WO2016084734A1 - ニトリルゴム組成物、高飽和ニトリルゴムのラテックス組成物、ゴム架橋物 - Google Patents
ニトリルゴム組成物、高飽和ニトリルゴムのラテックス組成物、ゴム架橋物 Download PDFInfo
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- WO2016084734A1 WO2016084734A1 PCT/JP2015/082674 JP2015082674W WO2016084734A1 WO 2016084734 A1 WO2016084734 A1 WO 2016084734A1 JP 2015082674 W JP2015082674 W JP 2015082674W WO 2016084734 A1 WO2016084734 A1 WO 2016084734A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
- C08L15/005—Hydrogenated nitrile rubber
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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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/26—Crosslinking, e.g. vulcanising, of macromolecules of latex
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L13/00—Compositions of rubbers containing carboxyl groups
- C08L13/02—Latex
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
- C08L9/04—Latex
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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
- C08J2415/00—Characterised by the use of rubber derivatives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
- C08L2312/02—Crosslinking with dienes
Definitions
- the present invention provides a nitrile rubber composition that has excellent processability and can give a rubber cross-linked product excellent in tensile stress, a latex composition of highly saturated nitrile rubber, and such a nitrile rubber composition, and The present invention relates to a rubber cross-linked product obtained by using a latex composition of highly saturated nitrile rubber.
- Nitrile rubber (acrylonitrile-butadiene copolymer rubber) has been used as a material for automotive rubber parts such as hoses, belts, tubes, etc., taking advantage of oil resistance, mechanical properties, chemical resistance, etc.
- Highly saturated nitrile rubber obtained by saturating the carbon-carbon double bond in the polymer main chain of nitrile rubber by hydrogenation is superior in heat resistance, so it is used for rubber parts such as seals, belts, hoses and gaskets.
- Patent Document 1 has an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit (a) and a conjugated diene monomer unit (b), and the conjugated diene monomer unit (b) A nitrile group-containing highly saturated copolymer rubber obtained by hydrogenating at least a part, wherein the content of ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit (a) is 37 to 45% by weight, ⁇ , ⁇ -Viscoelastic properties when the total of the ethylenically unsaturated nitrile monomer unit (a) and the conjugated diene monomer unit (b) is 93% by weight or more, the iodine value is 9 or less, and a crosslinked product is obtained.
- a nitrile group-containing highly saturated copolymer rubber is disclosed in which the half width of the peak of loss tangent tan ⁇ in the range of 5 to 20 ° C. is disclosed.
- the rubber cross-linked product obtained by using the nitrile group-containing highly saturated copolymer rubber of Patent Document 1 described above does not have sufficient tensile stress, and therefore is required to be particularly excellent in tensile stress for belt applications and the like. It was not suitable for the application.
- the present invention provides a nitrile rubber composition that has excellent processability and can give a rubber cross-linked product excellent in tensile stress, a latex composition of highly saturated nitrile rubber, and such a nitrile rubber composition, and
- An object of the present invention is to provide a rubber cross-linked product obtained by using a latex composition of highly saturated nitrile rubber.
- an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit is contained in a proportion of 8 to 60% by weight and an iodine value of 120 or less.
- Saturated nitrile rubber is blended with a predetermined amount of an alkylated phenol compound, and in a state where it is dispersed in water to form an aqueous dispersion, the amount of change in plasticity after storage at 70 ° C. for 7 days is within a predetermined range. It has been found that the above object can be achieved by the rubber composition inside, and the present invention has been completed.
- the content ratio of the alkylated phenol compound (B) to the total of the highly saturated nitrile rubber (A) and the alkylated phenol compound (B) is 0.01.
- nitrile rubber composition in which the difference ( ⁇ 2 ⁇ 1) is 12 or less.
- the content ratio of the alkylated phenol compound (B) to the total of the highly saturated nitrile rubber (A) and the alkylated phenol compound (B) is 0.01 to 0. It is preferably 95% by weight.
- the alkylated phenol compound (B) is preferably a compound represented by the following general formula (1) or a compound represented by the following general formula (2).
- each R 1 is independently substituted with an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an amino group, or an alkyl group having 1 to 4 carbon atoms.
- An amino group or a nitrogen-containing heterocyclic group, and n is an integer of 1 to 5.
- at least one of R 1 in the general formula (1) is an alkyl group having 1 to 7 carbon atoms.
- R 2 and R 3 each independently represents an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an amino group, or an alkyl group having 1 to 4 carbon atoms.
- a substituted amino group or a nitrogen-containing heterocyclic group is a chemical single bond or an alkylene group having 1 to 4 carbon atoms, and m and k are each independently an integer of 1 to 4
- at least one of R 2 in the general formula (2) is an alkyl group having 1 to 7 carbon atoms
- at least one of R 3 in the general formula (2) is (It is an alkyl group having 1 to 7 carbon atoms.)
- a highly saturated nitrile rubber (A) containing an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit in a proportion of 8 to 60% by weight and having an iodine value of 120 or less, and an alkylated phenol
- the content ratio of the alkylated phenol compound (B) to the total of the highly saturated nitrile rubber (A) and the alkylated phenol compound (B) is 0.01 to 1 It is a latex composition of highly saturated nitrile rubber in weight%, and the difference between the plasticity ⁇ 2 of the coagulated product after storage at 70 ° C.
- a latex composition of highly saturated nitrile rubber is provided.
- the content ratio of the alkylated phenol compound (B) to the total of the highly saturated nitrile rubber (A) and the alkylated phenol compound (B) is 0. It is preferably 0.01 to 0.95% by weight.
- the alkylated phenol compound (B) is a compound represented by the general formula (1) or a compound represented by the general formula (2). Is preferred.
- a crosslinkable nitrile rubber composition obtained by blending a nitrile rubber composition obtained by coagulating the above nitrile rubber composition or the latex composition of the above highly saturated nitrile rubber with a crosslinking agent. Things are provided.
- the crosslinkable nitrile rubber composition of the present invention preferably further contains organic short fibers.
- a crosslinked rubber product obtained by crosslinking the above crosslinkable nitrile rubber composition.
- a nitrile rubber composition capable of providing a rubber cross-linked product having excellent processability and excellent tensile stress, a latex composition of a highly saturated nitrile rubber, and such a nitrile rubber composition And a crosslinked rubber obtained by using a latex composition of a highly saturated nitrile rubber.
- Nitrile rubber composition contains ⁇ , ⁇ -ethylenically unsaturated nitrile monomer units in a proportion of 8 to 60% by weight and an iodine value of 120 or less.
- A) and the alkylated phenol compound (B) the content ratio of the alkylated phenol compound (B) to the total of the highly saturated nitrile rubber (A) and the alkylated phenol compound (B) is It is a composition of highly saturated nitrile rubber that is 0.01 to 1% by weight.
- the nitrile rubber composition of the present invention has a difference ( ⁇ 2) between the plasticity ⁇ 2 after storage at 70 ° C.
- the plasticity ⁇ 1 before storage in a state of being dispersed in water to form an aqueous dispersion. - ⁇ 1) is 12 or less.
- the “plasticity ⁇ 2” will be described in detail later.
- the “plasticity ⁇ 1” is a value measured before storing the nitrile rubber composition of the present invention as an aqueous dispersion under the above conditions, and the nitrile rubber composition before storage is an aqueous dispersion or solution. Is a value measured in the state of a solidified product obtained by solidifying these.
- the highly saturated nitrile rubber (A) used in the present invention is a rubber containing an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit in a proportion of 8 to 60% by weight and having an iodine value of 120 or less.
- the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer forming the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit contained in the highly saturated nitrile rubber (A) used in the present invention is not particularly limited. However, those having 3 to 18 carbon atoms are preferred, and those having 3 to 9 carbon atoms are particularly preferred. Specific examples thereof include acrylonitrile, methacrylonitrile, ⁇ -chloroacrylonitrile and the like, and among them, acrylonitrile is preferable. These ⁇ , ⁇ -ethylenically unsaturated nitrile monomers may be used alone or in combination of two or more.
- the content of the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit in the highly saturated nitrile rubber (A) is 8 to 60% by weight, preferably 12 to 58% by weight, more preferably 16 to 50%. % By weight. If the content of the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit is too low, the resulting rubber cross-linked product may be inferior in oil resistance, and conversely if too much, cold resistance may be reduced. There is.
- the highly saturated nitrile rubber (A) used in the present invention may further contain a diene monomer unit and / or an ⁇ -olefin monomer unit from the viewpoint of improving mechanical properties due to rubber elasticity. preferable.
- Examples of the diene monomer forming the diene monomer unit include conjugated dienes having 4 or more carbon atoms such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and the like.
- Non-conjugated dienes having 5 to 12 carbon atoms such as 1,4-pentadiene and 1,4-hexadiene; Of these, conjugated dienes are preferred, and 1,3-butadiene is more preferred.
- the ⁇ -olefin monomer forming the ⁇ -olefin monomer unit is preferably one having 2 to 12 carbon atoms, such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1- Examples include hexene and 1-octene. These diene monomers and ⁇ -olefin monomers may be used alone or in combination of two or more.
- the content of diene monomer units and / or ⁇ -olefin monomer units in the highly saturated nitrile rubber (A) is preferably 40 to 90% by weight, more preferably 41 to 85% by weight, still more preferably. 43 to 80% by weight.
- the nitrile group-containing copolymer rubber of the present invention may further contain an ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid ester monomer unit from the viewpoint of improving cold resistance.
- Examples of the ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid ester monomer forming the ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid ester monomer unit include, for example, methyl acrylate, ethyl acrylate, acrylic acid n -(Meth) acrylic acid esters having an alkyl group having 1 to 18 carbon atoms such as butyl, isobutyl acrylate, n-dodecyl acrylate, methyl methacrylate, ethyl methacrylate, etc.
- (meth) Acrylic acid ester (meth) ⁇ ⁇ acrylic acid ester having a hydroxyalkyl group having 1 to 12 carbon atoms, such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate; trifluoroethyl acrylate, (Meth) acrylic acid ester having a fluoroalkyl group having 1 to 12 carbon atoms such as tetrafluoropropyl methacrylate; These ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid ester monomers may be used alone or in combination of two or more.
- the content of the ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid ester monomer unit in the nitrile group-containing copolymer rubber of the present invention is preferably 5 to 50% by weight, more preferably 10 to 45% by weight. More preferably, it is 15 to 40% by weight.
- the nitrile group-containing copolymer rubber of the present invention may further contain a carboxyl group-containing monomer unit from the viewpoint that the low heat build-up can be further enhanced.
- the carboxyl group-containing monomer that forms the carboxyl group-containing monomer unit is an unsubstituted (non-esterified) copolymerizable with an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer.
- the monomer is not particularly limited as long as it is a monomer having one or more (free) carboxyl groups.
- Examples of the carboxyl group-containing monomer include ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid monomers, ⁇ , ⁇ -ethylenically unsaturated polycarboxylic acid monomers, and ⁇ , ⁇ -ethylenically unsaturated monomers. And dicarboxylic acid diester monomers 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.
- 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, ethylacrylic acid, crotonic acid, and cinnamic acid.
- Examples of ⁇ , ⁇ -ethylenically unsaturated polyvalent carboxylic acid monomers 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.
- ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid diester monomers include maleic acid diesters such as diethyl maleate; fumaric acid diesters such as dimethyl fumarate; citraconic acid diesters such as dimethyl citraconic acid; itacones such as dibutyl itaconate Acid diesters; and the like.
- 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; monofumaric acids such as monocyclopentyl fumarate, monocyclohexyl fumarate and monocycloheptyl fumarate Cycloalkyl esters; monoalkyl cycl
- the carboxyl group-containing monomer may be used alone or in combination of two or more.
- ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid monoester monomer is preferable, maleic acid monoalkyl ester is more preferable, and mono n-butyl maleate is preferable because the effect of the present invention becomes more remarkable. Is particularly preferred.
- the number of carbon atoms in the alkyl group of the alkyl ester is preferably 2-8.
- the content of the carboxyl group-containing monomer unit in the nitrile group-containing copolymer rubber of the present invention is preferably 1 to 30% by weight, more preferably 2 to 25% by weight, still more preferably 2 to 20% by weight. It is. By setting the content of the carboxyl group-containing monomer unit in the above range, it is possible to further improve the low exothermic property while improving the fatigue resistance of the obtained rubber cross-linked product.
- the nitrile group-containing copolymer rubber of the present invention contains units of other monomers that can be copolymerized with these monomers in addition to the units of the respective monomers described above. Also good.
