WO2018139466A1 - アクリルゴムの製造方法 - Google Patents
アクリルゴムの製造方法 Download PDFInfo
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- WO2018139466A1 WO2018139466A1 PCT/JP2018/002029 JP2018002029W WO2018139466A1 WO 2018139466 A1 WO2018139466 A1 WO 2018139466A1 JP 2018002029 W JP2018002029 W JP 2018002029W WO 2018139466 A1 WO2018139466 A1 WO 2018139466A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/002—Scale prevention in a polymerisation reactor or its auxiliary parts
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- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/14—Treatment of polymer emulsions
- C08F6/16—Purification
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/14—Treatment of polymer emulsions
- C08F6/22—Coagulation
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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
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
- C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
- C08J3/215—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase at least one additive being also premixed with a liquid phase
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- 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
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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
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
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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
- C08K5/134—Phenols containing ester groups
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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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
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/21—Rubbery or elastomeric properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2810/00—Chemical modification of a polymer
- C08F2810/20—Chemical modification of a polymer leading to a crosslinking, either explicitly or inherently
Definitions
- the present invention relates to a method for producing an acrylic rubber, and more specifically, a rubber cross-linked product that can appropriately suppress the occurrence of contamination of a polymerization apparatus during polymerization and that has high tensile strength and excellent heat resistance.
- the present invention relates to a method for producing acrylic rubber.
- Acrylic rubber is a polymer mainly composed of an acrylate ester and is generally known as a rubber excellent in heat resistance, oil resistance and ozone resistance, and is widely used in fields related to automobiles.
- Such an acrylic rubber is usually obtained by emulsion polymerization of a monomer mixture constituting the acrylic rubber, coagulating the resulting emulsion polymerization solution by adding a coagulant, and drying the hydrous crumb obtained by coagulation. (See, for example, Patent Document 1).
- the present invention has been made in view of such a situation, and can appropriately suppress the occurrence of contamination of the polymerization apparatus at the time of polymerization, and has a high tensile strength and excellent heat resistance.
- An object of the present invention is to provide a method for producing an acrylic rubber capable of providing
- the present inventors have prepared a solution of an anti-aging agent in an emulsion polymerization solution before coagulation obtained by emulsion polymerization of a monomer for forming an acrylic rubber. Or after adding in the state of a dispersion liquid, it discovered that the said objective can be achieved by coagulating, and came to complete this invention.
- a method for producing an acrylic rubber the emulsion polymerization step of obtaining an emulsion polymerization solution by emulsion polymerization of the monomer for forming the acrylic rubber, and the emulsion polymerization solution
- an anti-aging agent addition step of adding an anti-aging agent in the state of a solution or a dispersion and a coagulation step of adding a coagulant to the emulsion polymerization solution to which the anti-aging agent is added to obtain a hydrous crumb.
- a method for producing an acrylic rubber is provided.
- the acrylic rubber has an antiaging agent content of 500 ppm by weight or more.
- the acrylic rubber has an anti-aging content of 12,000 ppm by weight or less.
- the amount of the anti-aging agent added in the anti-aging agent adding step is 0.1 to 2 parts by weight with respect to 100 parts by weight of the acrylic rubber component contained in the emulsion polymerization liquid. It is preferable to do.
- the addition amount of the anti-aging agent in the anti-aging agent adding step is 0.2 to 1.2 wt. With respect to 100 parts by weight of the acrylic rubber component contained in the emulsion polymerization liquid. Part.
- the anti-aging agent is at least one selected from a phenol type anti-aging agent not containing a sulfur atom, a thiophenol type anti-aging agent, an amine type anti-aging agent and an imidazole type anti-aging agent.
- the antioxidant is stearyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,4-bis [(octylthio) methyl] -6-methyl.
- the anti-aging agent is preferably stearyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate.
- the anti-aging agent is preferably added in the form of an aqueous solution or an aqueous dispersion.
- the content of the anti-aging agent in the solution or the dispersion may be 10 to 90% by weight. preferable.
- the content of the anti-aging agent in the solution or the dispersion is preferably 20 to 60% by weight. preferable.
- the drying process which dries the said hydrous crumb at the temperature of 150 degreeC or more with a screw-type extrusion dryer or a hot air dryer.
- the emulsion polymerization of the monomer is preferably performed in the presence of a nonionic emulsifier and an anionic emulsifier.
- the nonionic emulsifier and the anionic emulsifier are preferably used in a weight ratio of nonionic emulsifier / anionic emulsifier of 50/50 to 75/25.
- a monomer, a polymerization initiator, and a reducing agent for forming the acrylic rubber are continuously dropped into the polymerization reaction system from the start of the polymerization reaction to an arbitrary time. It is preferable to carry out the emulsion polymerization reaction.
- the monomer for forming the acrylic rubber is in the state of a monomer emulsion mixed with an emulsifier and water, from the start of the polymerization reaction to an arbitrary time from the polymerization reaction system. It is preferable to carry out the emulsion polymerization reaction while continuously dropping the solution.
- blending a crosslinking agent with the acrylic rubber obtained by the said manufacturing method is provided. Furthermore, according to this invention, the manufacturing method of the rubber crosslinked material provided with the process of bridge
- a method for producing an acrylic rubber that can appropriately suppress the occurrence of contamination of a polymerization apparatus during polymerization and that can provide a crosslinked rubber product having high tensile strength and excellent heat resistance.
- the acrylic rubber manufactured by the manufacturing method of this invention is demonstrated.
- the acrylic rubber produced by the production method of the present invention is a (meth) acrylic acid ester as a main component in the molecule (in the present invention, it has 50% by weight or more in the total monomer units of rubber).
- Monomer meaning acrylic acid ester monomer and / or methacrylic acid ester monomer. The same applies to methyl (meth) acrylate.
- the (meth) acrylic acid ester monomer that forms the (meth) acrylic acid ester monomer unit that is the main component of the acrylic rubber produced by the production method of the present invention is not particularly limited. ) Acrylic acid alkyl ester monomer and (meth) acrylic acid alkoxyalkyl ester monomer.
- the (meth) acrylic acid alkyl ester monomer is not particularly limited, but is preferably an ester of an alkanol having 1 to 8 carbon atoms and (meth) acrylic acid, specifically, methyl (meth) acrylate, ( (Meth) ethyl acrylate, (meth) acrylic acid n-propyl, (meth) acrylic acid isopropyl, (meth) acrylic acid n-butyl, (meth) acrylic acid isobutyl, (meth) acrylic acid n-hexyl, (meth) Examples include 2-ethylhexyl acrylate and cyclohexyl (meth) acrylate.
- ethyl (meth) acrylate and n-butyl (meth) acrylate are preferable, and ethyl acrylate and n-butyl acrylate are particularly preferable. These can be used alone or in combination of two or more.
- the (meth) acrylic acid alkoxyalkyl ester monomer is not particularly limited, but an ester of an alkoxyalkyl alcohol having 2 to 8 carbon atoms and (meth) acrylic acid is preferable.
- (meth) acrylic acid Methoxymethyl, ethoxymethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-propoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate , 3-methoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, and the like.
- 2-ethoxyethyl (meth) acrylate and 2-methoxyethyl (meth) acrylate are preferable, and 2-ethoxyethyl acrylate and 2-methoxyethyl acrylate are particularly preferable. These can be used alone or in combination of two or more.
- the content of the (meth) acrylic acid ester monomer unit in the acrylic rubber produced by the production method of the present invention is usually from 50 to 99.9% by weight, preferably from 60 to 99.5% by weight. Preferably, it is 70 to 99.5% by weight. If the content of the (meth) acrylic acid ester monomer unit is too small, the weather resistance, heat resistance and oil resistance of the resulting rubber cross-linked product may be lowered. There is a risk that the heat resistance of the object will decrease.
- (meth) acrylic acid ester monomer unit (meth) acrylic acid alkyl ester monomer unit 30 to 100% by weight, and (meth) acrylic It is preferable to use an acid alkoxyalkyl ester monomer unit comprising 70 to 0% by weight.
- the acrylic rubber produced by the production method of the present invention may contain a crosslinkable monomer unit, if necessary, in addition to the (meth) acrylic acid alkoxyalkyl ester monomer unit.
- the crosslinkable monomer that forms the crosslinkable monomer unit is not particularly limited. For example, an ⁇ , ⁇ -ethylenically unsaturated carboxylic acid monomer; a monomer having an epoxy group; a halogen atom Monomer; diene monomer; and the like.
