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WO2018198998A1 - Procédé de production d'objet en caoutchouc réticulé - Google Patents

Procédé de production d'objet en caoutchouc réticulé Download PDF

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WO2018198998A1
WO2018198998A1 PCT/JP2018/016399 JP2018016399W WO2018198998A1 WO 2018198998 A1 WO2018198998 A1 WO 2018198998A1 JP 2018016399 W JP2018016399 W JP 2018016399W WO 2018198998 A1 WO2018198998 A1 WO 2018198998A1
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Prior art keywords
rubber
acid
weight
crosslinking
cross
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Japanese (ja)
Inventor
敦弘 塩野
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Zeon Corp
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Zeon Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/14—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules

Definitions

  • the present invention relates to a method for producing a rubber cross-linked product of a nitrile group-containing copolymer rubber, and more particularly, a rubber cross-linked product having good normal state properties and good tear strength and excellent compression set resistance. Is related with the manufacturing method of the rubber crosslinked material which can be manufactured with high productivity.
  • Nitrile rubber (acrylonitrile-butadiene copolymer rubber) has been used as a material for automotive rubber parts such as hoses and seals, taking advantage of oil resistance, mechanical properties, chemical resistance, etc.
  • Hydrogenated nitrile rubber (hydrogenated acrylonitrile-butadiene copolymer rubber) in which carbon-carbon double bonds in the polymer main chain of rubber are hydrogenated is further excellent in mechanical properties and heat resistance, so rubbers such as belts, hoses, diaphragms, etc. Used for parts.
  • Patent Document 1 has an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit and a monoester monomer unit of ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid, and has an iodine value of 120 or less.
  • a rubber composition containing a certain highly saturated nitrile rubber and a polyamine-based crosslinking agent is press-molded at 170 ° C. for 20 minutes, and then subjected to secondary crosslinking at 170 ° C. for 4 hours to obtain a crosslinked rubber product. Obtaining techniques are disclosed.
  • Patent Document 1 Although a normal rubber property and tear strength are good and a rubber cross-linked product having excellent compression set resistance can be obtained, it is long in the cross-linking step in obtaining the rubber cross-linked product. Time processing is required, and therefore improvement has been desired from the viewpoint of improving productivity.
  • the present invention has been made in view of such a situation, and is a rubber capable of producing a rubber cross-linked product having excellent normal properties and tear strength and having excellent compression set resistance with high productivity. It aims at providing the manufacturing method of a crosslinked material.
  • the present inventors have determined that a specific amount of ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit and a single amount of ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid monoester
  • a crosslinkable rubber composition containing a nitrile group-containing highly saturated copolymer rubber containing a body unit and having an iodine value of 120 or less and a polyamine crosslinking agent is heated at a temperature of 200 ° C. or more simultaneously with molding.
  • a crosslinkable rubber composition containing a nitrile group-containing copolymer rubber having an iodine value of 120 or less and a polyamine-based crosslinking agent is crosslinked by heating at a temperature of 200 ° C. or more simultaneously with molding.
  • a method for producing a rubber cross-linked product to obtain a rubber cross-linked product is provided.
  • the crosslinkable rubber composition is crosslinked by heating at a temperature of 200 ° C. or more for 10 to 60 minutes simultaneously with molding to obtain a crosslinked rubber product.
  • the heating operation is not performed after the crosslinking is performed by heating at a temperature of 200 ° C. or more simultaneously with the molding.
  • the nitrile group-containing copolymer rubber preferably further contains 20 to 89% by weight of a conjugated diene monomer unit (including a hydrogenated portion).
  • the crosslinkable rubber composition further contains a basic crosslinking accelerator having a cyclic amidine structure.
  • the method for producing a crosslinked rubber product of the present invention comprises 10 to 60% by weight of ⁇ , ⁇ -ethylenically unsaturated nitrile monomer units and 1 to 60 ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid monoester monomer units.
  • the crosslinkable rubber composition used in the present invention comprises 10 to 60% by weight of an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit and 1 to 1 ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid monoester monomer unit.
  • a nitrile group-containing copolymer rubber containing 60% by weight and having an iodine value of 120 or less and a polyamine-based crosslinking agent are contained.
  • the nitrile group-containing copolymer rubber and the polyamine crosslinking agent will be described in this order.
  • the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer forming the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit of the nitrile group-containing copolymer rubber used in the present invention includes ⁇ , ⁇ having a nitrile group.
  • -Ethylenically unsaturated compounds are not limited and include acrylonitrile; ⁇ -halogenoacrylonitriles such as ⁇ -chloroacrylonitrile and ⁇ -bromoacrylonitrile; ⁇ -alkylacrylonitriles such as methacrylonitrile and ethacrylonitrile; Among these, acrylonitrile and methacrylonitrile are preferable, and acrylonitrile is particularly preferable.
  • the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer may be used alone or in combination of two or more.
  • the content ratio of ⁇ , ⁇ -ethylenically unsaturated nitrile monomer units in the nitrile group-containing copolymer rubber used in the present invention is 10 to 60% by weight, preferably 10%, based on all monomer units. -50% by weight, more preferably 15-45% by weight. If the content ratio of the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit is too small, the oil resistance of the resulting rubber cross-linked product is lowered. On the other hand, if the amount is too large, the cold resistance of the resulting rubber cross-linked product is lowered.
  • the ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid monoester monomer unit forming the ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid monoester monomer unit includes monomethyl maleate, monoethyl maleate, monopropyl maleate, Maleic acid monoalkyl esters such as mono-n-butyl maleate; maleic acid monocycloalkyl esters such as monocyclopentyl maleate, monocyclohexyl maleate, monocycloheptyl maleate; monomethylcyclopentyl maleate, monoethylcyclohexyl maleate, etc.
  • Monoalkyl cycloalkyl esters of maleic acid monoalkyl esters of fumaric acid such as monomethyl fumarate, monoethyl fumarate, monopropyl fumarate, mono-n-butyl fumarate; monocyclopentyl fumarate, fumaric acid
  • monocycloalkyl esters of fumaric acid such as monocyclohexyl luric acid and monocycloheptyl fumarate
  • monomethylcyclopentyl fumarate monoalkylcycloalkyl fumaric acid such as monoethylcyclohexyl fumarate
  • Citraconic acid monoalkyl esters such as propyl and monon-butyl citraconic acid
  • Citraconic acid monocycloalkyl esters such as citraconic acid monocyclopentyl, citraconic acid monocyclohexyl and citraconic acid monocycl
  • the ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid monoester monomer may be used alone or in combination of two or more.
  • ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid monoalkyl ester monomers are more preferable, maleic acid monoalkyl esters are more preferable, and mono-n-butyl maleate is particularly preferable.
  • the number of carbon atoms in the alkyl group of the alkyl ester is preferably 2-8.
  • the content ratio of the ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid monoester monomer unit in the nitrile group-containing copolymer rubber used in the present invention is 1 to 60% by weight in the total monomer units, The amount is preferably 1 to 10% by weight, more preferably 3 to 8% by weight.
  • the content ratio of the ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid monoester monomer unit is too small, the compression set resistance of the resulting rubber cross-linked product is lowered.
  • the amount is too large, the elongation, which is one of the mechanical properties of the resulting rubber cross-linked product, is lowered.
  • the nitrile group-containing copolymer rubber used in the present invention preferably contains a conjugated diene monomer unit so that the resulting rubber cross-linked product has rubber elasticity.
  • conjugated diene monomer forming the conjugated diene monomer unit examples include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, chloroprene and the like having 4 to 4 carbon atoms. 6 conjugated diene monomers are preferred, 1,3-butadiene and isoprene are more preferred, and 1,3-butadiene is particularly preferred.
  • the conjugated diene monomer may be used alone or in combination of two or more.
  • the content of the conjugated diene monomer unit (including the hydrogenated part) is preferably 20 to 89% by weight, more preferably 30 to 80% by weight, and still more preferably based on the total monomer units. 40 to 75% by weight.
  • the nitrile group-containing copolymer rubber used in the present invention includes an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit and an ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid monoester monomer unit, and
  • units containing other monomers that can be copolymerized with the monomers that form them may also be contained.
  • Such other monomers include ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid monomers, ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid ester monomers, ⁇ , ⁇ -ethylenically unsaturated monomers.
  • Polyvalent carboxylic acid monomers except those corresponding to ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid monoester monomers
  • ethylene, ⁇ -olefin monomers, aromatic vinyl monomers, fluorine-containing Examples include vinyl monomers and copolymerizable anti-aging agents.
  • Examples of the ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid monomer include acrylic acid, methacrylic acid, ethyl acrylic acid, crotonic acid, and cinnamic acid.
  • Examples of ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid ester monomers include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-dodecyl acrylate, methyl methacrylate, and ethyl methacrylate.
  • (Meth) acrylic acid ester having an alkyl group having 1 to 18 carbon atoms (abbreviation of “methacrylic acid ester and acrylic acid ester”; the same shall apply hereinafter); methoxymethyl acrylate, methoxyethyl acrylate, ethoxypropyl acrylate, (Meth) acrylic acid ester having a C2-C18 alkoxyalkyl group such as methoxybutyl acrylate, ethoxydodecyl acrylate, methoxyethyl methacrylate, methoxybutyl methacrylate, ethoxypentyl methacrylate; ⁇ -cyanoethyl acrylate; (Meth) acrylic acid esters having a cyanoalkyl group having 2 to 12 carbon atoms such as ⁇ -cyanoethyl tacrylate and cyanobutyl methacrylate; 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyeth
  • Examples of the ⁇ , ⁇ -ethylenically unsaturated polyvalent carboxylic acid monomer include butenedionic acid such as fumaric acid and maleic acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, allylmalonic acid, and teraconic acid.
  • Examples of the anhydride of ⁇ , ⁇ -unsaturated polyvalent carboxylic acid include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like.
  • the ⁇ -olefin monomer preferably has 3 to 12 carbon atoms, and examples thereof include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene.
  • aromatic vinyl monomer examples include styrene, ⁇ -methylstyrene, vinyl pyridine and the like.
  • fluorine-containing vinyl monomer examples include fluoroethyl vinyl ether, fluoropropyl vinyl ether, o-trifluoromethylstyrene, vinyl pentafluorobenzoate, difluoroethylene, and tetrafluoroethylene.
  • copolymerizable anti-aging agents examples include N- (4-anilinophenyl) acrylamide, N- (4-anilinophenyl) methacrylamide, N- (4-anilinophenyl) cinnamamide, N- (4-anilino). Phenyl) crotonamide, N-phenyl-4- (3-vinylbenzyloxy) aniline, N-phenyl-4- (4-vinylbenzyloxy) aniline and the like.
  • the content of other monomer units is preferably 50% by weight or less, more preferably 40% by weight or less, and still more preferably 30%, based on all monomer units constituting the nitrile group-containing copolymer rubber. % By weight or less.
  • the iodine value of the nitrile group-containing copolymer rubber used in the present invention is 120 or less, preferably 60 or less, more preferably 50 or less, and particularly preferably 30 or less. If the iodine value of the nitrile group-containing copolymer rubber is too high, the heat resistance and ozone resistance of the resulting rubber cross-linked product may be lowered.
  • the polymer Mooney viscosity (ML1 + 4, 100 ° C.) of the nitrile group-containing copolymer rubber used in the present invention is preferably 10 to 200, more preferably 15 to 150, still more preferably 15 to 100, and particularly preferably 30 to 90. It is. By setting the polymer Mooney viscosity within the above range, the mechanical properties of the obtained rubber cross-linked product can be appropriately enhanced while improving the processability.
  • the method for producing the nitrile group-containing copolymer rubber used in the present invention is not particularly limited, but by copolymerizing the above-described monomers and hydrogenating the carbon-carbon double bonds in the resulting copolymer. Can be manufactured.
  • the polymerization method is not particularly limited and may be a known emulsion polymerization method or solution polymerization method. From the viewpoint of industrial productivity, the emulsion polymerization method is preferable. In emulsion polymerization, in addition to an emulsifier, a polymerization initiator, and a molecular weight modifier, a commonly used polymerization auxiliary material can be used.
