ１．２、ＶＯ（Ｏ（ｎ－Ｃ５Ｈ１１））１．８Ｃｌ１．２、ＶＯ（Ｏ（ｎ－Ｃ６Ｈ１３））１．８Ｃｌ１．２、ＶＯ（Ｏ（ｎ－Ｃ７Ｈ１５））１．８Ｃｌ１．２、及びＶＯ（Ｏ（ｎ－Ｃ８Ｈ１７））１．８Ｃｌ１．２が挙げられる。これらのうち、ＶＯ（ＯＣ２Ｈ５）Ｃｌ２、ＶＯ（ＯＣ２Ｈ５）０．５Ｃｌ２．５、ＶＯ（ＯＣ２Ｈ５）１．５Ｃｌ１．５、ＶＯ（ＯＣ２Ｈ５）０．８Ｃｌ２．２、及びＶＯ（ＯＣ２Ｈ５）１．８Ｃｌ１．２が特に好ましい。これらは単独で又は組み合わせて用いてもよい。 Specific examples of the vanadium compound represented by the formula (1) include VO (OCH 3 ) Cl 2 , VO (OC 2 H 5 ) Cl 2 , VO (O (nC 3 H 7 )) Cl 2 , VO (O (nC 4 H 9 )) Cl 2 , VO (O (nC 5 H 11 )) Cl 2 , VO (O (nC 6 H 13 )) Cl 2 , VO (O (n− C 7 H 15)) Cl 2 , VO (O (n-C 8 H 17)) Cl 2, VO (OCH 3) 0.5 Cl 2.5, VO (OC 2 H 5) 0.5 Cl 2. 5 , VO (O (nC 3 H 7 )) 0.5 Cl 2.5 , VO (O (nC 4 H 9 )) 0.5 Cl 2.5 , VO (O (nC 5) H 11)) 0.5 Cl 2.5, VO (O (n-C 6 H 13)) 0.5 Cl 2.5, VO (O (n-C 7 H 15)) 0.5 C 2.5, VO (O (n- C 8 H 17)) 0.5 Cl 2.5, VO (OCH 3) 1.5 Cl 1.5, VO (OC 2 H 5) 1.5 Cl 1. 5 , VO (O (nC 3 H 7 )) 1.5 Cl 1.5 , VO (O (nC 4 H 9 )) 1.5 Cl 1.5 , VO (O (nC 5) H 11 )) 1.5 Cl 1.5 , VO (O (n-C 6 H 13 )) 1.5 Cl 1.5 , VO (O (n-C 7 H 15 )) 1.5 Cl 1. 5 , VO (O (nC 8 H 17 )) 1.5 Cl 1.5 , VO (OCH 3 ) 0.8 Cl 2.2 , VO (OC 2 H 5 ) 0.8 Cl 2.2 , VO (O (nC 3 H 7 )) 0.8 Cl 2.2 , VO (O (nC 4 H 9 )) 0.8 Cl 2.2 , VO (O (nC 5 H 11) )) 0.8 Cl .2, VO (O (n- C 6 H 13)) 0.8 Cl 2.2, VO (O (n-C 7 H 15)) 0.8 Cl 2.2, and VO (O (n- C 8 H 17 )) 0.8 Cl 2.2 , VO (OCH 3 ) 1.8 Cl 1.2 , VO (OC 2 H 5 ) 1.8 Cl 1.2 , VO (O (n-C 3) H 7 )) 1.8 Cl 1.2 , VO (O (n-C 4 H 9 )) 1.8 Cl 1.2 , VO (O (n-C 5 H 11 )) 1.8 Cl 1. 2 , VO (O (nC 6 H 13 )) 1.8 Cl 1.2 , VO (O (nC 7 H 15 )) 1.8 Cl 1.2 , and VO (O (n-C 6 H 13 )) 8 H 17)) 1.8 Cl 1.2 and the like. Among them, VO (OC 2 H 5 ) Cl 2 , VO (OC 2 H 5 ) 0.5 Cl 2.5 , VO (OC 2 H 5 ) 1.5 Cl 1.5 , VO (OC 2 H 5) ) 0.8 Cl 2.2 and VO (OC 2 H 5 ) 1.8 Cl 1.2 are particularly preferred. These may be used alone or in combination.
　式（１）で表されるバナジウム化合物は、例えば、ＶＯＸ３とＲＯＨとを所定のモル比で反応させる方法により得られる。例えば、ＶＯＣｌ３とＣ２Ｈ５ＯＨとの反応は、次式で示される。ＶＯＸ３及びＲＯＨを重合槽に供給して、重合槽中で式（１）のバナジウム化合物を生成させてもよい。 The vanadium compound represented by the formula (1) is obtained, for example, by a method in which VOX 3 and ROH are reacted at a predetermined molar ratio. For example, the reaction between VOCl 3 and C 2 H 5 OH is represented by the following equation. VOX 3 and ROH may be supplied to a polymerization tank to generate a vanadium compound of the formula (1) in the polymerization tank.
　ＶＯＣｌ３＋ｍ・Ｃ２Ｈ５ＯＨ→ＶＯ（ＯＣ２Ｈ５）ｍＣｌ３－ｍ＋ｍ・ＨＣｌ VOCl 3 + m · C 2 H 5 OH → VO (OC 2 H 5 ) m Cl 3-m + m · HCl
　式（２）におけるＲ”は炭素原子数１～１０のアルキル基であってもよく、その具体例としては、メチル基、エチル基、ｎ－プロピル基、ｉｓｏ－プロピル基、ｎ－ブチル基、ｉｓｏ－ブチル基、ペンチル基、及びヘキシル基が挙げられる。Ｘ”としては、フッ素原子、塩素原子等が挙げられる。ｊは、好ましくは０＜ｊ≦２を充足する数である。 R ″ in the formula (2) may be an alkyl group having 1 to 10 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, Examples include an iso-butyl group, a pentyl group, and a hexyl group. X ″ includes a fluorine atom, a chlorine atom, and the like. j is preferably a number satisfying 0 <j ≦ 2.
　式（２）で表される有機アルミニウム化合物の具体例として、（Ｃ２Ｈ５）２ＡｌＣｌ、（ｎ－Ｃ４Ｈ９）２ＡｌＣｌ、（ｉｓｏ－Ｃ４Ｈ９）２ＡｌＣｌ、（ｎ－Ｃ６Ｈ１３）２ＡｌＣｌ、（Ｃ２Ｈ５）１．５ＡｌＣｌ１．５、（ｎ－Ｃ４Ｈ９）１．５ＡｌＣｌ１．５、（ｉｓｏ－Ｃ４Ｈ９）１．５ＡｌＣｌ１．５、（ｎ－Ｃ６Ｈ１３）１．５ＡｌＣｌ１．５、Ｃ２Ｈ５ＡｌＣｌ２、（ｎ－Ｃ４Ｈ９）ＡｌＣｌ２、（ｉｓｏ－Ｃ４Ｈ９）ＡｌＣｌ２、及び（ｎ－Ｃ６Ｈ１３）ＡｌＣｌ２が挙げられる。これらのうち、（Ｃ２Ｈ５）２ＡｌＣｌ、（Ｃ２Ｈ５）１．５ＡｌＣｌ１．５、及びＣ２Ｈ５ＡｌＣｌ２が特に好ましい。これらは単独で又は組み合わせて用いてもよい。 As specific examples of the organoaluminum compound represented by the formula (2), (C 2 H 5 ) 2 AlCl, (nC 4 H 9 ) 2 AlCl, (iso-C 4 H 9 ) 2 AlCl, (n- C 6 H 13 ) 2 AlCl, (C 2 H 5 ) 1.5 AlCl 1.5 , (nC 4 H 9 ) 1.5 AlCl 1.5 , (iso-C 4 H 9 ) 1.5 AlCl 1.5 , (nC 6 H 13 ) 1.5 AlCl 1.5 , C 2 H 5 AlCl 2 , (nC 4 H 9 ) AlCl 2 , (iso-C 4 H 9 ) AlCl 2 , and (NC 6 H 13 ) AlCl 2 . Of these, (C 2 H 5 ) 2 AlCl, (C 2 H 5 ) 1.5 AlCl 1.5 and C 2 H 5 AlCl 2 are particularly preferred. These may be used alone or in combination.
　式（２）の有機アルミニウム化合物と式（１）のバナジウム化合物との使用量のモル比（有機アルミニウム化合物のモル／バナジウム化合物のモル）は、０．１以上５０以下であることが好ましく、１以上３０以下であることがより好ましく、２以上１５以下であることが更に好ましく、３以上１０以下であることが特に好ましい。当該モル比を調整することにより、エチレン－α－オレフィン－非共役ポリエン共重合体ゴムの粘度、Ｍｗ／Ｍｎ等を調整することができる。例えば、当該モル比が大きいと、エチレン－α－オレフィン－非共役ポリエン共重合体ゴムの粘度が高くなる傾向、並びに、Ｍｗ／Ｍｎが小さくなる傾向がある。 The molar ratio of the amount of the organoaluminum compound of the formula (2) to the amount of the vanadium compound of the formula (1) (mol of the organoaluminum compound / mol of the vanadium compound) is preferably 0.1 or more and 50 or less. It is more preferably 30 or more, more preferably 2 or more and 15 or less, particularly preferably 3 or more and 10 or less. By adjusting the molar ratio, the viscosity, Mw / Mn, etc. of the ethylene-α-olefin-non-conjugated polyene copolymer rubber can be adjusted. For example, when the molar ratio is large, the viscosity of the ethylene-α-olefin-non-conjugated polyene copolymer rubber tends to increase, and Mw / Mn tends to decrease.