- the ⁇ , ⁇ -ethylenically unsaturated carboxylic acid monomer that forms the ⁇ , ⁇ -ethylenically unsaturated carboxylic acid monomer unit is not particularly limited, but examples thereof include ⁇ , ⁇ - having 3 to 12 carbon atoms.
- the acrylic rubber By using the ⁇ , ⁇ -ethylenically unsaturated carboxylic acid monomer, the acrylic rubber can be converted into a carboxyl group-containing acrylic rubber having a carboxyl group as a crosslinking point, and thus a rubber cross-linked product can be obtained. Further, the compression set resistance can be further improved.
- ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid having 3 to 12 carbon atoms include acrylic acid, methacrylic acid, ⁇ -ethylacrylic acid, crotonic acid, and cinnamic acid.
- ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid having 4 to 12 carbon atoms include butenedionic acid such as fumaric acid and maleic acid; itaconic acid; citraconic acid; chloromaleic acid;
- monoesters of ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acids having 4 to 12 carbon atoms and alkanols having 1 to 8 carbon atoms include monomethyl fumarate, monoethyl fumarate, mono n-butyl fumarate, malein Butenedionic acid mono-chain alkyl esters such as monomethyl acid, monoethyl maleate, and mono-n-butyl maleate; monocyclopentyl fumarate, monocyclohexyl fumarate, monocyclohexenyl fumarate, monocyclopentyl maleate, monocyclohexyl maleate, maleate And butenedionic acid monoesters having an alicyclic structure such
- Epoxy group containing (meth) acrylic acid ester such as glycidyl (meth) acrylate
- Epoxy group containing ethers such as allyl glycidyl ether and vinyl glycidyl ether; Is mentioned.
- unsaturated alcohol ester of a halogen-containing saturated carboxylic acid For example, unsaturated alcohol ester of a halogen-containing saturated carboxylic acid, (meth) acrylic acid haloalkyl ester, (meth) acrylic acid haloacyloxyalkyl ester, (meth) acrylic Examples include acid (haloacetylcarbamoyloxy) alkyl esters, halogen-containing unsaturated ethers, halogen-containing unsaturated ketones, halomethyl group-containing aromatic vinyl compounds, halogen-containing unsaturated amides, and haloacetyl group-containing unsaturated monomers.
- the unsaturated alcohol ester of a halogen-containing saturated carboxylic acid include vinyl chloroacetate, vinyl 2-chloropropionate, and allyl chloroacetate.
- Specific examples of (meth) acrylic acid haloalkyl esters include chloromethyl (meth) acrylate, 1-chloroethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, 1,2-dichloroethyl (meth) acrylate. , 2-chloropropyl (meth) acrylate, 3-chloropropyl (meth) acrylate, and 2,3-dichloropropyl (meth) acrylate.
- (meth) acrylic acid haloacyloxyalkyl esters include 2- (chloroacetoxy) ethyl (meth) acrylate, 2- (chloroacetoxy) propyl (meth) acrylate, and 3- (chloro) (meth) acrylic acid. Acetoxy) propyl and 3- (hydroxychloroacetoxy) propyl (meth) acrylate.
- (meth) acrylic acid (haloacetylcarbamoyloxy) alkyl esters include 2- (chloroacetylcarbamoyloxy) ethyl (meth) acrylate and 3- (chloroacetylcarbamoyloxy) propyl (meth) acrylate Is mentioned.
- halogen-containing unsaturated ether examples include chloromethyl vinyl ether, 2-chloroethyl vinyl ether, 3-chloropropyl vinyl ether, 2-chloroethyl allyl ether, and 3-chloropropyl allyl ether.
- halogen-containing unsaturated ketone examples include 2-chloroethyl vinyl ketone, 3-chloropropyl vinyl ketone, and 2-chloroethyl allyl ketone.
- halomethyl group-containing aromatic vinyl compound examples include p-chloromethylstyrene, m-chloromethylstyrene, o-chloromethylstyrene, and p-chloromethyl- ⁇ -methylstyrene.
- halogen-containing unsaturated amide examples include N-chloromethyl (meth) acrylamide.
- haloacetyl group-containing unsaturated monomer examples include 3- (hydroxychloroacetoxy) propyl allyl ether and p-vinylbenzyl chloroacetate.
- Examples of the diene monomer include conjugated diene monomers and non-conjugated diene monomers.
- Specific examples of the conjugated diene monomer include 1,3-butadiene, isoprene, and piperylene.
- Specific examples of the non-conjugated diene monomer include ethylidene norbornene, dicyclopentadiene, dicyclopentadienyl (meth) acrylate, and 2-dicyclopentadienyl ethyl (meth) acrylate. .
- the acrylic rubber when an ⁇ , ⁇ -ethylenically unsaturated carboxylic acid monomer is used, the acrylic rubber can be a carboxyl group-containing acrylic rubber. By making the acrylic rubber into a carboxyl group-containing acrylic rubber, it is possible to improve the compression set resistance while improving the oil resistance and heat resistance.
- the content of the crosslinkable monomer unit in the acrylic rubber produced by the production method of the present invention is preferably 0.1 to 10% by weight, more preferably 0.5 to 7% by weight, still more preferably 0. .5-5% by weight.
- the acrylic rubber produced by the production method of the present invention includes (meth) acrylic acid ester monomer units and other monomer units copolymerizable with these in addition to the crosslinkable monomer units used as necessary. You may have a unit of a mer.
- Such other copolymerizable monomers include aromatic vinyl monomers, ⁇ , ⁇ -ethylenically unsaturated nitrile monomers, acrylamide monomers, and other olefin monomers. Can be mentioned.
- aromatic vinyl monomers examples include styrene, ⁇ -methylstyrene, divinylbenzene and the like.
- Examples of the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer include acrylonitrile and methacrylonitrile.
- Examples of acrylamide monomers include acrylamide and methacrylamide.
- Other olefinic monomers include ethylene, propylene, vinyl chloride, vinylidene chloride, vinyl acetate, ethyl vinyl ether, butyl vinyl ether, and the like.
- styrene, acrylonitrile, methacrylonitrile, ethylene and vinyl acetate are preferable, and acrylonitrile, methacrylonitrile and ethylene are more preferable.
- the method for producing the acrylic rubber of the present invention comprises: An emulsion polymerization step of obtaining an emulsion polymerization liquid by emulsion polymerization of the monomer for forming the acrylic rubber; and An anti-aging agent adding step of adding an anti-aging agent to the emulsion polymerization solution in a solution or dispersion state; A coagulation step of adding a coagulant to the emulsion polymerization liquid to which the anti-aging agent is added to obtain a hydrous crumb.
- the emulsion polymerization step in the production method of the present invention is a step of obtaining an emulsion polymerization solution by emulsion polymerization of a monomer for forming an acrylic rubber.
- an ordinary method may be used, and an emulsifier, a polymerization initiator, a polymerization terminator and the like can be used according to a conventional method.
- the emulsifier is not particularly limited.
- polyoxyethylene alkyl ethers such as polyoxyethylene dodecyl ether, polyoxyethylene alkyl phenol ethers such as polyoxyethylene nonylphenyl ether, and polyoxyethylene alkyls such as polyoxyethylene stearate.
- Nonionic emulsifiers such as esters, polyoxyethylene sorbitan alkyl esters, polyethylene oxide polypropylene oxide copolymers such as polyethylene oxide polypropylene oxide glycol; salts of fatty acids such as myristic acid, palmitic acid, oleic acid, linolenic acid, dodecylbenzenesulfonic acid Alkylbenzene sulfonates such as sodium, higher alcohol sulfates such as sodium lauryl sulfate, Higher phosphate ester salts such as Rukirurin ester sodium, anionic emulsifiers such as alkyl sulfosuccinate salts; and the like; alkyl trimethyl ammonium chloride, dialkyl ammonium chloride, cationic emulsifiers such as ammonium chloride.
- emulsifiers can be used alone or in combination of two or more.
- nonionic emulsifiers polyoxyethylene polypropylene glycol, polyethylene glycol monostearate, polyoxyethylene alkyl ether, and polyoxyethylene alkylphenol ether are preferable.
- nonionic emulsifier those having a weight average molecular weight of less than 10,000 are preferable, those having a weight average molecular weight of 500 to 8000 are more preferable, and those having a weight average molecular weight of 600 to 5000 are more preferable.
- anionic emulsifiers higher phosphate ester salts and higher alcohol sulfate ester salts are preferred.