  • nonionic emulsifiers such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenol ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester; myristic acid, palmitic acid, oleic acid
  • anionic emulsifiers such as salts of fatty acids such as linolenic acid, alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, polycondensates of naphthalene sulfonate and formalin, higher alcohol sulfates, alkyl sulfosuccinates; , ⁇ -unsaturated carboxylic acid sulfoesters, ⁇ , ⁇ -unsaturated carboxylic acid sulfate esters, sulfoalkyl aryl ethers and other copolymerizable emuls
  • the polymerization initiator is not particularly limited as long as it is a radical initiator, but inorganic peroxides such as potassium persulfate, sodium persulfate, ammonium persulfate, potassium perphosphate, hydrogen peroxide; t-butyl peroxide, cumene Hydroperoxide, p-menthane hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, dibenzoyl peroxide, 3, 5, 5 Organic peroxides such as trimethylhexanoyl peroxide and t-butylperoxyisobutyrate; azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, methyl azobisisobutyrate, etc.
  • inorganic peroxides
  • polymerization initiators can be used alone or in combination of two or more.
  • an inorganic or organic peroxide is preferable.
  • a peroxide as the polymerization initiator, use it as a redox polymerization initiator in combination with a reducing agent such as sodium bisulfite, ferrous sulfate, sodium formaldehyde sulfoxylate and sodium ethylenediaminetetraacetate. You can also.
  • chelating agents such as sodium ethylenediaminetetraacetate tetrahydrate and builders such as sodium carbonate and sodium sulfate can be used in combination.
  • the addition amount of the polymerization initiator is preferably 0.01 to 2 parts by weight with respect to 100 parts by weight of the monomer used for the polymerization.
  • the molecular weight modifier is not particularly limited, but mercaptans such as t-dodecyl mercaptan, n-dodecyl mercaptan, octyl mercaptan; halogenated hydrocarbons such as carbon tetrachloride, methylene chloride, methylene bromide; ⁇ -methylstyrene dimer And sulfur-containing compounds such as tetraethylthiuram disulfide, dipentamethylene thiuram disulfide, and diisopropylxanthogen disulfide. These can be used alone or in combination of two or more.
  • the amount of the molecular weight modifier used is preferably 0.1 to 0.8 parts by weight with respect to 100 parts by weight of the total monomers.
  • Water is usually used as the emulsion polymerization medium.
  • the amount of water is preferably 80 to 500 parts by weight, more preferably 80 to 300 parts by weight with respect to 100 parts by weight of the monomer used for the polymerization.
  • polymerization auxiliary materials such as a stabilizer, a dispersant, a pH adjuster, an oxygen scavenger, and a particle size adjuster can be used as necessary. In using these, neither the kind nor the usage-amount is specifically limited.
  • the obtained copolymer may be subjected to hydrogenation (hydrogenation reaction) as necessary.
  • Hydrogenation may be carried out by a known method. After coagulating a latex of a copolymer obtained by emulsion polymerization, an oil layer hydrogenation method in which hydrogenation is performed in an oil layer, or a latex of the obtained copolymer is hydrogenated as it is. And water layer hydrogenation method.
  • the copolymer latex prepared by emulsion polymerization is preferably dissolved in an organic solvent through salting out, coagulation with alcohol, filtration and drying.
  • a hydrogenation reaction oil layer hydrogenation method
  • the resulting hydride is poured into a large amount of water and coagulated, washed with water, filtered and dried to obtain a nitrile group-containing copolymer rubber.
  • centrifugal dehydration may be performed.
  • a known coagulant such as sodium chloride, calcium chloride, aluminum sulfate, magnesium sulfate can be used.
  • coagulation may be performed using alcohol such as methanol, ethanol, or isopropyl alcohol.
  • the solvent for the oil layer hydrogenation method is not particularly limited as long as it is a liquid organic compound that dissolves the copolymer obtained by emulsion polymerization, but benzene, chlorobenzene, toluene, xylene, hexane, cyclohexane, tetrahydrofuran, methyl ethyl ketone, ethyl acetate. Cyclohexanone and acetone are preferably used.
  • any known selective hydrogenation catalyst can be used without limitation.
  • Palladium-based catalysts and rhodium-based catalysts are preferable, and palladium-based catalysts (such as palladium acetate, palladium chloride and palladium hydroxide) are preferred. More preferred. Two or more of these may be used in combination. In this case, it is preferable to use a palladium-based catalyst as the main active ingredient.
  • These catalysts are usually used by being supported on a carrier.
  • the carrier include silica, silica-alumina, alumina, diatomaceous earth, activated carbon and the like.
  • the amount of catalyst used is preferably 10 to 20000 ppm by weight, more preferably 50 to 15000 ppm by weight, based on the copolymer.
  • the latex of the copolymer prepared by the emulsion polymerization is diluted with water as necessary to perform a hydrogenation reaction.
  • the water layer hydrogenation method is a water layer direct hydrogenation method in which hydrogen is supplied to a reaction system in the presence of a hydrogenation catalyst to perform hydrogenation, and reduction and hydrogenation are performed in the presence of an oxidizing agent, a reducing agent and an activator.
  • An aqueous layer indirect hydrogenation method can be mentioned, and among these, the aqueous layer direct hydrogenation method is preferable.
  • the concentration of the copolymer in the aqueous layer is preferably 40% by weight or less in order to prevent aggregation.
  • a hydrogenation catalyst will not be specifically limited if it is a compound which is hard to decompose
  • the palladium catalyst include palladium salts of carboxylic acids such as formic acid, propionic acid, lauric acid, succinic acid, oleic acid, and phthalic acid; palladium chloride, dichloro (cyclooctadiene) palladium, dichloro (norbornadiene) palladium, Palladium chloride such as ammonium hexachloropalladium (IV); Iodide such as palladium iodide; Palladium nitrate; Palladium sulfate dihydrate and the like.
  • carboxylic acids such as formic acid, propionic acid, lauric acid, succinic acid, oleic acid, and phthalic acid
  • palladium chloride dichloro (cyclooctadiene) palladium, dichloro (norbornadiene) palladium
  • Palladium chloride such as ammonium hexachloropalladium (IV)
  • Iodide such as
  • palladium salts of carboxylic acids dichloro (norbornadiene) palladium, ammonium hexachloropalladium (IV) ammonium palladium chloride, and palladium nitrate are particularly preferable.