　重合反応は、例えば、１つの重合槽を用いて重合を行う方法、又は直列に連結した２つの重合槽を用いて行うことができる。重合槽にモノマー、触媒、及び必要により他の成分を供給し、重合槽中でモノマーを重合することができる。 The polymerization reaction can be performed by, for example, a method of performing polymerization using one polymerization tank, or using two polymerization tanks connected in series. A monomer, a catalyst and, if necessary, other components are supplied to the polymerization tank, and the monomer can be polymerized in the polymerization tank.
　重合反応は、通常、溶媒中で行われる。重合に用いる溶媒としては、例えば、プロパン、ブタン、イソブタン、ペンタン、ヘキサン、ヘプタン、オクタン等の脂肪族炭化水素；シクロペンタン、シクロヘキサン等の脂環族炭化水素等の不活性溶媒が挙げられる。これらは単独で又は組み合わせて用いてもよい。これらのうち、脂肪族炭化水素が好ましい。 The polymerization reaction is usually performed in a solvent. Examples of the solvent used for the polymerization include inert solvents such as aliphatic hydrocarbons such as propane, butane, isobutane, pentane, hexane, heptane, and octane; and alicyclic hydrocarbons such as cyclopentane and cyclohexane. These may be used alone or in combination. Of these, aliphatic hydrocarbons are preferred.
　重合温度は、通常、０℃以上２００℃以下であってもよく、好ましくは２０℃以上１５０℃以下であり、より好ましくは３０℃以上１２０℃以下である。重合圧力は、通常、０．１ＭＰａ以上１０ＭＰａ以下であってもよく、好ましくは０．１ＭＰａ以上５ＭＰａ以下であり、より好ましくは０．１ＭＰａ以上３ＭＰａ以下である。重合温度を調整することにより、成分（Ａ）のＭｗ／Ｍｎ等を調整することができる。例えば、重合温度が低いと、Ｍｗ／Ｍｎが小さくなる傾向がある。 (4) The polymerization temperature may be generally from 0 ° C to 200 ° C, preferably from 20 ° C to 150 ° C, and more preferably from 30 ° C to 120 ° C. The polymerization pressure may be generally from 0.1 MPa to 10 MPa, preferably from 0.1 MPa to 5 MPa, more preferably from 0.1 MPa to 3 MPa. By adjusting the polymerization temperature, the Mw / Mn of the component (A) can be adjusted. For example, when the polymerization temperature is low, Mw / Mn tends to decrease.
　重合に際しては、必要に応じて、分子量調節剤として水素を重合槽に供給してもよい。重合槽に供給される水素の量は、重合槽に供給される溶媒１ｋｇあたり、好ましくは０．００１～０．１ＮＬであり、より好ましくは０．００５～０．０５ＮＬであり、更に好ましくは０．０１～０．０４ＮＬである。水素の供給量を調整することにより、エチレン－α－オレフィン共重合体のＭｗ／Ｍｎ、及び粘度等を調整することができる。例えば、水素の供給量が多いと、Ｍｗ／Ｍｎが小さくなる傾向がある。水素の供給量が少ないと、粘度が大きくなる傾向がある。 During the polymerization, hydrogen may be supplied to the polymerization tank as a molecular weight regulator if necessary. The amount of hydrogen supplied to the polymerization tank is preferably 0.001 to 0.1 NL, more preferably 0.005 to 0.05 NL, and still more preferably 0 to 0.05 NL per kg of the solvent supplied to the polymerization tank. .01 to 0.04 NL. By adjusting the supply amount of hydrogen, the Mw / Mn, viscosity, and the like of the ethylene-α-olefin copolymer can be adjusted. For example, when the supply amount of hydrogen is large, Mw / Mn tends to decrease. When the supply amount of hydrogen is small, the viscosity tends to increase.
　重合槽に供給されるバナジウム化合物の量は、重合槽に供給される溶媒１００質量部あたり、好ましくは０．００２質量部以上０．２質量部以下であり、より好ましくは０．００３質量部以上０．１質量部以下である。溶媒に対するバナジウム化合物の量を調整することにより、エチレン－α－オレフィン－非共役ポリエン共重合体ゴムの粘度を調整することができる。例えば、当該バナジウム化合物の量を多くすることにより、粘度を大きくすることができる傾向がある。 The amount of the vanadium compound supplied to the polymerization tank is preferably 0.002 parts by mass or more and 0.2 parts by mass or less, more preferably 0.003 parts by mass or more, per 100 parts by mass of the solvent supplied to the polymerization tank. 0.1 parts by mass or less. By adjusting the amount of the vanadium compound with respect to the solvent, the viscosity of the ethylene-α-olefin-non-conjugated polyene copolymer rubber can be adjusted. For example, increasing the amount of the vanadium compound tends to increase the viscosity.
（Ｂ）有機硫黄化合物
　成分（Ｂ）の有機硫黄化合物は、分子内に１個以上のメルカプト基（－ＳＨ）又は１個以上のポリスルフィド結合（－Ｓｎ－、ｎは２以上の整数）と、１個以上の酸性官能基、又は、酸性官能基から誘導される１個以上の酸誘導基とを有する化合物である。メルカプト基の水素－硫黄結合又はポリスルフィド結合の硫黄原子同士の結合が開裂して形成するラジカル種の反応が、接着強度向上に寄与すると考えられる。（Ｂ）有機硫黄化合物は、１個若しくは２個のメルカプト基又は１個若しくは２個のポリスルフィド結合と、１個若しくは２個の酸性官能基又は１個若しくは２個の酸誘導基とを有する化合物であってもよい。有機硫黄化合物が酸性官能基及び酸誘導基を有していてもよい。ゴム組成物は、１種又は２種以上の有機硫黄化合物を含み得る。 (B) Organosulfur Compound The organosulfur compound of the component (B) has one or more mercapto groups (—SH) or one or more polysulfide bonds (—S n —, n is an integer of 2 or more) in the molecule. A compound having at least one acidic functional group or at least one acid-derived group derived from the acidic functional group. It is considered that the reaction of radical species formed by the cleavage of the hydrogen-sulfur bond of the mercapto group or the bond between the sulfur atoms of the polysulfide bond contributes to the improvement of the adhesive strength. (B) The organic sulfur compound has one or two mercapto groups or one or two polysulfide bonds, and one or two acidic functional groups or one or two acid-derived groups. It may be. The organic sulfur compound may have an acidic functional group and an acid-derived group. The rubber composition may include one or more organic sulfur compounds.
　酸性官能基は、酸性を示す官能基であれば、その種類は特に制限されない。酸性官能基の例としては、カルボキシル基（－ＣＯＯＨ）、スルホ基（－ＳＯ３Ｈ）、スルフェノ基（－ＳＯＨ）、スルフィノ基（－ＳＯ２Ｈ）、フェノール性水酸基、ホスホ基（－ＯＰ（＝Ｏ）（ＯＨ）２）、ホスホノ基（－Ｐ（＝Ｏ）（ＯＨ）２）、ボロノ基（－Ｂ（ＯＨ）２）、及びボリン酸基（－ＢＯＨ）がある。成分（Ｂ）の有機硫黄化合物は、これらから選ばれる１種以上の酸性官能基を有していてもよい。酸性官能基は、カルボキシル基、スルホ基、又はスルフェノ基であってもよく、カルボキシル基であってもよい。 The type of the acidic functional group is not particularly limited as long as it is a functional group exhibiting acidity. Examples of the acidic functional group include a carboxyl group (—COOH), a sulfo group (—SO 3 H), a sulfeno group (—SOH), a sulfino group (—SO 2 H), a phenolic hydroxyl group, a phospho group (—OP ( ＯO) (OH) 2 ), phosphono groups (—P (＝ O) (OH) 2 ), borono groups (—B (OH) 2 ), and borinic acid groups (—BOH). The organic sulfur compound of the component (B) may have one or more acidic functional groups selected from these. The acidic functional group may be a carboxyl group, a sulfo group, a sulfeno group, or may be a carboxyl group.
　酸誘導基は、特に制限されないが、例えば、金属塩、アミン塩（例えば、アンモニウム塩）、酸無水物、酸ハロゲン化物、又はエステルであってもよく、金属塩であってもよい。金属塩は、酸性官能基から水素が解離して形成されたアニオンと金属カチオンとで形成された官能基である。２分子の有機硫黄化合物が、１個の金属カチオンと金属塩を形成していてもよい。金属塩の例としては、カリウム塩、カルシウム塩、ナトリウム塩、マグネシウム塩、アルミニウム塩、及び亜鉛塩が挙げられる。酸誘導基は特に、カルボン酸金属塩であってもよい。金属塩を有する有機硫黄化合物を成分（Ａ）と混合してゴム組成物を調製してもよいし、酸性官能基を有する有機硫黄化合物及び金属酸化物を成分（Ａ）と混合し、混合物中で中和反応を進行させることによって、金属塩を形成してもよい。 The diacid-derived group is not particularly limited, but may be, for example, a metal salt, an amine salt (eg, an ammonium salt), an acid anhydride, an acid halide, or an ester, or may be a metal salt. A metal salt is a functional group formed by an anion formed by dissociation of hydrogen from an acidic functional group and a metal cation. Two molecules of the organic sulfur compound may form a metal salt with one metal cation. Examples of metal salts include potassium, calcium, sodium, magnesium, aluminum, and zinc salts. The acid-derived group may in particular be a metal carboxylate. The rubber composition may be prepared by mixing an organic sulfur compound having a metal salt with the component (A), or an organic sulfur compound having an acidic functional group and a metal oxide may be mixed with the component (A), and The metal salt may be formed by allowing the neutralization reaction to proceed.