- emulsifiers at least one of a nonionic emulsifier and an anionic emulsifier is preferable, an anionic emulsifier is more preferably included, and a nonionic emulsifier and an anionic emulsifier are more preferably used in combination.
- a combination of a nonionic emulsifier and an anionic emulsifier coagulation described later can be achieved while effectively suppressing the occurrence of soiling due to adhesion of polymer aggregates to a polymerization apparatus (for example, a polymerization tank) during emulsion polymerization. It is possible to reduce the amount of coagulant used in the process, and as a result, the amount of coagulant in the acrylic rubber finally obtained can be reduced, thereby improving the water resistance of the resulting rubber cross-linked product. Can be made.
- the emulsifying action can be enhanced, so that the amount of the emulsifier itself can also be reduced, and as a result, in the acrylic rubber finally obtained
- the residual amount of the emulsifier contained in can be reduced, whereby the water resistance of the resulting acrylic rubber can be further increased.
- the use amount of the emulsifier is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 4 parts by weight, based on the total amount of the emulsifier to be used with respect to 100 parts by weight of the monomer used for the polymerization. More preferably, it is 1 to 3 parts by weight. Further, when the nonionic emulsifier and the anionic emulsifier are used in combination, the amount of the nonionic emulsifier used is more than 0 parts by weight, preferably 4 parts by weight or less, preferably 100 parts by weight of the monomer used for the polymerization.
- the weight ratio of the nonionic emulsifier / anionic emulsifier is preferably 1/99 to 99/1, and preferably 10/90 to 80/20. More preferred is 25/75 to 75/25, still more preferred is 50/50 to 75/25, and even more preferred is 65/35 to 75/25.
- azo compounds such as azobisisobutyronitrile; organic peroxides such as diisopropylbenzene hydroperoxide, cumene hydroperoxide, paramentane hydroperoxide, benzoyl peroxide; sodium persulfate, persulfate Inorganic peroxides such as potassium, hydrogen peroxide, and ammonium persulfate; can be used.
- organic peroxides such as diisopropylbenzene hydroperoxide, cumene hydroperoxide, paramentane hydroperoxide, benzoyl peroxide
- sodium persulfate persulfate
- persulfate Inorganic peroxides such as potassium, hydrogen peroxide, and ammonium persulfate
- the organic peroxide and the inorganic peroxide as the polymerization initiator as a redox polymerization initiator in combination with a reducing agent.
- a reducing agent used in combination
- the compound containing metal ions in a reduced state such as ferrous sulfate, sodium hexamethylenediamine tetraacetate, cuprous naphthenate; ascorbic acid, sodium ascorbate Ascorbic acid (salt) such as potassium ascorbate; Erythorbic acid (salt) such as erythorbic acid, sodium erythorbate, potassium erythorbate; saccharides; Sulphinates such as sodium hydroxymethanesulfinate; Sodium hydrogen hydride, sodium aldehyde sodium hydrogen sulfite, potassium hydrogen sulfite; pyrosulfites such as sodium pyrosulfite, potassium pyrosulfite, sodium hydrogen bisulfit
- polymerization terminator examples include hydroxylamine, hydroxylamine sulfate, diethylhydroxylamine, hydroxylaminesulfonic acid and its alkali metal salt, sodium dimethyldithiocarbamate, hydroquinone and the like.
- the amount of the polymerization terminator used is not particularly limited, but is preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of the monomer used for the polymerization.
- the amount of water used is preferably 80 to 500 parts by weight, more preferably 100 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 molecular weight adjusting agent, a particle size adjusting agent, a chelating agent, and an oxygen scavenger can be used as necessary.
- the emulsion polymerization may be carried out by any of batch, semi-batch and continuous methods, but the semi-batch method is preferred. Specifically, in the reaction system containing the polymerization initiator and the reducing agent, the polymerization reaction is performed while continuously dropping the monomer used for the polymerization to the polymerization reaction system from the start of the polymerization reaction to an arbitrary time.
- the polymerization reaction is preferable to perform the polymerization reaction while continuously dropping into the polymerization reaction system from the start of the polymerization reaction to any time, It is more preferable to perform the polymerization reaction while continuously dropping the monomer, polymerization initiator, and reducing agent used for the polymerization from the start of the polymerization reaction to an arbitrary time while continuously dropping into the polymerization reaction system.
- the polymerization is usually performed in a temperature range of 0 to 70 ° C., preferably 5 to 50 ° C.
- the monomer used for polymerization is mixed with an emulsifier and water to form a monomer emulsion, It is preferable to drop continuously in the state of an emulsion.
- the method for preparing the monomer emulsion is not particularly limited, and includes a method of stirring the total amount of monomers used for polymerization, the total amount of emulsifier, and water using a stirrer such as a homomixer or a disk turbine. Can be mentioned.
- the amount of water used in the monomer emulsion is preferably 10 to 70 parts by weight, more preferably 20 to 50 parts by weight with respect to 100 parts by weight of the monomer used for the polymerization.
- the polymerization reaction when the polymerization reaction is carried out while continuously dropping into the polymerization reaction system from the start of the polymerization reaction to an arbitrary time for all of the monomer, polymerization initiator, and reducing agent used for the polymerization, these are separate. Or at least the polymerization initiator and the reducing agent may be mixed in advance and, if necessary, dropped into the polymerization system from the same dropping device as an aqueous solution. May be. After completion of dropping, the reaction may be continued for an arbitrary time in order to further improve the polymerization reaction rate.
- the anti-aging agent adding step in the production method of the present invention is a step of adding the anti-aging agent in the state of a solution or a dispersion to the emulsion polymerization solution obtained in the emulsion polymerization step before coagulation. .
- an anti-aging agent is added in the form of a solution or a dispersion to the emulsion polymerization liquid after emulsion polymerization and before coagulation.
- the resulting acrylic rubber is given a rubber cross-linked product having high tensile strength and excellent heat resistance while appropriately suppressing the occurrence of contamination due to adhesion of polymer aggregates to the polymerization apparatus (eg, polymerization tank) in It can be.
- the anti-aging agent is uniformly dispersed in the emulsion polymerization liquid by adding the anti-aging agent in a solution or dispersion state to the emulsion polymerization liquid after the emulsion polymerization and before coagulation.
- the anti-aging agent can be uniformly dispersed in the acrylic rubber (hydrous crumb) after coagulation in the coagulation step described later. And thereby, the effect of adding the anti-aging agent can be sufficiently exhibited, and it becomes possible to effectively suppress deterioration of the acrylic rubber due to heating in the drying step after coagulation, and as a result, the drying step The decrease in Mooney viscosity (polymer Mooney) due to heating in can be suppressed.
- an acrylic rubber that does not contain an anti-aging agent or an acrylic rubber that contains an anti-aging agent but has insufficient dispersion of the anti-aging agent
- Heat degradation due to heating in the drying step results in a decrease in Mooney viscosity, resulting in a problem that the tensile strength of the resulting rubber cross-linked product is decreased.
- an anti-aging agent is added before emulsion polymerization, aggregates are generated in the emulsion polymerization liquid obtained as a result of emulsion polymerization, and the generated aggregates are Adhesion causes contamination of the polymerization apparatus, resulting in a problem that productivity is lowered.
- the antioxidant is added in the form of a solution or a dispersion to the emulsion polymerization liquid after emulsion polymerization and before coagulation.
- the acrylic rubber obtained can be provided with a crosslinked rubber having high tensile strength and excellent heat resistance while appropriately suppressing the occurrence of contamination of the polymerization apparatus during polymerization. .
- an anti-aging agent is added in a state of a solution or a dispersion to the emulsion polymerization liquid after emulsion polymerization and before coagulation, which will be described later. Since the anti-aging agent can be uniformly dispersed in the acrylic rubber (hydrous crumb) after coagulation in the coagulation step, the coagulant can be appropriately removed in the water washing step after coagulation. And thereby, the amount of ash mainly attributable to the coagulant in the resulting acrylic rubber can be reduced, and as a result, the reduction in water resistance due to such ash can also be appropriately improved. Is.
- the antiaging agent is not particularly limited, but 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butylphenol, butylhydroxyanisole, 2,6-di-t-butyl- Styrenation of ⁇ -dimethylamino-p-cresol, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, mono (or di, or tri) ( ⁇ -methylbenzyl) phenol Phenol, 2,2'-methylene-bis (6- ⁇ -methyl-benzyl-p-cresol), 4,4'-methylenebis (2,6-di-t-butylfunol), 2,2'-methylene-bis (4-methyl-6-tert-butylphenol), 3- (3,5-di-tert-butyl-4-hydroxyphenyl) stearyl propionate, alkylated bi Phenolic antioxidants containing no sulfur atom such as phenol,
- anti-aging agents may be used alone or in combination of two or more.
