WO2017065218A1 - 架橋性ゴム組成物の製造方法 - Google Patents
架橋性ゴム組成物の製造方法 Download PDFInfo
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- WO2017065218A1 WO2017065218A1 PCT/JP2016/080384 JP2016080384W WO2017065218A1 WO 2017065218 A1 WO2017065218 A1 WO 2017065218A1 JP 2016080384 W JP2016080384 W JP 2016080384W WO 2017065218 A1 WO2017065218 A1 WO 2017065218A1
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- C08J3/00—Processes of treating or compounding macromolecular substances
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
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- C08L15/005—Hydrogenated nitrile rubber
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2313/00—Characterised by the use of rubbers containing carboxyl groups
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- C—CHEMISTRY; METALLURGY
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- C08J2315/00—Characterised by the use of rubber derivatives
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- C08J2413/00—Characterised by the use of rubbers containing carboxyl groups
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2433/08—Homopolymers or copolymers of acrylic acid esters
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- 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
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
Definitions
- the present invention relates to a method for producing a crosslinkable rubber composition, and more particularly to a method for producing a crosslinkable rubber composition capable of providing a crosslinked rubber having excellent mechanical strength and heat aging resistance.
- nitrile rubber has been used as a material for automotive rubber parts such as hoses and tubes, taking advantage of oil resistance, mechanical properties, chemical resistance, etc., and carbon in the polymer main chain of nitrile rubber -Nitrile rubbers with hydrogenated carbon double bonds are superior in heat resistance and are used in rubber parts such as hoses and seals.
- Patent Document 1 discloses a step of preparing a carboxyl group-containing nitrile copolymer rubber (A) having an iodine value of 120 or less, and a nitrile copolymer rubber (b1 having an iodine value of 120 or less). ) And an aromatic polyvalent amine crosslinking agent (b2) at a temperature equal to or higher than the melting point of the aromatic polyvalent amine crosslinking agent (b2) to obtain a master batch (B);
- a method for producing a crosslinkable nitrile rubber composition comprising: a step of blending a master batch (B) with a carboxyl group-containing nitrile copolymer rubber (A) as described below.
- the present invention has been made in view of such circumstances, and is obtained by a method for producing a crosslinkable rubber composition capable of providing a rubber crosslinked product having excellent mechanical strength and heat aging resistance, and the production method. It is an object of the present invention to provide a method for producing a crosslinked rubber product using the obtained crosslinkable rubber composition.
- the present inventors have added an acrylic rubber (b1) and an aromatic polyvalent amine crosslinking agent (b2) to a carboxyl group-containing nitrile copolymer rubber having an iodine value of 120 or less. It has been found that the above-mentioned object can be achieved by employing a step of mixing a masterbatch (B) containing, and the present invention has been completed.
- a method for producing a crosslinkable rubber composition the first step of preparing a carboxyl group-containing nitrile copolymer rubber (A) having an iodine value of 120 or less, and an acrylic rubber (b1 ) Is mixed with the aromatic polyvalent amine crosslinking agent (b2) to obtain a master batch (B), and the carboxyl group-containing nitrile copolymer rubber (A) is mixed with the master batch (B).
- a third step of producing a crosslinkable rubber composition the first step of preparing a carboxyl group-containing nitrile copolymer rubber (A) having an iodine value of 120 or less, and an acrylic rubber (b1 ) Is mixed with the aromatic polyvalent amine crosslinking agent (b2) to obtain a master batch (B), and the carboxyl group-containing nitrile copolymer rubber (A) is mixed with the master batch (B).
- the acrylic rubber (b1) and the aromatic polyvalent amine cross-linking agent (b2) at a temperature higher by 10 ° C. or more than the melting point of the aromatic polyvalent amine cross-linking agent (b2).
- the compounding amount of the master batch (B) is 0.1 to 40 parts by weight with respect to 100 parts by weight of the carboxyl group-containing nitrile copolymer rubber (A).
- the third step is a step of mixing the master batch (B) and silica with the carboxyl group-containing nitrile copolymer rubber (A).
- a method for producing a crosslinked rubber product comprising a step of crosslinking a crosslinkable rubber composition obtained by any one of the above production methods.
- the crosslinkable rubber composition which can give the rubber crosslinked material excellent in mechanical strength and heat aging resistance, and the rubber crosslinked material obtained by bridge
- the method for producing the crosslinkable rubber composition of the present invention comprises: Preparing a carboxyl group-containing nitrile copolymer rubber (A) having an iodine value of 120 or less; Mixing acrylic polyvalent amine crosslinking agent (b2) with acrylic rubber (b1) to obtain masterbatch (B); Mixing the master batch (B) with the carboxyl group-containing nitrile copolymer rubber (A).
- a crosslinkable rubber composition obtained by blending (B) can be obtained.
- the first step of the production method of the present invention is a step of preparing a carboxyl group-containing nitrile copolymer rubber (A) having an iodine value of 120 or less.
- the carboxyl group-containing nitrile copolymer rubber (A) having an iodine value of 120 or less used in the present invention (hereinafter abbreviated as “carboxyl group-containing nitrile copolymer rubber (A)”) is an ⁇ , ⁇ -ethylenic rubber.
- the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer is not particularly limited as long as it is an ⁇ , ⁇ -ethylenically unsaturated compound having a nitrile group.
- acrylonitrile; ⁇ -chloroacrylonitrile, ⁇ -bromoacrylonitrile, etc. ⁇ -halogenoacrylonitrile, ⁇ -alkylacrylonitrile such as methacrylonitrile, and the like 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 of the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit is preferably 10 to 60% by weight, more preferably 15 to 55% by weight, still more preferably 20 to 50% based on the total monomer units. % By weight. If the content of the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit is too small, the oil resistance of the resulting cross-linked product may be reduced, and conversely if too much, cold resistance may be reduced. .
- the carboxyl group-containing monomer is a monomer that can be copolymerized with an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer and has one or more unsubstituted (free) carboxyl groups that are not esterified. There is no particular limitation as long as it is a monomer. Examples of such carboxy group-containing monomers include ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid monomers, ⁇ , ⁇ -ethylenically unsaturated polycarboxylic acid monomers, and ⁇ , ⁇ - And ethylenically unsaturated dicarboxylic acid monoester monomers.
- the carboxyl group-containing monomer also includes monomers in which the carboxyl group of these monomers forms a carboxylate. Furthermore, an anhydride of an ⁇ , ⁇ -ethylenically unsaturated polyvalent carboxylic acid can also be used as a carboxyl group-containing monomer because it forms a carboxyl group by cleaving the acid anhydride group after copolymerization.
- Examples of the ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid monomer include acrylic acid, methacrylic acid, ethyl acrylic acid, crotonic acid, and cinnamic acid.
- Examples of the ⁇ , ⁇ -ethylenically unsaturated polyvalent carboxylic acid monomer include butenedionic acid such as fumaric acid and maleic acid, itaconic acid and citraconic acid.
- Examples of the anhydride of ⁇ , ⁇ -ethylenically unsaturated polyvalent carboxylic acid include maleic anhydride.
- maleic acid monoalkyl esters such as monomethyl maleate, monoethyl maleate, monopropyl maleate, mono n-butyl maleate; monocyclopentyl maleate, Maleic acid monocycloalkyl esters such as monocyclohexyl maleate and monocycloheptyl maleate; Monoalkyl cycloalkyl esters of maleic acid such as monomethylcyclopentyl maleate and monoethylcyclohexyl maleate; Monomethyl fumarate, monoethyl fumarate and monofumarate Monoalkyl esters of fumaric acid such as propyl and mono-n-butyl fumarate; fumaric acid such as monocyclopentyl fumarate, monocyclohexyl fumarate and monocycloheptyl fumarate Monocycloalkyl esters of fumaric acid such as monocyclopentyl fumarate, monocyclohexyl fumarate and monocycloheptyl fum
- ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid monoester is preferable from the viewpoint that the effect of the present invention becomes more remarkable, and mono n-butyl fumarate, mono n-butyl itaconate, mono acid maleate n-Butyl is more preferred, and mono-n-butyl maleate is particularly preferred.
- the content of the carboxyl group-containing monomer unit is preferably 0.1 to 20% by weight, more preferably 0.2 to 15% by weight, and further preferably 0.5 to 10% by weight based on the total monomer units. % By weight. If the content of the carboxyl group-containing monomer unit is too small, the mechanical strength and compression set resistance of the resulting crosslinked product may be deteriorated. Conversely, if the content is too large, the crosslinking nitrile rubber composition There is a possibility that the scorch stability is deteriorated and the fatigue resistance of the obtained crosslinked product is lowered.
- the carboxyl group-containing nitrile copolymer rubber (A) used in the present invention is characterized in that the resulting crosslinked product exhibits rubber elasticity together with the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer and the carboxyl group-containing monomer. More preferably, it is a copolymer of conjugated diene monomers.
- the proportion of each monomer in the case of copolymerization is preferably 10 to 60% by weight of ⁇ , ⁇ -ethylenically unsaturated nitrile monomer when the total amount of monomers used for copolymerization is 100 parts by weight.
- Parts more preferably 15 to 55 parts by weight, particularly preferably 20 to 50 parts by weight, and the carboxyl group-containing monomer is preferably 0.1 to 20 parts by weight, more preferably 0.2 to 15 parts by weight,
- the amount of conjugated diene monomer is preferably 20 to 89.9 parts by weight, more preferably 30 to 84.8 parts by weight, and particularly preferably 40 to 79.5 parts by weight. It is.