　メルカプト基及び酸性官能基を有する有機硫黄化合物の例としては、３－メルカプトプロピオン酸、メルカプトこはく酸、２－メルカプトプロピオン酸、チオグリコール酸、メルカプトブタン酸、メルカプト吉草酸、アミノ－４－メルカプト酪酸、オキソ－４－メルカプト酪酸、４－メルカプト－４－オキソブタン酸、テトラノルジヒドロリポ酸、３－（ジチオカルボキシ）プロピオン酸、（１－メルカプトメチルシクロプロピル）酢酸、３－（メルカプトメチル）－４－アミノブタン酸、ジメルカプト酢酸、２－メルカプトプロパン酸、メルカプトアクリル酸、メルカプトカプロン酸、メルカプトヘプタン酸、メルカプトオクタン酸、メルカプトノナン酸、メルカプトデカン酸、メルカプトドデカン酸、メルカプトドデカン酸、メルカプトテトラデカン酸、メルカプトヘキサデカン酸、メルカプトヘプタデカン酸、メルカプトオクタデカン酸、メルカプトマロン酸、メルカプトグルタル酸、ジメルカプトグルタル酸、メルカプトアジピン酸、ジメルカプトアジピン酸、メルカプトピメリン酸、メルカプトスベリン酸、メルカプトアゼライン酸、メルカプトセバシン酸、ジメルカプトセバシン酸、及びメルカプトフタル酸がある。メルカプト基及び酸性官能基を有する有機硫黄化合物は、３－メルカプトプロピオン酸、メルカプトこはく酸又はこれらの組み合わせであってもよい。 Examples of the organic sulfur compound having a mercapto group and an acidic functional group include 3-mercaptopropionic acid, mercaptosuccinic acid, 2-mercaptopropionic acid, thioglycolic acid, mercaptobutanoic acid, mercaptovaleric acid, and amino-4-mercaptobutyric acid Oxo-4-mercaptobutyric acid, 4-mercapto-4-oxobutanoic acid, tetranordihydrolipoic acid, 3- (dithiocarboxy) propionic acid, (1-mercaptomethylcyclopropyl) acetic acid, 3- (mercaptomethyl) -4 -Aminobutanoic acid, dimercaptoacetic acid, 2-mercaptopropanoic acid, mercaptoacrylic acid, mercaptocaproic acid, mercaptoheptanoic acid, mercaptooctanoic acid, mercaptononanoic acid, mercaptodecanoic acid, mercaptododecanoic acid, mercaptododecanoic acid, mercapto Tetradecanoic acid, mercaptohexadecanoic acid, mercaptoheptadecanoic acid, mercaptooctadecanoic acid, mercaptomalonic acid, mercaptoglutaric acid, dimercaptoglutaric acid, mercaptoadipic acid, dimercaptoadipic acid, mercaptopimelic acid, mercaptosuberic acid, mercaptoazerine acid , Mercaptosebacic acid, dimercaptosebacic acid, and mercaptophthalic acid. The organic sulfur compound having a mercapto group and an acidic functional group may be 3-mercaptopropionic acid, mercaptosuccinic acid, or a combination thereof.
　ポリスルフィド結合及び酸性官能基を有する有機硫黄化合物の例としては、３，３’－ジチオジプロピオン酸、ジチオグリコール酸、１，２－ジチアン－４－カルボン酸、４，４’－ジチオビス酪酸、ビス［３－カルボキシ－1－イミノプロピル］ペルスルフィド、１，２－ジチアン－３，６－ジカルボン酸、２，２’－ジチオビスプロピオン酸、２，２’－ジチオビスグリシン、ビスプロピオン酸ペルテトラスルフィド、ジチオビスギ酸、ジチオビスカプロン酸、ジチオビスヘプタン酸、ジチオビスオクタン酸、ジチオビスノナン酸、ジチオビスメルカプトデカン酸、ジチオビスメルカプトドデカン酸、ジチオビスドデカン酸、ジチオビステトラデカン酸、ジチオビスヘキサデカン酸、ジチオビスヘプタデカン酸、及びジチオビスオクタデカン酸がある。ポリスルフィド結合及び酸性官能基を有する有機硫黄化合物は、３，３’－ジチオジプロピオン酸であってもよい。 Examples of the organic sulfur compound having a polysulfide bond and an acidic functional group include 3,3′-dithiodipropionic acid, dithioglycolic acid, 1,2-dithiane-4-carboxylic acid, 4,4′-dithiobisbutyric acid, bis [3-carboxy-1-iminopropyl] persulfide, 1,2-dithiane-3,6-dicarboxylic acid, 2,2′-dithiobispropionic acid, 2,2′-dithiobisglycine, pertetrabispropionate Sulfide, dithiobisformic acid, dithiobiscaproic acid, dithiobisheptanoic acid, dithiobisoctanoic acid, dithiobisnonanoic acid, dithiobismercaptodecanoic acid, dithiobismercaptododecanoic acid, dithiobisdodecanoic acid, dithiobistetradecanoic acid, dithiobishexadecanoic acid, Dithiobisheptadecanoic acid and dithiobisoctade There is canic acid. The organic sulfur compound having a polysulfide bond and an acidic functional group may be 3,3'-dithiodipropionic acid.
　メルカプト基及び酸誘導基を有する有機硫黄化合物の例としては、３－メルカプトプロピオン酸メチル、３－メルカプトプロピオン酸エチル、３－メルカプトプロピオン酸プロピル、３－メルカプトプロピオン酸ブチル、３－メルカプトプロピオン酸カリウム塩、３－メルカプトプロピオン酸カルシウム塩、３－メルカプトプロピオン酸ナトリウム塩、３－メルカプトプロピオン酸マグネシウム塩、３－メルカプトプロピオン酸アルミニウム塩、３－メルカプトプロピオン酸亜鉛塩、メルカプトこはく酸ジメチル、メルカプトこはく酸ジエチル、メルカプトこはく酸ジプロピル、メルカプトこはく酸ジブチル、メルカプトこはく酸カリウム塩、メルカプトこはく酸カルシウム塩、メルカプトこはく酸ナトリウム塩、メルカプトこはく酸マグネシウム塩、メルカプトこはく酸アルミニウム塩、及びメルカプトこはく酸亜鉛塩がある。 Examples of the organic sulfur compound having a mercapto group and an acid-derived group include methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, propyl 3-mercaptopropionate, butyl 3-mercaptopropionate, and potassium 3-mercaptopropionate. Salt, calcium 3-mercaptopropionate, sodium 3-mercaptopropionate, magnesium 3-mercaptopropionate, aluminum 3-mercaptopropionate, zinc 3-mercaptopropionate, dimethyl mercaptosuccinate, mercaptosuccinate Diethyl, dipropyl mercaptosuccinate, dibutyl mercaptosuccinate, potassium mercaptosuccinate, calcium mercaptosuccinate, sodium mercaptosuccinate, magnesium mercaptosuccinate Siumu salts, mercapto succinic acid aluminum salt, and mercapto succinic acid zinc salt.
　ポリスルフィド結合及び酸誘導基を有する有機硫黄化合物の例としては、３，３’－ジチオジプロピオン酸ジメチル、３，３’－ジチオジプロピオン酸ジエチル、３，３’－ジチオジプロピオン酸ジプロピル、３，３’－ジチオジプロピオン酸ジブチル、３，３’－ジチオジプロピオン酸カリウム塩、３，３’－ジチオジプロピオン酸カルシウム塩、３，３’－ジチオジプロピオン酸ナトリウム塩、３，３’－ジチオジプロピオン酸マグネシウム塩、３，３’－ジチオジプロピオン酸アルミニウム塩、及び３，３’－ジチオジプロピオン酸亜鉛塩がある。 Examples of the organic sulfur compound having a polysulfide bond and an acid-derived group include dimethyl 3,3′-dithiodipropionate, diethyl 3,3′-dithiodipropionate, dipropyl 3,3′-dithiodipropionate, Dibutyl 3,3'-dithiodipropionate, potassium 3,3'-dithiodipropionate, calcium 3,3'-dithiodipropionate, sodium 3,3'-dithiodipropionate, 3,3 ' -Magnesium dithiodipropionate, aluminum 3,3'-dithiodipropionate, and zinc 3,3'-dithiodipropionate.
　ゴム組成物は、以上例示した化合物から選ばれる１種以上を、成分（Ｂ）として含有してもよい。 The rubber composition may contain one or more selected from the compounds exemplified above as the component (B).
　ゴム組成物における（Ｂ）有機硫黄化合物の含有量が大きいと、ゴム成形体の金属部材に対する接着性がより一層向上する傾向がある。係る観点から、（Ｂ）有機硫黄化合物の含有量は、エチレン－α－オレフィン－非共役ポリエン共重合体ゴム１００質量部に対して、１質量部以上、２．５質量部以上、３質量部以上、又は５質量部以上であってもよい。（Ｂ）有機硫黄化合物の含有量の上限は、特に制限されないが、１００質量部以下であってもよい。 (4) When the content of the organic sulfur compound (B) in the rubber composition is large, the adhesion of the rubber molded body to the metal member tends to be further improved. From this viewpoint, the content of the organic sulfur compound (B) is 1 part by mass or more, 2.5 parts by mass or more, and 3 parts by mass with respect to 100 parts by mass of the ethylene-α-olefin-non-conjugated polyene copolymer rubber. Or more than 5 parts by mass. The upper limit of the content of the organic sulfur compound (B) is not particularly limited, but may be 100 parts by mass or less.