- examples of such other monomers include non-conjugated diene monomers, aromatic vinyl monomers, crosslinkable monomers, and copolymerizable anti-aging agents.
- the non-conjugated diene monomer preferably has 5 to 12 carbon atoms, and examples thereof include 1,4-pentadiene, 1,4-hexadiene, vinylnorbornene, and dicyclopentadiene.
- examples of the aromatic vinyl monomer include styrene, ⁇ -methylstyrene, vinyl pyridine and the like.
- crosslinkable monomer examples include divinyl compounds such as divinylbenzene; di (meth) acrylates such as ethylene di (meth) acrylate, diethylene glycol di (meth) acrylate, and ethylene glycol di (meth) acrylate; trimethylol Self-crosslinking such as N-methylol (meth) acrylamide, N, N'-dimethylol (meth) acrylamide, in addition to polyfunctional ethylenically unsaturated monomers such as trimethacrylates such as propane tri (meth) acrylate; And other monomers.
- divinyl compounds such as divinylbenzene
- di (meth) acrylates such as ethylene di (meth) acrylate, diethylene glycol di (meth) acrylate, and ethylene glycol di (meth) acrylate
- trimethylol Self-crosslinking such as N-methylol (meth) acrylamide, N, N'-dimethylol (meth)
- 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 in the nitrile group-containing copolymer rubber of the present invention is preferably 50% by weight or less, more preferably 30% by weight or less, and still more preferably 10% by weight or less.
- the highly saturated nitrile rubber (A) used in the present invention preferably has a weight average molecular weight (Mw) of 10,000 to 1,000,000.
- a weight average molecular weight (Mw) can be measured using GPC.
- the iodine value of the highly saturated nitrile rubber (A) used in the present invention is not particularly limited, but is preferably 120 or less, more preferably 80 or less, from the viewpoint that heat aging resistance and ozone resistance can be further improved. More preferably, it is 60 or less, Most preferably, it is 30 or less.
- the production method of the highly saturated nitrile rubber (A) used in the present invention is not particularly limited, but the above-mentioned monomers are copolymerized and, if necessary, carbon-carbon double bonds in the resulting copolymer are removed. Obtained by hydrogenation.
- 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 And anionic emulsifiers such as salts of fatty acids such as linolenic acid, alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, higher alcohol sulfates, and alkyl sulfosuccinates; sulfoesters of ⁇ , ⁇ -unsaturated carboxylic acids, ⁇ , ⁇ -unsaturated carboxylic acid sulfate esters, sulfoalkyl aryl ethers and other copolymerizable emulsifiers.
- the amount of the emulsifier added is preferably 0.1
- 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 is used as the polymerization initiator, it can be used as a redox polymerization initiator in combination with a reducing agent such as sodium bisulfite or ferrous sulfate.
- 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. Of these, mercaptans are preferable, and t-dodecyl mercaptan is more preferable.
- water is used as a medium for emulsion polymerization.
- 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) of the copolymer 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. Subsequently, a hydrogenation reaction (oil layer hydrogenation method) is carried out, and the resulting hydride is poured into a large amount of water and coagulated, filtered and dried to obtain a highly saturated nitrile rubber (A).
- a known coagulant such as sodium chloride, calcium chloride, or aluminum sulfate can be used for coagulation of latex by salting out. Moreover, it may replace with solidification by salting out and may perform coagulation using alcohol, such as methanol.
- 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 5000 ppm by weight, more preferably 100 to 3000 ppm by weight, based on the copolymer.
- the latex of the copolymer prepared by emulsion polymerization is diluted with water as necessary to carry out the 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 copolymer concentration (concentration in the latex state) 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 sulfate dihydrate and the like.
- palladium salts of carboxylic acids, dichloro (norbornadiene) palladium and ammonium hexachloropalladium (IV) are particularly preferred.
- the amount of the hydrogenation catalyst used may be appropriately determined, but is preferably 5 to 6000 ppm by weight, more preferably 10 to 4000 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, and then the latex is filtered or centrifuged. It is also possible to leave it in the latex without removing the hydrogenation catalyst.
- the latex after the hydrogenation reaction thus obtained is subjected to coagulation by salting out, filtration, drying and the like to obtain a highly saturated nitrile rubber (A).
- A highly saturated nitrile rubber
- the filtration and drying steps subsequent to coagulation can be performed by known methods.
- Alkylated phenolic compound (B) used in the present invention is a phenol compound having at least one phenolic hydroxyl group and at least one alkyl group.
- the alkylated phenol compound (B) usually acts as an anti-aging agent in the nitrile rubber composition of the present invention.
- the alkylated phenol compound (B) used in the present invention may be any compound having at least one phenolic hydroxyl group and at least one alkyl group, but having one or two phenolic hydroxyl groups, And it is preferable that it has an at least 1 alkyl group in the ortho-position, meta-position, or para-position of a phenolic hydroxyl group. Moreover, you may have groups other than an alkyl group in the ortho position, meta position, or para position of a phenolic hydroxyl group.
- Examples of the alkylated phenol compound (B) used in the present invention include a compound represented by the following general formula (1) or a compound represented by the following general formula (2).
- each R 1 independently represents an amino group substituted with an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an amino group, or an alkyl group having 1 to 4 carbon atoms.
- at least one of R 1 is an alkyl group having 1 to 7 carbon atoms.
- R 2 and R 3 are each independently substituted with an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an amino group, or an alkyl group having 1 to 4 carbon atoms.
- An amino group or a nitrogen-containing heterocyclic group, A is a chemical single bond or an alkylene group having 1 to 4 carbon atoms, and m and k are each independently an integer of 1 to 4. is there.
- at least one of R 2 in the general formula (2) is an alkyl group having 1 to 7 carbon atoms
- at least one of R 3 in the general formula (2) is 1 carbon atom. 7 to 7 alkyl groups.
- an alkyl group having 1 to 5 carbon atoms as R 1 is selected from phenolic compounds because the effects of the present invention can be made more remarkable. Those having at least the ortho-position or para-position of the hydroxyl group are preferred, and those having an alkyl group having 1 to 5 carbon atoms at all of the two ortho-positions and para-positions of the phenolic hydroxyl group are particularly preferred. .
- the compound represented by the following general formula (3) is preferable among the compounds represented by the above general formula (2) from the viewpoint that the effects of the present invention can be made more remarkable.
- the compounds represented by the following general formula (3) ortho positions of two phenolic hydroxyl groups each having an alkyl group having 1 to 5 carbon atoms as R 2 and R 3 in two aromatic rings, respectively. Or those having at least a para position, preferably having an alkyl group having 1 to 5 carbon atoms in all of the ortho and para positions of the two phenolic hydroxyl groups respectively provided in the two aromatic rings. are particularly preferred.
- R 2 , R 3 , A, m, and k are the same as those in the general formula (2).
- alkylated phenol compound (B) examples include 2-isopropyl-5-methylphenol, 3-methyl-4-isopropylphenol, butylhydroxyanisole, 2- (2H-benzotriazol-2-yl) -4, 6-di-tert-butylphenol, 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butyl- ⁇ -dimethylamino-p-cresol, 2,6-di-tert-butylphenol And 2,4,6-tri-tert-butylphenol and ortho-tert-butylphenol, mono ( ⁇ -methylbenzyl) phenol, di ( ⁇ -methylbenzyl) phenol, tri ( ⁇ -methylbenzyl) phenol, alkyl and A mixture of aralkyl-substituted phenols, 2,2'-methylenebis ( 4-methyl-6-tert-butylphenol), 2,2'-methylene-bis- (4-methyl-6-cyclohexyl
- the content of the alkylated phenol compound (B) in the nitrile rubber composition of the present invention is 0.01 to about the total of the highly saturated nitrile rubber (A) and the alkylated phenol compound (B). 1% by weight, preferably 0.01 to 0.95% by weight, more preferably 0.02 to 0.95% by weight, still more preferably 0.02 to 0.7% by weight, still more preferably It is 0.02 to 0.5% by weight, particularly preferably 0.02 to 0.4% by weight. If the content of the alkylated phenol compound (B) is too small or too large, an effect of improving processability as a nitrile rubber composition and an effect of improving tensile stress when a rubber cross-linked product is obtained can be obtained. It will disappear.
- the content of the alkylated phenol compound (B) is 0.01% by weight or more, and preferably 0.95% by weight or less, more preferably 0.7% by weight or less. More preferably 0.5 wt% or less, particularly preferably 0.4 wt% or less, the difference in plasticity ⁇ 1, ⁇ 2 ( ⁇ 2 - ⁇ 1) can be suitably within the predetermined range of the present invention. Thereby, the workability as a nitrile rubber composition and the tensile stress when a rubber cross-linked product is obtained can be appropriately improved.
- the nitrile rubber composition of the present invention comprises the above-described highly saturated nitrile rubber (A) and the alkylated phenol compound (B), and the preparation method thereof is particularly limited. However, any method can be used as long as it can contain them simultaneously. For example, the following method can be used.
- a monomer for forming the highly saturated nitrile rubber (A) used in the present invention is copolymerized by an emulsion polymerization method to obtain a latex of the copolymer.
- the copolymer latex obtained by emulsion polymerization in a state where the alkylated phenol compound (B) is blended with the latex of the obtained copolymer and the alkylated phenol compound (B) is blended is hydrogenated. (Hydrogenation reaction), and then coagulation and drying to obtain the nitrile rubber composition of the present invention containing the highly saturated nitrile rubber (A) and the alkylated phenol compound (B). Can do.
- the nitrile rubber composition of the present invention can usually be obtained in a solid state.
- the nitrile rubber composition of the present invention when hydrogenation is performed by the oil layer hydrogenation method, usually has a highly saturated nitrile rubber (A) and an alkylated phenol compound (B) dissolved in an organic solvent. It will be obtained in the state of a solution.
- the nitrile rubber composition of the present invention can be obtained in a solid state by pouring the solution of the nitrile rubber composition of the present invention into a large amount of water and coagulating, filtering and drying. .
- the nitrile rubber composition of the present invention when hydrogenation is performed by the aqueous layer hydrogenation method, usually has a highly saturated nitrile rubber (A) and an alkylated phenol compound (B) dispersed in water. To be obtained in the state of a dispersion.
- the nitrile rubber composition of the present invention can be obtained in a solid state by subjecting such an aqueous dispersion of the nitrile rubber composition of the present invention to solidification by salting out, filtration and drying.
- the alkylated phenol compound (B) when preparing the nitrile rubber composition of the present invention as in the above method, when employing a method of blending the alkylated phenol compound (B) with the latex of the copolymer before hydrogenation, although the amount of the alkylated phenol compound (B) may vary depending on the subsequent coagulation step, in the nitrile rubber composition of the present invention, the alkylated phenol compound after the variation after the subsequent coagulation step. What is necessary is just to let the content rate of (B) be the range mentioned above.
- the nitrile rubber composition of the present invention has a difference ( ⁇ 2) between the plasticity ⁇ 2 after storage at 70 ° C. for 7 days and the plasticity ⁇ 1 before storage in a state of being dispersed in water to form an aqueous dispersion.
- - ⁇ 1 is 12 or less, preferably 10 or less, more preferably 8 or less.
- the nitrile rubber composition when the plasticity ⁇ 2 is measured, is dispersed in water to form an aqueous dispersion, which is stored at 70 ° C. for 7 days, and then coagulated.
- the solid content concentration in the aqueous dispersion is not particularly limited, but is preferably 5 to 47% by weight, more preferably 8 to 45% by weight.
- the nitrile rubber composition of the present invention when the nitrile rubber composition of the present invention is prepared, hydrogenation is performed by the aqueous layer hydrogenation method, and the nitrile rubber composition of the present invention is obtained in the form of a dispersion liquid dispersed in water. Can be used as is.
- hydrogenation is performed by an oil layer hydrogenation method, and the nitrile rubber composition of the present invention is obtained in the form of a solution obtained by dissolving in an organic solvent.
- the dispersion and the emulsifier aqueous solution are mixed by a known phase inversion method, emulsified and dispersed in water by vigorous stirring, and the organic solvent is removed to obtain a dispersion liquid dispersed in water. .
- the nitrile rubber composition of the present invention when obtained in a solid state, the solid nitrile rubber composition is dissolved in an organic solvent in which the nitrile rubber composition is soluble, and then the solution is obtained by a known phase inversion method. And an emulsifier aqueous solution are mixed, emulsified and dispersed in water by vigorous stirring, and the organic solvent is removed to obtain a dispersion liquid dispersed in water.