- the conjugated diene monomer is not particularly limited as long as it is copolymerizable with an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer and a carboxyl group-containing monomer, and 1,3-butadiene, C4-C6 conjugated diene monomers such as isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene 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 is preferably 20 to 89.9% by weight, more preferably 30 to 84.8% by weight, still more preferably 40 to 79.5% by weight based on the total monomer units. %. If the content of the conjugated diene monomer unit is too small, the rubber elasticity of the resulting crosslinked product may be lowered. Conversely, if the content is too large, heat resistance and chemical stability may be impaired. In addition, content of the said conjugated diene monomer unit is content also including the hydrogenated part, when the below-mentioned copolymer is hydrogenated.
- the carboxyl group-containing nitrile copolymer rubber (A) used in the present invention is copolymerized with an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer, a carboxyl group-containing monomer, and a conjugated diene monomer.
- the other possible monomer (I) may be copolymerized.
- examples of such other monomer (I) include ethylene, ⁇ -olefin monomer, aromatic vinyl monomer, ⁇ , ⁇ -ethylenically unsaturated carboxylic acid ester monomer (the above-mentioned “carboxyl group”). Excluding those corresponding to “containing monomers”), fluorine-containing vinyl monomers, copolymerizable anti-aging agents 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.
- Examples of the ⁇ , ⁇ -ethylenically unsaturated carboxylic acid ester monomer include carbon numbers such as methyl acrylate, ethyl acrylate, n-butyl acrylate, n-dodecyl acrylate, methyl methacrylate, and ethyl methacrylate.
- (Meth) acrylic acid ester having 1 to 18 alkyl groups abbreviation of “methacrylic acid ester and acrylic acid ester”; the same shall apply hereinafter
- Acid ester 2-hydroxyethyl acrylate (Meth) acrylic acid esters having a hydroxyalkyl group having 1 to 12 carbon atoms such as 2-hydroxypropyl acrylate and 2-hydroxyethyl methacrylate; carbon numbers such as trifluoroethyl acrylate and tetrafluoropropyl methacrylate (Meth) acrylic acid ester having 1 to 12 fluoroalkyl groups; ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid dialkyl ester such as dimethyl maleate, dimethyl fumarate, dimethyl itaconate, diethyl itaconate; dimethylaminomethyl acrylate Dialkylamino group-containing ⁇ , ⁇ -ethylenically unsaturated carboxylic acid ester such as diethylaminoethyl acrylate, 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- Anilinophenyl) 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 30% by weight or less, and still more preferably 10% by weight or less based on the total monomer units.
- the iodine value of the carboxyl group-containing nitrile copolymer rubber (A) is 120 or less, preferably 80 or less, more preferably 25 or less, and particularly preferably 15 or less. If the iodine value of the carboxyl group-containing nitrile copolymer rubber (A) is too high, the heat resistance and ozone resistance of the resulting crosslinked product may be lowered.
- the polymer Mooney viscosity (ML 1 + 4 , 100 ° C.) of the carboxyl group-containing nitrile copolymer rubber (A) is preferably 15 to 200, more preferably 20 to 150, and particularly preferably 30 to 120. If the polymer Mooney viscosity of the carboxyl group-containing nitrile copolymer rubber (A) is too low, the mechanical strength of the resulting cross-linked product may be reduced. Conversely, if it is too high, the processability of the cross-linkable nitrile rubber composition will decrease. May be reduced.
- the carboxyl group content in the carboxyl group-containing nitrile copolymer rubber (A), that is, the number of moles of carboxyl groups per 100 g of the carboxyl group-containing nitrile copolymer rubber (A) is preferably 5 ⁇ 10 ⁇ 4 to 5 ⁇ 10 ⁇ 1 ephr, more preferably 1 ⁇ 10 ⁇ 3 to 1 ⁇ 10 ⁇ 1 ephr, and further preferably 5 ⁇ 10 ⁇ 3 to 6 ⁇ 10 ⁇ 2 ephr. If the carboxyl group content of the carboxyl group-containing nitrile copolymer rubber (A) is too low, the mechanical strength of the resulting crosslinked product may be reduced, and if too high, the cold resistance of the crosslinked product may be reduced.
- the production method of the carboxyl group-containing nitrile copolymer rubber (A) used in the present invention is not particularly limited.
- the polymerization method any of the known emulsion polymerization method, suspension polymerization method, bulk polymerization method and solution polymerization method can be used, but the emulsion polymerization method is preferable because the polymerization reaction can be easily controlled.
- the hydrogenation method is not particularly limited, and a known method may be employed.
- the 2nd process of the manufacturing method of this invention is a process of mixing an aromatic polyvalent amine crosslinking agent (b2) with an acrylic rubber (b1), and obtaining a masterbatch (B).
- the acrylic rubber (b1) acts as a binder for the masterbatch (B), and the aromatic polyvalent amine crosslinking agent (b2) is dispersed in the masterbatch (B) by the acrylic rubber (b1).
- the dispersibility of the aromatic polyvalent amine crosslinking agent (b2) with respect to the group-containing nitrile copolymer rubber (A) can be improved.
- the acrylic rubber (b1) has (meth) acrylic acid ester monomer [acrylic acid ester monomer and as a main component (preferably having 50% by weight or more in all monomer units) in the molecule. // Methyl methacrylate monomer. The same applies to methyl (meth) acrylate. It is not particularly limited as long as it contains a unit.
- the acrylic rubber (b1) used in the present invention includes 50 to 100% by weight of a (meth) acrylic acid ester monomer unit as a main component and 0 to 10% by weight of a crosslinkable monomer unit in the molecule. And the like.
- the (meth) acrylic acid ester monomer forming the (meth) acrylic acid ester monomer unit suitable as the main component of the acrylic rubber (b1) used in the present invention is not particularly limited. ) Acrylic acid alkyl ester monomer and (meth) acrylic acid alkoxyalkyl ester monomer.
- the (meth) acrylic acid alkyl ester monomer is not particularly limited, but is preferably an ester of an alkanol having 1 to 8 carbon atoms and (meth) acrylic acid, specifically, methyl (meth) acrylate, ( (Meth) ethyl acrylate, (meth) acrylic acid n-propyl, (meth) acrylic acid isopropyl, (meth) acrylic acid n-butyl, (meth) acrylic acid isobutyl, (meth) acrylic acid n-hexyl, (meth) Examples include 2-ethylhexyl acrylate and cyclohexyl (meth) acrylate.
- ethyl (meth) acrylate and n-butyl (meth) acrylate are preferable, and ethyl acrylate and n-butyl acrylate are particularly preferable. These can be used alone or in combination of two or more.
- the (meth) acrylic acid alkoxyalkyl ester monomer is not particularly limited, but an ester of an alkoxyalkyl alcohol having 2 to 8 carbon atoms and (meth) acrylic acid is preferable.
- (meth) acrylic acid Methoxymethyl, ethoxymethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate , 3-methoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, and the like.
- 2-ethoxyethyl (meth) acrylate and 2-methoxyethyl (meth) acrylate are preferable, and 2-ethoxyethyl acrylate and 2-methoxyethyl acrylate are particularly preferable. These can be used alone or in combination of two or more.
- the content of the (meth) acrylic acid ester monomer unit in the acrylic rubber (b1) used in the present invention is preferably 50 to 100% by weight, more preferably 50 to 99.9% by weight, and still more preferably 60%. To 99.5% by weight, particularly preferably 70 to 99.5% by weight. When there is too little content of a (meth) acrylic acid ester monomer unit, there exists a possibility that the heat aging resistance of the rubber crosslinked material obtained may fall.
- the (meth) acrylic acid ester monomer units are 30 to 100% by weight of (meth) acrylic acid alkyl ester monomer units and 70 to (meth) acrylic acid alkoxyalkyl ester monomer units. It is preferable to consist of 0% by weight.
- the crosslinkable monomer that forms the crosslinkable monomer unit is not particularly limited.
- an ⁇ , ⁇ -ethylenically unsaturated carboxylic acid monomer a monomer having an epoxy group; a halogen atom Monomer; diene monomer; and the like.
- the ⁇ , ⁇ -ethylenically unsaturated carboxylic acid monomer is not particularly limited, and examples thereof include ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids having 3 to 12 carbon atoms and ⁇ , ⁇ having 4 to 12 carbon atoms.
- ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid having 3 to 12 carbon atoms include acrylic acid, methacrylic acid, ⁇ -ethylacrylic acid, crotonic acid, and cinnamic acid.
- ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid having 4 to 12 carbon atoms include butenedionic acid such as fumaric acid and maleic acid; itaconic acid; citraconic acid; chloromaleic acid;
- monoesters of ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acids having 4 to 12 carbon atoms and alkanols having 1 to 8 carbon atoms include monomethyl fumarate, monoethyl fumarate, mono n-butyl fumarate, malein Butenedionic acid mono-chain alkyl esters such as monomethyl acid, monoethyl maleate, and mono-n-butyl maleate; monocyclopentyl fumarate, monocyclohexyl fumarate, monocyclohexenyl fumarate, monocyclopentyl maleate, monocyclohexyl maleate, maleate And butenedionic acid monoesters having an alicyclic structure such
- ⁇ , ⁇ -ethylenically unsaturated carboxylic acid monomers can be used alone or in combination of two or more.
- dicarboxylic acids include those that exist as anhydrides.
- the monomer having an epoxy group is not particularly limited, and examples thereof include an epoxy group-containing (meth) acrylic acid ester and an epoxy group-containing ether.
- epoxy group-containing (meth) acrylic acid ester examples include glycidyl (meth) acrylate.
- Specific examples of the epoxy group-containing ether include allyl glycidyl ether and vinyl glycidyl ether. Among these, glycidyl methacrylate and allyl glycidyl ether are preferable. These monomers having an epoxy group can be used alone or in combination of two or more.
- unsaturated alcohol ester of halogen-containing saturated carboxylic acid for example, unsaturated alcohol ester of halogen-containing saturated carboxylic acid, (meth) acrylic acid haloalkyl ester, (meth) acrylic acid haloacyloxyalkyl ester, (meth) acrylic Examples include acid (haloacetylcarbamoyloxy) alkyl esters, halogen-containing unsaturated ethers, halogen-containing unsaturated ketones, halomethyl group-containing aromatic vinyl compounds, halogen-containing unsaturated amides, and haloacetyl group-containing unsaturated monomers.