　ここで、本明細書において、（Ｂ）有機硫黄化合物が酸誘導基を有する化合物である場合、酸誘導基を有する当該化合物の物質量と同じ物質量の、当該化合物の酸誘導基をこれを誘導する酸性官能基に置き換えた化合物の量が、（Ｂ）有機硫黄化合物の含有量とみなされる。例えば、（Ｂ）有機硫黄化合物がカルボキレート基と金属カチオンとから形成されたカルボン酸金属塩を有する、Ｒ－ＣＯＯ－Ｍ＋（Ｒはメルカプト基又はポリスルフィド結合を含む１価の有機基を示し、Ｍ＋は金属カチオンを示す。）で表される化合物である場合、その量が、当該化合物の－ＣＯＯ－Ｍ＋を－ＣＯＯＨに置き換えたＲ－ＣＯＯＨで表される化合物の量に換算される。すなわち、ゴム組成物に含有されるＲ－ＣＯＯ－Ｍ＋で表される当該化合物の物質量と同じ物質量の、Ｒ－ＣＯＯＨで表される化合物の量が、（Ｂ）有機硫黄化合物の含有量とみなされる。同様に、カルボン酸アミン塩、カルボン酸無水物、カルボン酸ハロゲン化物、又はカルボン酸エステルを有する有機硫黄化合物の量は、これら酸誘導基がカルボキシル基に置き換えられた化合物の量に換算される。 Here, in the present specification, when (B) the organic sulfur compound is a compound having an acid-derived group, the acid-derived group of the compound having the same substance amount as that of the compound having the acid-derived group is replaced with this. The amount of the compound replaced by the deriving acidic functional group is regarded as the content of the organic sulfur compound (B). For example, (B) R-COO − M + (R represents a mercapto group or a monovalent organic group containing a polysulfide bond, in which the organic sulfur compound has a carboxylate metal salt formed from a carbochelate group and a metal cation. , M + represents a metal cation.), The amount is converted to the amount of a compound represented by R-COOH in which -COO − M + of the compound is replaced with -COOH. You. That is, the amount of the compound represented by R-COOH, which is the same as the amount of the compound represented by R-COO - M + , contained in the rubber composition is (B) the content of the organic sulfur compound Considered as quantity. Similarly, the amount of an organic sulfur compound having a carboxylic acid amine salt, a carboxylic acid anhydride, a carboxylic acid halide, or a carboxylic acid ester is converted to the amount of a compound in which these acid-derived groups have been replaced with carboxyl groups.
（Ｃ）架橋剤
　架橋剤は、特に制限されず、ゴムの架橋又は加硫のために通常用いられている化合物から選択することができる。架橋剤は、例えば、有機過酸化物、硫黄、硫黄化合物、オキシム化合物、ニトロソ化合物、ポリアミン化合物、アルキルフェノール・ホルムアルデヒド縮合体、又はこれらから選ばれる２種以上の組み合わせを含んでもよい。ただし、本明細書において、架橋剤としての硫黄化合物は、上述の（Ｂ）有機硫黄化合物以外の化合物を意味する。架橋剤は、有機過酸化物を含んでもよい。 (C) Crosslinking Agent The crosslinking agent is not particularly limited, and can be selected from compounds commonly used for crosslinking or vulcanizing rubber. The cross-linking agent may include, for example, an organic peroxide, sulfur, a sulfur compound, an oxime compound, a nitroso compound, a polyamine compound, an alkylphenol-formaldehyde condensate, or a combination of two or more selected from these. However, in this specification, a sulfur compound as a crosslinking agent means a compound other than the above-mentioned (B) organic sulfur compound. The crosslinker may include an organic peroxide.
　有機過酸化物の例としては、ケトンパーオキサイド、ジアシルパーオキサイド、ハイドロパーオキサイド、ジアルキルパーオキサイド、パーオキシケタール、アルキルパーエステル、パーカーボネート、パーオキシジカーボネート、及びパーオキシエステルが挙げられる。 Examples of the organic peroxide include ketone peroxide, diacyl peroxide, hydroperoxide, dialkyl peroxide, peroxyketal, alkyl perester, percarbonate, peroxydicarbonate, and peroxyester.
　有機過酸化物の具体例として、ジクミルパーオキサイド、２，５－ジメチル－２，５－ジ（ｔ－ブチルパーオキシ）ヘキサン、２，５－ジメチル－２，５－ジ（ｔ－ブチルパーオキシ）ヘキシン、１，３－ビス（ｔ－ブチルパーオキシイソプロピル）ベンゼン、ｔ－ブチルクミルパーオキサイド、ジ－ｔ－ブチルパーオキサイド、２，２，４－トリメチルペンチル－２－ハイドロパ－オキサイド、ジイソプロピルベンゾハイドロパーオキサイド、クメンパーオキサイド、ｔ－ブチルパーオキサイド、１，１－ジ（ｔ－ブチルパーオキシ）３，５，５－トリメチルシクロヘキサン、１，１－ジ－ｔ－ブチルパーオキシシクロヘキサン、イソブチルパーオキサイド、２，４－ジクロロベンゾイルパーオキサイド、ｏ－メチルベンゾイルパーオキサイド、ビス－３，５，５－トリメチルヘキサノイルパーオキサイド、ラウロイルパーオキサイド、ベンゾイルパーオキサイド、及びｐ－クロロベンゾイルパーオキサイドが挙げられる。有機過酸化物として、単独の化合物、又は２種以上の化合物を用いてもよい。 Specific examples of the organic peroxide include dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, and 2,5-dimethyl-2,5-di (t-butylperoxide). Oxy) hexyne, 1,3-bis (t-butylperoxyisopropyl) benzene, t-butylcumyl peroxide, di-t-butyl peroxide, 2,2,4-trimethylpentyl-2-hydroperoxide, diisopropyl Benzohydroperoxide, cumene peroxide, t-butyl peroxide, 1,1-di (t-butylperoxy) 3,5,5-trimethylcyclohexane, 1,1-di-t-butylperoxycyclohexane, isobutyl Peroxide, 2,4-dichlorobenzoyl peroxide, o-methylbenzoyl peroxy Id, bis-3,5,5-trimethyl hexanoyl peroxide, lauroyl peroxide, benzoyl peroxide, and p- chlorobenzoyl peroxide. A single compound or two or more compounds may be used as the organic peroxide.
（その他の成分）
　本実施形態のゴム組成物は、本発明の効果を著しく損なわない範囲で、以上説明した成分に加えて、その他の成分を更に含有することができる。その他の成分の例としては、補強剤、軟化剤、架橋助剤、加工助剤、及び、上記エチレン－α－オレフィン－非共役ポリエン共重合体ゴム以外のゴム成分が挙げられる。 (Other components)
The rubber composition of the present embodiment may further contain other components in addition to the components described above, as long as the effects of the present invention are not significantly impaired. Examples of other components include a reinforcing agent, a softening agent, a crosslinking aid, a processing aid, and rubber components other than the ethylene-α-olefin-non-conjugated polyene copolymer rubber.
　補強剤としては、例えばＳＲＦ、ＧＰＦ、ＦＥＦ、ＭＡＦ、ＩＳＡＦ、ＳＡＦ、ＦＴ、ＭＴ等の各種カーボンブラック、乾式法シリカ、湿式法シリカ、合成ケイ酸塩系シリカ、コロイダルシリカ、炭酸カルシウム、マイカ、ケイ酸マグネシウム、ケイ酸アルミニウム、リグニン、水酸化アルミニウム、及び水酸化マグネシウム等が挙げられる。これらは単独で又は２種以上を組み合わせて用いられる。ゴム組成物における補強剤の含有量は、エチレン－α－オレフィン－非共役ポリエン共重合体ゴム１００質量部に対して、２００質量部以下、又は１５０質量部以下であってもよい。 Examples of the reinforcing agent include various carbon blacks such as SRF, GPF, FEF, MAF, ISAF, SAF, FT, and MT, dry silica, wet silica, synthetic silicate silica, colloidal silica, calcium carbonate, mica, Examples include magnesium silicate, aluminum silicate, lignin, aluminum hydroxide, and magnesium hydroxide. These are used alone or in combination of two or more. The content of the reinforcing agent in the rubber composition may be 200 parts by mass or less, or 150 parts by mass or less based on 100 parts by mass of the ethylene-α-olefin-nonconjugated polyene copolymer rubber.
　軟化剤の例としては、プロセスオイル、潤滑油、パラフィン、流動パラフィン等のパラフィン系オイル、ナフテン系オイル、石油アスファルト、ワセリン、コールタールピッチ、ヒマシ油、アマニ油、サブ、密ロウ、及びリシノール酸が挙げられる。これらは単独で又は２種以上を組み合わせて用いられる。ゴム組成物における軟化剤の含有量は、エチレン－α－オレフィン－非共役ポリエン共重合体ゴム１００質量部に対して、１５０質量部以下、又は１００質量部以下であってもよい。 Examples of softeners include process oils, lubricating oils, paraffins, paraffinic oils such as liquid paraffin, naphthenic oils, petroleum asphalt, petrolatum, coal tar pitch, castor oil, linseed oil, sub, beeswax, and ricinoleic acid. Is mentioned. These are used alone or in combination of two or more. The content of the softener in the rubber composition may be 150 parts by mass or less, or 100 parts by mass or less based on 100 parts by mass of the ethylene-α-olefin-non-conjugated polyene copolymer rubber.