- the plasticity ⁇ 1 and ⁇ 2 of the nitrile rubber composition can be measured according to “Plasticity by Rapid Plastometer” defined in JIS K6300-3.
- the nitrile rubber composition of the present invention is obtained as a dispersion formed by dispersing in water or obtained as a solution formed by dissolving in an organic solvent, these are coagulated.
- the obtained solidified product is measured for plasticity ⁇ 1 in accordance with “plasticity by rapid plastometer” defined in JIS K6300-3.
- the plasticity ⁇ 2 as described above, in a state of being dispersed in water to obtain an aqueous dispersion, it was stored at 70 ° C. for 7 days and then coagulated, and the obtained coagulated product was subjected to JIS K6300-3. Measurement is performed in accordance with “Plasticity measured by a rapid plastometer” specified in 1.
- the method for setting the difference ( ⁇ 2 ⁇ 1) between the plasticity ⁇ 2 and the plasticity ⁇ 1 in the above range is not particularly limited.
- the highly saturated nitrile rubber (A) is produced by an emulsion polymerization method.
- the method of adjusting the usage-amount and kind of a polymerization terminator used for 1), the method of adjusting the usage-amount of metal containing compounds, such as a chelating agent, the method of adjusting the pH of the aqueous dispersion obtained, etc. are mentioned.
- the highly saturated nitrile rubber (A) does not contain an ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid ester monomer unit.
- a polymerization terminator a method of using a quinone type polymerization terminator and an amine type polymerization terminator in combination, and the amount of the polymerization terminator used are based on 100 parts by weight of the monomer used for the polymerization. Preferably 0.01 to 1 part by weight, a method of adjusting the pH of the resulting aqueous dispersion to preferably 6 to 13, and the amount of metal-containing compound such as a chelating agent used. Examples thereof include a method of controlling to 100 parts by weight of the monomer used for polymerization in terms of metal (by weight of metal), preferably 0.001 to 0.1 parts by weight.
- the nitrile rubber composition when obtained in the form of an aqueous dispersion, it remains in the state of the aqueous dispersion without being solidified (ie, as a latex composition of a highly saturated nitrile rubber). ), And can be used for various purposes.
- the crosslinkable nitrile rubber composition of the present invention is a highly saturated nitrile rubber composition obtained by adding a crosslinking agent to the nitrile rubber composition of the present invention described above.
- the crosslinking agent is not particularly limited, and examples thereof include a sulfur crosslinking agent and an organic peroxide crosslinking agent.
- a polyamine is used.
- a crosslinking agent can also be used.
- Sulfur-based crosslinking agents include powdered sulfur, sulfur white, precipitated sulfur, colloidal sulfur, surface-treated sulfur, insoluble sulfur, and other sulfur; sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, dibenzothiazyl disulfide, N, Sulfur-containing compounds such as N′-dithio-bis (hexahydro-2H-azenopine-2), phosphorus-containing polysulfides, polymer polysulfides; tetramethylthiuram disulfide, selenium dimethyldithiocarbamate, 2- (4′-morpholinodithio) And sulfur donating compounds such as benzothiazole; These can be used individually by 1 type or in combination of multiple types.
- organic peroxide crosslinking agents include dicumyl peroxide, cumene hydroperoxide, t-butylcumyl peroxide, paramentane hydroperoxide, di-t-butyl peroxide, 1,3-bis (t-butylperoxyisopropyl) benzene, 1,4-bis (t-butylperoxyisopropyl) benzene, 1,1-di-t-butylperoxy-3,3-trimethylcyclohexane, 4,4-bis- (t-butyl-peroxy) -n-butylvale 2,5-dimethyl-2,5-di-t-butylperoxyhexane, 2,5-dimethyl-2,5-di-t-butylperoxyhexyne-3, 1,1-di-t-butyl Peroxy-3,5,5-trimethylcyclohexane, p-chlorobenzoyl peroxide, t-butyl
- 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 nitrile rubber composition of the present invention is not particularly limited, but is preferably 0.1 to 10 parts by weight, more preferably 100 parts by weight with respect to 100 parts by weight of the highly saturated nitrile rubber (A). 0.2 to 5 parts by weight.
- a polyamine type crosslinking agent when using a polyamine type crosslinking agent as a crosslinking agent, it is preferable to further contain a basic crosslinking accelerator.
- the basic crosslinking accelerator 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-dimethyl-2-ethylimida 1-methyl-2-methoxyimidazole, 1-methyl-2-ethoxyimidazole, 1-methyl-4-methoxyimidazole, 1-methyl-2-methoxyimidazole, 1-ethoxymethylimidazole, -Methyl-4-nitroimi
- a guanidine basic crosslinking accelerator, a secondary amine basic crosslinking accelerator and a basic crosslinking accelerator having a cyclic amidine structure are preferable, and a basic crosslinking accelerator having a cyclic amidine structure is more preferable.
- 1,8-diazabicyclo [5,4,0] undecene-7 and 1,5-diazabicyclo [4,3,0] nonene-5 are more preferred, and 1,8-diazabicyclo [5,4,0] undecene-7 Is particularly preferred.
- the basic crosslinking accelerator having a cyclic amidine structure may form a salt with an organic carboxylic acid or an alkyl phosphoric acid.
- the secondary amine basic crosslinking accelerator may be a mixture of an alkylene glycol or an alcohol such as an alkyl alcohol having 5 to 20 carbon atoms, and further contains an inorganic acid and / or an organic acid. You may go out.
- the secondary amine basic cross-linking accelerator and the inorganic acid and / or organic acid may form a salt and further form a complex with the alkylene glycol.
- the blending amount in the crosslinkable nitrile rubber composition of the present invention is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the highly saturated nitrile rubber (A). More preferably 0.2 to 15 parts by weight, still more preferably 0.5 to 10 parts by weight.
- crosslinkable nitrile rubber composition of the present invention further contains organic short fibers.
- the organic short fiber is not particularly limited as long as it is a fibrous organic material having an average fiber length in the range of 0.1 to 12 mm.
- the average fiber length of the organic short fiber is obtained, for example, by taking a photograph with an optical microscope, measuring the length of 100 short fibers randomly selected in the obtained photograph, and averaging this. Can be sought.
- the average fiber length is in the above range, the tensile stress of the resulting rubber cross-linked product is appropriately increased while effectively preventing a decrease in dispersibility in the cross-linkable nitrile rubber composition caused by entanglement between short fibers. Can do.
- the average fiber length of the organic short fibers is preferably 0.5 to 10 mm, more preferably 0.5 to 6 mm.
- the average fiber diameter of the organic short fibers is not particularly limited, but is preferably 0.5 to 100 ⁇ m, more preferably 1 to 50 ⁇ m, and further preferably 2 to 20 ⁇ m.
- the average fiber diameter of the organic short fibers is measured by, for example, taking a photograph with an optical microscope and measuring the diameter (diameter) of the thickest part of 100 short fibers randomly selected in the obtained photograph. Can be obtained by arithmetic averaging.
- the aspect ratio of the organic short fibers (“average fiber length of organic short fibers” / “average fiber diameter of organic short fibers”) is not particularly limited, but is preferably 5 to 1000, more preferably 50 to 800. .
- Organic short fibers used in the present invention include natural fibers such as cotton and wood cellulose fibers; polyamide, polyester, polyvinyl alcohol, rayon, polyparaphenylene benzobisoxazole, polyethylene, polypropylene, polyarylate, polyimide, polyphenylene sulfide, and polyether.
- natural fibers such as cotton and wood cellulose fibers
- polyamide polyester, polyvinyl alcohol, rayon, polyparaphenylene benzobisoxazole, polyethylene, polypropylene, polyarylate, polyimide, polyphenylene sulfide, and polyether.
- fibers made of synthetic resins such as ether ketone, polylactic acid, polycaprolactone, polybutylene succinate, and fluorine-based polymer.
- Polyamides include polycapramide, poly- ⁇ -aminoheptanoic acid, poly- ⁇ -aminononanoic acid, polyundecanamide, polyethylenediamine adipamide, polytetramethylene adipamide, polyhexamethylene adipamide, polyhexamethylene sebaca Aliphatic polyamides such as amide, polyhexamethylene dodecamide, polyoctamethylene adipamide, polydecamethylene adipamide; polyparaphenylene terephthalamide (trade name "Kevlar”, manufactured by Toray DuPont), polymetaphenylene Isophthalamide (trade name "Conex”, manufactured by Teijin Techno Products), copolyparaphenylene 3,4'oxydiphenylene terephthalamide (trade name "Technora”, manufactured by Teijin Techno Products), polymetaxylylene adipa Mido, polymetaxy Renpimeramido, poly-m-xylylene azelamide, polyparaxy
- aromatic polyamide that is, aramid is preferable from the viewpoint that the tensile stress of the rubber cross-linked product obtained can be further improved, and polyparaphenylene terephthalamide, polymetaphenylene isophthalamide, and copolyparaffin.
- Phenylene / 3,4′oxydiphenylene / terephthalamide is more preferable, and copolyparaphenylene / 3,4′oxydiphenylene / terephthalamide is particularly preferable.
- the short fiber made of polyamide is preferably an aramid short fiber, such as a polyparaphenylene terephthalamide short fiber, a polymetaphenylene isophthalamide short fiber, and a copolyparaphenylene 3,4′oxydiphenylene terephthalamide short fiber. More preferred are copolyparaphenylene • 3,4′oxydiphenylene • terephthalamide short fibers.
- the organic short fibers may be in the form of chopped fibers (cut fibers) or pulp having fibrils, and may be further treated with an epoxy adhesive, an isocyanate adhesive, resorcin-formaldehyde resin / latex, etc. It may be applied.
- the blending amount of the organic short fibers in the crosslinkable nitrile rubber composition of the present invention is preferably 0.5 to 80 parts by weight, more preferably 1 to 50 parts per 100 parts by weight of the highly saturated nitrile rubber (A). Part by weight, more preferably 1 to 30 parts by weight.
- the crosslinkable nitrile rubber composition of the present invention may be blended with other compounding agents usually used in the rubber processing field.
- compounding agents include, for example, reinforcing agents, fillers, light stabilizers, scorch inhibitors, plasticizers, processing aids, lubricants, adhesives, lubricants, flame retardants, acid acceptors, antifungal agents, Examples thereof include an antistatic agent, a colorant, a silane coupling agent, a crosslinking aid, a co-crosslinking agent, a crosslinking accelerator, a crosslinking retarder, and a foaming agent.
- an amount corresponding to the compounding purpose can be appropriately adopted.
- the plasticizer is not particularly limited, and a trimellitic acid plasticizer or an ether ester plasticizer can be used.
- a trimellitic acid plasticizer or an ether ester plasticizer can be used.
- Specific examples include trimellitic acid tri-2-ethylhexyl, trimellitic acid isononyl ester, bis [2- (2-butoxyethoxy) ethyl] adipate, diheptanoate, di-2-ethylhexanoate, didecanoate, and the like. Can be mentioned. These can be used individually by 1 type or in combination of 2 or more types.
- the crosslinkable nitrile rubber composition of the present invention may be blended with a rubber other than the above-described highly saturated nitrile rubber (A) as long as the effects of the present invention are not impaired.
- 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 nitrile rubber composition is preferably 30 parts by weight or less with respect to 100 parts by weight of the highly saturated nitrile rubber (A). Preferably it is 20 weight part or less, More preferably, it is 10 weight part or less.
- the crosslinkable nitrile rubber composition of the present invention is prepared by mixing each of the above components preferably in a non-aqueous system.
- the method for preparing the crosslinkable nitrile rubber composition of the present invention is not limited, but usually the components excluding the crosslinking agent and the heat-labile co-crosslinking agent are mixed into a mixer such as a Banbury mixer, an intermixer, or a kneader. After the primary kneading, it is prepared by transferring to an open roll and adding a cross-linking agent or a heat-unstable co-cross-linking agent, followed by secondary kneading.
- 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 90 ° C., Preferably, 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 crosslinkable nitrile rubber composition of the present invention thus obtained has a compound Mooney viscosity (ML 1 + 4 , 100 ° C.) of preferably 10 to 200, more preferably 40 to 140, and further preferably 50 to 100. It is excellent in workability.
- Cross-linked rubber The cross-linked rubber of the present invention is obtained by cross-linking the cross-linkable nitrile rubber composition of the present invention described above.