- the unsaturated alcohol ester of a halogen-containing saturated carboxylic acid include vinyl chloroacetate, vinyl 2-chloropropionate, and allyl chloroacetate.
- Specific examples of (meth) acrylic acid haloalkyl esters include chloromethyl (meth) acrylate, 1-chloroethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 1,2-dichloroethyl (meth) acrylate. , 2-chloropropyl (meth) acrylate, 3-chloropropyl (meth) acrylate, and 2,3-dichloropropyl (meth) acrylate.
- (meth) acrylic acid haloacyloxyalkyl esters include 2- (chloroacetoxy) ethyl (meth) acrylate, 2- (chloroacetoxy) propyl (meth) acrylate, and 3- (chloro) (meth) acrylic acid. Acetoxy) propyl and 3- (hydroxychloroacetoxy) propyl (meth) acrylate.
- (meth) acrylic acid (haloacetylcarbamoyloxy) alkyl esters include 2- (chloroacetylcarbamoyloxy) ethyl (meth) acrylate and 3- (chloroacetylcarbamoyloxy) propyl (meth) acrylate Is mentioned.
- Specific examples of the halogen-containing unsaturated ether include chloromethyl vinyl ether, 2-chloroethyl vinyl ether, 3-chloropropyl vinyl ether, 2-chloroethyl allyl ether, and 3-chloropropyl allyl ether.
- halogen-containing unsaturated ketone examples include 2-chloroethyl vinyl ketone, 3-chloropropyl vinyl ketone, and 2-chloroethyl allyl ketone.
- halomethyl group-containing aromatic vinyl compound examples include p-chloromethylstyrene, m-chloromethylstyrene, o-chloromethylstyrene, and p-chloromethyl- ⁇ -methylstyrene.
- Specific examples of the halogen-containing unsaturated amide include N-chloromethyl (meth) acrylamide.
- Specific examples of the haloacetyl group-containing unsaturated monomer include 3- (hydroxychloroacetoxy) propyl allyl ether and p-vinylbenzyl chloroacetate.
- unsaturated alcohol esters of halogen-containing saturated carboxylic acids and halogen-containing unsaturated ethers are preferred, vinyl chloroacetate and 2-chloroethyl vinyl ether are more preferred, and vinyl chloroacetate is even more preferred.
- vinyl chloroacetate and 2-chloroethyl vinyl ether are more preferred, and vinyl chloroacetate is even more preferred.
- diene monomer examples include conjugated diene monomers and non-conjugated diene monomers.
- conjugated diene monomer examples include 1,3-butadiene, isoprene, and piperylene.
- non-conjugated diene monomer examples include ethylidene norbornene, dicyclopentadiene, dicyclopentadienyl (meth) acrylate, and 2-dicyclopentadienyl ethyl (meth) acrylate. .
- the content of the crosslinkable monomer unit is preferably 0 to 10% by weight, more preferably 0.1 to 10% by weight, still more preferably 0.5 to 7% by weight, particularly preferably 1 to 5% by weight. is there.
- the acrylic rubber (b1) used in the present invention may be a (meth) acrylate monomer or in addition, other monomer units copolymerizable with the crosslinkable monomer may be included.
- monomers that can be copolymerized are not particularly limited, and examples thereof include aromatic vinyl monomers, ⁇ , ⁇ -ethylenically unsaturated nitrile monomers, and monomers having two or more acryloyloxy groups. (Hereinafter, referred to as “polyfunctional acrylic monomer”), olefin monomers, vinyl ether compounds, and the like.
- aromatic vinyl monomer examples include styrene, ⁇ -methylstyrene, divinylbenzene, and the like.
- ⁇ , ⁇ -ethylenically unsaturated nitrile monomer include acrylonitrile and methacrylonitrile.
- polyfunctional acrylic monomer examples include ethylene glycol di (meth) acrylate and propylene glycol di (meth) acrylate.
- olefin monomer include ethylene, propylene, 1-butene, and 1-octene.
- vinyl ether compound examples include vinyl acetate, ethyl vinyl ether, and n-butyl vinyl ether.
- styrene, acrylonitrile, methacrylonitrile, ethylene and vinyl acetate are preferable, and acrylonitrile, methacrylonitrile, ethylene and vinyl acetate are more preferable.
- the content of other monomer units in the acrylic rubber (b1) used in the present invention is 0 to 50% by weight, preferably 0 to 49.9% by weight, more preferably 0 to 39.5% by weight. More preferably, it is 0 to 29.5% by weight, particularly preferably 0 to 29% by weight.
- the acrylic rubber (b1) used in the present invention includes 50 to 99.9% by weight of (meth) acrylic acid ester monomer units as main components and 0 to 10 crosslinkable monomer units in the molecule.
- an ethylene-acrylate rubber containing 0.1 to 50 weight percent of ethylene monomer units may be used.
- the content of the (meth) acrylic acid ester monomer unit in the ethylene-acrylate rubber is preferably 50 to 99.9% by weight, more preferably 59.9 to 99.4% by weight, still more preferably 67 to It is 98.5% by weight, particularly preferably 69 to 98% by weight.
- the content of the (meth) acrylic acid ester monomer unit in the ethylene-acrylate rubber is preferably 50 to 99.9% by weight, more preferably 59.9 to 99.4% by weight, still more preferably 67 to It is 98.5% by weight, particularly preferably 69 to 98% by weight.
- the ethylene unit content in the ethylene-acrylate rubber is preferably 0.1 to 50% by weight, more preferably 0.5 to 40% by weight, and still more preferably 1 to 30% by weight.
- content of the ethylene unit is within the above range, mechanical properties such as strength of the obtained rubber cross-linked product can be further improved.
- the content of the crosslinkable monomer unit in the ethylene-acrylate rubber is preferably 0 to 10% by weight, more preferably 0.1 to 10% by weight, still more preferably 0.5 to 7% by weight, Particularly preferred is 1 to 5% by weight.
- the acrylic rubber (b1) used in the present invention can be obtained by polymerizing the above monomers.
- any of an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, a high-pressure radical polymerization, and a solution polymerization method can be used, but conventionally known from the viewpoint of easy control of the polymerization reaction. It is preferable to use an emulsion polymerization method under normal pressure, which is generally used as a method for producing the acrylic rubber.
- Emulsion polymerization may be any of batch, semi-batch and continuous.
- the polymerization is usually performed in a temperature range of 0 to 70 ° C, preferably 5 to 50 ° C.
- the aromatic polyvalent amine crosslinking agent (b2) used in the present invention is a polyvalent amine crosslinking agent having one or more aromatic rings in the molecule.
- an aromatic polyvalent amine crosslinking agent (b2) (1) a compound having one or more aromatic rings in the molecule and having two or more amino groups, or (2) an intramolecular
- a compound substituted with a group or a hydrazide structure (a structure represented by —CONHNH 2 , CO represents a carbonyl group) is preferable.
- aromatic polyvalent amine crosslinking agent (b2) 4,4′-methylenedianiline, p-phenylenediamine, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4 ′-(m -Phenylenediisopropylidene) dianiline (melting point: 114-116 ° C), 4,4 '-(p-phenylenediisopropylidene) dianiline (melting point: 164-166 ° C), 2,2-bis [4- (4- Aminophenoxy) phenyl] propane (melting point: 126 ° C.), 4,4′-diaminobenzanilide, 4,4′-bis (4-aminophenoxy) biphenyl, 1,3,5-benzenetriamine, 4,4′- Methylenebis (o-chloroaniline), 1,3-bis (3-aminophenoxy) benzene (melting point)
- the number of amino groups in one molecule is preferably 2 to 5, more preferably 2 to 3, and more preferably 2. Some are particularly preferred. Further, the number of aromatic rings in one molecule is preferably 1 to 8, more preferably 2 to 7, and particularly preferably 3 to 6. Those having a phenoxy group in one molecule are preferred, those having 1 to 4 phenoxy groups in the molecule are more preferred, and 2,2-bis [4- (4-aminophenoxy) phenyl] propane is particularly preferred. .
- an aromatic polyvalent amine crosslinking agent (b2) may be used individually by 1 type, or may be used in combination of 2 or more type.
- the aromatic polyvalent amine crosslinking agent (b2) was mixed with the acrylic rubber (b1) in the second step to obtain a master batch (B), which was obtained in the third step described later.
- the dispersibility of the aromatic polyvalent amine crosslinking agent (b2) in the carboxyl group-containing nitrile copolymer rubber (A) is improved by mixing the master batch (B) with the carboxyl group-containing nitrile copolymer rubber (A).
- the rubber cross-linked product obtained thereby can be made excellent in mechanical strength and heat aging resistance.
- the ratio of the acrylic rubber (b1) to the aromatic polyvalent amine crosslinking agent (b2) is “acrylic rubber (b1): aromatic polyvalent amine crosslinking agent (b2)”.
- the weight ratio is preferably 20:80 to 90:10, more preferably 30:70 to 80:20, still more preferably 30:70 to 70:30.
- the content of the acrylic rubber (b1) is too small, the dispersibility of the master batch (B) in the carboxyl group-containing nitrile copolymer rubber (A), that is, the dispersion of the aromatic polyvalent amine crosslinking agent (b2).
- the mechanical strength of the resulting rubber cross-linked product may be reduced.
- the temperature of the mixed system is changed to the aromatic polyvalent amine cross-linking.