- phenol-based anti-aging agents containing no sulfur atom thiophenol-based anti-aging agents, amine-based anti-aging agents, and imidazole-based anti-aging agents are preferred, and 3- (3,5-di-tert.
- a solvent used when adding an antioxidant in the state of a solution or a dispersion For example, water; Alcohols, such as methanol, ethanol, isopropyl alcohol; Butane, pentane, hexane, heptane, etc. Chain aliphatic hydrocarbons; cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene;
- the content of the anti-aging agent in the solution or dispersion is preferably 10 to 90% by weight, more preferably 15 to 70% by weight. %, More preferably 20 to 60% by weight, particularly preferably 35 to 60% by weight.
- the addition amount of the anti-aging agent in the anti-aging agent adding step is preferably 0.1 to 2 parts by weight, more preferably 0.2 to 1.2 parts with respect to 100 parts by weight of the acrylic rubber component in the emulsion polymerization liquid. Parts by weight.
- an anti-aging agent is added in the form of a solution or a dispersion to the emulsion polymerization liquid after emulsion polymerization and before coagulation, thereby preventing aging. Since the agent can be uniformly dispersed, the effect of the addition can be sufficiently exhibited even with such a relatively small addition amount.
- the anti-aging agent is added to the emulsion polymerization liquid after the emulsion polymerization and before the coagulation, the added anti-aging agent is substantially used in the subsequent coagulation, washing, drying, etc. Since it is not removed, even when it is added to the emulsion polymerization solution, the effect of addition can be sufficiently exhibited.
- the compounding agents to be blended with acrylic rubber specifically, a lubricant and / or an ethylene oxide type
- the polymer is also preferably contained in advance in the emulsion polymerization liquid before coagulation.
- the resulting acrylic rubber can be contained in a state in which the lubricant is well dispersed.
- the resulting acrylic rubber Can be appropriately reduced, thereby preventing adhesion to the dryer during drying, improving operability during drying, and the resulting acrylic rubber, It can be excellent in roll processability.
- the amount of lubricant added is preferably 0.1 to 0.4 parts by weight, more preferably 0.15 to 0.3 parts by weight, and still more preferably 0 to 100 parts by weight of the acrylic rubber component in the emulsion polymerization liquid. .2 to 0.3 parts by weight.
- the lubricant is not particularly limited, and examples thereof include phosphate esters, fatty acid esters, fatty acid amides, and higher fatty acids.
- examples of the method for incorporating the lubricant into the emulsion polymerization liquid include a method of adding to the emulsion polymerization liquid after emulsion polymerization and before coagulation, and a method of adding to the solution before emulsion polymerization. It is done.
- the ethylene oxide polymer may be a polymer having a polyethylene oxide structure as the main chain structure, and is not particularly limited, and examples thereof include polyethylene oxide, polypropylene oxide, ethylene oxide / propylene oxide copolymer, and the like. Ethylene oxide is preferred.
- the blending amount of the ethylene oxide polymer is preferably 0.01 to 1 part by weight, more preferably 0.01 to 0.6 part by weight, still more preferably 100 parts by weight of the acrylic rubber component in the emulsion polymerization liquid. 0.02 to 0.5 parts by weight.
- the weight average molecular weight of the ethylene oxide polymer is preferably 10,000 to 1,000,000, more preferably 10,000 to 200,000, and still more preferably 20,000 to 120,000.
- a method of adding an ethylene oxide polymer to an emulsion polymerization solution it is added to an emulsion polymerization solution after emulsion polymerization and before coagulation, or added to a solution before emulsion polymerization. A method is mentioned.
- a lubricant and / or an ethylene oxide polymer is added to the emulsion polymerization liquid after emulsion polymerization and before coagulation in addition to the anti-aging agent in the state of the solution or dispersion.
- the order is not particularly limited, and may be selected as appropriate.
- the coagulation step in the production method of the present invention is a step of obtaining a hydrous crumb by adding a coagulant to the emulsion polymerization liquid obtained by the emulsion polymerization step.
- the coagulant is not particularly limited, and examples thereof include monovalent to trivalent metal salts.
- the monovalent to trivalent metal salt is a salt containing a metal that becomes a monovalent to trivalent metal ion when dissolved in water, and is not particularly limited.
- an inorganic acid selected from hydrochloric acid, nitric acid, sulfuric acid, and the like
- a salt of an organic acid such as acetic acid or the like with a metal selected from sodium, potassium, lithium, magnesium, calcium, zinc, titanium, manganese, iron, cobalt, nickel, aluminum, tin and the like.
- hydroxides of these metals can also be used.
- monovalent to trivalent metal salts include sodium chloride, potassium chloride, lithium chloride, magnesium chloride, calcium chloride, zinc chloride, titanium chloride, manganese chloride, iron chloride, cobalt chloride, nickel chloride, aluminum chloride, and chloride.
- Metal chlorides such as tin; nitrates such as sodium nitrate, potassium nitrate, lithium nitrate, magnesium nitrate, calcium nitrate, zinc nitrate, titanium nitrate, manganese nitrate, iron nitrate, cobalt nitrate, nickel nitrate, aluminum nitrate, tin nitrate; sodium sulfate And sulfates such as potassium sulfate, lithium sulfate, magnesium sulfate, calcium sulfate, zinc sulfate, titanium sulfate, manganese sulfate, iron sulfate, cobalt sulfate, nickel sulfate, aluminum sulfate and tin sulfate; Among these, calcium chloride, sodium chloride, aluminum sulfate, magnesium chloride, magnesium sulfate, zinc chloride, zinc sulfate, and sodium sulfate are prefer
- monovalent or divalent metal salts are preferable, calcium chloride, sodium chloride, magnesium sulfate, and sodium sulfate are more preferable, and magnesium sulfate and sodium sulfate are more preferable. Moreover, these can be used individually by 1 type or in combination of multiple types.
- the use amount of the coagulant can reduce the residual amount of the coagulant in the acrylic rubber finally obtained while making the coagulation of the acrylic rubber sufficient, and in this way, when the rubber cross-linked product is obtained.
- the amount is preferably 1 to 100 parts by weight, more preferably 2 to 40 parts by weight, and still more preferably 100 parts by weight of the acrylic rubber component in the emulsion polymerization liquid. 3 to 20 parts by weight, particularly preferably 3 to 12 parts by weight. If the amount of the coagulant used is too small, coagulation becomes insufficient and the yield of acrylic rubber deteriorates. On the other hand, if the amount is too large, the residual amount of coagulant in the finally obtained acrylic rubber increases. Too much water resistance.
- the solidification temperature is not particularly limited, but is preferably 50 to 90 ° C, more preferably 60 to 90 ° C, and still more preferably 78 to 90 ° C.
- the washing method is not particularly limited, and examples thereof include a method of washing with water by using water as a washing liquid and mixing the added water together with the hydrated crumb.
- the temperature at the time of washing with water is not particularly limited, but is preferably 5 to 60 ° C., more preferably 10 to 50 ° C., and the mixing time is 1 to 60 minutes, more preferably 2 to 30 minutes.
- the amount of water to be added to the hydrated crumb at the time of washing with water is not particularly limited, but from the viewpoint that the residual amount of coagulant in the finally obtained acrylic rubber can be effectively reduced,
- the amount of water per washing is preferably 50 to 9,800 parts by weight, more preferably 300 to 1,800 parts per 100 parts by weight of the solid content (mainly acrylic rubber component) contained in the hydrous crumb. Parts by weight.
- the number of times of washing with water is not particularly limited, and may be one, but is preferably 2 to 10 times, more preferably 3 to 8 from the viewpoint of reducing the residual amount of coagulant in the finally obtained acrylic rubber. Times.
- the number of washings is in the above range because the influence of the decrease in productivity is increased by increasing the number of steps.
- acid washing using an acid as a washing solution may be performed.
- the compression set resistance in the case of a rubber cross-linked product can be further improved.
- the acrylic rubber is a carboxyl group-containing acrylic rubber having a carboxyl group, this acid cleaning
- the effect of improving the compression set resistance is particularly great.
- the acid used for the acid cleaning is not particularly limited, and sulfuric acid, hydrochloric acid, phosphoric acid and the like can be used without limitation.