- the rubber cross-linked product of the present invention uses the cross-linkable nitrile rubber composition of the present invention, is molded by a molding machine corresponding to a desired shape, for example, an extruder, an injection molding machine, a compressor, a roll, etc., and is heated. It can manufacture by performing a crosslinking reaction and fixing a shape as a crosslinked product. In this case, 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 1 hour.
- secondary cross-linking may be performed by heating.
- a heating method a general method used for crosslinking of rubber such as press heating, steam heating, oven heating, and hot air heating may be appropriately selected.
- the rubber cross-linked product of the present invention thus obtained is obtained by cross-linking the cross-linkable nitrile rubber composition of the present invention described above, and is excellent in tensile stress. For this reason, the rubber cross-linked product of the present invention makes use of such characteristics, and O-rings, packings, diaphragms, oil seals, shaft seals, bearing seals, well head seals, pneumatic equipment seals, and air conditioner cooling devices.
- Various seal materials such as seals for valves (rolling bearings, automotive hub units, automotive water pumps, linear guide devices, ball screws, etc.), valves and valve seats, BOP (Blow Out Preventar), platters; intake manifolds and cylinders Attach to the connection with the head Intake manifold gasket, cylinder head gasket attached to the connection between the cylinder block and cylinder head, rocker cover gasket attached to the connection between the rocker cover and cylinder head, oil pan and cylinder block or transmission case
- Various gaskets such as an oil pan gasket attached to the connecting part, a gasket for a fuel cell separator attached between a pair of housings sandwiching a unit cell having a positive electrode, an electrolyte plate, and a negative electrode; a top cover gasket for a hard disk drive;
- the iodine value of the highly saturated nitrile rubber was measured according to JIS K6235.
- the plasticity ⁇ 1 and ⁇ 2 of the plasticity nitrile rubber composition were measured using a sample for measuring plasticity ⁇ 1 and a sample for measuring plasticity ⁇ 2 according to JIS K6300-3 as “RAPID PLASTIMETER P14VT”. (Manufactured by Wallace) ".
- the difference ( ⁇ 2 ⁇ 1) between the plasticity ⁇ 1 and ⁇ 2 obtained as a result of the measurement was calculated.
- the capillary extrudable nitrile rubber composition was evaluated for fluidity using a rubber capillary rheometer (trade name “Rubber Capillary Rheometer”, manufactured by Goettfert). Specifically, the piston temperature was set to 100 ° C., the chamber temperature was set to 100 ° C., the nitrile rubber composition was charged, and after preheating for 3 minutes, the piston was extruded at a pressure of 200 bar and the extrusion amount after 60 seconds (mm 3 ) was measured. It can be determined that the greater the amount of extrusion at this time, the better the workability (fluidity).
- a GC-2010 manufactured by Shimadzu Corporation hydrogen flame ionization detector was used, and a Zebron ZB 130 m ⁇ 0.25 mm ⁇ 0.3 ⁇ m column was used.
- the content of N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine was measured instead of the content of the alkylated phenol compound.
- the crosslinkable nitrile 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 press-molded at 170 ° C. for 20 minutes while being pressed at a press pressure of 10 MPa to obtain a sheet-like rubber cross-linked product. .
- the obtained sheet-like rubber cross-linked product was punched out with a No. 3 dumbbell to prepare a test piece.
- 20% tensile stress of the rubber cross-linked product was measured according to JIS K6251 using the obtained test piece.
- the latex was coagulated by adding to an aqueous solution of aluminum sulfate in an amount of 3% by weight based on the nitrile rubber content of the latex obtained above, coagulated with latex, and filtered while washing with water. For 12 hours to obtain a nitrile rubber.
- the obtained nitrile rubber was dissolved in acetone so as to have a concentration of 12% by weight, and this was put in an autoclave.
- a palladium-silica catalyst was added at 600 ppm by weight with respect to the nitrile rubber, and the hydrogen pressure was 3.0 MPa.
- a part of the solution of the obtained nitrile rubber composition (a-1) is taken out, poured into a large amount of water to coagulate, filtered and dried to obtain a solid nitrile rubber composition (a -1) was obtained.
- the composition of the highly saturated nitrile rubber (A-1) contained in the resulting nitrile rubber composition (a-1) is 36% by weight of acrylonitrile units, 74% by weight of butadiene units (including a saturated portion). %, The iodine value was 8, and the polymer Mooney viscosity [ML 1 + 4 , 100 ° C.] was 63.
- Part of the obtained solid nitrile rubber composition (a-1) was designated as “sample for measuring plasticity ⁇ 1”.
- the remaining part of the solution of the obtained nitrile rubber composition (a-1) is mixed with water containing potassium oleate as an emulsifier, and acetone is removed by steam stripping.
- an aqueous dispersion of the nitrile rubber composition (a-1) was obtained.
- the resulting aqueous dispersion of nitrile rubber composition (a-1) was stored at 70 ° C. for 7 days.
- the solid matter (crumb) was taken out by filtration, and this was vacuum-dried at 60 ° C.
- a nitrile rubber composition (a-1) was obtained after storage at 70 ° C. for 7 days. Then, by using a part of the obtained nitrile rubber composition (a-1) after storage at 70 ° C. for 7 days, capillary extrudability was evaluated according to the above method, and the obtained 70 ° C., 7 A part of the nitrile rubber composition (a-1) that had been stored for a day was separately collected as a “sample for measuring the plasticity ⁇ 2”. Then, using the “sample for measuring plasticity ⁇ 1” and “sample for measuring plasticity ⁇ 2” obtained above, the difference between the plasticity ⁇ 2 and the plasticity ⁇ 1 ( ⁇ 2 ⁇ 1) was measured.
- the polymerization reaction was stopped by adding 0.05 part and 0.05 part of N-isopropylhydroxylamine (polymerization terminator), and 2,6-di-tert-butyl-4-methyl as the alkylated phenol compound (B) After adding 0.45 part of phenol, the residual monomer was removed using a rotary evaporator at a water temperature of 60 ° C. to obtain a latex of nitrile rubber (solid content concentration: about 25% by weight). The latex obtained had a pH of 10.1.
- the latex was coagulated by adding to an aqueous solution of aluminum sulfate in an amount of 3% by weight based on the nitrile rubber content of the latex obtained above, coagulated with latex, and filtered while washing with water. For 12 hours to obtain a nitrile rubber.
- the obtained nitrile rubber was dissolved in acetone so as to have a concentration of 12% by weight, and this was put in an autoclave, and 500 ppm by weight of palladium / silica catalyst was added to the nitrile rubber, and the hydrogen pressure was 3.0 MPa.
- nitrile rubber composition (a-2) a part of the solution of the obtained nitrile rubber composition (a-2) is taken out, poured into a large amount of water to coagulate, filtered and dried to obtain a solid nitrile rubber composition (a -2) was obtained.
- the composition of the highly saturated nitrile rubber (A-2) contained in the resulting nitrile rubber composition (a-2) is 26.2% by weight of acrylonitrile units, 29.3% by weight of n-butyl acrylate units, The butadiene unit (including the saturated portion) was 44.5% by weight, the iodine value was 15, and the polymer Mooney viscosity [ML 1 + 4 , 100 ° C.] was 68.
- Part of the obtained solid nitrile rubber composition (a-2) was designated as “sample for measuring plasticity ⁇ 1”.
- an aqueous dispersion of the nitrile rubber composition (a-2) was prepared using the remaining part of the solution of the obtained nitrile rubber composition (a-2). This was stored at 70 ° C. for 7 days. And after adding 2 volumes of methanol to the aqueous dispersion after storage at 70 ° C. for 7 days and coagulating, the solid matter (crumb) was taken out by filtration, and this was vacuum-dried at 60 ° C. for 12 hours, A nitrile rubber composition (a-2) was obtained after storage at 70 ° C. for 7 days. Then, using a part of the obtained nitrile rubber composition (a-2) after storage at 70 ° C.
- the capillary extrudability was evaluated according to the above method, and the obtained 70 ° C., 7 A part of the nitrile rubber composition (a-2) that had been stored for a day was separately collected as a “sample for measuring the plasticity ⁇ 2”. Then, using the “sample for measuring plasticity ⁇ 1” and “sample for measuring plasticity ⁇ 2” obtained above, the difference between the plasticity ⁇ 2 and the plasticity ⁇ 1 ( ⁇ 2 ⁇ 1) is calculated according to the above method. It was measured.
- Production Example 3 (Production of nitrile rubber composition (a-3))
- a reactor 180 parts of ion-exchanged water, 25 parts of a 10% strength by weight aqueous sodium dodecylbenzenesulfonate solution, 37 parts of acrylonitrile, 6 parts of mono-n-butyl maleate, and 0.5 t-dodecyl mercaptan (molecular weight regulator)
- the parts were charged in this order, and the internal gas was replaced with nitrogen three times, and then 57 parts of 1,3-butadiene was charged.
- 0.1 part of cumene hydroperoxide (polymerization initiator) was charged, and the polymerization reaction was continued for 16 hours while stirring.
- the latex and palladium catalyst (ion exchange with an equivalent weight of 1 wt% palladium acetate / acetone solution) in the autoclave so that the amount of palladium is 1,000 ppm by weight with respect to the dry weight of the rubber contained in the latex.
- a solution in which water was mixed was added and a hydrogenation reaction was carried out at a hydrogen pressure of 3 MPa and a temperature of 50 ° C. for 6 hours to obtain a highly saturated nitrile rubber (A-3) and 2,2 as an alkylated phenol compound (B).
- An aqueous dispersion of a nitrile rubber composition (a-3) containing '-methylenebis (4-methyl-6-tert-butylphenol) was obtained.
- a part of the obtained aqueous dispersion of the nitrile rubber composition (a-3) is taken out, solidified by adding 2 volumes of methanol, and then filtered to take out a solid (crumb).
- a solid nitrile rubber composition (a-3) was vacuum-dried at 60 ° C. for 12 hours to obtain a solid nitrile rubber composition (a-3).
- the composition of the highly saturated nitrile rubber (A-3) contained in the obtained nitrile rubber composition (a-3) is 35.6% by weight of acrylonitrile units and butadiene units (including a saturated portion).
- the remainder of the obtained aqueous dispersion of the nitrile rubber composition (a-3) was stored at 70 ° C. for 7 days.
- the solid matter (crumb) was taken out by filtration, and this was vacuum-dried at 60 ° C. for 12 hours, A nitrile rubber composition (a-3) was obtained after storage at 70 ° C. for 7 days. Then, using a part of the obtained nitrile rubber composition (a-3) after storage at 70 ° C.
- the capillary extrudability was evaluated according to the above method, and the obtained 70 ° C., 7 A part of the nitrile rubber composition (a-3) that had been stored for a day was separately collected as a “sample for measuring the plasticity ⁇ 2”. Then, using the “sample for measuring plasticity ⁇ 1” and “sample for measuring plasticity ⁇ 2” obtained above, the difference between the plasticity ⁇ 2 and the plasticity ⁇ 1 ( ⁇ 2 ⁇ 1) was measured.
- Production Example 4 (Production of nitrile rubber composition (a-4)) After stopping the polymerization reaction, 2,2′-methylenebis (4-methyl-6) was used as the alkylated phenol compound (B) instead of 0.4 part of 2,6-di-tert-butyl-4-methylphenol. Except for adding 0.13 part of (tert-butylphenol), 2,2′-methylenebis (A) as the highly saturated nitrile rubber (A-1) and the alkylated phenol compound (B) was prepared in the same manner as in Production Example 1. A solution of a nitrile rubber composition (a-4) containing 4-methyl-6-tert-butylphenol was obtained, and similarly stored at 70 ° C. for 7 days and measured.
- Production Example 5 (Production of nitrile rubber composition (a-5)) After stopping the polymerization reaction, 2,6-di-tert-butyl was substituted for 0.25 part of 2,2′-methylenebis (4-methyl-6-tert-butylphenol) as the alkylated phenol compound (B).
- a highly saturated nitrile rubber (A-3) and 2,6-di-tert as an alkylated phenol compound (B) were prepared in the same manner as in Production Example 3, except that 0.4 parts of -4-methylphenol was added.
- An aqueous dispersion of a nitrile rubber composition (a-5) containing -butyl-4-methylphenol was obtained, and similarly stored at 70 ° C. for 7 days and measured.