  • the amount of the hydrogenation catalyst used may be appropriately determined, but is preferably 5 to 20000 ppm by weight, more preferably 10 to 15000 ppm by weight, based on the copolymer obtained by polymerization.
  • the hydrogenation catalyst in the latex is removed after completion of the hydrogenation reaction.
  • an adsorbent such as activated carbon or ion exchange resin is added to adsorb the hydrogenation catalyst with stirring, or a complex of the hydrogenation catalyst is formed using a complexing agent together with an oxidizing agent or a reducing agent.
  • the thus-obtained latex after the hydrogenation reaction is subjected to coagulation, washing with water, filtration and drying by alcohol, such as methanol, ethanol or isopropyl alcohol, or salting out.
  • alcohol such as methanol, ethanol or isopropyl alcohol
  • salting out a nitrile group-containing copolymer rubber
  • the water washing, filtration and drying steps subsequent to coagulation can be performed by known methods.
  • a known coagulant such as sodium chloride, calcium chloride, aluminum sulfate, magnesium sulfate can be used.
  • centrifugal dehydration may be performed.
  • an anti-aging agent can also be added to the oil layer or water layer before solidification.
  • the anti-aging agent is not particularly limited, but 2,6-di-t-butyl-4-cresol (Antage BHT, manufactured by Kawaguchi Chemical Co., Ltd.), 2,2′-methylenebis (4-methyl-6-tert- Butylphenol) (Sandant 2246, manufactured by Sanshin Chemical Industry Co., Ltd.), Bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide (Sandant 103, manufactured by Sanshin Chemical Industry Co., Ltd.), Pentaerythritol Tetrakis [ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (Irganox 1010, manufactured by BASF Japan), octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate (Irganox 1076, manufactured by BASF Japan), isooctyl-3- (3,5-di- tert-
  • the crosslinkable rubber composition used in the present invention contains a polyamine-based crosslinking agent in addition to the nitrile group-containing copolymer rubber described above.
  • the polyamine-based crosslinking agent is not particularly limited as long as it is a compound having two or more amino groups or a compound having two or more amino groups at the time of crosslinking.
  • a compound in which a plurality of hydrogen atoms of a group hydrocarbon are substituted with an amino group or a hydrazide structure (a structure represented by —CONHNH 2 , CO represents a carbonyl group), and a compound that is in the form of the compound upon crosslinking are preferred .
  • polyamine-based cross-linking agent examples include aliphatic polyvalent compounds such as hexamethylene diamine, hexamethylene diamine carbamate, N, N-dicinnamylidene-1,6-hexane diamine, tetramethylene pentamine, and hexamethylene diamine cinnamaldehyde adduct.
  • aliphatic polyvalent amines and aromatic polyvalent amines are preferable from the viewpoint that the effects of the present invention can be made more remarkable, and hexamethylenediamine carbamate and 2,2-bis [ 4- (4-Aminophenoxy) phenyl] propane is more preferred, and hexamethylenediamine carbamate is particularly preferred.
  • the content of the crosslinking agent in the crosslinkable rubber composition used in the present invention is not particularly limited, but is preferably 0.1 to 20 parts by weight, more preferably 1 to 100 parts by weight of the nitrile group-containing copolymer rubber. -15 parts by weight, more preferably 1-10 parts by weight, particularly preferably 1-5 parts by weight.
  • crosslinkable rubber composition used in the present invention further contains a basic crosslinking accelerator.
  • basic crosslinking accelerators include compounds represented by the following general formula (1), basic crosslinking accelerators having a cyclic amidine structure, guanidine basic crosslinking accelerators, and aldehyde amine basic crosslinking accelerators. Agents and the like.
  • R 1 and R 2 may each independently have an alkyl group having 1 to 12 carbon atoms which may have a substituent, or may have a substituent.
  • It is a cycloalkyl group having 5 to 12 carbon atoms.
  • R 1 and R 2 are each an optionally substituted alkyl group having 1 to 12 carbon atoms or an optionally substituted cycloalkyl group having 5 to 12 carbon atoms.
  • a cycloalkyl group having 5 to 12 carbon atoms which may have a group is preferable, and a cycloalkyl group having 5 to 8 carbon atoms which may have a substituent is particularly preferable.
  • R 1 and R 2 are preferably not substituted.
  • R 1 and R 2 have a substituent include a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, an amino group, and a halogen atom.
  • a compound represented by the following general formula (2) is more preferable from the viewpoint that processability and scorch stability can be further improved.
  • R 3 and R 4 are each independently a cycloalkyl group having 5 to 8 carbon atoms which may have a substituent.
  • R 3 and R 4 are cycloalkyl groups having 5 to 8 carbon atoms which may have a substituent, but may be cycloalkyl groups which may have a substituent having 5 or 6 carbon atoms. Is preferable, and a cycloalkyl group which may have a substituent having 6 carbon atoms is more preferable. R 3 and R 4 preferably have no substituent.
  • R 3 and R 4 have a substituent include a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, an amino group, and a halogen atom.
  • Specific examples of the compound represented by the general formula (1) include dicycloalkylamines such as dicyclopentylamine, dicyclohexylamine and dicycloheptylamine; N-methylcyclopentylamine, N-butylcyclopentylamine and N-heptyl.
  • Examples of the basic crosslinking accelerator having a cyclic amidine structure include 1,8-diazabicyclo [5,4,0] undecene-7 (hereinafter sometimes abbreviated as “DBU”) and 1,5-diazabicyclo [4, 3,0] nonene-5 (hereinafter sometimes abbreviated as “DBN”), 1-methylimidazole, 1-ethylimidazole, 1-phenylimidazole, 1-benzylimidazole, 1,2-dimethylimidazole, 1-ethyl- 2-methylimidazole, 1-methoxyethylimidazole, 1-phenyl-2-methylimidazole, 1-benzyl-2-methylimidazole, 1-methyl-2-phenylimidazole, 1-methyl-2-benzylimidazole, 1,4 -Dimethylimidazole, 1,5-dimethylimidazole, 1,2,4-trimethylimidazole, 1,4- Methyl-2-ethylimidazole,
  • 1,8-diazabicyclo [5,4,0] undecene-7 and 1,5-diazabicyclo [4,3,0] nonene-5 are preferred, , 8-diazabicyclo [5,4,0] undecene-7 is more preferred.