　架橋助剤は、分子内に２個以上の二重結合を有する化合物を含んでいてもよい。架橋助剤として、例えば、Ｎ，Ｎ’－ｍ－フェニレンビスマレイミド、トルイレンビスマレイミド、トリアリルイソシアヌレート、トリアリルシアヌレート、ｐ－キノンジオキシム、ニトロベンゼン、ジフェニルグアニジン、ジビニルベンゼン、エチレングリコールジメタクリレート、ポリエチレングリコールジメタクリレート、トリメチロールプロパントリメタクリレート、トリメチロールプロパントリアクリレート、及びアリルメタクリレートが挙げられる。これらは単独で又は２種以上を組み合わせて用いてもよい。ゴム組成物における架橋助剤の含有量は、エチレン－α－オレフィン－非共役ポリエン共重合体ゴム１００質量部に対して、０．０５質量部以上２０質量部以下、又は０．１質量部以上８質量部以下であってもよい。 (4) The crosslinking aid may include a compound having two or more double bonds in the molecule. Examples of the crosslinking assistant include N, N′-m-phenylenebismaleimide, toluylenebismaleimide, triallyl isocyanurate, triallyl cyanurate, p-quinonedioxime, nitrobenzene, diphenylguanidine, divinylbenzene, ethylene glycol diethylene Examples include methacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, and allyl methacrylate. These may be used alone or in combination of two or more. The content of the crosslinking aid in the rubber composition is 0.05 to 20 parts by mass, or 0.1 or more parts by mass based on 100 parts by mass of the ethylene-α-olefin-non-conjugated polyene copolymer rubber. It may be 8 parts by mass or less.
　加工助剤としては、例えば、オレイン酸、パルミチン酸及びステアリン酸等の脂肪酸；ラウリン酸亜鉛、ステアリン酸亜鉛、ステアリン酸バリウム及びステアリン酸カルシウム等の脂肪酸金属塩；脂肪酸エステル；エチレングリコール及びポリエチレングリコール等のグリコールが挙げられる。これらは単独で又は組み合わせて用いることが可能である。ゴム組成物における加工助剤の含有量は、エチレン－α－オレフィン－非共役ポリエン共重合体ゴム１００質量部に対して、０．２質量部以上１０質量部以下、又は０．３質量部以上８質量部以下であってもよい。 Examples of the processing aid include fatty acids such as oleic acid, palmitic acid and stearic acid; metal salts of fatty acids such as zinc laurate, zinc stearate, barium stearate and calcium stearate; fatty acid esters; Glycol. These can be used alone or in combination. The content of the processing aid in the rubber composition is 0.2 parts by mass or more and 10 parts by mass or less, or 0.3 parts by mass or more based on 100 parts by mass of the ethylene-α-olefin-nonconjugated polyene copolymer rubber. It may be 8 parts by mass or less.
　エチレン－α－オレフィン－非共役ポリエン共重合体ゴム以外のゴム成分としては、例えば、天然ゴム、イソプレンゴム、ブタジエンゴム、スチレンブタジエンゴム、ブチルゴムが挙げられる。ゴム組成物における系共重合体ゴム以外のゴム成分の含有量は、エチレン－α－オレフィン－非共役ポリエン共重合体ゴム１００質量部に対して、１０質量部以上４０質量部以下、又は１５質量部以上３０質量部以下であってもよい。 {Rubber components other than ethylene-α-olefin-non-conjugated polyene copolymer rubber include, for example, natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, and butyl rubber. The content of the rubber component other than the system copolymer rubber in the rubber composition is from 10 parts by mass to 40 parts by mass, or 15 parts by mass, based on 100 parts by mass of the ethylene-α-olefin-nonconjugated polyene copolymer rubber. To 30 parts by mass.
　ゴム組成物は、例えば、エチレン－α－オレフィン－非共役ポリエン共重合体ゴムと、他の成分とを含む混合物を混練することにより、得ることができる。混練は、ミキサー、ニーダー及び二軸押出機等の密閉式混練機を用いて行うことができる。混練は、各成分が均一に混合されるまで行うことができる。混練時間は１分以上６０分以下であってもよい。混練温度は４０℃以上２００℃以下であってもよい。エチレン－α－オレフィン－非共役ポリエン共重合体ゴムと、パラフィン系オイル、及びナフテン系オイル等のプロセスオイルとを混合して得られる油展ゴムを、ゴム組成物の製造に用いてもよい。 The rubber composition can be obtained, for example, by kneading a mixture containing an ethylene-α-olefin-non-conjugated polyene copolymer rubber and other components. The kneading can be performed using a closed kneader such as a mixer, a kneader, and a twin-screw extruder. Kneading can be performed until the components are uniformly mixed. The kneading time may be 1 minute or more and 60 minutes or less. The kneading temperature may be 40 ° C or more and 200 ° C or less. An oil-extended rubber obtained by mixing an ethylene-α-olefin-non-conjugated polyene copolymer rubber with a process oil such as a paraffinic oil and a naphthenic oil may be used for the production of the rubber composition.
金属－ゴム複合成形体
　図１は、金属－ゴム複合成形体の一実施形態を示す断面図である。図１に示す金属－ゴム複合成形体５は、金属部材１と、金属部材１に直接接着したゴム成形体３とを備える。ゴム成形体３は、上述の実施形態に係るゴム組成物の加硫物を含む。言い換えると、ゴム成形体３は、加硫されたゴム組成物からなる。ゴム成形体３は、接着剤を介さずに金属部材１の表面に直接接着されている。このゴム成形体３は、例えば、ゴム組成物を、金属部材と接触させた状態で金型内で成形することで、金属部材１に直接接着したゴム成形体３を形成させることと、ゴム組成物を加硫することとを含む方法によって得ることができる。ゴム成形体３を加熱成形しながらゴム組成物を加硫してもよいし、ゴム成形体３を形成した後、ゴム成形体３を形成しているゴム組成物を加硫してもよい。 Metal-Rubber Composite Molded Product FIG. 1 is a cross-sectional view showing one embodiment of a metal-rubber composite molded product. The metal-rubber composite molded body 5 shown in FIG. 1 includes a metal member 1 and a rubber molded body 3 directly adhered to the metal member 1. The rubber molded body 3 includes a vulcanized product of the rubber composition according to the above-described embodiment. In other words, the rubber molded body 3 is made of a vulcanized rubber composition. The rubber molded body 3 is directly bonded to the surface of the metal member 1 without using an adhesive. The rubber molded body 3 is formed, for example, by molding the rubber composition in a mold in contact with the metal member, thereby forming the rubber molded body 3 directly adhered to the metal member 1; And vulcanizing the product. The rubber composition may be vulcanized while the rubber molded body 3 is formed by heating, or after the rubber molded body 3 is formed, the rubber composition forming the rubber molded body 3 may be vulcanized.
　ゴム組成物を、例えば、射出成形機、圧縮成形機、熱空気加硫装置等の成形機で、１００℃以上２５０℃以下、又は１２０℃以上２３０℃以下に加熱しながら金型内で成形することで、金属部材に接着するとともに加硫されたゴム成形体を形成させることができる。成形時間は、例えば１分以上６０分以下である。 The rubber composition is molded in a mold while being heated to 100 ° C. or more and 250 ° C. or less, or 120 ° C. or more and 230 ° C. or less using a molding machine such as an injection molding machine, a compression molding machine, or a hot air vulcanizing device. Thereby, it is possible to form a vulcanized rubber molded body that is bonded to the metal member. The molding time is, for example, 1 minute or more and 60 minutes or less.
　金属部材を構成する金属は、特に制限はなく、広範な範囲の金属から選択され得る。金属部材は、例えば、マグネシウム、カルシウム、バリウム、チタン、ジルコニウム、鉄、コバルト、ベリリウム、アルミニウム、クロム、マンガン、ニッケル、銅、亜鉛、錫、カドミウム、銀、白金、金、鉛、又はこれらの組み合わせを含む合金の成形体であってもよい。金属部材は、鉄、アルミニウム、銅又はこれらのいずれかを含む合金の成形体であってもよい。金属部材が鋼の成形体であってもよい。金属部材が、メッキ処理された表面を有する成形体であってもよい。メッキ処理は、黄銅メッキ処理以外の処理であり、例えばクロムメッキ処理であってもよい。 金属 The metal constituting the metal member is not particularly limited, and can be selected from a wide range of metals. The metal member is, for example, magnesium, calcium, barium, titanium, zirconium, iron, cobalt, beryllium, aluminum, chromium, manganese, nickel, copper, zinc, tin, cadmium, silver, platinum, gold, lead, or a combination thereof. A molded article of an alloy containing The metal member may be a formed body of iron, aluminum, copper, or an alloy containing any of these. The metal member may be a steel compact. The metal member may be a molded body having a plated surface. The plating process is a process other than the brass plating process, and may be, for example, a chrome plating process.
　金属－ゴム複合成形体は、例えば、ゴムロール、自動車用防振ゴム、建築用免震ゴム等の各種部材に用いることができる。金属部材及びゴム成形体の形状は、特に限定されず、用途に応じて設計される。 The metal-rubber composite molded article can be used for various members such as a rubber roll, an anti-vibration rubber for an automobile, and a seismic isolation rubber for a building. The shapes of the metal member and the rubber molded body are not particularly limited, and are designed according to the application.
　以下、実施例を挙げて本発明についてさらに具体的に説明する。ただし、本発明はこれら実施例に限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
１．エチレン－α－オレフィン－非共役ポリエン共重合体ゴムの評価方法
（１）エチレン単位の含有量及びプロピレン単位の含有量
　エチレン－α－オレフィン－非共役ポリエン共重合体ゴムをホットプレス機により成形して、厚み約０．１ｍｍのフィルムを作製した。このフィルムの赤外吸収スペクトルを、赤外分光光度計（日本分光社製ＩＲ－８１０）により測定した。得られた赤外吸収スペクトルから、参考文献（「赤外吸収スペクトルによるポリエチレンのキャラクタリゼーション」、高山、宇佐美等著、又はＤｉｅ　Ｍａｋｒｏｍｏｌｅｋｕｌａｒｅ　Ｃｈｅｍｉｅ，１７７，４６１（１９７６）Ｍｃ　Ｒａｅ，Ｍ．Ａ．，ＭａｄｄａｍＳ，Ｗ．Ｆ．等著）に記載の方法に従って、エチレン単位の含有量及びプロピレン単位の含有量を求めた。 1. Evaluation method of ethylene-α-olefin-non-conjugated polyene copolymer rubber (1) Content of ethylene unit and content of propylene unit An ethylene-α-olefin-non-conjugated polyene copolymer rubber is molded by a hot press machine. Thus, a film having a thickness of about 0.1 mm was produced. The infrared absorption spectrum of this film was measured with an infrared spectrophotometer (IR-810, manufactured by JASCO Corporation). From the obtained infrared absorption spectrum, a reference document (“Characterization of polyethylene by infrared absorption spectrum”, written by Takayama and Usami, or Die Makromolekulare Chemie, 177, 461 (1976) Mc Rae, MA, MaddamS) , WF, et al.), The content of ethylene units and the content of propylene units were determined.