- Production Example 6 (Production of nitrile rubber composition (a-6)) Similar to Production Example 3, except that after the polymerization reaction was stopped, 0.25 part of 2,2′-methylenebis (4-methyl-6-tert-butylphenol) as the alkylated phenol compound (B) was not added. Thus, an aqueous dispersion of the nitrile rubber composition (a-6) containing the highly saturated nitrile rubber (A-3) was obtained, and similarly stored at 70 ° C. for 7 days and measured.
- Production Example 7 (Production of nitrile rubber composition (a-7)) In the same manner as in Production Example 1, except that 0.4 part of 2,6-di-tert-butyl-4-methylphenol as the alkylated phenol compound (B) was not added after stopping the polymerization reaction, A solution of the nitrile rubber composition (a-7) containing the highly saturated nitrile rubber (A-1) was obtained, and similarly stored at 70 ° C. for 7 days and measured.
- Production Example 8 (Production of nitrile rubber composition (a-8)) Except that 0.45 part of 2,6-di-tert-butyl-4-methylphenol as the alkylated phenol compound (B) was not added after stopping the polymerization reaction, A solution of a nitrile rubber composition (a-8) containing a highly saturated nitrile rubber (A-2) was obtained, and similarly stored at 70 ° C. for 7 days and measured.
- N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine (0.45 parts) was added, and the residual monomer was removed using a rotary evaporator at a water temperature of 60 ° C.
- a rubber latex (solid content concentration of about 25% by weight) was obtained.
- the latex was coagulated by adding to an aqueous solution of aluminum sulfate in an amount of 3% by weight based on the nitrile rubber content of the latex obtained above, coagulated with latex, and filtered while washing with water. For 12 hours to obtain a nitrile rubber.
- the obtained nitrile rubber was dissolved in acetone so as to have a concentration of 12% by weight, and this was put in an autoclave, and 500 ppm by weight of palladium / silica catalyst was added to the nitrile rubber, and the hydrogen pressure was 3.0 MPa.
- a part of the solution of the obtained nitrile rubber composition (a-9) is taken out, poured into a large amount of water to coagulate, filtered and dried to obtain a solid nitrile rubber composition (a-9).
- the composition of the highly saturated nitrile rubber (A-4) contained in the obtained nitrile rubber composition (a-9) is 36% by weight of acrylonitrile units, 74% by weight of butadiene units (including a saturated portion).
- the iodine value was 13, and the polymer Mooney viscosity [ML 1 + 4 , 100 ° C.] was 83.
- Part of the obtained solid nitrile rubber composition (a-9) was designated as “sample for measuring plasticity ⁇ 1”.
- an aqueous dispersion of the nitrile rubber composition (a-9) was prepared using the remaining part of the solution of the obtained nitrile rubber composition (a-9). This was stored at 70 ° C. for 7 days. And after adding 2 volumes of methanol to the aqueous dispersion after storage at 70 ° C. for 7 days and coagulating, the solid matter (crumb) was taken out by filtration, and this was vacuum-dried at 60 ° C. for 12 hours, A nitrile rubber composition (a-9) was obtained after storage at 70 ° C. for 7 days. Then, by using a part of the obtained nitrile rubber composition (a-9) after storage at 70 ° C.
- the capillary extrudability was evaluated according to the above method, and the obtained 70 ° C., 7 A part of the nitrile rubber composition (a-9) that had been stored for a day was separately taken as a “sample for measuring the plasticity ⁇ 2”. Then, using the “sample for measuring plasticity ⁇ 1” and “sample for measuring plasticity ⁇ 2” obtained above, the difference between the plasticity ⁇ 2 and the plasticity ⁇ 1 ( ⁇ 2 ⁇ 1) was measured.
- Production Example 10 (Production of nitrile rubber composition (a-10))
- a-10 nitrile rubber composition
- sodium carbonate was dissolved in 200 parts of ion-exchanged water, and 2.25 parts of fatty acid potassium soap (potassium salt of fatty acid) was added thereto to prepare an aqueous soap solution.
- fatty acid potassium soap potassium salt of fatty acid
- 38 parts of acrylonitrile and 0.45 part of t-dodecyl mercaptan (molecular weight regulator) were charged in this order in this soap solution, and the internal gas was replaced with nitrogen three times, and then 62 parts of 1,3-butadiene were added.
- t-dodecyl mercaptan molecular weight regulator
- the latex was coagulated by adding to an aqueous solution of aluminum sulfate in an amount of 3% by weight based on the nitrile rubber content of the latex obtained above, coagulated with latex, and filtered while washing with water. For 12 hours to obtain a nitrile rubber.
- the obtained nitrile rubber was dissolved in acetone so as to have a concentration of 12% by weight, and this was put in an autoclave, and 500 ppm by weight of palladium / silica catalyst was added to the nitrile rubber, and the hydrogen pressure was 3.0 MPa.
- Nitrile rubber composition containing highly saturated nitrile rubber (A-5) and 2,2′-methylenebis (4-methyl-6-tert-butylphenol) as alkylated phenol compound (B) by performing addition reaction A solution of product (a-10) was obtained.
- a part of the solution of the obtained nitrile rubber composition (a-10) is taken out, poured into a large amount of water to coagulate, filtered and dried to obtain a solid nitrile rubber composition ( a-10) was obtained.
- the composition of the highly saturated nitrile rubber (A-5) contained in the obtained nitrile rubber composition (a-10) is 36% by weight of acrylonitrile units, 74% by weight of butadiene units (including a saturated portion).
- the iodine value was 13, and the polymer Mooney viscosity [ML 1 + 4 , 100 ° C.] was 83.
- Part of the obtained solid nitrile rubber composition (a-10) was designated as “sample for measuring plasticity ⁇ 1”.
- an aqueous dispersion of the nitrile rubber composition (a-10) was prepared using the remaining part of the solution of the obtained nitrile rubber composition (a-10). This was stored at 70 ° C. for 7 days. And after adding 2 volumes of methanol to the aqueous dispersion after storage at 70 ° C. for 7 days and coagulating, the solid matter (crumb) was taken out by filtration, and this was vacuum-dried at 60 ° C. for 12 hours, A nitrile rubber composition (a-10) was obtained after storage at 70 ° C. for 7 days. Then, by using a part of the obtained nitrile rubber composition (a-10) stored at 70 ° C.
- the capillary extrudability was evaluated according to the above method, and the obtained 70 ° C., 7 A part of the nitrile rubber composition (a-10) that had been stored for a day was separately collected as a “sample for measuring the plasticity ⁇ 2”. Then, using the “sample for measuring plasticity ⁇ 1” and “sample for measuring plasticity ⁇ 2” obtained above, the difference between the plasticity ⁇ 2 and the plasticity ⁇ 1 ( ⁇ 2 ⁇ 1) was measured.
- Production Example 11 (Production of nitrile rubber composition (a-11))
- a reactor 0.2 parts of sodium carbonate was dissolved in 200 parts of ion-exchanged water, and 2.25 parts of fatty acid potassium soap (potassium salt of fatty acid) was added thereto to prepare an aqueous soap solution.
- fatty acid potassium soap potassium salt of fatty acid
- the inside of the reactor was kept at 5 ° C., and 0.5 parts of cumene hydroperoxide (polymerization initiator), appropriate amounts of a reducing agent and a chelating agent were charged, and the polymerization reaction was continued for 8 hours while stirring.
- the amount of the chelating agent charged was 50 times the amount of the charge in Production Example 1 (1.2 parts in terms of metal (weight of metal)).
- 0.2 part of hydroquinone aqueous solution (polymerization terminator) having a concentration of 10% by weight and 0.3 part of N-isopropylhydroxylamine (polymerization terminator) were added to terminate the polymerization reaction to obtain an alkylated phenol compound (B).
- the latex was coagulated by adding to an aqueous solution of aluminum sulfate in an amount of 3% by weight based on the nitrile rubber content of the latex obtained above, coagulated with latex, and filtered while washing with water. For 12 hours to obtain a nitrile rubber.
- the obtained nitrile rubber was dissolved in acetone so as to have a concentration of 12% by weight, and this was put in an autoclave, and 500 ppm by weight of palladium / silica catalyst was added to the nitrile rubber, and the hydrogen pressure was 3.0 MPa.
- Nitrile rubber composition containing highly saturated nitrile rubber (A-6) and 2,2′-methylenebis (4-methyl-6-tert-butylphenol) as alkylated phenol compound (B) by addition reaction A solution of product (a-11) was obtained.
- nitrile rubber composition (a-11) a part of the solution of the obtained nitrile rubber composition (a-11) is taken out, poured into a large amount of water to solidify, filtered and dried to obtain a solid nitrile rubber composition ( a-11) was obtained.
- the composition of the highly saturated nitrile rubber (A-6) contained in the obtained nitrile rubber composition (a-11) is 26.2% by weight of acrylonitrile units, 29.3% by weight of n-butyl acrylate units, The butadiene unit (including the saturated portion) was 44.5% by weight, the iodine value was 15, and the polymer Mooney viscosity [ML 1 + 4 , 100 ° C.] was 70.
- Part of the obtained solid nitrile rubber composition (a-11) was designated as “sample for measuring plasticity ⁇ 1”.
- an aqueous dispersion of the nitrile rubber composition (a-11) was prepared using the remaining part of the solution of the obtained nitrile rubber composition (a-11). This was stored at 70 ° C. for 7 days. And after adding 2 volumes of methanol to the aqueous dispersion after storage at 70 ° C. for 7 days and coagulating, the solid matter (crumb) was taken out by filtration, and this was vacuum-dried at 60 ° C. for 12 hours, A nitrile rubber composition (a-11) was obtained after storage at 70 ° C. for 7 days. A part of the obtained nitrile rubber composition (a-11) after storage at 70 ° C.
- Production Example 12 (Production of nitrile rubber composition (a-12)) After the polymerization reaction was stopped, the amount of 2,2′-methylenebis (4-methyl-6-tert-butylphenol) added as the alkylated phenol compound (B) was changed from 0.13 parts to 3.0 parts. In the same manner as in Production Example 4, except that highly saturated nitrile rubber (A-1) and 2,2′-methylenebis (4-methyl-6-tert-butylphenol) as alkylated phenol compound (B) are contained A solution of the nitrile rubber composition (a-12) to be obtained was obtained, stored at 70 ° C. for 7 days, and measured in the same manner.
- Table 1 summarizes the nitrile rubber compositions obtained in the respective production examples.
- Example 1 Using a Banbury mixer, 100 parts of the nitrile rubber composition (a-1) obtained in Production Example 1 and copolyparaphenylene 3,4′oxydiphenylene terephthalamide short fiber (trade name “Technola ZCF T323SB 1 mm” ", 10 parts of Teijin Techno Products, aramid short fibers having an average fiber length of 1 mm and an average fiber diameter of 12 ⁇ m). Next, the mixture was transferred to a roll, and 8 parts of 1,3-bis (t-butylperoxyisopropyl) benzene 40% product (trade name “Vul Cup 40KE”, manufactured by Arkema Co., Ltd., an organic peroxide crosslinking agent) was added.
- a-1 nitrile rubber composition obtained in Production Example 1
- copolyparaphenylene 3,4′oxydiphenylene terephthalamide short fiber trade name “Technola ZCF T323SB 1 mm” ", 10 parts of Teijin Techno Products, ara
- nitrile rubber composition (a-1) one obtained by storing in an aqueous dispersion at 70 ° C. for 7 days and then solidifying was used (Examples described later). The same applies to 2 to 5 and Comparative Examples 1 to 8.)
- Example 2 In the same manner as in Example 1, except that the nitrile rubber composition (a-2) obtained in Production Example 2 was used instead of the nitrile rubber composition (a-1) obtained in Production Example 1. A crosslinkable nitrile rubber composition was obtained and evaluated in the same manner. The results are shown in Table 2.
- Example 3 Using a Banbury mixer, 100 parts of the nitrile rubber composition (a-3) obtained in Production Example 3, and copolyparaphenylene 3,4′oxydiphenylene terephthalamide short fiber (trade name “Technola ZCF T323SB 1 mm” ", 10 parts of Teijin Techno Products, aramid short fibers having an average fiber length of 1 mm and an average fiber diameter of 12 ⁇ m). The mixture was then transferred to a roll and 6.3 parts 2,2-bis [4- (4-aminophenoxy) phenyl] propane (polyamine crosslinker) and 1,8-diazabicyclo [5,4,0] undecene.