- the acid washing method is not particularly limited, and examples thereof include a method of mixing an aqueous solution of the added acid together with water-containing crumb.
- the temperature during the acid cleaning is not particularly limited, but is preferably 5 to 60 ° C., more preferably 10 to 50 ° C., and the mixing time is 1 to 60 minutes, more preferably 2 to 30 minutes.
- the pH of the acid-washed wash water can be determined, for example, by measuring the pH of the water contained in the hydrous crumb after the acid wash.
- the water washing conditions may be the same as those described above.
- the drying method in the drying step is not particularly limited.
- a single screw or twin screw extruder, a kneader dryer, an expander dryer, a hot air dryer, a vacuum dryer, or the like is used. And can be dried. Moreover, you may use the drying method which combined these.
- the water-containing crumb may be filtered using a sieve such as a rotary screen or a vibrating screen; a centrifugal dehydrator; Among these, it is preferable to perform drying with a screw-type extruder or hot air dryer, and the drying temperature in this case is preferably 150 ° C. or higher, and preferably 160 ° C. or higher.
- the upper limit of the drying temperature is not particularly limited, but is 180 ° C. or lower.
- the anti-aging agent is added in the form of a solution or a dispersion to the emulsion polymerization liquid after emulsion polymerization and before coagulation.
- the anti-aging agent can be uniformly dispersed therein, whereby the effect of adding the anti-aging agent can be sufficiently exhibited. Therefore, even when drying is performed at a relatively high temperature as described above, the drying time can be shortened while appropriately suppressing the occurrence of deterioration due to drying, and as a result, productivity can be improved. .
- acrylic rubber can be obtained as described above.
- the Mooney viscosity (ML1 + 4, 100 ° C.) of the acrylic rubber thus produced is preferably 10 to 80, more preferably 20 to 70, and further preferably 25 to 60.
- the content of the anti-aging agent contained in the acrylic rubber is preferably 500 ppm by weight or more, more preferably 1,000 ppm by weight or more, and still more preferably. Is 2,000 ppm by weight or more.
- the upper limit of the content of the antiaging agent is not particularly limited, but is usually 5,000 ppm by weight or less.
- the residual amount of coagulant contained in the acrylic rubber is preferably 10,000 ppm by weight or less, more preferably 7,000 ppm by weight or less, Preferably it is 5,000 weight ppm or less, Most preferably, it is 3,500 weight ppm or less.
- the lower limit of the residual amount of the coagulant is not particularly limited, but is preferably 10 ppm by weight or more.
- the residual coagulant in the acrylic rubber can be reduced.
- a method of reducing the amount is also conceivable, since coagulation becomes insufficient and the recovery rate of acrylic rubber is deteriorated or it is necessary to increase washing with water, from the viewpoint of stable production, the coagulant in acrylic rubber
- the residual amount is preferably 200 ppm by weight or more, more preferably 500 ppm by weight or more.
- the residual amount of the coagulant can be determined, for example, by performing elemental analysis on acrylic rubber and measuring the content of the element contained in the coagulant.
- the method of setting the residual amount of the coagulant as described above is not particularly limited, and examples thereof include a method of setting the addition amount of the coagulant as described above, a method of adjusting the washing conditions as described above, and the like. It is done.
- the residual amount of the emulsifier contained in the acrylic rubber is preferably 22,000 ppm by weight or less, more preferably 20,000 ppm by weight or less, and further preferably Is 18,000 ppm by weight or less, particularly preferably 17,000 ppm by weight or less.
- the minimum of the residual amount of an emulsifier is not specifically limited, Preferably it is 10 weight ppm or more, More preferably, it is 200 weight ppm or more, More preferably, it is 500 weight ppm or more.
- the residual amount of an emulsifier can be calculated
- the method of setting the residual amount of the emulsifier as described above is not particularly limited.
- a nonionic emulsifier and an anionic emulsifier are used in combination as the emulsifier, and the addition amount thereof is described above. The method of making it into the range which was carried out is mentioned.
- the acrylic rubber produced by the production method of the present invention preferably contains a coagulant as described above, but the acrylic rubber component contained in the acrylic rubber produced by the production method of the present invention.
- the amount is preferably 95% by weight or more, more preferably 97% by weight or more, and still more preferably 98% by weight or more. That is, the acrylic rubber produced by the production method of the present invention preferably contains 95% by weight or more (more preferably 97% by weight or more, more preferably 98% by weight or more) of an acrylic rubber component. It can also be said.
- the acrylic rubber composition of the present invention is obtained by blending a crosslinking agent with the acrylic rubber obtained by the above-described production method of the present invention.
- crosslinking agent for example, polyvalent amine compounds, such as a diamine compound, and its carbonate; Sulfur; Sulfur donor; Triazine thiol compound; Polyvalent epoxy compound; Organic carboxylic acid ammonium salt; Conventionally known crosslinking agents such as a compound, dithiocarbamic acid metal salt, polyvalent carboxylic acid, quaternary onium salt, imidazole compound, isocyanuric acid compound, organic peroxide, and the like can be used. These crosslinking agents can be used alone or in combination of two or more. The crosslinking agent is preferably selected as appropriate according to the type of the crosslinkable monomer unit.
- the acrylic rubber produced by the production method of the present invention has an ⁇ , ⁇ -ethylenically unsaturated carboxylic acid monomer unit as a crosslinkable monomer unit, as a crosslinking agent, It is preferable to use a polyvalent amine compound and a carbonate thereof.
- the polyvalent amine compound and carbonate thereof are not particularly limited, but polyvalent amine compounds having 4 to 30 carbon atoms and carbonates thereof are preferred. Examples of such polyvalent amine compounds and carbonates thereof include aliphatic polyvalent amine compounds, carbonates thereof, and aromatic polyvalent amine compounds.
- the aliphatic polyvalent amine compound and the carbonate thereof are not particularly limited, and examples thereof include hexamethylene diamine, hexamethylene diamine carbamate, and N, N′-dicinnamylidene-1,6-hexane diamine. Among these, hexamethylenediamine carbamate is preferable.
- the aromatic polyvalent amine compound is not particularly limited.
- the content of the crosslinking agent in the acrylic rubber composition of the present invention is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, and particularly preferably 0.1 parts by weight with respect to 100 parts by weight of the acrylic rubber. 2 to 4 parts by weight.
- the acrylic rubber composition of the present invention preferably further contains a crosslinking accelerator.
- the crosslinking accelerator is not particularly limited, but the acrylic rubber produced by the production method of the present invention has a carboxyl group as a crosslinkable group, and the crosslinking agent is a polyvalent amine compound or carbonic acid thereof.
- the crosslinking agent is a polyvalent amine compound or carbonic acid thereof.
- a salt guanidine compound, diazabicycloalkene compound, imidazole compound, quaternary onium salt, tertiary phosphine compound, aliphatic monovalent secondary amine compound, aliphatic monovalent tertiary amine compound, etc. Can be used.
- guanidine compounds diazabicycloalkene compounds, and aliphatic monovalent secondary amine compounds are preferable, and guanidine compounds are particularly preferable.
- These basic crosslinking accelerators can be used singly or in combination of two or more.
- guanidine compound examples include 1,3-di-o-tolylguanidine, 1,3-diphenylguanidine and the like.
- diazabicycloalkene compound examples include 1,8-diazabicyclo [5.4.0] unde-7-cene, 1,5-diazabicyclo [4.3.0] no-5-ene and the like.
- imidazole compound examples include 2-methylimidazole and 2-phenylimidazole.
- quaternary onium salt include tetra n-butylammonium bromide and octadecyltri n-butylammonium bromide.
- tertiary phosphine compound include triphenylphosphine and tri-p-tolylphosphine.
- An aliphatic monovalent secondary amine compound is a compound in which two hydrogen atoms of ammonia are substituted with an aliphatic hydrocarbon group.
- the aliphatic hydrocarbon group substituted for the hydrogen atom is preferably one having 1 to 30 carbon atoms.
- aliphatic monovalent secondary amine compound examples include dimethylamine, diethylamine, dipropylamine, diallylamine, diisopropylamine, di-n-butylamine, di-t-butylamine, di-sec-butylamine, dihexylamine, di Examples include heptylamine, dioctylamine, dinonylamine, didecylamine, diundecylamine, didodecylamine, ditridecylamine, ditetradecylamine, dipentadecylamine, dicetylamine, di-2-ethylhexylamine, and dioctadecylamine.
- An aliphatic monovalent tertiary amine compound is a compound in which all three hydrogen atoms of ammonia are substituted with an aliphatic hydrocarbon group.