- the acrylic rubber (b1) and the aromatic polyvalent amine crosslinking agent (b2) are preferably mixed at a temperature 10 ° C. or higher than the melting point of the agent (b2), more preferably the aromatic polyvalent amine crosslink It is preferable to mix at a temperature of 15 ° C. or higher than the melting point of the agent (b2), more preferably at a temperature of 20 ° C. or higher than the melting point of the aromatic polyvalent amine crosslinking agent (b2).
- the upper limit of the temperature of a mixing system in mixing an acrylic rubber (b1) and an aromatic polyvalent amine crosslinking agent (b2) is not specifically limited, Usually, it is 200 degrees C or less.
- the acrylic rubber (b1) and the aromatic polyvalent amine crosslinking agent (b2) When mixing the acrylic rubber (b1) and the aromatic polyvalent amine crosslinking agent (b2), by mixing at a temperature higher by 10 ° C. than the melting point of the aromatic polyvalent amine crosslinking agent (b2), Since mixing can be performed in a state where the aromatic polyvalent amine crosslinking agent (b2) is appropriately melted, the aromatic polyvalent amine crosslinking agent (b2) is more uniformly mixed in the acrylic rubber (b1). be able to. And thereby, the master batch (B) obtained by mixing the aromatic polyvalent amine cross-linking agent (b2) with the acrylic rubber (b1) is a carboxyl group-containing nitrile copolymer rubber in the third step described later.
- the dispersibility of the aromatic polyvalent amine cross-linking agent (b2) in the carboxyl group-containing nitrile copolymer rubber (A) can be appropriately increased, and thereby the resulting rubber cross-link
- the product can be made particularly excellent in mechanical strength and heat aging resistance.
- the acrylic rubber (b1) is used as a polymer component for forming the masterbatch (B).
- the acrylic rubber (b1) has a high heat-resistant temperature. )
- Even when mixing is performed at a temperature higher by 10 ° C. or more than the melting point of the aromatic polyvalent amine crosslinking agent (b2) deterioration due to such high temperature mixing can be effectively prevented. Therefore, according to the present invention, by using the acrylic rubber (b1), the aromatic polyvalent amine crosslinking agent (b2) can be uniformly distributed in the acrylic rubber (b1) without deteriorating the acrylic rubber (b1).
- an aromatic polyvalent amine crosslinking agent ( b2) can be dispersed well, and as a result, the resulting rubber cross-linked product can be made particularly excellent in mechanical strength and heat aging resistance.
- the aromatic polyvalent amine crosslinking agent (b2) preferably has a melting point in the range of 100 to 200 ° C., and more preferably has a melting point in the range of 100 to 180 ° C.
- the master batch (B) prepared in the second step is mixed with the carboxyl group-containing nitrile copolymer rubber (A) prepared in the first step, so that the crosslinking property is obtained.
- This is a step of obtaining a rubber composition.
- the compounding amount of the master batch (B) is preferably 0.1 to 40 parts by weight, more preferably 0.2 to 30 parts by weight, further preferably 100 parts by weight of the carboxyl group-containing nitrile copolymer rubber (A). Is 1 to 15 parts by weight.
- bridge crosslinking will become inadequate and there exists a possibility that the mechanical characteristics and heat aging resistance of the crosslinked product obtained may fall.
- the amount is too large, the fatigue resistance of the rubber cross-linked product may be reduced.
- the blending amount of the aromatic polyvalent amine crosslinking agent (b2) is preferably 0.01 to 30 weights with respect to 100 weight parts of the carboxyl group-containing nitrile copolymer rubber (A). Parts, more preferably 0.1 to 15 parts by weight, still more preferably 0.5 to 10 parts by weight. If the blending amount of the aromatic polyvalent amine crosslinking agent (b2) is too small, crosslinking may be insufficient, and the mechanical properties and compression set resistance of the resulting rubber crosslinked product may be reduced. On the other hand, if the amount is too large, the fatigue resistance of the rubber cross-linked product may be reduced.
- the carboxyl group-containing nitrile copolymer rubber (A) and the masterbatch (B) in addition to the carboxyl group-containing nitrile copolymer rubber (A) and the masterbatch (B), other compounding agents usually used in the rubber processing field are mixed. May be.
- a compounding agent include reinforcing agents such as carbon black and silica, fillers, antioxidants, light stabilizers, scorch inhibitors, plasticizers, processing aids, lubricants, adhesives, lubricants, Examples include a flame retardant, an acid acceptor, an antifungal agent, an antistatic agent, a colorant, a silane coupling agent, a co-crosslinking agent, a crosslinking aid, a crosslinking retarder, and a foaming agent.
- the compounding amount of these compounding agents an amount corresponding to the compounding purpose can be appropriately adopted.
- 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. Silica may be surface-treated with a silane coupling agent or the like.
- the silane coupling agent is not particularly limited, and specific examples thereof include ⁇ -mercaptopropyltrimethoxysilane, ⁇ -mercaptomethyltrimethoxylane, ⁇ -mercaptomethyltriethoxylane, ⁇ -mercaptohexamethyldisilazane, bis Silane coupling agents containing sulfur such as (3-triethoxysilylpropyl) tetrasulfane, bis (3-triethoxysilylpropyldisulfane); ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidyloxypropyltri Epoxy group-containing silane coupling agents such as methoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane; N- ( ⁇ -amino Til
- Alkyl group-containing silane coupling agents such as acetoalkoxyaluminum diisopropylate; isopropyltriisostearoyl titanate, isopropyltris (dioctylpyrophosphate) titanate, isopropyltri (N-aminoethyl-aminoethyl) Titanate, tetraoctylbis (ditridecylphosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditride) Zil) phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, tetraisopropyl bis (dioctyl phosphite) titanate, titanate coupling agents such as isopropyl triisostearoy
- 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
- blend rubbers other than the said carboxyl group containing nitrile copolymer rubber (A) and acrylic rubber (b1) in the range which does not inhibit the effect of this invention include styrene-butadiene copolymer rubber, polybutadiene rubber, ethylene-propylene copolymer rubber, ethylene-propylene-diene terpolymer rubber, epichlorohydrin rubber, urethane rubber, chloroprene rubber, silicone. Examples thereof include rubber, fluororubber, natural rubber, and polyisoprene rubber.
- the blending amount is 100 parts by weight in total of the carboxyl group-containing nitrile copolymer rubber (A) and the acrylic rubber (b1). On the other hand, it is preferably 60 parts by weight or less, more preferably 30 parts by weight or less, and still more preferably 10 parts by weight or less.
- the master batch (B) when the master batch (B) is mixed with the carboxyl group-containing nitrile copolymer rubber (A), these are preferably mixed in a non-aqueous system.
- the masterbatch (B) and a heat-sensitive crosslinking aid are added.
- the removed components are first kneaded in a mixer such as a Banbury mixer, intermixer, kneader, etc., then transferred to an open roll, etc., and added to a masterbatch (B), a thermally unstable crosslinking aid, etc., and secondarily kneaded. It is preferable to adopt the method.
- the primary kneading is usually performed at a temperature of 10 to 200 ° C., preferably 30 to 180 ° C. for 1 minute to 1 hour, preferably 1 minute to 30 minutes, and the secondary kneading is usually 10 to 100 ° 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.
- the method for producing a crosslinked rubber product of the present invention is to obtain a crosslinked rubber product by crosslinking the crosslinkable rubber composition obtained by the above-described method for producing a crosslinkable rubber composition of the present invention.
- the crosslinkable rubber composition obtained by the method for producing the crosslinkable rubber composition of the present invention described above is used, for example, a molding machine corresponding to a desired shape, for example, Examples include a method of obtaining a crosslinked rubber product by molding with an extruder, an injection molding machine, a compressor, a roll, etc., performing a crosslinking reaction by heating, and fixing the shape as a crosslinked product.
- crosslinking may be performed after molding in advance, or crosslinking may be performed simultaneously with molding.
- the molding temperature is usually 10 to 200 ° C, preferably 25 to 120 ° C.
- the crosslinking temperature is usually 100 to 200 ° C., preferably 130 to 190 ° C.
- the crosslinking time is usually 1 minute to 24 hours, preferably 2 minutes to 12 hours, particularly preferably 3 minutes to 6 hours.
- secondary cross-linking may be performed by heating.
- crosslinking method a general method used for rubber crosslinking such as press crosslinking, steam crosslinking, oven crosslinking, or the like can be appropriately selected.
- the rubber cross-linked product obtained by the production method of the present invention is excellent in mechanical strength and heat aging resistance. Taking advantage of such characteristics, O-rings, packings, diaphragms, oil seals, shaft seals are used. , Bearing seals, well head seals, pneumatic equipment seals, chlorofluorocarbon or carbon dioxide sealing seals used in air conditioner cooling devices and air conditioner refrigerator compressors, precision cleaning media Seals for sealing of supercritical carbon dioxide or subcritical carbon dioxide used, seals for rolling devices (rolling bearings, automotive hub units, automotive water pumps, linear guide devices, ball screws, etc.), valves and valve seats , BOP (Blow Out Presenter), platter Which sealing material: Intake manifold gasket attached to the connecting part of the intake manifold and cylinder head, Cylinder head gasket attached to the connecting part of the cylinder block and cylinder head, and attached to the connecting part of the rocker cover and cylinder head Rocker cover gasket to be mounted, oil pan gasket to be connected to the connecting portion between the oil pan and
- the iodine value of the carboxyl group-containing nitrile copolymer rubber was measured according to JIS K6235.
- Mooney viscosity (polymer Mooney) of the carboxyl group-containing nitrile copolymer rubber was measured according to JIS K6300 (unit: (ML 1 + 4 , 100 ° C.)).
- the crosslinkable rubber composition was placed in a mold having a length of 15 cm, a width of 15 cm, and a depth of 0.2 cm, and subjected to primary crosslinking by pressing at 170 ° C. for 20 minutes while pressing at a press pressure of 10 MPa, and then the obtained primary was obtained.