- a-3 nitrile rubber composition obtained in Production Example 3
- copolyparaphenylene 3,4′oxydiphenylene terephthalamide short fiber trade name “Technola ZCF T323SB 1 mm” ", 10 parts of Teijin Techno Products, aramid short fibers having an average fiber length of 1 mm
- DBU (trade name “RHENOGRAN XLA-60 (GE2014)”, manufactured by Rhein Chemie, DBU 60% (including zinc dialkyldiphosphate salt), 4 parts of basic crosslinking accelerator) Then, a cross-linkable nitrile rubber composition was obtained by kneading.
- Example 4 In the same manner as in Example 1, except that the nitrile rubber composition (a-4) obtained in Production Example 4 was used instead of the nitrile rubber composition (a-1) obtained in Production Example 1. A crosslinkable nitrile rubber composition was obtained and evaluated in the same manner. The results are shown in Table 2.
- Example 5 In the same manner as in Example 3, except that the nitrile rubber composition (a-5) obtained in Production Example 5 was used instead of the nitrile rubber composition (a-3) obtained in Production Example 3, A crosslinkable nitrile rubber composition was obtained and evaluated in the same manner. The results are shown in Table 2.
- Comparative Example 2 The nitrile rubber composition (a-7) obtained in Production Example 7 was used in place of the nitrile rubber composition (a-1) obtained in Production Example 1, and copolyparaphenylene 3,4′oxy was used. A crosslinkable nitrile rubber composition was obtained and evaluated in the same manner as in Example 1 except that 10 parts of diphenylene terephthalamide short fibers were not added. The results are shown in Table 2.
- Comparative Example 3 In the same manner as in Example 1, except that the nitrile rubber composition (a-7) obtained in Production Example 7 was used instead of the nitrile rubber composition (a-1) obtained in Production Example 1, A crosslinkable nitrile rubber composition was obtained and evaluated in the same manner. The results are shown in Table 2.
- Comparative Example 4 In the same manner as in Comparative Example 2, except that the nitrile rubber composition (a-8) obtained in Production Example 8 was used instead of the nitrile rubber composition (a-7) obtained in Production Example 7, A crosslinkable nitrile rubber composition was obtained and evaluated in the same manner. The results are shown in Table 2.
- Comparative Example 5 In the same manner as in Example 1, except that the nitrile rubber composition (a-9) obtained in Production Example 9 was used instead of the nitrile rubber composition (a-1) obtained in Production Example 1, A crosslinkable nitrile rubber composition was obtained and evaluated in the same manner. The results are shown in Table 2.
- Comparative Example 7 In the same manner as in Example 1, except that the nitrile rubber composition (a-11) obtained in Production Example 11 was used instead of the nitrile rubber composition (a-1) obtained in Production Example 1. A crosslinkable nitrile rubber composition was obtained and evaluated in the same manner. The results are shown in Table 2.
- Comparative Example 8 In the same manner as in Example 1, except that the nitrile rubber composition (a-12) obtained in Production Example 12 was used instead of the nitrile rubber composition (a-1) obtained in Production Example 1, A crosslinkable nitrile rubber composition was obtained and evaluated in the same manner. The results are shown in Table 2.
- the high-saturated nitrile rubber (A) and a predetermined amount of the alkylated phenol compound (B), and the plasticity ⁇ 2 after storage at 70 ° C. for 7 days The nitrile rubber composition having a difference from the plasticity ⁇ 1 ( ⁇ 2 ⁇ 1) of 12 or less has a large amount of extrusion in the evaluation of capillary extrudability, and is excellent in processability (fluidity).
- the crosslinked product was excellent in 20% tensile stress (Production Examples 1 to 5 and Examples 1 to 5).
- the evaluation of capillary extrudability and 20% tensile stress was used after being stored in an aqueous dispersion at 70 ° C. for 7 days and then solidified. In the field of rubber compositions such as nitrile rubber compositions, these are considered because they are often used after being stored for a relatively long time after production (for example, at room temperature for 1440 hours or more). Is.
- the resulting nitrile rubber composition has a small amount of extrusion in the capillary extrusion property evaluation, and is inferior in workability (fluidity).
- the obtained rubber cross-linked product was inferior to 20% tensile stress (Production Examples 6 to 8, Comparative Examples 1 to 4).
- N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine is used in place of the alkylated phenol compound (B), the 20% tensile stress when a rubber cross-linked product is used. It was inferior (Production Example 9, Comparative Example 5).
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Abstract
Description
本発明のニトリルゴム組成物において、前記高飽和ニトリルゴム(A)と、前記アルキル化フェノール化合物(B)との合計に対する、前記アルキル化フェノール化合物(B)の含有割合が、0.01~0.95重量%であることが好ましい。
本発明のニトリルゴム組成物において、前記アルキル化フェノール化合物(B)が、下記一般式(1)で表される化合物、または下記一般式(2)で表される化合物であることが好ましい。
本発明の高飽和ニトリルゴムのラテックス組成物において、前記高飽和ニトリルゴム(A)と、前記アルキル化フェノール化合物(B)との合計に対する、前記アルキル化フェノール化合物(B)の含有割合が、0.01~0.95重量%であることが好ましい。
本発明の高飽和ニトリルゴムのラテックス組成物において、前記アルキル化フェノール化合物(B)が、上記一般式(1)で表される化合物、または上記一般式(2)で表される化合物であることが好ましい。
本発明のニトリルゴム組成物は、α,β-エチレン性不飽和ニトリル単量体単位を8~60重量%の割合で含有し、ヨウ素価が120以下である高飽和ニトリルゴム(A)と、アルキル化フェノール化合物(B)とを含有し、高飽和ニトリルゴム(A)と、前記アルキル化フェノール化合物(B)との合計に対する、アルキル化フェノール化合物(B)の含有割合が、0.01~1重量%である高飽和ニトリルゴムの組成物である。
また、本発明のニトリルゴム組成物は、水中に分散させて水分散液とした状態において、70℃、7日間保存した後における可塑度η2と、該保存前の可塑度η1との差(η2-η1)が12以下であるものである。
尚、前記の「可塑度η2」は、後に詳述するが、本発明のニトリルゴム組成物を、水中に分散させて水分散液とした状態において、70℃、7日間保存した後に、該水分散体を凝固させて得られる凝固物の状態で測定される値である。
また、前記の「可塑度η1」は、本発明のニトリルゴム組成物を水分散液として前記条件で保存する前に測定される値であり、保存前のニトリルゴム組成物が水分散体や溶液として得られる場合は、これらを凝固させて得られる凝固物の状態で測定される値である。
本発明で用いる高飽和ニトリルゴム(A)は、α,β-エチレン性不飽和ニトリル単量体単位を8~60重量%の割合で含有し、ヨウ素価が120以下であるゴムである。
芳香族ビニル単量体としては、たとえば、スチレン、α-メチルスチレン、ビニルピリジンなどが挙げられる。
本発明で用いるアルキル化フェノール化合物(B)は、少なくとも1つのフェノール性水酸基と、少なくとも1つのアルキル基とを有するフェノール化合物である。アルキル化フェノール化合物(B)は、本発明のニトリルゴム組成物中において、通常、老化防止剤として作用する。
本発明のニトリルゴム組成物は、上述した高飽和ニトリルゴム(A)と、アルキル化フェノール化合物(B)とを含有してなるものであり、その調製方法は特に限定されず、これらを同時に含有させることのできる方法であればよいが、たとえば、次の方法により得ることができる。
本発明の架橋性ニトリルゴム組成物は、上述した本発明のニトリルゴム組成物に、架橋剤を添加してなる高飽和ニトリルゴムの組成物である。架橋剤としては、特に限定されず、硫黄系架橋剤、有機過酸化物系架橋剤が挙げられるが、高飽和ニトリルゴム(A)が、カルボキシル基含有単量体単位を有する場合には、ポリアミン架橋剤を用いることもできる。