（２）ヨウ素価
　「ＪＩＳ　Ｋ００７０－１９９２　６．ヨウ素価」に準拠し、異なる既知のヨウ素価を有する三種類のエチレン－プロピレン－５－エチリデン－２－ノルボルネン共重合体ゴムをそれぞれ、ホットプレス機により成形して、厚み約０．２ｍｍのフィルムを作製した。各フィルムの赤外吸収スペクトルを、赤外分光光度計（日本分光株式会社製ＩＲ－７００）によって測定した。得られた赤外吸収スペクトルから、各フィルムの５－エチリデン－２－ノルボルネン由来のピーク（１６８６ｃｍ－１の吸収ピーク）とベースピーク（１６６４～１６７４ｃｍ－１の吸収ピーク）の透過率を求め、下記式（Ｉ）によりＩＲインデックスを算出した。Ａはベースピークの透過率、Ｂは５－エチリデン－２－ノルボルネン由来のピークの透過率、Ｄ（ｍｍ）はフィルムの厚みである。
　ＩＲインデックス＝Ｌｏｇ（Ａ／Ｂ）／Ｄ・・・式（Ｉ）
　ＩＲインデックスと上記の既知のヨウ素価から、下記式（ＩＩ）で表されるヨウ素価の検量線を得た。式（ＩＩ）におけるα及びβはそれぞれ定数である。
　ヨウ素価＝α×ＩＲインデックス＋β・・・式（ＩＩ）
　エチレン－α－オレフィン－非共役ポリエン共重合体ゴムを成形して得たフィルムのＩＲインデックスを測定し、その値と上記の検量線から、エチレン－α－オレフィン－非共役ポリエン共重合体ゴムのヨウ素価を求めた。 (2) Iodine value Each of three types of ethylene-propylene-5-ethylidene-2-norbornene copolymer rubbers having different known iodine values based on “JIS K0070-1992 6. Iodine value” was hot-pressed. To form a film having a thickness of about 0.2 mm. The infrared absorption spectrum of each film was measured with an infrared spectrophotometer (IR-700 manufactured by JASCO Corporation). From the obtained infrared absorption spectrum, the transmittance of the peak derived from 5-ethylidene-2-norbornene (the absorption peak at 1686 cm -1 ) and the base peak (the absorption peak at 1664 to 1674 cm -1 ) of each film were determined. The IR index was calculated according to the formula (I). A is the transmittance of the base peak, B is the transmittance of the peak derived from 5-ethylidene-2-norbornene, and D (mm) is the thickness of the film.
IR index = Log (A / B) / D Expression (I)
From the IR index and the known iodine value, a calibration curve of the iodine value represented by the following formula (II) was obtained. Α and β in the formula (II) are constants, respectively.
Iodine value = α × IR index + β ... Formula (II)
The IR index of the film obtained by molding the ethylene-α-olefin-non-conjugated polyene copolymer rubber was measured, and from the value and the above calibration curve, the ethylene-α-olefin-non-conjugated polyene copolymer rubber was obtained. The iodine value was determined.
（３）分子量分布
　ゲルパーミエイションクロマトグラフ（ＧＰＣ）法によって、下記の条件で、エチレン－α－オレフィン－非共役ポリエン共重合体ゴムの重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）の標準ポリスチレン換算値を測定した。
・ＧＰＣ装置：東ソー株式会社製、商品名ＨＬＣ－８１２１ＧＰＣ／ＨＴ
・カラム：東ソー株式会社製、商品名ＴＳＫｇｅｌ　ＧＭＨＨＲ－Ｈ（Ｓ）ＨＴ
・分子量標準物質：分子量５００以上２０，０００，０００以下のポリスチレン
・溶出溶媒流速：１．０ｍＬ／ｍｉｎ
・試料濃度：１ｍｇ／ｍＬ
・測定温度：１４０℃
・溶出溶媒：オルトジクロロベンゼン
・注入量：５００μＬ
・検出器：示差屈折計 (3) Molecular weight distribution The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the ethylene-α-olefin-non-conjugated polyene copolymer rubber were determined by gel permeation chromatography (GPC) under the following conditions. The standard polystyrene equivalent value was measured.
・ GPC device: manufactured by Tosoh Corporation, trade name: HLC-8121GPC / HT
-Column: TSKgel GMHHR-H (S) HT, manufactured by Tosoh Corporation
-Molecular weight standard substance: polystyrene having a molecular weight of 500 or more and 20,000,000 or less-Elution solvent flow rate: 1.0 mL / min
-Sample concentration: 1 mg / mL
・ Measurement temperature: 140 ° C
・ Eluent solvent: ortho-dichlorobenzene ・ Injection volume: 500 μL
・ Detector: Differential refractometer
２．ゴム組成物の調製とその評価
　以下の原料を準備した。
（Ａ）エチレン－α－オレフィン－非共役ポリエン共重合体ゴム
・ＥＰＤＭ－１：以下の特性を有するエチレン－プロピレン－５－エチリデン－２－ノルボルネン共重合体ゴム
　エチレン単位の含有量：５０質量％
　プロピレン単位の含有量：４０．０質量％
　ヨウ素価：２１．５
　分子量分布：３．２
・ＥＰＤＭ－２：以下の特性を有するエチレン－プロピレン－５－エチリデン－２－ノルボルネン共重合体ゴム
　エチレン単位の含有量：５６質量％
　プロピレン単位の含有量：４０質量％
　ヨウ素価：９．５
　分子量分布：２．３ 2. Preparation of Rubber Composition and Its Evaluation The following raw materials were prepared.
(A) Ethylene-α-olefin-non-conjugated polyene copolymer rubber / EPDM-1: Ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber having the following characteristics: Ethylene unit content: 50% by mass
Content of propylene unit: 40.0% by mass
Iodine value: 21.5
Molecular weight distribution: 3.2
EPDM-2: an ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber having the following properties: Ethylene unit content: 56% by mass
Content of propylene unit: 40% by mass
Iodine value: 9.5
Molecular weight distribution: 2.3
（Ｂ）有機硫黄化合物
・メルカプトこはく酸：式１の化合物、試薬特級、富士フイルム和光純薬社製
・メルカプト酢酸カルシウム三水和物：式２の化合物、試薬特級、富士フイルム和光純薬社製
・３，３’－ジチオジプロピオン酸：式３の化合物、試薬特級、富士フイルム和光純薬社製
・３－メルカプトプロピオン酸：式４の化合物、試薬特級、富士フイルム和光純薬社製
Figure JPOXMLDOC01-appb-C000001
 (B) Organic sulfur compound / mercaptosuccinic acid: Compound of formula 1, special grade reagent, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Calcium acetate trihydrate: compound of formula 2 specialty reagent, special grade of reagent, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.・ 3,3′-dithiodipropionic acid: a compound of formula 3, special reagent, manufactured by Fujifilm Wako Pure Chemical Co., Ltd. ・ 3-mercaptopropionic acid: a compound of formula 4, special reagent, manufactured by Fujifilm Wako Pure Chemical
Figure JPOXMLDOC01-appb-C000001
（Ｃ）架橋剤
・ジクミルパーオキサイド：パークミルＤ（商品名）、日油社製 (C) Crosslinking agent / dicumyl peroxide: Parkmill D (trade name), manufactured by NOF Corporation
（その他）
・カーボンブラック：旭６０ＵＧ（商品名）、旭カーボン社製
・パラフィンオイル：Ｄｉａｎａ　ＰＷ３８０（商品名）、出光興産株式会社製
・エチレングリコールジメタクリレート：アクリエステルＥＤ（商品名）、三菱ケミカル社製
・アクリル酸亜鉛：ＺＤＡ－９０（商品名）：アクリル酸亜鉛、浅田化学株式会社製
・１－ヘプタノール：試薬特級、富士フイルム和光純薬社製
・ステアリン酸：５０Ｓ（商品名）、新日本理化社製
・リンゴ酸：試薬特級、富士フイルム和光純薬社製
・４－アミノベンゼンチオール：試薬特級、富士フイルム和光純薬社製
・メチオニン：試薬特級、富士フイルム和光純薬社製
・酸化亜鉛：２種（商品名）、正同化学工業社製
・酸化カルシウム：ＶＥＳＴＡ－ＰＰ（商品名）、井上石灰工業社製 (Other)
-Carbon black: Asahi 60UG (trade name), manufactured by Asahi Carbon Co., Ltd.-Paraffin oil: Diana PW380 (trade name), manufactured by Idemitsu Kosan Co., Ltd.-Ethylene glycol dimethacrylate: acrylic ester ED (trade name), manufactured by Mitsubishi Chemical Corporation. Zinc acrylate: ZDA-90 (trade name): Zinc acrylate, manufactured by Asada Chemical Co., Ltd. 1-Heptanol: Special grade reagent, manufactured by Fujifilm Wako Pure Chemical Co., Ltd. Stearic acid: 50S (trade name), Shin-Nippon Rikasha -Malic acid: Reagent special grade, manufactured by Fujifilm Wako Pure Chemical Co., Ltd.-4-Aminobenzenethiol: Reagent special grade, manufactured by Fujifilm Wako Pure Chemical Co., Ltd.-Methionine: Reagent special grade, manufactured by Fujifilm Wako Pure Chemical Co., Ltd.-Zinc oxide: 2 Seed (trade name), manufactured by Shodo Chemical Co., Ltd. ・ Calcium oxide: VESTA-PP (trade name), manufactured by Inoue Lime Industry Co.