  • the guanidine-based basic crosslinking accelerator include tetramethylguanidine, tetraethylguanidine, diphenylguanidine, 1,3-di-ortho-tolylguanidine, orthotolyl biguanide and the like.
  • aldehyde amine basic crosslinking accelerator include n-butyraldehyde aniline and acetaldehyde ammonia.
  • guanidine basic crosslinking accelerators compounds represented by the above general formula (1), guanidine basic crosslinking accelerators, and basic crosslinking accelerators having a cyclic amidine structure are preferable.
  • the compound represented and the basic crosslinking accelerator having a cyclic amidine structure are more preferable, and the basic crosslinking accelerator having a cyclic amidine structure is more preferable.
  • the compound represented by the general formula (1) may be a mixture of an alkylene glycol or an alcohol such as an alkyl alcohol having 5 to 20 carbon atoms, and an inorganic acid and / or an organic acid. May be included. Further, as the compound represented by the general formula (1), a salt is formed by the compound represented by the general formula (1) and the inorganic acid and / or organic acid, and a complex is formed with alkylene glycol. It may be.
  • the basic crosslinking accelerator having a cyclic amidine structure may form a salt with an organic carboxylic acid or an alkyl phosphoric acid.
  • the blending amount in the crosslinkable rubber composition used in the present invention is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the nitrile group-containing copolymer rubber. More preferably 0.2 to 15 parts by weight, still more preferably 0.5 to 10 parts by weight.
  • the crosslinkable rubber composition used in the present invention includes compounding agents commonly used in the rubber field, for example, reinforcing agents such as carbon black and silica, fillers such as calcium carbonate, talc and clay, Metal oxides such as zinc oxide and magnesium oxide, ⁇ , ⁇ -ethylenically unsaturated carboxylic acid metal salts such as zinc methacrylate and zinc acrylate, co-crosslinking agent, crosslinking aid, crosslinking retarder, anti-aging agent, oxidation Anti-scorching agent such as inhibitor, light stabilizer, primary amine, activator such as diethylene glycol, coupling agent, plasticizer, processing aid, lubricant, adhesive, lubricant, flame retardant, antifungal agent, acid acceptor Further, an antistatic agent, a pigment, a foaming agent and the like can be blended.
  • the compounding amount of these compounding agents is not particularly limited as long as it does not impair the object and effect of the present invention, and an amount corresponding to the compounding purpose
  • the coupling agent examples include silane coupling agents, aluminum coupling agents, titanate coupling agents, and the like.
  • the silane coupling agent is not particularly limited, and specific examples thereof include ⁇ -mercaptopropyltrimethoxysilane, ⁇ -mercaptomethyltrimethoxysilane, ⁇ -mercaptomethyltriethoxysilane, ⁇ -mercaptohexamethyldisilazane, bis Silane coupling agents containing sulfur such as (3-triethoxysilylpropyl) tetrasulfane and bis (3-triethoxysilylpropyl) disulfane; ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyl Epoxy group-containing silane coupling agents such as dimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxy
  • the aluminum coupling agent is not particularly limited, and specific examples thereof include acetoalkoxyaluminum diisopropylate.
  • the titanate coupling agent is not particularly limited, and specific examples thereof include isopropyl triisostearoyl titanate, isopropyl tris (dioctylpyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, tetraoctyl bis ( Ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl phosphite) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, tetra Examples thereof include isopropyl bis (dioctyl phosphite) titanate and is
  • carbon black examples include furnace black, acetylene black, thermal black, channel black, Austin black, and graphite. These can be used alone or in combination.
  • silica examples include natural silica such as quartz powder and silica powder; synthetic silica such as anhydrous silicic acid (silica gel, aerosil, etc.) and hydrous silicic acid. Among these, synthetic silica is preferable.
  • These silicas may be surface-treated with a coupling agent or the like. As the coupling agent used for the surface treatment, for example, those described above can be used.
  • the co-crosslinking agent is not particularly limited, but is preferably a low molecular or high molecular compound having a plurality of radical-reactive unsaturated groups in the molecule.
  • a polyfunctional vinyl compound such as divinylbenzene or divinylnaphthalene; Isocyanurates such as allyl isocyanurate and trimethallyl isocyanurate; cyanurates such as triallyl cyanurate; maleimides such as N, N′-m-phenylene dimaleimide; diallyl phthalate, diallyl isophthalate, diallyl maleate, diallyl Allyl esters of polyvalent acids such as fumarate, diallyl sebacate, triallyl phosphate; diethylene glycol bisallyl carbonate; ethylene glycol diallyl ether, triallyl ether of trimethylolpropane, pentaerythritol Allyl ethers such as partial trityl ethers of trit; ally
  • the plasticizer is not particularly limited, but trimellitic acid plasticizer, pyromellitic acid plasticizer, ether ester plasticizer, polyester plasticizer, phthalic acid plasticizer, adipate ester plasticizer, phosphoric acid
  • trimellitic acid plasticizer pyromellitic acid plasticizer
  • ether ester plasticizer polyester plasticizer
  • phthalic acid plasticizer adipate ester plasticizer
  • phosphoric acid An ester plasticizer, a sebacic acid ester plasticizer, an alkyl sulfonic acid ester compound plasticizer, an epoxidized vegetable oil plasticizer, or the like can be used.
  • trimellitic acid tri-2-ethylhexyl trimellitic acid isononyl ester, trimellitic acid mixed linear alkyl ester, dipentaerythritol ester, pyromellitic acid 2-ethylhexyl ester, polyether ester (molecular weight 300 to About 5,000), bis [2- (2-butoxyethoxy) ethyl adipate], dioctyl adipate, polyester based on adipic acid (molecular weight about 300 to 5000), dioctyl phthalate, diisononyl phthalate, dibutyl phthalate, phosphoric acid
  • examples include tricresyl, dibutyl sebacate, alkylsulfonic acid phenyl ester, epoxidized soybean oil, diheptanoate, di-2-ethylhexanoate, and didecanoate. These can be used alone or in combination.
  • blend rubbers other than the nitrile group containing copolymer rubber mentioned above with the crosslinkable rubber composition used by this invention in the range which does not inhibit the effect of this invention.