塩基性架橋促進剤の具体例としては、1,8-ジアザビシクロ[5,4,0]ウンデセン-7(以下「DBU」と略す場合がある)、1,5-ジアザビシクロ[4,3,0]ノネン-5(以下「DBN」と略す場合がある)、1-メチルイミダゾール、1-エチルイミダゾール、1-フェニルイミダゾール、1-ベンジルイミダゾール、1,2-ジメチルイミダゾール、1-エチル-2-メチルイミダゾール、1-メトキシエチルイミダゾール、1-フェニル-2-メチルイミダゾール、1-ベンジル-2-メチルイミダゾール、1-メチル-2-フェニルイミダゾール、1-メチル-2-ベンジルイミダゾール、1,4-ジメチルイミダゾール、1,5-ジメチルイミダゾール、1,2,4-トリメチルイミダゾール、1,4-ジメチル-2-エチルイミダゾール、1-メチル-2-メトキシイミダゾール、1-メチル-2-エトキシイミダゾール、1-メチル-4-メトキシイミダゾール、1-メチル-2-メトキシイミダゾール、1-エトキシメチル-2-メチルイミダゾール、1-メチル-4-ニトロイミダゾール、1,2-ジメチル-5-ニトロイミダゾール、1,2-ジメチル-5-アミノイミダゾール、1-メチル-4-(2-アミノエチル)イミダゾール、1-メチルベンゾイミダゾール、1-メチル-2-ベンジルベンゾイミダゾール、1-メチル-5-ニトロベンゾイミダゾール、1-メチルイミダゾリン、1,2-ジメチルイミダゾリン、1,2,4-トリメチルイミダゾリン、1,4-ジメチル-2-エチルイミダゾリン、1-メチル-フェニルイミダゾリン、1-メチル-2-ベンジルイミダゾリン、1-メチル-2-エトキシイミダゾリン、1-メチル-2-ヘプチルイミダゾリン、1-メチル-2-ウンデシルイミダゾリン、1-メチル-2-ヘプタデシルイミダゾリン、1-メチル-2-エトキシメチルイミダゾリン、1-エトキシメチル-2-メチルイミダゾリンなどの環状アミジン構造を有する塩基性架橋促進剤;テトラメチルグアニジン、テトラエチルグアニジン、ジフェニルグアニジン、1,3-ジ-オルト-トリルグアニジン、オルトトリルビグアニドなどのグアニジン系塩基性架橋促進剤;n-ブチルアルデヒドアニリン、アセトアルデヒドアンモニアなどのアルデヒドアミン系塩基性架橋促進剤;ジシクロペンチルアミン、ジシクロヘキシルアミン、ジシクロヘプチルアミンなどのジシクロアルキルアミン;N-メチルシクロペンチルアミン、N-ブチルシクロペンチルアミン、N-ヘプチルシクロペンチルアミン、N-オクチルシクロペンチルアミン、N-エチルシクロヘキシルアミン、N-ブチルシクロヘキシルアミン、N-ヘプチルシクロヘキシルアミン、N-オクチルシクロオクチルアミン、N-ヒドロキシメチルシクロペンチルアミン、N-ヒドロキシブチルシクロヘキシルアミン、N-メトキシエチルシクロペンチルアミン、N-エトキシブチルシクロヘキシルアミン、N-メトキシカルボニルブチルシクロペンチルアミン、N-メトキシカルボニルヘプチルシクロヘキシルアミン、N-アミノプロピルシクロペンチルアミン、N-アミノヘプチルシクロヘキシルアミン、ジ(2-クロロシクロペンチル)アミン、ジ(3-クロロシクロペンチル)アミンなどの二級アミン系塩基性架橋促進剤;などが挙げられる。これらのなかでも、グアニジン系塩基性架橋促進剤、二級アミン系塩基性架橋促進剤および環状アミジン構造を有する塩基性架橋促進剤が好ましく、環状アミジン構造を有する塩基性架橋促進剤がより好ましく、1,8-ジアザビシクロ[5,4,0]ウンデセン-7および1,5-ジアザビシクロ[4,3,0]ノネン-5がさらに好ましく、1,8-ジアザビシクロ[5,4,0]ウンデセン-7が特に好ましい。なお、上記環状アミジン構造を有する塩基性架橋促進剤は、有機カルボン酸やアルキルリン酸などと塩を形成していてもよい。また、上記二級アミン系塩基性架橋促進剤は、アルキレングリコールや炭素数5~20のアルキルアルコールなどのアルコール類が混合されたものであってもよく、さらに無機酸および/または有機酸を含んでいてもよい。そして、当該二級アミン系塩基性架橋促進剤と前記無機酸および/または有機酸とが塩を形成しさらに前記アルキレングリコールと複合体を形成していてもよい。
すなわち、ポリアミドからなる短繊維としては、アラミド短繊維が好ましく、ポリパラフェニレンテレフタラミド短繊維、ポリメタフェニレンイソフタラミド短繊維およびコポリパラフェニレン・3,4’オキシジフェニレン・テレフタラミド短繊維がより好ましく、コポリパラフェニレン・3,4’オキシジフェニレン・テレフタラミド短繊維が特に好ましい。
このようなゴムとしては、アクリルゴム、エチレン-アクリル酸共重合体ゴム、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、フッ素ゴム、ウレタンゴム、クロロプレンゴム、シリコーンゴム、天然ゴム、ポリイソプレンゴムなどが挙げられる。
本発明のゴム架橋物は、上述した本発明の架橋性ニトリルゴム組成物を架橋してなるものである。
本発明のゴム架橋物は、本発明の架橋性ニトリルゴム組成物を用い、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製造することができる。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~1時間である。
加熱方法としては、プレス加熱、スチーム加熱、オーブン加熱、熱風加熱などのゴムの架橋に用いられる一般的な方法を適宜選択すればよい。
このため、本発明のゴム架橋物は、このような特性を活かし、O-リング、パッキン、ダイアフラム、オイルシール、シャフトシール、ベアリングシール、ウェルヘッドシール、空気圧機器用シール、エアコンディショナの冷却装置や空調装置の冷凍機用コンプレッサに使用されるフロン若しくはフルオロ炭化水素または二酸化炭素の密封用シール、精密洗浄の洗浄媒体に使用される超臨界二酸化炭素または亜臨界二酸化炭素の密封用シール、転動装置(転がり軸受、自動車用ハブユニット、自動車用ウォーターポンプ、リニアガイド装置およびボールねじ等)用のシール、バルブおよびバルブシート、BOP(Blow Out Preventar)、プラターなどの各種シール材;インテークマニホールドとシリンダヘッドとの連接部に装着されるインテークマニホールドガスケット、シリンダブロックとシリンダヘッドとの連接部に装着されるシリンダヘッドガスケット、ロッカーカバーとシリンダヘッドとの連接部に装着されるロッカーカバーガスケット、オイルパンとシリンダブロックあるいはトランスミッションケースとの連接部に装着されるオイルパンガスケット、正極、電解質板および負極を備えた単位セルを挟み込む一対のハウジング間に装着される燃料電池セパレーター用ガスケット、ハードディスクドライブのトップカバー用ガスケットなどの各種ガスケット;印刷用ロール、製鉄用ロール、製紙用ロール、工業用ロール、事務機用ロールなどの各種ロール;平ベルト(フィルムコア平ベルト、コード平ベルト、積層式平ベルト、単体式平ベルト等)、Vベルト(ラップドVベルト、ローエッジVベルト等)、Vリブドベルト(シングルVリブドベルト、ダブルVリブドベルト、ラップドVリブドベルト、背面ゴムVリブドベルト、上コグVリブドベルト等)、CVT用ベルト、タイミングベルト、歯付ベルト、コンベアーベルト、などの各種ベルト;燃料ホース、ターボエアーホース、オイルホース、ラジェターホース、ヒーターホース、ウォーターホース、バキュームブレーキホース、コントロールホース、エアコンホース、ブレーキホース、パワーステアリングホース、エアーホース、マリンホース、ライザー、フローラインなどの各種ホース;CVJブーツ、プロペラシャフトブーツ、等速ジョイントブーツ、ラックアンドピニオンブーツなどの各種ブーツ;クッション材、ダイナミックダンパ、ゴムカップリング、空気バネ、防振材、クラッチフェーシング材などの減衰材ゴム部品;ダストカバー、自動車内装部材、摩擦材、タイヤ、被覆ケーブル、靴底、電磁波シールド、フレキシブルプリント基板用接着剤等の接着剤、燃料電池セパレーターの他、エレクトロニクス分野など幅広い用途に使用することができる。これらのなかでも、本発明のゴム架橋物は、引張応力に特に優れるものであるため、ベルトとして特に好適である。
高飽和ニトリルゴムのヨウ素価は、JIS K6235に準じて測定した。
ニトリルゴム組成物の可塑度η1,η2は、可塑度η1測定用の試料、および可塑度η2測定用の試料を用いて、JIS K6300-3に準じて、測定装置として、「RAPID PLASTIMETER P14VT(Wallace社製)」を用いて測定した。そして、測定の結果得られた可塑度η1,η2について、これらの差(η2-η1)を算出した。
ニトリルゴム組成物について、ゴム用キャピラリーレオメータ(商品名「Rubber Capillary Rheometer」、Goettfert社製)を用いて、流動性の評価を行った。具体的には、ピストン温度100℃、チャンバー温度100℃に設定し、ニトリルゴム組成物を投入し、3分間余熱した後、ピストンにより200barの圧力で押し出し、60秒後の押出量(mm3)を測定した。この時の押出量が多いほど、加工性(流動性)に優れると判断できる。
JIS K6229に従い、ニトリルゴム組成物についてメタノール抽出を行った。そして、得られた抽出物をクロロホルムに溶解し、JIS K0114およびJIS K6231を参照して、ガスクロマトグラフィーによりピーク面積の測定を行い、検量線法によって、ニトリルゴム組成物中のアルキル化フェノール化合物の含有量(すなわち、高飽和ニトリルゴムと、アルキル化フェノール化合物との合計に対する、アルキル化フェノール化合物の含有割合)を測定した。ガスクロマト装置としては、GC-2010(島津製作所社製)水素炎イオン化型検出器を用い、ZebronZB130m×0.25mm×0.3μmのカラムを使用した。なお、製造例9については、アルキル化フェノール化合物の含有量に代えて、N-フェニル-N’-(1,3-ジメチルブチル)-p-フェニレンジアミンの含有量を測定した。
架橋性ニトリルゴム組成物を、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分間プレス成形してシート状のゴム架橋物を得た。得られたシート状のゴム架橋物を3号形ダンベルで打ち抜いて試験片を作製した。そして、得られた試験片を用いて、JIS K6251に従い、ゴム架橋物の20%引張応力を測定した。
反応器内でイオン交換水200部に、炭酸ナトリウム0.2部を溶解し、それに脂肪酸カリウム石鹸(脂肪酸のカリウム塩)2.25部を添加して石鹸水溶液を調製した。そして、この石鹸水溶液に、アクリロニトリル38部、およびt-ドデシルメルカプタン(分子量調整剤)0.45部をこの順に仕込み、内部の気体を窒素で3回置換した後、1,3-ブタジエン62部を仕込んだ。次いで、反応器内を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、還元剤、およびキレート剤適量を仕込み、重合反応を開始した。そして、重合転化率が80%になった時点で、濃度10%のハイドロキノン(重合停止剤)水溶液0.05部とN-イソプロピルヒドロキシルアミン(重合停止剤)0.05部とを加えて重合反応を停止し、アルキル化フェノール化合物(B)としての2,6-ジ-tert-ブチル-4-メチルフェノール0.4部添加し、水温60℃のロータリーエバポレ-タを用いて残留単量体を除去して、ニトリルゴムのラテックス(固形分濃度約25重量%)を得た。なお、得られたラテックスのpHは9.6であった。
反応器内でイオン交換水200部に、炭酸ナトリウム0.2部を溶解し、それに脂肪酸カリウム石鹸(脂肪酸のカリウム塩)2.25部を添加して石鹸水溶液を調製した。そして、この石鹸水溶液に、アクリロニトリル13部、アクリル酸n-ブチル29部および、t-ドデシルメルカプタン(分子量調整剤)0.45部を仕込み、内部の気体を窒素で3回置換した後、1,3-ブタジエン21部を仕込んだ。次いで、反応器内を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、還元剤、およびキレート剤適量を仕込み、重合反応を開始した。反応転化率が60%になった時点で、アクリロニトリル12部、1,3-ブタジエン25部を添加し、重合転化率が85%になった時点で、濃度10%のハイドロキノン(重合停止剤)水溶液0.05部とN-イソプロピルヒドロキシルアミン(重合停止剤)0.05部を加えて重合反応を停止し、アルキル化フェノール化合物(B)としての2,6-ジ-tert-ブチル-4-メチルフェノール0.45部を添加した後、水温60℃のロータリーエバポレ-タを用いて残留単量体を除去して、ニトリルゴムのラテックス(固形分濃度約25重量%)を得た。なお、得られたラテックスのpHは10.1であった。
反応器に、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、およびt-ドデシルメルカプタン(分子量調整剤)0.5部を、この順に仕込み、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。反応器を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、攪拌しながら16時間重合反応を継続した。次いで、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た後、アルキル化フェノール化合物(B)としての2,2’-メチレンビス(4-メチル-6-tert-ブチルフェノール)0.25部を添加した。次いで、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、ニトリルゴムのラテックス(固形分濃度約30重量%)を得た。なお、得られたラテックスのpHは3.0であった。
重合反応を停止した後、アルキル化フェノール化合物(B)として、2,6-ジ-tert-ブチル-4-メチルフェノール0.4部に代えて、2,2’-メチレンビス(4-メチル-6-tert-ブチルフェノール)0.13部を添加した以外は、製造例1と同様にして、高飽和ニトリルゴム(A-1)、およびアルキル化フェノール化合物(B)としての2,2’-メチレンビス(4-メチル-6-tert-ブチルフェノール)を含有するニトリルゴム組成物(a-4)の溶液を得て、同様に70℃、7日間の保存、および各測定を行った。
重合反応を停止した後、アルキル化フェノール化合物(B)として、2,2’-メチレンビス(4-メチル-6-tert-ブチルフェノール)0.25部に代えて、2,6-ジ-tert-ブチル-4-メチルフェノール0.4部を添加した以外は、製造例3と同様にして、高飽和ニトリルゴム(A-3)、およびアルキル化フェノール化合物(B)としての2,6-ジ-tert-ブチル-4-メチルフェノールを含有するニトリルゴム組成物(a-5)の水分散液を得て、同様に70℃、7日間の保存、および各測定を行った。
重合反応を停止した後、アルキル化フェノール化合物(B)としての2,2’-メチレンビス(4-メチル-6-tert-ブチルフェノール)0.25部を添加しなかった以外は、製造例3と同様にして、高飽和ニトリルゴム(A-3)を含有するニトリルゴム組成物(a-6)の水分散液を得て、同様に70℃、7日間の保存、および各測定を行った。