（金属部材）
・鋼板：ＳＳ４００（長さ６０ｍｍ、幅２５ｍｍ、板厚２．０ｍｍ）
・ステンレス板：ＳＵＳ３０４（長さ６０ｍｍ、幅２５ｍｍ、板厚２．０ｍｍ）
・アルミ板：純アルミ板（純度９９．５％、長さ６０ｍｍ、幅２５ｍｍ、板厚３．０ｍｍ）
・銅板：Ｃ１０２０（長さ６０ｍｍ、幅２５ｍｍ、板厚３．０ｍｍ）
・冷間圧延鋼板：ＳＰＣＣ－ＳＤ（長さ６０ｍｍ、幅２５ｍｍ、板厚２．０ｍｍ）
・アルミ合金板：Ａ５０５２Ｐ（長さ６０ｍｍ、幅２５ｍｍ、板厚３．０ｍｍ）
・硬質クロムメッキ処理鋼板：Ｉｃｒ３０による硬質クロムメッキ処理された鋼板（ＳＳ４００、長さ６０ｍｍ、幅２５ｍｍ、板厚２．０ｍｍ） (Metal members)
-Steel plate: SS400 (length 60 mm, width 25 mm, plate thickness 2.0 mm)
・ Stainless steel plate: SUS304 (length 60 mm, width 25 mm, plate thickness 2.0 mm)
・ Aluminum plate: Pure aluminum plate (purity 99.5%, length 60mm, width 25mm, plate thickness 3.0mm)
-Copper plate: C1020 (length 60 mm, width 25 mm, plate thickness 3.0 mm)
・ Cold rolled steel plate: SPCC-SD (length 60mm, width 25mm, thickness 2.0mm)
・ Aluminum alloy plate: A5052P (length: 60 mm, width: 25 mm, plate thickness: 3.0 mm)
-Hard chrome plated steel plate: Steel plate that has been subjected to hard chrome plating by Icr30 (SS400, length 60 mm, width 25 mm, plate thickness 2.0 mm)
＜検討１＞：実施例１～６、比較例１～８
１－１．ゴム組成物の調製
実施例１
　ＥＰＤＭ－１を１００質量部、メルカプトこはく酸を３質量部、及び、その他の成分として以下の添加剤を、スタート温度７０℃に調整した１７００ｍＬのバンバリーミキサー（神戸製鋼社製）を用い、ローター回転数８０ｒｐｍで４分間混練した。
その他の成分：
・カーボンブラック：１００質量部
・パラフィンオイル：５０質量部
　得られた混練物２５３質量部と、ジクミルパーオキサイド２．７質量部と、エチレングリコールジメタクリレート２．０質量部とを、８インチのオープンロール（関西ロール株式会社製）用いて、ロール温度４０℃で混練し、ゴム組成物を得た。 <Study 1>: Examples 1 to 6, Comparative Examples 1 to 8
1-1. Preparation Example 1 of Rubber Composition
100 parts by mass of EPDM-1, 3 parts by mass of mercaptosuccinic acid, and the following additives as other components, using a 1700 mL Banbury mixer (manufactured by Kobe Steel Co., Ltd.) adjusted to a starting temperature of 70 ° C., and rotated by a rotor. Kneading was performed at several 80 rpm for 4 minutes.
Other ingredients:
-Carbon black: 100 parts by mass-paraffin oil: 50 parts by mass The obtained kneaded material (253 parts by mass), dicumyl peroxide (2.7 parts by mass), and ethylene glycol dimethacrylate (2.0 parts by mass) were mixed with each other by 8 inches. Using an open roll (manufactured by Kansai Roll Co., Ltd.), the mixture was kneaded at a roll temperature of 40 ° C. to obtain a rubber composition.
実施例２～６、比較例１～８
　各成分の種類及び配合比を表１又は表２に示す通りに変更したこと以外は実施例１と同様にして、ゴム組成物を調製した。各表に示される配合比は質量部である。表に明記されない成分の種類及び配合比は、全ての実施例及び比較例において共通である。比較例３～８では、バンバリーミキサーを用いた混練の際に、メルカプトこはく酸に代えてアクリル酸亜鉛、１－ヘプタノール、ステアリン酸、リンゴ酸、４－アミノベンゼンチオール、又はメチオニンを用いた。 Examples 2 to 6, Comparative Examples 1 to 8
A rubber composition was prepared in the same manner as in Example 1 except that the type and the mixing ratio of each component were changed as shown in Table 1 or Table 2. The mixing ratio shown in each table is parts by mass. The types and mixing ratios of the components not specified in the table are common to all Examples and Comparative Examples. In Comparative Examples 3 to 8, zinc acrylate, 1-heptanol, stearic acid, malic acid, 4-aminobenzenethiol, or methionine was used in place of mercaptosuccinic acid during kneading using a Banbury mixer.
１－２．金属－ゴム複合成形体の作製とその評価
　ゴム組成物を、金型内の鋼板（ＳＳ４００、長さ６０ｍｍ、幅２５ｍｍ、板厚２．０ｍｍ）上に載せ、その状態で、１７０℃に設定された１００トンプレス（商品名：ＰＳＦ－Ｂ０１０、関西ロール株式会社製）を用いて、プレス機のプレス面をゴム組成物に押し当て、ゴム組成物を３０分間、加熱及び圧縮した。これにより、鋼板と、鋼板表面に直接加硫接着したシート状のゴム成形体（長さ１２５ｍｍ、幅２５ｍｍ、厚み：６ｍｍ）とからなる金属－ゴム複合部材（全体厚み：８ｍｍ）を形成させた。プレス機のプレス面とゴム組成物との間にテフロン（登録商標）シートを敷くことにより、プレス機のプレス面へのゴムの接着を防止した。
　得られた金属－ゴム複合成形体を用いて、鋼板に対するゴム成形体の接着性を、ＪＩＳ　Ｋ　６２５６－２に準拠して測定した。 1-2. Preparation of Metal-Rubber Composite Molded Article and Its Evaluation The rubber composition was placed on a steel plate (SS400, length 60 mm, width 25 mm, plate thickness 2.0 mm) in a mold, and set to 170 ° C. in that state. Using a 100-ton press (trade name: PSF-B010, manufactured by Kansai Roll Co., Ltd.), the press surface of the press was pressed against the rubber composition, and the rubber composition was heated and compressed for 30 minutes. As a result, a metal-rubber composite member (total thickness: 8 mm) consisting of a steel sheet and a sheet-like rubber molded body (length 125 mm, width 25 mm, thickness: 6 mm) directly vulcanized and bonded to the surface of the steel sheet was formed. . By laying a Teflon (registered trademark) sheet between the press surface of the press and the rubber composition, adhesion of the rubber to the press surface of the press was prevented.
Using the obtained metal-rubber composite molded product, the adhesiveness of the rubber molded product to a steel plate was measured in accordance with JIS K 6256-2.
１－３．ゴム成形体の製造とその評価
　ゴム組成物を、１００トンプレス（商品名：ＰＳＦ－Ｂ０１０、関西ロール株式会社製）を用いて、設定温度１７０℃で加熱しながら金型内で２０分間圧縮することで、加硫しながら成形し、厚み２ｍｍの加硫シートを作製した。プレス機のプレス面とゴム組成物との間にテフロン（登録商標）シートを敷くことにより、プレス機のプレス面へのゴムの接着を防止した。
　得られたゴム成形体を用いて、ゴム成形体の耐久性を定伸長疲労試験により評価した。定伸長疲労試験はＪＩＳ　Ｋ　６２７０に準拠して、ダンベル状３号形の試験片（厚み２ｍｍ）を用い、伸長率５０％、周波数５Ｈｚ、２３℃の条件で行った。４個の試験片の試験を行い、５０％伸長を２万回繰り返した。４個の試験片がそれぞれ破断した時点の伸長回数の平均値を記録した。 1-3. Production of Rubber Molded Article and Its Evaluation The rubber composition is compressed for 20 minutes in a mold while heating at a set temperature of 170 ° C. using a 100-ton press (trade name: PSF-B010, manufactured by Kansai Roll Co., Ltd.). In this way, molding was performed while vulcanizing to prepare a vulcanized sheet having a thickness of 2 mm. By laying a Teflon (registered trademark) sheet between the press surface of the press and the rubber composition, adhesion of the rubber to the press surface of the press was prevented.
Using the obtained rubber molded body, the durability of the rubber molded body was evaluated by a constant elongation fatigue test. The constant elongation fatigue test was performed using a dumbbell-shaped No. 3 test piece (thickness: 2 mm) in accordance with JIS K 6270 under the conditions of an elongation ratio of 50%, a frequency of 5 Hz, and 23 ° C. Four specimens were tested and 50% elongation was repeated 20,000 times. The average value of the number of elongations at the time when each of the four test pieces broke was recorded.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表１及び表２に示されるように、実施例のゴム組成物から形成されたゴム成形体は、接着剤を介さずに鋼板に対する高い接着性を示した。加えて、各実施例のゴム成形体は、耐久性試験において伸長回数が２万回に到達するまで破断しないという優れた耐久性を示した。これに対して、アクリル酸亜鉛を含む比較例３のゴム組成物は、鋼板に対する接着性は優れていたものの、耐久性が十分でなかった。他の比較例のゴム組成物は、耐久性の点では優れていたものの、鋼板に対する接着性が低かった。なお、架橋剤を含まない比較例２のゴム組成物は、架橋が十分に進行しないために、接着強度及び耐久性の評価に供するための試験片を形成することができなかった。 As shown in Tables 1 and 2, the rubber molded article formed from the rubber composition of the example exhibited high adhesiveness to a steel sheet without using an adhesive. In addition, the rubber molded articles of the examples exhibited excellent durability such that they did not break until the number of elongations reached 20,000 in a durability test. On the other hand, the rubber composition of Comparative Example 3 containing zinc acrylate was excellent in adhesion to a steel sheet, but was insufficient in durability. The rubber compositions of the other comparative examples were excellent in durability, but had low adhesion to steel plates. Note that the rubber composition of Comparative Example 2 containing no crosslinking agent could not form a test piece for evaluation of adhesive strength and durability because crosslinking did not proceed sufficiently.