- the crosslinked product was further subjected to secondary crosslinking by heating at 170 ° C. for 4 hours in a gear oven to obtain a sheet-like rubber crosslinked product.
- the obtained rubber cross-linked product was punched out with a No. 3 dumbbell to prepare a test piece. Next, using this test piece, tensile strength and elongation at break were measured according to JIS K6251.
- the crosslinkable rubber composition was subjected to primary crosslinking by pressing at a temperature of 170 ° C. for 25 minutes using a mold to obtain a cylindrical primary crosslinked product having a diameter of 29 mm and a height of 12.7 mm, and then obtained.
- the primary crosslinked product was further subjected to secondary crosslinking by heating at 170 ° C. for 4 hours in a gear-type oven to obtain a press-crosslinked product.
- the press-crosslinked product was compressed by 25% and placed in an environment of 150 ° C. for 168 hours, and then the compression set was measured. The smaller this value, the better the compression set resistance.
- the metal bottle was kept at 5 ° C., 0.1 part of cumene hydroperoxide (polymerization initiator) was charged, and the polymerization reaction was carried out for 16 hours while rotating the metal bottle. Thereafter, 0.1 part of a 10% by weight hydroquinone aqueous solution (polymerization terminator) was added to stop the polymerization reaction, and then the residual monomer was removed using a rotary evaporator at a water temperature of 60 ° C. to obtain acrylonitrile-butadiene. -A latex of mono-n-butyl maleate copolymer rubber (solid content concentration of about 30% by weight) was obtained.
- a palladium catalyst (a solution in which 1 wt% palladium acetate / acetone solution and equal weight of ion exchange water are mixed) is added to the autoclave so that the palladium content becomes 1000 ppm with respect to the rubber weight contained in the latex.
- a hydrogenation reaction was performed at a hydrogen pressure of 3 MPa and a temperature of 50 ° C. for 6 hours to obtain a latex of carboxyl group-containing nitrile copolymer rubber (A-1).
- the resulting carboxyl group-containing nitrile copolymer rubber (A-1) latex was coagulated by adding twice the volume of methanol and then vacuum-dried at 60 ° C.
- the obtained carboxyl group-containing nitrile copolymer rubber (A-1) had an iodine value of 10, a carboxyl group content of 3.2 ⁇ 10 ⁇ 2 ephr, and a polymer Mooney viscosity (ML 1 + 4 , 100 ° C.) of 45. It was.
- the acrylonitrile unit content was determined by the Kjeldahl method, the mono n-butyl maleate unit content was determined from the carboxyl group content, and the carboxyl group-containing nitrile copolymer rubber obtained by calculation with the remainder as 1,3-butadiene units (
- the composition of A-1) was 35.6% by weight of acrylonitrile units, 58.8% by weight of butadiene units (including hydrogenated ones), and 5.6% by weight of mono n-butyl maleate units.
- ⁇ Production Example 2 Production of carboxyl group-containing nitrile copolymer rubber (A-2)> Carboxyl groups were prepared in the same manner as in Production Example 1, except that the amount of acrylonitrile was 45 parts, the amount of mono-n-butyl maleate was 6 parts, and the amount of 1,3-butadiene was 49 parts. A nitrile copolymer rubber (A-2) was obtained. The composition of the resulting carboxyl group-containing nitrile copolymer rubber (A-2) is 45.4% by weight of acrylonitrile units, 50.6% by weight of butadiene units (including hydrogenated), mono-n-butyl maleate The unit was 4.9% by weight.
- composition of the resulting carboxyl group-containing nitrile copolymer rubber (A-3) was composed of 24% by weight of acrylonitrile units, 46.6% by weight of butadiene units (including hydrogenated ones), 6 units of mono n-butyl maleate units. It was 5% by weight and methoxyethyl acrylate unit was 22.9% by weight.
- composition of the resulting carboxyl group-containing nitrile copolymer rubber (A-4) was 20.8% by weight of acrylonitrile units, 44.2% by weight of butadiene units (including hydrogenated ones), mono-n-butyl maleate The unit was 4.9% by weight and the butyl acrylate unit was 30.1% by weight.
- the obtained emulsion polymerization solution was coagulated with an aqueous calcium chloride solution, washed with water and dried to obtain acrylic rubber (b1-1).
- the composition of the obtained acrylic rubber (b1-1) was 60% by weight of ethyl acrylate units and 40% by weight of butyl acrylate units.
- BAPP aromatic polyvalent amine cross-linking agent
- ⁇ Production Example 8 Production of master batch (B-2)> The same procedure as in Production Example 7, except that the amount of acrylic rubber (b1-1) was 70 parts and the amount of 2,2-bis [4- (4-aminophenoxy) phenyl] propane was 30 parts.
- a masterbatch (B-2) having an acrylic rubber (b1-1): 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP) 70: 30 (weight ratio) was produced.
- ⁇ Production Example 10 Production of master batch (B-4)> Similar to Production Example 7 except that 50 parts of ethylene acrylate rubber (b1-3) (trade name “Vamac® ULTRA IP”, manufactured by DuPont) was used instead of 50 parts of acrylic rubber (b1-1).
- a master batch (B-4) in which ethylene acrylate rubber (b1-3): 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP) 50: 50 (weight ratio) was prepared Manufactured.
- Example 1 Using a Banbury mixer, 100 parts of the carboxyl group-containing nitrile copolymer rubber (A-1) obtained in Production Example 1, 40 parts of FEF carbon black (trade name: Seast SO, manufactured by Tokai Carbon Co., Ltd.), trimellitic acid Tri-2-ethylhexyl (trade name: Adeka Sizer C-8, manufactured by ADEKA, plasticizer), 5 parts, 4,4′-di- ( ⁇ , ⁇ ′-dimethylbenzyl) diphenylamine (trade name: Nowguard 445, Crompton) 1.5 parts by anti-aging agent, 1 part by stearic acid (crosslinking accelerator), polyoxyethylene alkyl ether phosphate ester (trade name: Phosphanol RL210, manufactured by Toho Chemical Industry Co., Ltd., processing aid) 1 part was added and mixed at 50 ° C.
- FEF carbon black trade name: Seast SO, manufactured by Tokai Carbon Co., Ltd.
- Example 2 to 4 Instead of the master batch (B-1), the master batches (B-2) to (B-4) obtained in Production Examples 8 to 10 were used in the blending amounts shown in Table 1, respectively. In the same manner as in Example 1, a crosslinkable rubber composition was obtained and evaluated in the same manner. The results are shown in Table 1.
- Examples 5 to 7> instead of the carboxyl group-containing nitrile copolymer rubber (A-1), the carboxyl group-containing nitrile copolymer rubbers (A-1) to (A-3) obtained in Production Examples 2 to 4 are shown in Table 1, respectively.
- a crosslinkable rubber composition was obtained in the same manner as in Example 1 except that the blending amounts of the master batch (B-1) and carbon black were changed to the blending amounts shown in Table 1. Were similarly evaluated. The results are shown in Table 1.
- Example 8> Instead of 40 parts of FEF carbon black, 50 parts of silica (trade name “Nipsil ER”, manufactured by Tosoh Silica) was replaced with 5 parts of tri-2-ethylhexyl trimellitic acid, and polyether ester (trade name “ADEKA” A crosslinkable rubber composition was obtained and evaluated in the same manner as in Example 1 except that 5 parts of “SIZER RS700” (manufactured by ADEKA, plasticizer) were used. The results are shown in Table 1.
- Example 9 to 11> instead of the carboxyl group-containing nitrile copolymer rubber (A-1), the carboxyl group-containing nitrile copolymer rubbers (A-1) to (A-3) obtained in Production Examples 2 to 4 are shown in Table 1, respectively.
- a crosslinkable rubber composition was obtained in the same manner as in Example 8, except that the blending amounts of the master batch (B-1) and silica were changed to the blending amounts shown in Table 1 Evaluation was performed in the same manner. The results are shown in Table 1.
- Example 12 A crosslinkable rubber in the same manner as in Example 8 except that 0.5 part of ⁇ -aminopropyltriethoxysilane (trade name “Dynasylan® AMEO”, manufactured by Evonik Industries, Inc., silane coupling agent) was further added. A composition was obtained and evaluated in the same manner. The results are shown in Table 1.
- ⁇ -aminopropyltriethoxysilane trade name “Dynasylan® AMEO”, manufactured by Evonik Industries, Inc., silane coupling agent
- Examples 13 to 15> instead of the carboxyl group-containing nitrile copolymer rubber (A-1), the carboxyl group-containing nitrile copolymer rubbers (A-1) to (A-3) obtained in Production Examples 2 to 4 are shown in Table 1, respectively.
- a crosslinkable rubber composition was obtained in the same manner as in Example 12, except that the compounding amount of the master batch (B-1) and silica was changed to the compounding amount shown in Table 1 Evaluation was performed in the same manner. The results are shown in Table 1.
- Example 16 Crosslinkability in the same manner as in Example 8 except that 0.5 part of ⁇ -glycidyloxypropyltrimethoxysilane (trade name “Dynasylan® GLYMO”, manufactured by Evonik Industries, Inc., silane coupling agent) was further added. A rubber composition was obtained and evaluated in the same manner. The results are shown in Table 2.
- Examples 17 to 19> instead of the carboxyl group-containing nitrile copolymer rubber (A-1), the carboxyl group-containing nitrile copolymer rubbers (A-1) to (A-3) obtained in Production Examples 2 to 4 are shown in Table 2, respectively.
- a crosslinkable rubber composition was obtained in the same manner as in Example 16 except that the blending amount of the master batch (B-1) and silica was changed to the blending amount shown in Table 2 Evaluation was performed in the same manner. The results are shown in Table 2.