- the aliphatic hydrocarbon group substituted for the hydrogen atom is preferably one having 1 to 30 carbon atoms.
- Specific examples of the aliphatic monovalent tertiary amine compound include trimethylamine, triethylamine, tripropylamine, triallylamine, triisopropylamine, tri-n-butylamine, tri-t-butylamine, tri-sec-butylamine, trihexylamine. , Triheptylamine, trioctylamine, trinonylamine, tridecylamine, triundecylamine, and tridodecylamine.
- the content of the crosslinking accelerator in the acrylic rubber composition of the present invention is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 7.5 parts by weight with respect to 100 parts by weight of the acrylic rubber. Parts, particularly preferably 1 to 5 parts by weight.
- the acrylic rubber composition of the present invention can contain a compounding agent usually used in the field of rubber processing, in addition to the above components.
- compounding agents include reinforcing fillers such as silica and carbon black; non-reinforcing fillers such as calcium carbonate and clay; anti-aging agents; light stabilizers; scorch inhibitors; plasticizers; Adhesives; Adhesives; Lubricants; Lubricants; Flame retardants; Antifungal agents; Antistatic agents; Colorants;
- the compounding amount of these compounding agents is not particularly limited as long as it does not impair the object and effect of the present invention, and an amount corresponding to the compounding purpose can be appropriately compounded.
- rubbers, elastomers, resins and the like other than the acrylic rubber of the present invention described above may be further blended within a range not impairing the effects of the present invention.
- rubber other than acrylic rubber such as acrylic rubber other than the acrylic rubber of the present invention, natural rubber, polybutadiene rubber, polyisoprene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, silicon rubber, fluorine rubber, etc .
- Elastomers such as elastomers, styrene elastomers, vinyl chloride elastomers, polyester elastomers, polyamide elastomers, polyurethane elastomers, polysiloxane elastomers
- the total blending amount of the rubber, elastomer, and resin other than the acrylic rubber of the present invention described above is preferably 50 parts by weight or less, more preferably 10 parts by weight or less, further preferably 100 parts by weight of acrylic rubber. 1 part by weight or less.
- the acrylic rubber is blended with a crosslinking agent and other various compounding agents used as necessary, mixed and kneaded with a Banbury mixer or a kneader, and then using a kneading roll. Further, it is prepared by kneading.
- the blending order of each component is not particularly limited, but after sufficiently mixing components that are difficult to react and decompose with heat, a crosslinking agent that is a component that easily reacts and decomposes with heat at a temperature at which reaction and decomposition do not occur. It is preferable to mix in a short time.
- the rubber cross-linked product of the present invention is obtained by cross-linking the acrylic rubber composition of the present invention described above.
- the rubber cross-linked product of the present invention uses the acrylic 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, and a roll, and is heated. It can be produced by carrying out a cross-linking reaction and fixing the shape as a rubber cross-linked 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 130 to 220 ° C., preferably 150 to 190 ° C.
- the crosslinking time is usually 2 minutes to 10 hours, preferably 3 minutes to 5 hours.
- a heating method a 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 may be further heated to perform secondary crosslinking.
- the secondary crosslinking varies depending on the heating method, crosslinking temperature, shape, etc., but is preferably performed for 1 to 48 hours. What is necessary is just to select a heating method and heating temperature suitably.
- the rubber cross-linked product of the present invention since the rubber cross-linked product of the present invention thus obtained is obtained by using the acrylic rubber obtained by the above-described production method of the present invention, high tensile strength is achieved while realizing excellent heat resistance. It has strength. Therefore, the rubber cross-linked product of the present invention makes use of such characteristics, for example, seals such as O-rings, packings, oil seals, bearing seals and the like in a wide range of transportation machines such as automobiles, general equipment, and electrical equipment. Materials: gaskets; cushioning materials, vibration-proof materials; electric wire covering materials; industrial belts; tubes and hoses; sheets;
- Mooney viscosity (ML1 + 4, 100 ° C.) The Mooney viscosity (polymer Mooney) of the acrylic rubber was measured according to JIS K6300.
- Aggregate content (% by weight) ⁇ ( ⁇ ) / ( ⁇ ⁇ ⁇ ) ⁇ ⁇ 100
- ⁇ represents the weight of the wire mesh and dried aggregate after drying
- ⁇ represents the weight of the wire mesh
- ⁇ represents the weight of the emulsion polymerization solution
- ⁇ represents the solid content of the emulsion polymerization solution.
- the content rate of the solid content of the emulsion polymerization liquid was obtained by drying the emulsion polymerization liquid and calculating the weight based on the following formula from the weight of the emulsion polymerization liquid before drying and the weight after drying.
- Content ratio ( ⁇ ) of solid content of emulsion polymerization liquid weight after drying / weight of emulsion polymerization liquid before drying
- the acrylic 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 was subjected to primary crosslinking by pressing at 170 ° C. for 20 minutes while being pressed at a press pressure of 10 MPa.
- the product was further subjected to secondary crosslinking by heating at 170 ° C. for 4 hours in a gear-type oven to obtain a sheet-like rubber crosslinked product.
- the obtained rubber cross-linked product was punched with a No. 3 type dumbbell to prepare a test piece. Next, using this test piece, tensile strength and elongation were measured according to JIS K6251.
- Heat aging test A specimen prepared in the same manner as the specimen used for the evaluation of the tensile strength and elongation in the normal state was placed in a gear oven in an environment at a temperature of 175 ° C. for 504 hours, and then the tensile strength and elongation were measured. The heat aging resistance was evaluated by comparing the obtained results with the normal tensile strength and elongation measured according to the above method. Tensile strength and elongation were measured according to JIS K6251. About tensile strength, the one where the measured value of the sample after a heating is large is excellent in heat resistance.
- the heat resistance is better when the elongation change rate (percentage), which is the change rate of the measured value of the sample after heating with respect to the measured value of the sample that has not been heat-aged (normally measured value), is close to zero.
- the acrylic 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 was subjected to primary crosslinking by pressing at 170 ° C. for 20 minutes while being pressed at a press pressure of 10 MPa.
- the product was further subjected to secondary crosslinking by heating at 170 ° C. for 4 hours in a gear-type oven to obtain a sheet-like rubber crosslinked product.
- volume change rate before and after immersion (Volume of specimen after immersion ⁇ Volume of specimen before immersion) ⁇ Volume of specimen before immersion ⁇ 100
- stearyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (trade name “Irganox 1076”, BASF) as an anti-aging agent.
- 3,5-di-tert-butyl-4 was added to 50 parts of an aqueous solution of 50% by weight aqueous solution (0.2% by weight sodium lauryl sulfate (trade name “Emar 2FG”, manufactured by Kao Corporation)).
- monomers used in producing emulsion polymerization liquid ie ethyl acrylate, acrylic acid n
- the obtained mixed liquid was transferred to a coagulation tank.
- 60 parts of industrial water was added and the temperature was raised to 85 ° C., and then the mixed liquid was stirred at a temperature of 85 ° C.
- 3.3 parts of sodium sulfate as a coagulant (10 parts with respect to 100 parts of the polymer contained in the mixed solution) was continuously added to solidify the polymer, and then filtered to remove acrylic.
- a water-containing crumb of rubber (A1) was obtained.
- a sulfuric acid aqueous solution obtained by mixing 388 parts of industrial water and 0.13 part of concentrated sulfuric acid is added to 100 parts of the solid content of the hydrated crumb which has been washed with water in the above, and in the coagulation tank. After stirring for 5 minutes at room temperature, the water-containing crumb was pickled by draining water from the coagulation tank. The pH of the hydrated crumb after pickling (pH of water in the hydrated crumb) was measured, and the pH was 3.
- the resulting acrylic rubber (A1) had a Mooney viscosity (ML1 + 4, 100 ° C.) of 33, and the composition of the acrylic rubber (A1) was 49.3% by weight of ethyl acrylate units and 49.3% of n-butyl acrylate units. % By weight and mono-n-butyl fumarate units of 1.4% by weight. Moreover, about acrylic rubber (A1), the amount of ash content and content of antioxidant in acrylic rubber (A1) were measured according to the said method. The results are shown in Table 1.
- the water-containing crumb of the obtained acrylic rubber (A2) is subjected to four times of water washing, pickling, pure water washing and drying with a hot air dryer in the same manner as in Production Example 1, so that solid acrylic rubber is obtained.
- (A2) was obtained.