重合反応を停止した後、アルキル化フェノール化合物(B)としての2,6-ジ-tert-ブチル-4-メチルフェノール0.4部を添加しなかった以外は、製造例1と同様にして、高飽和ニトリルゴム(A-1)を含有するニトリルゴム組成物(a-7)の溶液を得て、同様に70℃、7日間の保存、および各測定を行った。
重合反応を停止した後、アルキル化フェノール化合物(B)としての2,6-ジ-tert-ブチル-4-メチルフェノール0.45部を添加しなかった以外は、製造例2と同様にして、高飽和ニトリルゴム(A-2)を含有するニトリルゴム組成物(a-8)の溶液を得て、同様に70℃、7日間の保存、および各測定を行った。
反応器内でイオン交換水200部に、炭酸ナトリウム0.2部を溶解し、それに脂肪酸カリウム石鹸(脂肪酸のカリウム塩)2.25部を添加して石鹸水溶液を調製した。そして、この石鹸水溶液に、アクリロニトリル38部、およびt-ドデシルメルカプタン(分子量調整剤)0.45部をこの順に仕込み、内部の気体を窒素で3回置換した後、1,3-ブタジエン62部を仕込んだ。次いで、反応器内を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、還元剤、およびキレート剤適量を仕込み、重合反応を開始した。重合転化率が80%になった時点で、濃度10%のハイドロキノン(重合停止剤)水溶液0.05部およびN-イソプロピルヒドロキシルアミン(重合停止剤)0.05部を加えて重合反応を停止し、N-フェニル-N’-(1,3-ジメチルブチル)-p-フェニレンジアミン0.45部添加し、水温60℃のロータリーエバポレ-タを用いて残留単量体を除去して、ニトリルゴムのラテックス(固形分濃度約25重量%)を得た。
反応器内でイオン交換水200部に、炭酸ナトリウム0.2部を溶解し、それに脂肪酸カリウム石鹸(脂肪酸のカリウム塩)2.25部を添加して石鹸水溶液を調製した。そして、この石鹸水溶液に、アクリロニトリル38部、およびt-ドデシルメルカプタン(分子量調整剤)0.45部をこの順に仕込み、内部の気体を窒素で3回置換した後、1,3-ブタジエン62部を仕込んだ。次いで、反応器内を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、還元剤、およびキレート剤適量を仕込み、重合反応を開始した。そして、重合転化率が80%になった時点で、濃度10%のハイドロキノン(重合停止剤)水溶液0.05部を加えて重合反応を停止し、アルキル化フェノール化合物(B)としての2,2’-メチレンビス(4-メチル-6-tert-ブチルフェノール)0.1部添加し、水温60℃のロータリーエバポレ-タを用いて残留単量体を除去して、ニトリルゴムのラテックス(固形分濃度約25重量%)を得た。
反応器内でイオン交換水200部に、炭酸ナトリウム0.2部を溶解し、それに脂肪酸カリウム石鹸(脂肪酸のカリウム塩)2.25部を添加して石鹸水溶液を調製した。そして、この石鹸水溶液に、アクリロニトリル13部、アクリル酸n-ブチル29部および、分子量調整剤0.45部を仕込み、内部の気体を窒素で3回置換した後、1,3-ブタジエン21部を仕込んだ。次いで、反応器内を5℃に保ち、クメンハイドロパーオキサイド(重合開始剤)0.5部、適量の還元剤、およびキレート剤を仕込み、攪拌しながら8時間重合反応を継続した。なお、本製造例においては、キレート剤の仕込み量を製造例1における仕込み量に対し、50倍の量(金属換算で(金属の重量で)、1.2部)とした。次いで、濃度10重量%のハイドロキノン水溶液(重合停止剤)0.2部およびN-イソプロピルヒドロキシルアミン(重合停止剤)0.3部を加えて重合反応を停止し、アルキル化フェノール化合物(B)としての2,2’-メチレンビス(4-メチル-6-tert-ブチルフェノール)0.4部を添加した後、pH調整剤を適量仕込み、pHを4とし、水温70℃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、ニトリルゴムのラテックス(固形分濃度約30重量%)を得た。
重合反応を停止した後における、アルキル化フェノール化合物(B)としての2,2’-メチレンビス(4-メチル-6-tert-ブチルフェノール)の添加量を0.13部から3.0部に変更した以外は、製造例4と同様にして、高飽和ニトリルゴム(A-1)、およびアルキル化フェノール化合物(B)としての2,2’-メチレンビス(4-メチル-6-tert-ブチルフェノール)を含有するニトリルゴム組成物(a-12)の溶液を得て、同様に70℃、7日間の保存、および各測定を行った。
バンバリーミキサを用いて、製造例1にて得られたニトリルゴム組成物(a-1)100部、およびコポリパラフェニレン・3,4’オキシジフェニレン・テレフタラミド短繊維(商品名「テクノーラZCF T323SB 1mm」、帝人テクノプロダクツ社製、平均繊維長1mm、平均繊維径12μmのアラミド短繊維)10部を混練した。次いで、混合物をロールに移して、1,3-ビス(t-ブチルペルオキシイソプロピル)ベンゼン40%品(商品名「Vul Cup 40KE」、アルケマ社製、有機過酸化物架橋剤)8部を添加して混練することで、架橋性ニトリルゴム組成物を得た。なお、本実施例においては、ニトリルゴム組成物(a-1)として、水分散液の状態で70℃、7日間保存した後、凝固することにより得られたものを使用した(後述する実施例2~5、比較例1~8も同様。)。
製造例1で得られたニトリルゴム組成物(a-1)に代えて、製造例2で得られたニトリルゴム組成物(a-2)を使用した以外は、実施例1と同様にして、架橋性ニトリルゴム組成物を得て、同様に評価を行った。結果を表2に示す。
バンバリーミキサを用いて、製造例3にて得られたニトリルゴム組成物(a-3)100部、およびコポリパラフェニレン・3,4’オキシジフェニレン・テレフタラミド短繊維(商品名「テクノーラZCF T323SB 1mm」、帝人テクノプロダクツ社製、平均繊維長1mm、平均繊維径12μmのアラミド短繊維)10部を混練した。次いで、混合物をロールに移して、2,2-ビス[4-(4-アミノフェノキシ)フェニル]プロパン(ポリアミン架橋剤)6.3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)、塩基性架橋促進剤)4部を添加して混練することで、架橋性ニトリルゴム組成物を得た。
製造例1で得られたニトリルゴム組成物(a-1)に代えて、製造例4で得られたニトリルゴム組成物(a-4)を使用した以外は、実施例1と同様にして、架橋性ニトリルゴム組成物を得て、同様に評価を行った。結果を表2に示す。
製造例3で得られたニトリルゴム組成物(a-3)に代えて、製造例5で得られたニトリルゴム組成物(a-5)を使用した以外は、実施例3と同様にして、架橋性ニトリルゴム組成物を得て、同様に評価を行った。結果を表2に示す。
製造例3で得られたニトリルゴム組成物(a-3)に代えて、製造例6で得られたニトリルゴム組成物(a-6)を使用した以外は、実施例3と同様にして、架橋性ニトリルゴム組成物を得て、同様に評価を行った。結果を表2に示す。
製造例1で得られたニトリルゴム組成物(a-1)に代えて、製造例7で得られたニトリルゴム組成物(a-7)を使用するとともに、コポリパラフェニレン・3,4’オキシジフェニレン・テレフタラミド短繊維10部を添加しなかった以外は、実施例1と同様にして、架橋性ニトリルゴム組成物を得て、同様に評価を行った。結果を表2に示す。
製造例1で得られたニトリルゴム組成物(a-1)に代えて、製造例7で得られたニトリルゴム組成物(a-7)を使用した以外は、実施例1と同様にして、架橋性ニトリルゴム組成物を得て、同様に評価を行った。結果を表2に示す。
製造例7で得られたニトリルゴム組成物(a-7)に代えて、製造例8で得られたニトリルゴム組成物(a-8)を使用した以外は、比較例2と同様にして、架橋性ニトリルゴム組成物を得て、同様に評価を行った。結果を表2に示す。
製造例1で得られたニトリルゴム組成物(a-1)に代えて、製造例9で得られたニトリルゴム組成物(a-9)を使用した以外は、実施例1と同様にして、架橋性ニトリルゴム組成物を得て、同様に評価を行った。結果を表2に示す。
製造例1で得られたニトリルゴム組成物(a-1)に代えて、製造例10で得られたニトリルゴム組成物(a-10)を使用した以外は、実施例1と同様にして、架橋性ニトリルゴム組成物を得て、同様に評価を行った。結果を表2に示す。
製造例1で得られたニトリルゴム組成物(a-1)に代えて、製造例11で得られたニトリルゴム組成物(a-11)を使用した以外は、実施例1と同様にして、架橋性ニトリルゴム組成物を得て、同様に評価を行った。結果を表2に示す。
製造例1で得られたニトリルゴム組成物(a-1)に代えて、製造例12で得られたニトリルゴム組成物(a-12)を使用した以外は、実施例1と同様にして、架橋性ニトリルゴム組成物を得て、同様に評価を行った。結果を表2に示す。
アルキル化フェノール化合物(B)の代わりに、N-フェニル-N’-(1,3-ジメチルブチル)-p-フェニレンジアミンを使用した場合には、ゴム架橋物とした場合の20%引張応力に劣るものであった(製造例9、比較例5)。
また、アルキル化フェノール化合物(B)を配合した場合でも、70℃、7日間保存した後における可塑度η2と、保存前の可塑度η1との差(η2-η1)が12を超える場合には、キャピラリー押し出し性評価における押し出し量が少なく、加工性(流動性)に劣るものとなったり、さらには、ゴム架橋物とした場合の20%引張応力に劣るものであった(製造例10,11、比較例6,7)。
さらに、アルキル化フェノール化合物(B)の含有量が多すぎる場合には、ゴム架橋物とした場合の20%引張応力に劣るものであった(製造例12、比較例8)。
Claims (9)
- α,β-エチレン性不飽和ニトリル単量体単位を8~60重量%の割合で含有し、ヨウ素価が120以下である高飽和ニトリルゴム(A)と、
アルキル化フェノール化合物(B)とを含有し、
前記高飽和ニトリルゴム(A)と、前記アルキル化フェノール化合物(B)との合計に対する、前記アルキル化フェノール化合物(B)の含有割合が、0.01~1重量%であるニトリルゴム組成物であって、
水中に分散させて水分散液とした状態において、70℃、7日間保存した後における可塑度η2と、該保存前の可塑度η1との差(η2-η1)が12以下であることを特徴とするニトリルゴム組成物。 - 前記高飽和ニトリルゴム(A)と、前記アルキル化フェノール化合物(B)との合計に対する、前記アルキル化フェノール化合物(B)の含有割合が、0.01~0.95重量%である請求項1に記載のニトリルゴム組成物。
- 前記アルキル化フェノール化合物(B)が、下記一般式(1)で表される化合物、または下記一般式(2)で表される化合物である請求項1または2に記載のニトリルゴム組成物。
- α,β-エチレン性不飽和ニトリル単量体単位を8~60重量%の割合で含有し、ヨウ素価が120以下である高飽和ニトリルゴム(A)と、
アルキル化フェノール化合物(B)とを含有し、
前記高飽和ニトリルゴム(A)と、前記アルキル化フェノール化合物(B)との合計に対する、前記アルキル化フェノール化合物(B)の含有割合が、0.01~1重量%である高飽和ニトリルゴムのラテックス組成物であって、
70℃、7日間保存した後における凝固物の可塑度η2と、該保存前の凝固物の可塑度η1との差(η2-η1)が12以下であることを特徴とする高飽和ニトリルゴムのラテックス組成物。 - 前記高飽和ニトリルゴム(A)と、前記アルキル化フェノール化合物(B)との合計に対する、前記アルキル化フェノール化合物(B)の含有割合が、0.01~0.95重量%である請求項4に記載の高飽和ニトリルゴムのラテックス組成物。
- 前記アルキル化フェノール化合物(B)が、下記一般式(1)で表される化合物、または下記一般式(2)で表される化合物である請求項4または5に記載の高飽和ニトリルゴムのラテックス組成物。
- 請求項1~3のいずれかに記載のニトリルゴム組成物、または請求項4~6のいずれかに記載の高飽和ニトリルゴムのラテックス組成物を凝固して得られるニトリルゴム組成物に、架橋剤を配合してなる架橋性ニトリルゴム組成物。
- 有機短繊維をさらに含有する請求項7に記載の架橋性ニトリルゴム組成物。
- 請求項7または8に記載の架橋性ニトリルゴム組成物を架橋してなるゴム架橋物。
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JP7115317B2 (ja) | 2016-12-27 | 2022-08-09 | 日本ゼオン株式会社 | カルボキシル基含有ニトリルゴムおよびその製造方法、架橋性ニトリルゴム組成物およびゴム架橋物 |
CN110088154A (zh) * | 2016-12-27 | 2019-08-02 | 日本瑞翁株式会社 | 含羧基腈橡胶及其制造方法、交联性腈橡胶组合物和橡胶交联物 |
KR20190092495A (ko) * | 2016-12-27 | 2019-08-07 | 니폰 제온 가부시키가이샤 | 카르복실기 함유 니트릴 고무 및 그 제조 방법, 가교성 니트릴 고무 조성물 및 고무 가교물 |
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WO2020174857A1 (ja) * | 2019-02-26 | 2020-09-03 | 横浜ゴム株式会社 | マリンホース用ゴム組成物及びこれを用いたマリンホース |
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EP3225658B1 (en) | 2019-10-16 |
CA2968351C (en) | 2019-08-13 |
BR112017010446A2 (pt) | 2017-12-26 |
US20170327672A1 (en) | 2017-11-16 |
KR20170089874A (ko) | 2017-08-04 |
US10308793B2 (en) | 2019-06-04 |
HUE047528T2 (hu) | 2020-04-28 |
CN107001715A (zh) | 2017-08-01 |
JP6658537B2 (ja) | 2020-03-04 |
CN107001715B (zh) | 2019-08-13 |
MX2017006423A (es) | 2018-02-13 |
EP3225658A1 (en) | 2017-10-04 |
RU2664145C1 (ru) | 2018-08-15 |
CA2968351A1 (en) | 2016-06-02 |
BR112017010446B1 (pt) | 2022-04-05 |
JPWO2016084734A1 (ja) | 2017-09-07 |
ES2759774T3 (es) | 2020-05-12 |
KR102401457B1 (ko) | 2022-05-23 |
EP3225658A4 (en) | 2018-07-25 |
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