- ACM (b1-1) indicates acrylic rubber (b1-1)
- ACM (b1-2) indicates acrylic rubber (b1-2)
- AEM (b1-3) “Represents ethylene acrylate rubber (b1-3)
- HNBR represents hydrogenated nitrile rubber
- BAPP represents 2,2-bis [4- (4-aminophenoxy) phenyl] propane.
- the resulting crosslinkable rubber composition has good dispersibility of the crosslinking agent, and has normal physical properties (tensile strength, elongation at break), heat aging resistance (elongation after heat aging). It can be confirmed that a rubber cross-linked product having excellent change rate) and compression set resistance is obtained (Examples 1 to 19).
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Abstract
Description
好ましくは、前記マスターバッチ(B)の配合量が、前記カルボキシル基含有ニトリル共重合ゴム(A)100重量部に対して、0.1~40重量部である。
好ましくは、前記アクリルゴム(b1)と前記芳香族多価アミン架橋剤(b2)との混合比率が、重量比で、アクリルゴム(b1):芳香族多価アミン架橋剤(b2)=20:80~90:10である。
好ましくは、前記第3工程が、前記カルボキシル基含有ニトリル共重合ゴム(A)に、前記マスターバッチ(B)およびシリカを混合する工程である。
本発明の架橋性ゴム組成物の製造方法は、
ヨウ素価が120以下であるカルボキシル基含有ニトリル共重合ゴム(A)を準備する工程と、
アクリルゴム(b1)に、芳香族多価アミン架橋剤(b2)を混合してマスターバッチ(B)を得る工程と、
前記カルボキシル基含有ニトリル共重合ゴム(A)に、前記マスターバッチ(B)を混合する工程と、を備える。
本発明の製造方法の第1工程は、ヨウ素価が120以下であるカルボキシル基含有ニトリル共重合ゴム(A)を準備する工程である。
共重合する場合の各単量体の割合は、共重合に供する全単量体量を100重量部とした場合に、α,β-エチレン性不飽和ニトリル単量体が好ましくは10~60重量部、より好ましくは15~55重量部、特に好ましくは20~50重量部であり、カルボキシル基含有単量体が好ましくは0.1~20重量部、より好ましくは0.2~15重量部、特に好ましくは0.5~10重量部であり、共役ジエン単量体が好ましくは20~89.9重量部、より好ましくは30~84.8重量部、特に好ましくは40~79.5重量部である。
本発明の製造方法の第2工程は、アクリルゴム(b1)に、芳香族多価アミン架橋剤(b2)を混合してマスターバッチ(B)を得る工程である。
炭素数4~12のα,β-エチレン性不飽和ジカルボン酸の具体例としては、フマル酸、マレイン酸などのブテンジオン酸;イタコン酸;シトラコン酸;クロロマレイン酸;などが挙げられる。
炭素数4~12のα,β-エチレン性不飽和ジカルボン酸と炭素数1~8のアルカノールとのモノエステルの具体例としては、フマル酸モノメチル、フマル酸モノエチル、フマル酸モノn-ブチル、マレイン酸モノメチル、マレイン酸モノエチル、マレイン酸モノn-ブチルなどのブテンジオン酸モノ鎖状アルキルエステル;フマル酸モノシクロペンチル、フマル酸モノシクロヘキシル、フマル酸モノシクロヘキセニル、マレイン酸モノシクロペンチル、マレイン酸モノシクロヘキシル、マレイン酸モノシクロヘキセニルなどの脂環構造を有するブテンジオン酸モノエステル;イタコン酸モノメチル、イタコン酸モノエチル、イタコン酸モノn-ブチル、イタコン酸モノシクロヘキシルなどのイタコン酸モノエステル;などが挙げられる。
これらの中でも、ブテンジオン酸モノ鎖状アルキルエステル、または脂環構造を有するブテンジオン酸モノエステルが好ましく、フマル酸モノn-ブチル、マレイン酸モノn-ブチル、フマル酸モノシクロヘキシル、およびマレイン酸モノシクロヘキシルがより好ましく、フマル酸モノn-ブチルがさらに好ましい。これらのα,β-エチレン性不飽和カルボン酸単量体は、1種単独で、または2種以上を併せて使用することができる。なお、上記単量体のうち、ジカルボン酸には、無水物として存在しているものも含まれる。
エポキシ基含有エーテルの具体例としては、アリルグリシジルエーテルおよびビニルグリシジルエーテルなどが挙げられる。これらの中でも、メタクリル酸グリシジルおよびアリルグリシジルエーテルが好ましい。これらエポキシ基を有する単量体は、1種単独で、または2種以上を併せて使用することができる。
(メタ)アクリル酸ハロアルキルエステルの具体例としては、(メタ)アクリル酸クロロメチル、(メタ)アクリル酸1-クロロエチル、(メタ)アクリル酸2-クロロエチル、(メタ)アクリル酸1,2-ジクロロエチル、(メタ)アクリル酸2-クロロプロピル、(メタ)アクリル酸3-クロロプロピル、および(メタ)アクリル酸2,3-ジクロロプロピルなどが挙げられる。
(メタ)アクリル酸ハロアシロキシアルキルエステルの具体例としては、(メタ)アクリル酸2-(クロロアセトキシ)エチル、(メタ)アクリル酸2-(クロロアセトキシ)プロピル、(メタ)アクリル酸3-(クロロアセトキシ)プロピル、および(メタ)アクリル酸3-(ヒドロキシクロロアセトキシ)プロピルなどが挙げられる。
(メタ)アクリル酸(ハロアセチルカルバモイルオキシ)アルキルエステルの具体例としては、(メタ)アクリル酸2-(クロロアセチルカルバモイルオキシ)エチル、および(メタ)アクリル酸3-(クロロアセチルカルバモイルオキシ)プロピルなどが挙げられる。
ハロゲン含有不飽和エーテルの具体例としては、クロロメチルビニルエーテル、2-クロロエチルビニルエーテル、3-クロロプロピルビニルエーテル、2-クロロエチルアリルエーテル、および3-クロロプロピルアリルエーテルなどが挙げられる。
ハロゲン含有不飽和ケトンの具体例としては、2-クロロエチルビニルケトン、3-クロロプロピルビニルケトン、および2-クロロエチルアリルケトンなどが挙げられる。
ハロメチル基含有芳香族ビニル化合物の具体例としては、p-クロロメチルスチレン、m-クロロメチルスチレン、o-クロロメチルスチレン、およびp-クロロメチル-α-メチルスチレンなどが挙げられる。
ハロゲン含有不飽和アミドの具体例としては、N-クロロメチル(メタ)アクリルアミドなどが挙げられる。
ハロアセチル基含有不飽和単量体の具体例としては、3-(ヒドロキシクロロアセトキシ)プロピルアリルエーテル、p-ビニルベンジルクロロ酢酸エステルなどが挙げられる。
非共役ジエン単量体の具体例としては、エチリデンノルボルネン、ジシクロペンタジエン、(メタ)アクリル酸ジシクロペンタジエニル、および(メタ)アクリル酸2-ジシクロペンタジエニルエチルなどを挙げることができる。
α,β-エチレン性不飽和ニトリル単量体の具体例としては、アクリロニトリル、メタクリロニトリルなどが挙げられる。
多官能アクリル単量体の具体例としては、エチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレートなどが挙げられる。
オレフィン系単量体の具体例としては、エチレン、プロピレン、1-ブテン、および1-オクテンなどが挙げられる。
ビニルエーテル化合物の具体例としては、酢酸ビニル、エチルビニルエーテル、およびn-ブチルビニルエーテルなどが挙げられる。
本発明の製造方法の第3工程は、第1工程にて準備したカルボキシル基含有ニトリル共重合ゴム(A)に、第2工程にて調製したマスターバッチ(B)を混合することで、架橋性ゴム組成物を得る工程である。
このようなゴムとしては、スチレン-ブタジエン共重合体ゴム、ポリブタジエンゴム、エチレン-プロピレン共重合体ゴム、エチレン-プロピレン-ジエン三元共重合体ゴム、エピクロロヒドリンゴム、ウレタンゴム、クロロプレンゴム、シリコーンゴム、フッ素ゴム、天然ゴム、ポリイソプレンゴムなどが挙げられる。
カルボキシル基含有ニトリル共重合ゴム(A)およびアクリルゴム(b1)以外のゴムを配合する場合における配合量は、カルボキシル基含有ニトリル共重合ゴム(A)およびアクリルゴム(b1)の合計100重量部に対して、好ましくは60重量部以下、より好ましくは30重量部以下、さらに好ましくは10重量部以下である。
本発明のゴム架橋物の製造方法は、上述した本発明の架橋性ゴム組成物の製造方法により得られた架橋性ゴム組成物を架橋することで、ゴム架橋物を得るものである。
本発明のゴム架橋物の製造方法においては、上述した本発明の架橋性ゴム組成物の製造方法により得られた架橋性ゴム組成物を用い、たとえば、所望の形状に対応した成形機、たとえば、押出機、射出成形機、圧縮機、ロールなどにより成形を行い、加熱することにより架橋反応を行い、架橋物として形状を固定化することにより、ゴム架橋物を得る方法などが挙げられる。この場合においては、予め成形した後に架橋しても、成形と同時に架橋を行ってもよい。成形温度は、通常、10~200℃、好ましくは25~120℃である。架橋温度は、通常、100~200℃、好ましくは130~190℃であり、架橋時間は、通常、1分~24時間、好ましくは2分~12時間、特に好ましくは3分~6時間である。