- the resulting acrylic rubber (A2) had a Mooney viscosity (ML1 + 4, 100 ° C.) of 33, and the composition of the acrylic rubber (A2) was 49.3% by weight of ethyl acrylate units and 49.3% of n-butyl acrylate units. % By weight and mono-n-butyl fumarate units of 1.4% by weight.
- the amount of ash and the content of the anti-aging agent in the acrylic rubber (A2) were measured according to the above methods. The results are shown in Table 1.
- the water-containing crumb of the obtained acrylic rubber (A3) is subjected to four times of water washing, pickling, pure water washing and drying with a hot air dryer in the same manner as in Production Example 1 to obtain a solid acrylic rubber.
- (A3) was obtained.
- the resulting acrylic rubber (A3) has a Mooney viscosity (ML1 + 4, 100 ° C.) of 33.
- the acrylic rubber (A3) has a composition of 49.3% by weight of ethyl acrylate units and 49.3% of n-butyl acrylate units. % By weight and mono-n-butyl fumarate units of 1.4% by weight.
- the amount of ash and the content of the anti-aging agent in the acrylic rubber (A3) were measured according to the above methods. The results are shown in Table 1.
- the water-containing crumb of the obtained acrylic rubber (A4) was subjected to four times of water washing, pickling, pure water washing and drying with a hot air dryer in the same manner as in Production Example 1 to obtain a solid acrylic rubber. (A4) was obtained.
- the resulting acrylic rubber (A4) has a Mooney viscosity (ML1 + 4, 100 ° C.) of 33.
- the acrylic rubber (A4) has a composition of 49.3% by weight of ethyl acrylate units and 49.3% of n-butyl acrylate units. % By weight and mono-n-butyl fumarate units of 1.4% by weight.
- the amount of ash and the content of the anti-aging agent in the acrylic rubber (A4) were measured according to the above methods. The results are shown in Table 1.
- the water-containing crumb of the obtained acrylic rubber (A5) was subjected to four times of water washing, pickling, pure water washing and drying with a hot air dryer in the same manner as in Production Example 1, thereby solid acrylic rubber. (A5) was obtained.
- the resulting acrylic rubber (A5) has a Mooney viscosity (ML1 + 4, 100 ° C.) of 32.
- the composition of the acrylic rubber (A5) is 49.3% by weight of ethyl acrylate units and 49.3% of n-butyl acrylate units. % By weight and mono-n-butyl fumarate units of 1.4% by weight.
- the amount of ash and the content of the anti-aging agent in the acrylic rubber (A5) were measured according to the above methods. The results are shown in Table 1.
- the water-containing crumb of the obtained acrylic rubber (A6) was subjected to four times of water washing, pickling, pure water washing, and drying with a hot air dryer in the same manner as in Production Example 1 to obtain a solid acrylic rubber.
- (A6) was obtained.
- the resulting acrylic rubber (A6) had a Mooney viscosity (ML1 + 4, 100 ° C.) of 33.
- the acrylic rubber (A6) had a composition of 49.3% by weight of ethyl acrylate units and 49.3% of n-butyl acrylate units. % By weight and mono-n-butyl fumarate units of 1.4% by weight.
- the amount of ash and the content of the antioxidant in the acrylic rubber (A6) were measured according to the above methods. The results are shown in Table 1.
- the water-containing crumb of the obtained acrylic rubber (A7) was subjected to four times of water washing, pickling, pure water washing and drying with a hot air dryer in the same manner as in Production Example 1 to obtain a solid acrylic rubber. (A7) was obtained.
- the resulting acrylic rubber (A7) has a Mooney viscosity (ML1 + 4, 100 ° C.) of 33.
- the acrylic rubber (A7) has a composition of 49.3% by weight of ethyl acrylate units and 49.3% of n-butyl acrylate units. % By weight and mono-n-butyl fumarate units of 1.4% by weight.
- the amount of ash and the content of the antioxidant in the acrylic rubber (A7) were measured according to the above methods. The results are shown in Table 1.
- the water-containing crumb of the obtained acrylic rubber (A8) was subjected to four times of water washing, pickling, pure water washing and drying with a hot air dryer in the same manner as in Production Example 1 to obtain a solid acrylic rubber. (A8) was obtained.
- the resulting acrylic rubber (A8) had a Mooney viscosity (ML1 + 4, 100 ° C.) of 28.
- the acrylic rubber (A8) had a composition of 49.3% by weight of ethyl acrylate units and 49.3% of n-butyl acrylate units. % By weight and mono-n-butyl fumarate units of 1.4% by weight.
- the amount of ash and the content of the antioxidant in the acrylic rubber (A8) were measured according to the above methods. The results are shown in Table 1.
- the water-containing crumb of the obtained acrylic rubber (A9) was subjected to four times of water washing, pickling, pure water washing, and drying with a hot air dryer in the same manner as in Production Example 1 to obtain a solid acrylic rubber. (A9) was obtained.
- the resulting acrylic rubber (A9) has a Mooney viscosity (ML1 + 4, 100 ° C.) of 27, and the composition of the acrylic rubber (A9) is 49.3% by weight of ethyl acrylate units and 49.3% of n-butyl acrylate units. % By weight and mono-n-butyl fumarate units of 1.4% by weight.
- the amount of ash and the content of the anti-aging agent in the acrylic rubber (A9) were measured according to the above methods. The results are shown in Table 1.
- the water-containing crumb of the obtained acrylic rubber (A10) was subjected to four times of water washing, pickling, pure water washing and drying with a hot air dryer in the same manner as in Production Example 1, thereby solid acrylic rubber. (A10) was obtained.
- the resulting acrylic rubber (A10) has a Mooney viscosity (ML1 + 4, 100 ° C.) of 29, and the composition of the acrylic rubber (A10) is 49.3% by weight of ethyl acrylate units and 49.3% of n-butyl acrylate units. % By weight and mono-n-butyl fumarate units of 1.4% by weight.
- the amount of ash and the content of the antioxidant in the acrylic rubber (A10) were measured according to the above methods. The results are shown in Table 1.
- the water-containing crumb of the obtained acrylic rubber (A11) was subjected to four times of water washing, pickling, pure water washing, and drying with a hot air dryer in the same manner as in Production Example 1 to obtain a solid acrylic rubber.
- (A11) was obtained.
- the resulting acrylic rubber (A11) had a Mooney viscosity (ML1 + 4, 100 ° C.) of 27.
- the acrylic rubber (A11) had a composition of 49.3% by weight of ethyl acrylate units and 49.3% of n-butyl acrylate units. % By weight and mono-n-butyl fumarate units of 1.4% by weight.
- the amount of ash and the content of the antioxidant in the acrylic rubber (A11) were measured according to the above methods. The results are shown in Table 1.
- the water-containing crumb of the obtained acrylic rubber (A12) is subjected to four times of water washing, pickling, pure water washing, and drying with a hot air dryer in the same manner as in Production Example 1, so that solid acrylic rubber is obtained.
- (A12) was obtained.
- the resulting acrylic rubber (A12) had a Mooney viscosity (ML1 + 4, 100 ° C.) of 28.
- the acrylic rubber (A12) had a composition of 49.3% by weight of ethyl acrylate units and 49.3% of n-butyl acrylate units. % By weight and mono-n-butyl fumarate units of 1.4% by weight.
- the amount of ash and the content of the antioxidant in the acrylic rubber (A12) were measured according to the above methods. The results are shown in Table 1.
- the water-containing crumb of the obtained acrylic rubber (A13) was subjected to four times of water washing, pickling, pure water washing and drying with a hot air dryer in the same manner as in Production Example 1 to obtain a solid acrylic rubber.
- (A13) was obtained.
- the resulting acrylic rubber (A13) has a Mooney viscosity (ML1 + 4, 100 ° C.) of 27.
- the acrylic rubber (A13) has a composition of 49.3% by weight of ethyl acrylate units and 49.3% of n-butyl acrylate units. % By weight and mono-n-butyl fumarate units of 1.4% by weight.
- the amount of ash and the content of the antioxidant in the acrylic rubber (A13) were measured according to the above methods. The results are shown in Table 1.
- the water-containing crumb of the obtained acrylic rubber (A14) was subjected to four times of water washing, pickling, pure water washing and drying with a hot air dryer in the same manner as in Production Example 1, thereby solid acrylic rubber. (A14) was obtained.