  • examples of such rubbers include acrylic rubber, ethylene-acrylic acid copolymer rubber, styrene-butadiene copolymer rubber, polybutadiene rubber, ethylene-propylene copolymer rubber, ethylene-propylene-diene terpolymer rubber, Examples include epichlorohydrin rubber, fluorine rubber, urethane rubber, chloroprene rubber, silicone rubber, natural rubber, and polyisoprene rubber.
  • the blending amount in the crosslinkable rubber composition is preferably 30 parts by weight with respect to 100 parts by weight of the nitrile group-containing copolymer rubber used in the present invention.
  • the amount is more preferably 20 parts by weight or less, still more preferably 10 parts by weight or less.
  • the crosslinkable rubber composition used in the present invention is prepared by mixing each of the above components preferably in a non-aqueous system.
  • the method for preparing the crosslinkable rubber composition used in the present invention is not limited, but usually the components excluding the crosslinking agent and the heat unstable component are primarily kneaded with a mixer such as a Banbury mixer, an intermixer, or a kneader. Then, it can be prepared by transferring to an open roll or the like and adding a cross-linking agent or a heat labile component and then secondary kneading.
  • the primary kneading is usually performed at a temperature of 10 to 200 ° C., preferably 30 to 180 ° C.
  • the reaction is performed at a temperature of 20 to 60 ° C. for 1 minute to 1 hour, preferably 1 minute to 30 minutes.
  • Manufacturing method of rubber cross-linked product is to cross-link the above-mentioned cross-linkable rubber composition by heating at a temperature of 200 ° C. or more simultaneously with molding to obtain a rubber cross-linked product.
  • crosslinking by heating at a temperature of 200 ° C. or more simultaneously with molding means that the above-described crosslinkable rubber composition is molded into a desired shape with a molding machine corresponding to the desired shape.
  • the crosslinkable rubber composition is heated at a temperature of 200 ° C. or more to advance the crosslinking, thereby fixing the shape of the crosslinked rubber and the crosslinking reaction.
  • the production method of the present invention by adopting such a molding and cross-linking method, the resulting rubber cross-linked product has good normal properties and tear strength, and is resistant to compression without performing secondary cross-linking. It can be excellent in permanent distortion. Further, according to the production method of the present invention, since it is not necessary to perform secondary crosslinking, a rubber crosslinked product can be produced with high productivity.
  • the molding machine used for crosslinking simultaneously with molding is not particularly limited as long as it is a molding machine capable of crosslinking simultaneously with molding. Examples include a molding machine and a transfer molding machine.
  • the heating time when performing crosslinking simultaneously with molding is preferably 10 to 60 minutes, more preferably 10 to 50 minutes, and further preferably 15 to 40 minutes.
  • the heating time is preferably 20 to 60 minutes, and when the heating temperature is higher than 220 ° C., the heating time is preferably 15 to 40 minutes. Further, at a higher temperature or for a longer time, the O-ring compression set may increase (become worse).
  • the press pressure is preferably 1 to 20 MPa, more preferably 5 to 15 MPa, and further preferably 7 to 12 MPa.
  • Such a crosslinked rubber product obtained by the production method of the present invention can be produced with high productivity, has good normal physical properties and good tear strength, and has excellent compression set resistance. is there. For this reason, the rubber cross-linked product obtained by the production method of the present invention makes use of such characteristics, and O-rings, packings, diaphragms, oil seals, shaft seals, bearing seals, well head seals, shock absorber seals, long lifespans.
  • Coolant seals such as coolant (LLC), seals for oil coolant, oil coolant seals, pneumatic equipment seals, CFCs or fluorohydrocarbons used in air conditioner cooling devices and compressors for air conditioner refrigerators
  • CO sealing seal, supercritical carbon dioxide or subcritical carbon dioxide sealing seal used for precision cleaning media rolling devices (rolling bearings, automotive hub units, automotive water pumps, linear guide devices and Ball screw)
  • Various sealing materials such as lubes and valve seats, BOP (Blow Out Preventer), bladder, etc .
  • intake manifold gaskets attached to the connecting part between the intake manifold and the cylinder head, and cylinders attached to the connecting part between the cylinder block and the cylinder head
  • a unit comprising a head gasket, a rocker cover gasket attached to the connecting portion between the rocker cover and the cylinder head, an oil pan gasket attached to the connecting portion between the oil pan and the cylinder block or the transmission case, a positive electrode, an electrolyte plate, and a negative electrode
  • the iodine value of the nitrile group-containing copolymer rubber was measured according to JIS K 6235.
  • composition of nitrile group-containing copolymer rubber The content ratio of each monomer unit constituting the nitrile group-containing copolymer rubber was measured by the following method. That is, the content ratio of the mono-n-butyl maleate unit was determined by determining the number of moles of carboxyl groups relative to 100 g of the nitrile group-containing copolymer rubber after hydrogenation by the above-mentioned “carboxyl group content” measurement method. The number was calculated by converting to the amount of mono-n-butyl maleate units.
  • the content ratio of 1,3-butadiene units was calculated by measuring the iodine value (according to JIS K6235) using a nitrile group-containing copolymer rubber before hydrogenation.
  • the content ratio of the acrylonitrile unit was calculated according to JIS K6384 by measuring the nitrogen content in the nitrile group-containing copolymer rubber after hydrogenation by the semi-micro Kjeldahl method or the modified Dumas method.
  • the Mooney viscosity (polymer Mooney viscosity) (ML1 + 4, 100 ° C.) of the nitrile group-containing copolymer rubber was measured according to JIS K6300.
  • test piece was produced by punching a sheet-like rubber cross-linked product with a No. 3 dumbbell, and the tensile strength and elongation were measured according to JIS K6251 using this test piece.
  • the tear strength was evaluated by using a sheet-like rubber cross-linked product according to JIS K6252-1: 2015 according to Test Method B-Procedure (a): Method using an angle-shaped test piece without cutting.
  • Compression set test (O-ring compression set) Using an O-ring-shaped rubber cross-linked product, the distance between two planes sandwiching the O-ring-shaped rubber cross-linked product was placed in an environment of 150 ° C. for 168 hours in a state compressed by 25% in the ring thickness direction. Thereafter, compression set was measured according to JIS K6262. The smaller this value, the better the compression set resistance.