また、ゴム架橋物の形状、大きさなどによっては、表面が架橋していても内部まで十分に架橋していない場合があるので、さらに加熱して二次架橋を行ってもよい。
カルボキシル基含有ニトリル共重合ゴムのヨウ素価は、JIS K6235に準じて、測定した。
2mm角のカルボキシル基含有ニトリル共重合ゴム0.2gに、エタノール20mlおよび水10mlを加え、攪拌しながら水酸化カリウムの0.02N含水エタノール溶液を用いて、室温でチモールフタレインを指示薬とする滴定により、カルボキシル基含有ニトリル共重合ゴム100gに対するカルボキシル基のモル数として求めた(単位はephr)。
JIS K6384に従い、ケルダール法によって測定したカルボキシル基含有ニトリル共重合ゴム中の窒素含有量から計算により求めた(単位は重量%)。
カルボキシル基含有ニトリル共重合ゴムのムーニー粘度(ポリマームーニー)をJIS K6300に従って測定した(単位は(ML1+4、100℃))。
二次混練後の架橋性ゴム組成物を用いて、表面および内部にある架橋剤の塊(分散不良)を目視で観察することにより、評価した。なお、架橋剤の分散性は、以下の基準で評価した。
○:架橋剤の塊が目視では確認できない(分散良)
×:架橋剤の塊が目視で確認できる(分散不良)
架橋性ゴム組成物を、縦15cm、横15cm、深さ0.2cmの金型に入れ、プレス圧10MPaで加圧しながら170℃で20分間プレスすることにより一次架橋し、次いで、得られた一次架橋物を、ギヤー式オーブンにて、さらに170℃、4時間の条件で加熱して二次架橋させることにより、シート状のゴム架橋物を得た。そして、得られたゴム架橋物を3号形ダンベルで打ち抜いて試験片を作製した。次にこの試験片を用いて、JIS K6251に従い引張強さおよび破断伸びを測定した。
上記常態物性の評価と同様にして作製したシート状のゴム架橋物を用いて、JIS K6257(ノーマルオーブン法)に従い、170℃における168時間後の破断伸びを測定し、上記常態物性の評価により測定された破断伸びと、熱老化後の伸びとから、下記式に従って、熱老化による伸びの変化率(%)を求めた。
熱老化による伸びの変化率(%)=100×(熱老化後の破断伸び-常態での破断伸び)/常態での破断伸び
架橋性ゴム組成物を、金型を用いて、温度170℃で25分間プレスすることにより一次架橋し、直径29mm、高さ12.7mmの円柱型の一次架橋物を得て、次いで、得られた一次架橋物を、ギヤー式オーブンにて、さらに170℃、4時間の条件で加熱して二次架橋させることにより、プレス架橋物を得た。そして、得られたプレス架橋物を用いて、JIS K6262に従い、プレス架橋物を25%圧縮させた状態で、150℃の環境下に168時間置いた後、圧縮永久歪みを測定した。
この値が小さいほど、耐圧縮永久歪み性に優れる。
金属製ボトルに、イオン交換水180部、濃度10重量%のドデシルベンゼンスルホン酸ナトリウム水溶液25部、アクリロニトリル37部、マレイン酸モノn-ブチル6部、t-ドデシルメルカプタン(分子量調整剤)0.75部の順に仕込み、内部の気体を窒素で3回置換した後、1,3-ブタジエン57部を仕込んだ。金属製ボトルを5℃に保ち、クメンハイドロパーオキサイド(重合開始剤)0.1部を仕込み、金属製ボトルを回転させながら16時間重合反応した。その後、濃度10重量%のハイドロキノン水溶液(重合停止剤)0.1部を加えて重合反応を停止し、引き続いて、水温60℃のロータリーエバポレータを用いて残留単量体を除去し、アクリロニトリル-ブタジエン-マレイン酸モノn-ブチル共重合体ゴムのラテックス(固形分濃度約30重量%)を得た。
そして、得られたカルボキシル基含有ニトリル共重合ゴム(A-1)のラテックスに2倍容量のメタノールを加えて凝固した後、60℃で12時間真空乾燥することにより、カルボキシル基含有ニトリル共重合ゴム(A-1)を得た。得られたカルボキシル基含有ニトリル共重合ゴム(A-1)は、ヨウ素価が10、カルボキシル基含有量は3.2×10-2ephr、ポリマームーニー粘度(ML1+4、100℃)は45であった。
なお、ケルダール法でアクリロニトリル単位含有量を求め、カルボキシル基含有量からマレイン酸モノn-ブチル単位含有量を求め、残部を1,3-ブタジエン単位として計算により求めたカルボキシル基含有ニトリル共重合ゴム(A-1)の組成は、アクリロニトリル単位35.6重量%、ブタジエン単位(水素化されたものも含む)58.8重量%、マレイン酸モノn-ブチル単位5.6重量%であった。
アクリロニトリルの配合量を45部、マレイン酸モノn-ブチルの配合量を6部、1,3-ブタジエンの配合量を49部に、それぞれ変更した以外は、製造例1と同様にして、カルボキシル基含有ニトリル共重合ゴム(A-2)を得た。得られたカルボキシル基含有ニトリル共重合ゴム(A-2)の組成は、アクリロニトリル単位45.4重量%、ブタジエン単位(水素化されたものも含む)50.6重量%、マレイン酸モノn-ブチル単位4.9重量%であった。
アクリロニトリルの配合量を23部、マレイン酸モノn-ブチルの配合量を6.5部、1,3-ブタジエンの配合量を40部に、それぞれ変更し、かつ、アクリル酸メトキシエチル30.5部をさらに配合した以外は、製造例1と同様にして、カルボキシル基含有ニトリル共重合ゴム(A-3)を得た。得られたカルボキシル基含有ニトリル共重合ゴム(A-3)の組成は、アクリロニトリル単位24重量%、ブタジエン単位(水素化されたものも含む)46.6重量%、マレイン酸モノn-ブチル単位6.5重量%、アクリル酸メトキシエチル単位22.9重量%であった。
アクリロニトリルの配合量を21部、マレイン酸モノn-ブチルの配合量を5部、1,3-ブタジエンの配合量を44部に、それぞれ変更し、かつ、アクリル酸ブチル30部をさらに配合した以外は、製造例1と同様にして、カルボキシル基含有ニトリル共重合ゴム(A-4)を得た。得られたカルボキシル基含有ニトリル共重合ゴム(A-4)の組成は、アクリロニトリル単位20.8重量%、ブタジエン単位(水素化されたものも含む)44.2重量%、マレイン酸モノn-ブチル単位4.9重量%、アクリル酸ブチル単位30.1重量%であった。
温度計、攪拌装置を備えた重合反応器に、水200部、ラウリル硫酸ナトリウム3部、アクリル酸エチル60部、アクリル酸ブチル40部を仕込んだ。その後、減圧脱気および窒素置換を2度行って酸素を十分除去した後、クメンハイドロパーオキシド0.005部、およびホルムアルデヒドスルホキシル酸ナトリウム0.002部を加えて常圧下、温度30℃で乳化重合を開始し、重合転化率が95%に達するまで反応させた。得られた乳化重合液を塩化カルシウム水溶液で凝固し、水洗、乾燥してアクリルゴム(b1-1)を得た。得られたアクリルゴム(b1-1)の組成は、アクリル酸エチル単位60重量%、アクリル酸ブチル単位40重量%であった。
アクリル酸エチルの配合量を40部、アクリル酸ブチルの配合量を30部に、それぞれ変更し、かつ、アクリル酸メトキシエチル30部をさらに配合した以外は、製造例5と同様にして、アクリルゴム(b1-2)を得た。得られたアクリルゴム(b1-2)の組成は、アクリル酸エチル単位40重量%、アクリル酸ブチル単位30重量%、およびアクリル酸メトキシエチル単位30重量%であった。
容量55mlのブラベンダータイプミキサー中で、製造例5で得られたアクリルゴム(b1-1)50部を1分間素練りし、次いで、2,2-ビス[4-(4-アミノフェノキシ)フェニル]プロパン(BAPP、芳香族多価アミン架橋剤(b2)、融点126℃)50部を添加して、温度を150℃とし、2,2-ビス[4-(4-アミノフェノキシ)フェニル]プロパンを溶融させた状態で、5分間混練することで、アクリルゴム(b1-1):2,2-ビス[4-(4-アミノフェノキシ)フェニル]プロパン(BAPP)=50:50(重量比)であるマスターバッチ(B-1)を製造した。
アクリルゴム(b1-1)の配合量を70部とし、2,2-ビス[4-(4-アミノフェノキシ)フェニル]プロパンの配合量を30部とした以外は、製造例7と同様にして、アクリルゴム(b1-1):2,2-ビス[4-(4-アミノフェノキシ)フェニル]プロパン(BAPP)=70:30(重量比)であるマスターバッチ(B-2)を製造した。
アクリルゴム(b1-1)50部に代えて、製造例2で得られたアクリルゴム(b1-2)50部を使用した以外は、製造例7と同様にして、アクリルゴム(b1-2):2,2-ビス[4-(4-アミノフェノキシ)フェニル]プロパン(BAPP)=50:50(重量比)であるマスターバッチ(B-3)を製造した。
アクリルゴム(b1-1)50部に代えて、エチレンアクリレートゴム(b1-3)(商品名「Vamac(R) ULTRA IP」、DuPont社製)50部を使用した以外は、製造例7と同様にして、エチレンアクリレートゴム(b1-3):2,2-ビス[4-(4-アミノフェノキシ)フェニル]プロパン(BAPP)=50:50(重量比)であるマスターバッチ(B-4)を製造した。
アクリルゴム(b1-1)50部に代えて、水素化ニトリルゴム(商品名:Zetpol 2000L、日本ゼオン社製、アクリロニトリル単位含有量36重量%、ブタジエン単位(水素化されたものも含む)64重量%、ヨウ素価4、ムーニー粘度65)50部を使用した以外は、製造例7と同様にして、水素化ニトリルゴム:2,2-ビス[4-(4-アミノフェノキシ)フェニル]プロパン(BAPP)=50:50(重量比)であるマスターバッチ(B’-5)を製造した。