＜検討２＞：実施例７～１４
実施例７～１１
　バンバリーミキサーを用いた混練の際に、酸化カルシウム又は酸化亜鉛を更に加え、各成分の配合比を表３に示される質量部に変更したこと以外は実施例５と同様にして、ゴム組成物を調製した。 <Examination 2>: Examples 7 to 14
Examples 7 to 11
During kneading using a Banbury mixer, calcium oxide or zinc oxide was further added, and a rubber composition was prepared in the same manner as in Example 5 except that the mixing ratio of each component was changed to the parts by mass shown in Table 3. Prepared.
実施例１２～１４
　バンバリーミキサーを用いた混練の際に、メルカプトこはく酸に代えて、メルカプト酢酸カルシウム三水和物、３，３’－ジチオプロピオン酸、又は３－メルカプトプロピオン酸を用い、各成分の配合比を表３に示される質量部に変更したこと以外は実施例５と同様にして、ゴム組成物を調製した。表３において、メルカプト酢酸カルシウム三水和物の配合比の括弧内の数値は、用いられたメルカプト酢酸カルシウム三無水物と同じ物質量のメルカプト酢酸の量に換算された配合比である。 Examples 12 to 14
At the time of kneading using a Banbury mixer, instead of mercaptosuccinic acid, calcium mercaptoacetate trihydrate, 3,3'-dithiopropionic acid, or 3-mercaptopropionic acid was used. A rubber composition was prepared in the same manner as in Example 5, except that the parts were changed to parts by mass shown in No. 3. In Table 3, the numerical values in parentheses of the blending ratio of calcium mercaptoacetate trihydrate are the blending ratios converted to the amount of mercaptoacetic acid having the same substance amount as the calcium mercaptoacetate trianhydride used.
評価
　得られたゴム組成物を用いて、金属－ゴム複合成形体及びゴム成形体を「検討１」と同様の手順で作製し、それらの接着強度及び耐久性を評価した。表３に評価結果が示される。実施例７～１１のゴム組成物に含まれる有機硫黄化合物は、ゴム組成物を得るための混練の間にカルボキシル基と金属酸化物との反応によって形成された金属塩を有すると考えられる。混練の過程で形成された金属塩を有する有機硫黄化合物を用いた場合も、接着性及び耐久性の点で優れた効果が得られることが確認された。さらに、メルカプトこはく酸以外の有機硫黄化合物を用いた場合も、優れた接着性及び耐久性の点で優れた効果が得られうことが確認された。 Evaluation Using the obtained rubber composition, a metal-rubber composite molded article and a rubber molded article were produced in the same procedure as in “Study 1”, and their adhesive strength and durability were evaluated. Table 3 shows the evaluation results. It is considered that the organic sulfur compound contained in the rubber compositions of Examples 7 to 11 has a metal salt formed by a reaction between a carboxyl group and a metal oxide during kneading to obtain the rubber composition. It was confirmed that even when an organic sulfur compound having a metal salt formed during the kneading process was used, excellent effects were obtained in terms of adhesion and durability. Furthermore, it was confirmed that when an organic sulfur compound other than mercaptosuccinic acid was used, excellent effects in terms of excellent adhesiveness and durability could be obtained.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
＜検討３＞：実施例１５～１７
　実施例８のゴム組成物を用いて、鋼板に代えてステンレス板、アルミニウム板銅板、冷間圧延鋼板、アルミ合金板、又は硬質クロムメッキ処理鋼板を用いて金属－ゴム複合成形体を作製し、接着強度を評価した。 <Examination 3>: Examples 15 to 17
Using the rubber composition of Example 8, a metal-rubber composite molded body was produced using a stainless steel plate, an aluminum plate copper plate, a cold-rolled steel plate, an aluminum alloy plate, or a hard chromium-plated steel plate instead of a steel plate, The adhesive strength was evaluated.
　表４に示す評価結果から、（Ｂ）有機硫黄化合物を含むゴム組成物から形成されるゴム成形体は、鋼板以外の金属部材、又は硬質クロムメッキ等によって処理された鋼板に対しても、接着剤を介することなく高い接着性を示すことが確認された。 From the evaluation results shown in Table 4, (B) the rubber molded article formed from the rubber composition containing the organic sulfur compound adheres to a metal member other than a steel plate or a steel plate treated by hard chrome plating or the like. It was confirmed that high adhesiveness was exhibited without the use of an agent.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　以上の結果からも、本発明に係るゴム組成物によれば、接着剤を介さずに良好な接着性で金属部材に接着し、しかも十分な耐久性を有するゴム成形体、及びこれを有するゴム＝金属複合成形体が得られることが確認された。 From the above results, according to the rubber composition according to the present invention, a rubber molded body that adheres to a metal member with good adhesiveness without using an adhesive and has sufficient durability, and a rubber having the same = It was confirmed that a metal composite molded body was obtained.
　１…金属部材、３…ゴム成形体、５…金属－ゴム複合成形体。 1: metal member, 3: rubber molded body, 5: metal-rubber composite molded body.

Claims (8)

  1. 　（Ａ）エチレン単位、炭素数３以上のα－オレフィン単位及び非共役ポリエン単位を含むエチレン－α－オレフィン－非共役ポリエン共重合体ゴムと、
    　（Ｂ）有機硫黄化合物と、
    　（Ｃ）架橋剤と、
    を含有し、
    　前記有機硫黄化合物が、
    　メルカプト基又はポリスルフィド結合と、
    　酸性官能基、又は、酸性官能基から誘導される酸誘導基と、
    を有する、ゴム組成物。     (A) an ethylene-α-olefin-non-conjugated polyene copolymer rubber containing an ethylene unit, an α-olefin unit having 3 or more carbon atoms and a non-conjugated polyene unit;
    (B) an organic sulfur compound;
    (C) a crosslinking agent;
    Containing
    The organic sulfur compound,
    A mercapto group or a polysulfide bond,
    An acidic functional group, or an acid-derived group derived from the acidic functional group,
    A rubber composition having:
  2. 　前記酸性官能基が、カルボキシル基、スルホ基又はスルフェノ基である、請求項１に記載のゴム組成物。 The rubber composition according to claim 1, wherein the acidic functional group is a carboxyl group, a sulfo group, or a sulfeno group.
  3. 　前記酸誘導基が、金属塩、アミン塩、酸無水物、酸ハロゲン化物、又はエステルである、請求項１又は２に記載のゴム組成物。 The rubber composition according to claim 1, wherein the acid-derived group is a metal salt, an amine salt, an acid anhydride, an acid halide, or an ester.
  4. 　前記架橋剤が、有機過酸化物を含む、請求項１～３のいずれか一項に記載のゴム組成物。 ゴ ム The rubber composition according to any one of claims 1 to 3, wherein the crosslinking agent contains an organic peroxide.
  5. 　前記有機硫黄化合物の含有量が、前記エチレン－α－オレフィン－非共役ポリエン共重合体ゴム１００質量部に対して、１～１００質量部であり、
    　前記有機硫黄化合物が前記酸誘導基を有する化合物であるとき、前記酸誘導基を有する当該化合物の物質量と同じ物質量の、当該化合物の前記酸誘導基をこれを誘導する酸性官能基に置き換えた化合物の量が、前記有機硫黄化合物の含有量とみなされる、
    請求項１～４のいずれか一項に記載のゴム組成物。     The content of the organic sulfur compound is 1 to 100 parts by mass with respect to 100 parts by mass of the ethylene-α-olefin-non-conjugated polyene copolymer rubber;
    When the organic sulfur compound is a compound having the acid-derived group, the same amount of the substance as the compound having the acid-derived group, the acid-derived group of the compound is replaced with an acidic functional group that induces the same. The amount of the compound obtained is regarded as the content of the organic sulfur compound,
    The rubber composition according to any one of claims 1 to 4.
  6. 　金属部材と、前記金属部材に直接接着し請求項１～５のいずれか一項に記載のゴム組成物の加硫物を含むゴム成形体と、を備える金属－ゴム複合成形体。 (6) A metal-rubber composite molded article comprising: a metal member; and a rubber molded article directly adhered to the metal member and containing a vulcanized product of the rubber composition according to any one of (1) to (5).
  7. 　請求項１～５のいずれか一項に記載のゴム組成物を金属部材と接触させた状態で成形することで、前記金属部材に直接接着したゴム成形体を形成させることと、前記ゴム組成物を加硫することとを含む、金属－ゴム複合成形体を製造する方法。 The rubber composition according to any one of claims 1 to 5, wherein the rubber composition is formed in a state in which the rubber composition is in contact with the metal member, thereby forming a rubber molded body directly adhered to the metal member. Vulcanizing a metal-rubber composite molded article.
  8. 　前記金属部材が鉄、アルミニウム、銅、又はこれらのいずれかを含む合金の成形体である、請求項７に記載の方法。 8. The method according to claim 7, wherein the metal member is a formed body of iron, aluminum, copper, or an alloy containing any of these.
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