  • Production Example 1 (Production of nitrile group-containing copolymer rubber (n1))
  • a reactor 180 parts of ion-exchanged water, 25 parts of a 10% strength sodium dodecylbenzenesulfonate aqueous solution, 5 parts of a sodium salt of a 10% strength naphthalene sulfonate formalin condensate, 35.5 parts of acrylonitrile, mono-n- maleate 5.5 parts of butyl and 0.75 parts of t-dodecyl mercaptan (molecular weight modifier) were charged in this order, and the internal gas was substituted three times with nitrogen, and then 59 parts of 1,3-butadiene was charged.
  • t-dodecyl mercaptan molecular weight modifier
  • the reactor was kept at 10 ° C., and 0.1 parts of cumene hydroperoxide (polymerization initiator), a reducing agent, a chelating agent and an appropriate amount of a builder were charged, and the polymerization reaction was continued while stirring, with a polymerization conversion of 80%. Then, 4 parts of a 2,2,6,6-tetramethylpiperidine-1-oxyl aqueous solution (polymerization terminator) having a concentration of 2.5% by weight was added to terminate the polymerization reaction. Subsequently, the residual monomer was removed at a water temperature of 60 ° C. to obtain a latex of nitrile group-containing copolymer rubber (X1) (solid content concentration 25% by weight).
  • X1 solid content concentration 25% by weight
  • the nitrile group-containing copolymer weight is adjusted so that the palladium content relative to the dry weight of the rubber contained in the latex of the nitrile group-containing copolymer rubber (X1) obtained above is 3000 ppm.
  • a latex of coalesced rubber (X1) and a palladium catalyst a solution in which 1% by weight palladium acetate / acetone solution and equal weight of ion exchange water are mixed
  • hydrogen pressure 3 MPa
  • temperature 50 ° C. solid content concentration 15% by weight.
  • a hydrogenation reaction was performed for 6 hours to obtain a latex of the nitrile group-containing copolymer rubber (n1).
  • 0.1 part of 4,6-bis (octylthiomethyl) -o-cresol Irganox 1520L, manufactured by BASF Japan, anti-aging agent
  • the latex of the resulting nitrile group-containing copolymer rubber (n1) was adjusted to pH 4 with 1 wt% sulfuric acid, solidified by adding 3 volumes of isopropyl alcohol, and then vacuum dried at 60 ° C. for 12 hours. A group-containing copolymer rubber (n1) was obtained.
  • the iodine value of the obtained nitrile group-containing copolymer rubber (n1) was 10, and the polymer Mooney viscosity (ML1 + 4, 100 ° C.) was 50.
  • the monomer composition of the resulting nitrile group-containing copolymer rubber (n1) was 36% by weight of acrylonitrile units, 6% by weight of mono n-butyl maleate units, and 58% by weight of 1,3-butadiene units. there were.
  • Example 1 Using a Banbury mixer, 100 parts of the nitrile group-containing copolymer rubber (n1) obtained in Production Example 1, 40 parts of FEF carbon (trade name “Seast SO”, carbon black manufactured by Tokai Carbon Co., Ltd.) Mellitic acid tri-2-ethylhexyl (trade name “Adekasizer C-8”, plasticizer, manufactured by ADEKA), 1 part stearic acid, polyoxyethylene alkyl ether phosphate ester (trade name “phosphanol RL210”) 1 part of Toho Chemical Industries, Ltd., processing aid), and 4,4′-di- ( ⁇ , ⁇ ′-dimethylbenzyl) diphenylamine (trade name “NOCRACK CD”, manufactured by Ouchi Shinsei Chemical Co., Ltd., anti-aging agent ) 1.5 parts is added and kneaded, then the mixture is transferred to a roll and 1,8-diazabicyclo [5,4,0] undecene-7 (DBU) (trade name: “R
  • Example 2 Similar to Example 1, except that the crosslinkable rubber composition obtained in the same manner as in Example 1 was used, and the conditions for performing molding and crosslinking simultaneously were 20 MPa at a press pressure of 10 MPa and a temperature of 220 ° C. Thus, a sheet-like rubber cross-linked product and an O-ring-shaped rubber cross-linked product were obtained. Then, according to the above method, the obtained sheet-like rubber cross-linked product is used to measure normal properties and tear strength, and the obtained O-ring-like rubber cross-linked product is used to measure compression set. Measurements were made. The results are shown in Table 1.
  • Example 3 Similar to Example 1 except that the crosslinkable rubber composition obtained in the same manner as in Example 1 was used, and the conditions for carrying out molding and crosslinking simultaneously were 20 MPa at a press pressure of 10 MPa and a temperature of 210 ° C. Thus, a sheet-like rubber cross-linked product and an O-ring-shaped rubber cross-linked product were obtained. Then, according to the above method, the obtained sheet-like rubber cross-linked product is used to measure normal properties and tear strength, and the obtained O-ring-like rubber cross-linked product is used to measure compression set. Measurements were made. The results are shown in Table 1.
  • Example 4 Similar to Example 1 except that the crosslinkable rubber composition obtained in the same manner as in Example 1 was used, and the conditions for simultaneous molding and crosslinking were set at a press pressure of 10 MPa and a temperature of 205 ° C. for 25 minutes. Thus, a sheet-like rubber cross-linked product and an O-ring-shaped rubber cross-linked product were obtained. Then, according to the above method, the obtained sheet-like rubber cross-linked product is used to measure normal properties and tear strength, and the obtained O-ring-like rubber cross-linked product is used to measure compression set. Measurements were made. The results are shown in Table 1.
  • Example 5 Similar to Example 1 except that the crosslinkable rubber composition obtained in the same manner as in Example 1 was used, and the conditions for simultaneous molding and crosslinking were set at a press pressure of 10 MPa and a temperature of 250 ° C. for 20 minutes. Thus, a sheet-like rubber cross-linked product and an O-ring-shaped rubber cross-linked product were obtained. Then, according to the above method, the obtained sheet-like rubber cross-linked product is used to measure normal properties and tear strength, and the obtained O-ring-like rubber cross-linked product is used to measure compression set. Measurements were made. The results are shown in Table 1.