混練時の温度を120℃に変更した以外は、製造例11と同様にして、水素化ニトリルゴム:2,2-ビス[4-(4-アミノフェノキシ)フェニル]プロパン(BAPP)=50:50(重量比)であるマスターバッチ(B’-6)を製造した。
バンバリーミキサを用いて、製造例1で得られたカルボキシル基含有ニトリル共重合ゴム(A-1)100部に、FEFカーボンブラック(商品名:シーストSO、東海カーボン社製)40部、トリメリット酸トリ-2-エチルヘキシル(商品名:アデカサイザーC-8、ADEKA社製、可塑剤)5部、4,4’-ジ-(α,α’-ジメチルベンジル)ジフェニルアミン(商品名:ナウガード445、Crompton社製、老化防止剤)1.5部、ステアリン酸(架橋促進助剤)1部、ポリオキシエチレンアルキルエーテルリン酸エステル(商品名:フォスファノールRL210、東邦化学工業社製、加工助剤)1部を添加して、50℃で5分間混合した。次いで、得られた混合物を50℃のロールに移して、製造例7で製造したマスターバッチ(B-1)12.6部、および1,8-ジアザビシクロ[5,4,0]-ウンデセン-7(DBU)(商品名「RHENOGRAN XLA-60(GE2014)」、RheinChemie社製、DBU60%(ジンクジアルキルジフォスフェイト塩になっている部分も含む)4部を配合して、混練することにより、架橋性ゴム組成物を得た。
マスターバッチ(B-1)に代えて、製造例8~10にて得られたマスターバッチ(B-2)~(B-4)を、それぞれ表1に示す配合量にて使用した以外は、実施例1と同様にして、架橋性ゴム組成物を得て同様に評価を行った。結果を表1に示す。
カルボキシル基含有ニトリル共重合ゴム(A-1)に代えて、製造例2~4にて得られたカルボキシル基含有ニトリル共重合ゴム(A-1)~(A-3)を、それぞれ表1に示す配合量にて使用するとともに、マスターバッチ(B-1)およびカーボンブラックの配合量を表1に示す配合量に変更した以外は、実施例1と同様にして、架橋性ゴム組成物を得て同様に評価を行った。結果を表1に示す。
FEFカーボンブラック40部に代えて、シリカ(商品名「Nipsil ER」、東ソー・シリカ社製)50部を、トリメリット酸トリ-2-エチルヘキシル5部に代えて、ポリエーテルエステル(商品名「アデカサイザーRS700」、ADEKA社製、可塑剤)5部を、それぞれ使用した以外は、実施例1と同様にして、架橋性ゴム組成物を得て同様に評価を行った。結果を表1に示す。
カルボキシル基含有ニトリル共重合ゴム(A-1)に代えて、製造例2~4にて得られたカルボキシル基含有ニトリル共重合ゴム(A-1)~(A-3)を、それぞれ表1に示す配合量にて使用するとともに、マスターバッチ(B-1)およびシリカの配合量を表1に示す配合量に変更した以外は、実施例8と同様にして、架橋性ゴム組成物を得て同様に評価を行った。結果を表1に示す。
γ-アミノプロピルトリエトキシシラン(商品名「Dynasylan(R)AMEO」、エボニック インダストリーズ社製、シランカップリング剤)0.5部をさらに配合した以外は、実施例8と同様にして、架橋性ゴム組成物を得て同様に評価を行った。結果を表1に示す。
カルボキシル基含有ニトリル共重合ゴム(A-1)に代えて、製造例2~4にて得られたカルボキシル基含有ニトリル共重合ゴム(A-1)~(A-3)を、それぞれ表1に示す配合量にて使用するとともに、マスターバッチ(B-1)およびシリカの配合量を表1に示す配合量に変更した以外は、実施例12と同様にして、架橋性ゴム組成物を得て同様に評価を行った。結果を表1に示す。
γ-グリシジルオキシプロピルトリメトキシシラン(商品名「Dynasylan(R)GLYMO」、エボニック インダストリーズ社製、シランカップリング剤)0.5部をさらに配合した以外は、実施例8と同様にして、架橋性ゴム組成物を得て同様に評価を行った。結果を表2に示す。
カルボキシル基含有ニトリル共重合ゴム(A-1)に代えて、製造例2~4にて得られたカルボキシル基含有ニトリル共重合ゴム(A-1)~(A-3)を、それぞれ表2に示す配合量にて使用するとともに、マスターバッチ(B-1)およびシリカの配合量を表2に示す配合量に変更した以外は、実施例16と同様にして、架橋性ゴム組成物を得て同様に評価を行った。結果を表2に示す。
マスターバッチ(B-1)12.6部に代えて、2,2-ビス[4-(4-アミノフェノキシ)フェニル]プロパン6.3部を、マスターバッチ化せずに、そのまま配合した以外は、実施例1と同様にして、架橋性ゴム組成物を得て同様に評価を行った。結果を表2に示す。
マスターバッチ(B-1)12.6部に代えて、製造例11で得られたマスターバッチ(B’-5)12.6部を使用した以外は、実施例1と同様にして、架橋性ゴム組成物を得て同様に評価を行った。結果を表2に示す。
マスターバッチ(B-1)12.6部に代えて、製造例12で得られたマスターバッチ(B’-6)12.6部を使用した以外は、実施例1と同様にして、架橋性ゴム組成物を得て同様に評価を行った。結果を表2に示す。
マスターバッチ(B-1)12.6部に代えて、ヘキサメチレンジアミンカルバメート(商品名:Diak#1、デュポンダウエラストマー社製、脂肪族多価アミン架橋剤)2.4部を使用した以外は、実施例1と同様にして、架橋性ゴム組成物を得て同様に評価を行った。結果を表2に示す。
マスターバッチ(B-1)12.6部に代えて、N,N’-ジシンナミリデン-1,6-ヘキサンジアミン(商品名「Diak#3」、デュポンダウエラストマー社製)5部を使用した以外は、実施例1と同様にして、架橋性ゴム組成物を得て同様に評価を行った。結果を表2に示す。
また、芳香族多価アミン架橋剤(b2)のマスターバッチを得る際に、アクリルゴム(b1)の代わりに、水素化ニトリルゴムを使用した場合には、150℃で混合したものを用いた場合には、架橋剤の分散性は良好となったものの、得られるゴム架橋物の耐熱老化性(熱老化後の伸び変化率)が悪化する結果となり、また、120℃で混合したものを用いた場合には、架橋剤の分散性が悪く、得られるゴム架橋物の耐熱老化性(熱老化後の伸び変化率)も悪化する結果となった(比較例2,3)。
さらに、アクリルゴム(b1)と芳香族多価アミン架橋剤(b2)とを含むマスターバッチ(B)の代わりに、ヘキサメチレンジアミンカルバメート、またはN,N‘-ジシンナミリデン-1,6-ヘキサンジアミンを使用した場合には、得られるゴム架橋物は、耐熱老化性(熱老化後の伸び変化率)に劣るものであった(比較例4,5)。
Claims (9)
- 架橋性ゴム組成物を製造する方法であって、
ヨウ素価が120以下であるカルボキシル基含有ニトリル共重合ゴム(A)を準備する第1工程と、
アクリルゴム(b1)に、芳香族多価アミン架橋剤(b2)を混合してマスターバッチ(B)を得る第2工程と、
前記カルボキシル基含有ニトリル共重合ゴム(A)に、前記マスターバッチ(B)を混合する第3工程と、を備える架橋性ゴム組成物の製造方法。 - 前記第2工程が、前記芳香族多価アミン架橋剤(b2)の融点よりも10℃以上高い温度にて、前記アクリルゴム(b1)と前記芳香族多価アミン架橋剤(b2)とを混合する工程である請求項1に記載の架橋性ゴム組成物の製造方法。
- 前記マスターバッチ(B)の配合量が、前記カルボキシル基含有ニトリル共重合ゴム(A)100重量部に対して、0.1~40重量部である請求項1または2に記載の架橋性ゴム組成物の製造方法。
- 前記アクリルゴム(b1)と前記芳香族多価アミン架橋剤(b2)との混合比率が、重量比で、アクリルゴム(b1):芳香族多価アミン架橋剤(b2)=20:80~90:10である請求項1~3のいずれかに記載の架橋性ゴム組成物の製造方法。
- 前記第3工程が、前記カルボキシル基含有ニトリル共重合ゴム(A)に、前記マスターバッチ(B)およびシリカを混合する工程である請求項1~4のいずれかに記載の架橋性ゴム組成物の製造方法。
- 前記アクリルゴム(b1)が、(メタ)アクリル酸エステル単量体単位50~100重量%、および架橋性単量体単位0~10重量%を含有する請求項1~5のいずれかに記載の架橋性ゴム組成物の製造方法。
- 前記アクリルゴム(b1)が、(メタ)アクリル酸エステル単量体単位50~99.9重量%、架橋性単量体単位0~10重量%、およびエチレン単量体単位0.1~50重量%を含有する請求項1~5のいずれかに記載の架橋性ゴム組成物の製造方法。
- 前記芳香族多価アミン架橋剤(b2)がフェノキシ基を有する請求項1~7のいずれかに記載の架橋性ゴム組成物の製造方法。
- 請求項1~8のいずれかに記載の製造方法により得られた架橋性ゴム組成物を架橋する工程を備えるゴム架橋物の製造方法。
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WO2019198398A1 (ja) * | 2018-04-09 | 2019-10-17 | 住友ゴム工業株式会社 | ゴム組成物 |
WO2020261975A1 (ja) * | 2019-06-28 | 2020-12-30 | Nok株式会社 | ゴム組成物、ゴム金属積層体、ガスケット及びゴム金属積層体の製造方法 |
WO2023249096A1 (ja) * | 2022-06-24 | 2023-12-28 | 株式会社大阪ソーダ | 架橋剤マスターバッチ、架橋剤マスターバッチを含むゴム組成物及びその架橋物 |
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