  • Example 6 Similar to Example 1 except that the crosslinkable rubber composition obtained in the same manner as in Example 1 was used, and the conditions for simultaneous molding and crosslinking were set at a press pressure of 10 MPa and a temperature of 200 ° C. for 60 minutes. Thus, a sheet-like rubber cross-linked product and an O-ring-shaped rubber cross-linked product were obtained. Then, according to the above method, the obtained sheet-like rubber cross-linked product is used to measure normal properties and tear strength, and the obtained O-ring-like rubber cross-linked product is used to measure compression set. Measurements were made. The results are shown in Table 1.
  • Comparative Example 1 Using the crosslinkable rubber composition obtained in the same manner as in Example 1, the conditions for carrying out molding and crosslinking at the same time were set at a press pressure of 10 MPa and a temperature of 170 ° C. for 20 minutes to obtain a primary crosslinked product.
  • the primary cross-linked product was transferred to a gear-type oven and further heated at 170 ° C. for 4 hours to perform secondary cross-linking in the same manner as in Example 1, except that a sheet-like rubber cross-linked product and An O-ring-like rubber cross-linked product was obtained.
  • the obtained sheet-like rubber cross-linked product is used to measure normal properties and tear strength, and the obtained O-ring-like rubber cross-linked product is used to measure compression set. Measurements were made. The results are shown in Table 1.
  • Comparative Example 2 Similar to Example 1 except that the crosslinkable rubber composition obtained in the same manner as in Example 1 was used, and the conditions for carrying out molding and crosslinking simultaneously were 20 MPa at a press pressure of 10 MPa and a temperature of 170 ° C. Thus, a sheet-like rubber cross-linked product and an O-ring-shaped rubber cross-linked product were obtained. Then, according to the above method, the obtained sheet-like rubber cross-linked product is used to measure normal properties and tear strength, and the obtained O-ring-like rubber cross-linked product is used to measure compression set. Measurements were made. The results are shown in Table 1.
  • Comparative Example 3 Similar to Example 1 except that the crosslinkable rubber composition obtained in the same manner as in Example 1 was used, and the conditions for simultaneous molding and crosslinking were set at a press pressure of 10 MPa and a temperature of 190 ° C. for 30 minutes. Thus, a sheet-like rubber cross-linked product and an O-ring-shaped rubber cross-linked product were obtained. Then, according to the above method, the obtained sheet-like rubber cross-linked product is used to measure normal properties and tear strength, and the obtained O-ring-like rubber cross-linked product is used to measure compression set. Measurements were made. The results are shown in Table 1.
  • Example 6 was excellent in tensile strength and elongation to the same extent as Comparative Example 1 in which primary crosslinking was performed at the same time as molding and then secondary crosslinking, and in compression set (O-ring compression set) and tear strength. It was excellent. That is, according to Examples 1 to 6, it is possible to realize characteristics comparable to those obtained when primary crosslinking and secondary crosslinking are performed with fewer crosslinking operations and with a short crosslinking operation, and excellent productivity. It was a thing. In particular, among Examples 1 to 6, in Examples 2 to 5 in which the heating temperature when performing crosslinking simultaneously with molding exceeded 200 ° C., the heating time when performing crosslinking simultaneously with molding, that is, molding and crosslinking The time can be shortened and the productivity is more excellent.

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Abstract

L'invention concerne un procédé de production d'un objet en caoutchouc réticulé, le procédé comprenant le moulage et le chauffage simultané d'une composition de caoutchouc réticulable à une température de 200°C ou plus pour obtenir l'objet en caoutchouc réticulé, la composition de caoutchouc réticulable comprenant : un caoutchouc de copolymère contenant un groupe nitrile comprenant 10-60 % en poids de motifs d'un monomère de type nitrile éthyléniquement α,β-insaturé et 1-60 % en poids de motifs d'un monomère de type monoester dicarboxylique éthyléniquement α,β-insaturé et présentant une valeur d'iode de 120 ou moins ; et un agent de réticulation à base de polyamine.
PCT/JP2018/016399 2017-04-26 2018-04-23 Procédé de production d'objet en caoutchouc réticulé Ceased WO2018198998A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0819275B2 (ja) * 1987-09-09 1996-02-28 日本合成ゴム株式会社 加硫可能なエラストマー組成物の製造方法
JP2007224215A (ja) * 2006-02-24 2007-09-06 Nippon Zeon Co Ltd 半導電性ゴム組成物、架橋性ゴム組成物およびゴム架橋物
JP4168189B2 (ja) * 1998-01-14 2008-10-22 ソルバーユ ソレクシス エッセ．ピー．ア． アクリルゴムとフッ素ゴムとの複合体、その製造方法および加硫性ゴム組成物
WO2010038720A1 (fr) * 2008-09-30 2010-04-08 日本ゼオン株式会社 Caoutchouc copolymère hautement saturé contenant un groupe nitrile, composition de caoutchouc réticulable en contenant et produit réticulé
JP2013018936A (ja) * 2011-07-14 2013-01-31 Nippon Zeon Co Ltd 架橋性ゴム組成物およびゴム架橋物
JP2015147855A (ja) * 2014-02-06 2015-08-20 内山工業株式会社 ゴム組成物及びそれを架橋させてなる成形品

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0819275B2 (ja) * 1987-09-09 1996-02-28 日本合成ゴム株式会社 加硫可能なエラストマー組成物の製造方法
JP4168189B2 (ja) * 1998-01-14 2008-10-22 ソルバーユ ソレクシス エッセ．ピー．ア． アクリルゴムとフッ素ゴムとの複合体、その製造方法および加硫性ゴム組成物
JP2007224215A (ja) * 2006-02-24 2007-09-06 Nippon Zeon Co Ltd 半導電性ゴム組成物、架橋性ゴム組成物およびゴム架橋物
WO2010038720A1 (fr) * 2008-09-30 2010-04-08 日本ゼオン株式会社 Caoutchouc copolymère hautement saturé contenant un groupe nitrile, composition de caoutchouc réticulable en contenant et produit réticulé
JP2013018936A (ja) * 2011-07-14 2013-01-31 Nippon Zeon Co Ltd 架橋性ゴム組成物およびゴム架橋物
JP2015147855A (ja) * 2014-02-06 2015-08-20 内山工業株式会社 ゴム組成物及びそれを架橋させてなる成形品

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