- the resulting acrylic rubber (A14) has a Mooney viscosity (ML1 + 4, 100 ° C.) of 30, and the composition of the acrylic rubber (A14) is 49.3% by weight of ethyl acrylate units and n-butyl acrylate units of 49.3. % By weight and mono-n-butyl fumarate units of 1.4% by weight.
- the amount of ash and the content of the antioxidant in the acrylic rubber (A14) were measured according to the above methods. The results are shown in Table 1.
- emulsion polymerization was performed in the same manner as in Production Example 14 to obtain an emulsion polymerization solution.
- the aggregate content in the emulsion polymerization liquid was measured according to the above method. The aggregate content was 0.5% by weight, and contamination due to the adhesion of the aggregate in the stirring device was confirmed.
- a mixed liquid was prepared in the same manner as in Production Example 14, and then the polymer was solidified to obtain a hydrous crumb of acrylic rubber (A15).
- the water-containing crumb of the obtained acrylic rubber (A15) was subjected to four times of water washing, pickling, pure water washing and drying with a hot air dryer in the same manner as in Production Example 1 to obtain a solid acrylic rubber.
- (A15) was obtained.
- the resulting acrylic rubber (A15) had a Mooney viscosity (ML1 + 4, 100 ° C.) of 29, and the composition of the acrylic rubber (A15) was 49.3% by weight of ethyl acrylate units and 49.3% of n-butyl acrylate units. % By weight and mono-n-butyl fumarate units of 1.4% by weight.
- the amount of ash and the content of the antioxidant in the acrylic rubber (A15) were measured according to the above methods. The results are shown in Table 1.
- emulsion polymerization was performed in the same manner as in Production Example 14 to obtain an emulsion polymerization solution.
- the aggregate content in the emulsion polymerization liquid was measured in accordance with the above method. The aggregate content was 0.4% by weight, and contamination due to the adhesion of the aggregate in the stirring device was confirmed.
- a mixed liquid was prepared in the same manner as in Production Example 14, and then the polymer was solidified to obtain a hydrous crumb of acrylic rubber (A16).
- the water-containing crumb of the obtained acrylic rubber (A16) was subjected to four times of water washing, pickling, pure water washing and drying with a hot air dryer in the same manner as in Production Example 1 to obtain a solid acrylic rubber. (A16) was obtained.
- the resulting acrylic rubber (A16) has a Mooney viscosity (ML1 + 4, 100 ° C.) of 28, and the composition of the acrylic rubber (A16) is 49.3% by weight of ethyl acrylate units and 49.3% of n-butyl acrylate units. % By weight and mono-n-butyl fumarate units of 1.4% by weight.
- the amount of ash and the content of the anti-aging agent in the acrylic rubber (A16) were measured according to the above methods. The results are shown in Table 1.
- emulsion polymerization was performed in the same manner as in Production Example 14 to obtain an emulsion polymerization solution.
- the aggregate content in the emulsion polymerization liquid was measured according to the above method. As a result, the aggregate content was 0.3% by weight, and contamination due to the adhesion of the aggregate in the stirring device was confirmed.
- a mixed liquid was prepared in the same manner as in Production Example 14, and then the polymer was solidified to obtain a hydrous crumb of acrylic rubber (A17). Subsequently, the water-containing crumb of the obtained acrylic rubber (A17) was subjected to washing with water four times, pickling, pure water washing and drying with a hot air dryer in the same manner as in Production Example 1 to obtain a solid acrylic rubber. (A17) was obtained.
- the resulting acrylic rubber (A17) had a Mooney viscosity (ML1 + 4, 100 ° C.) of 28, and the composition of the acrylic rubber (A17) was 49.3% by weight of ethyl acrylate units and 49.3% of n-butyl acrylate units. % By weight and mono-n-butyl fumarate units of 1.4% by weight. Further, the amount of ash and the content of the anti-aging agent in the acrylic rubber (A17) were measured according to the above methods. The results are shown in Table 1.
- emulsion polymerization was performed in the same manner as in Production Example 14 to obtain an emulsion polymerization solution.
- the aggregate content in the emulsion polymerization liquid was measured in accordance with the above method. The aggregate content was 0.4% by weight, and contamination due to the adhesion of the aggregate in the stirring device was confirmed.
- a mixed liquid was prepared in the same manner as in Production Example 14, and then the polymer was solidified to obtain a water-containing crumb of acrylic rubber (A18).
- the water-containing crumb of the obtained acrylic rubber (A18) was subjected to four times of water washing, pickling, pure water washing and drying with a hot air dryer in the same manner as in Production Example 1 to obtain a solid acrylic rubber. (A18) was obtained.
- the resulting acrylic rubber (A18) had a Mooney viscosity (ML1 + 4, 100 ° C.) of 29, and the composition of the acrylic rubber (A18) was 49.3% by weight of ethyl acrylate units and 49.3% of n-butyl acrylate units. % By weight and mono-n-butyl fumarate units of 1.4% by weight. Further, the amount of ash and the content of the anti-aging agent in the acrylic rubber (A18) were measured according to the above methods. The results are shown in Table 1.
- emulsion polymerization was performed in the same manner as in Production Example 14 to obtain an emulsion polymerization solution.
- the aggregate content in the emulsion polymerization liquid was measured according to the above method. As a result, no aggregate was confirmed, and the content was 0% by weight.
- a mixed liquid was prepared in the same manner as in Production Example 14, and then the polymer was solidified to obtain a hydrous crumb of acrylic rubber (A19).
- the water-containing crumb of the obtained acrylic rubber (A19) was subjected to four times of water washing, pickling, pure water washing, and drying with a hot air dryer in the same manner as in Production Example 1 to obtain a solid acrylic rubber. (A19) was obtained.
- the resulting acrylic rubber (A19) has a Mooney viscosity (ML1 + 4, 100 ° C.) of 27, and the composition of the acrylic rubber (A19) is 49.3% by weight of ethyl acrylate units and 49.3% of n-butyl acrylate units. % By weight and mono-n-butyl fumarate units of 1.4% by weight. Further, the amount of ash and the content of the anti-aging agent in the acrylic rubber (A19) were measured according to the above methods. The results are shown in Table 1.
- Example 1 Using a Banbury mixer, 100 parts of the acrylic rubber (A1) obtained in Production Example 1, 60 parts of carbon black (trade name “SEAST SO”, manufactured by Tokai Carbon Co., Ltd.), 2 parts of stearic acid, ester wax (product) Name "Grec G-8205", manufactured by Dainippon Ink & Chemicals, Inc.) and 4,4'-bis ( ⁇ , ⁇ -dimethylbenzyl) diphenylamine (trade name "NOCRACK CD”, manufactured by Ouchi Shinsei Chemical Industry Co., Ltd. 2 parts were added and mixed at 50 ° C. for 5 minutes.
- the obtained mixture was transferred to a roll at 50 ° C., and 0.5 parts of hexamethylenediamine carbamate (trade name “Diak # 1”, manufactured by DuPont Dow Elastomer Co., Ltd., aliphatic polyvalent amine compound) and 1,3 -2 parts of di-o-tolylguanidine (trade name “Noxeller DT”, manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., crosslinking accelerator) was blended and kneaded to obtain an acrylic rubber composition.
- hexamethylenediamine carbamate trade name “Diak # 1”, manufactured by DuPont Dow Elastomer Co., Ltd., aliphatic polyvalent amine compound
- 1,3 -2 parts of di-o-tolylguanidine trade name “Noxeller DT”, manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., crosslinking accelerator
- Example 2 to 7 An acrylic resin was prepared in the same manner as in Example 1 except that the acrylic rubbers (A2) to (A7) obtained in Production Examples 2 to 7 were used in place of the acrylic rubber (A1) obtained in Production Example 1. Table 2 shows the results of measurement and evaluation in the same manner after obtaining the rubber composition.
- (* 1) The addition amount of the compounding agent for preparing the monomer emulsion is shown by the compounding amount with respect to 100 parts of the charged monomer.
- (* 2) The addition amount of the compounding agent added to the emulsion polymerization solution before coagulation was shown as the compounding amount with respect to 100 parts of the emulsion polymerization solution.
- (* 3) 50% by weight aqueous dispersion is prepared by adding and mixing 50 parts of an antioxidant to 50 parts of an aqueous solution of 0.2% by weight sodium lauryl sulfate (trade name “Emar 2FG”, manufactured by Kao Corporation). It was prepared by.
- Production Examples 8 to 13 in which the anti-aging agent was not added to the emulsion polymerization solution after emulsion polymerization and before coagulation, the Mooney viscosity was reduced by drying.
- the rubber cross-linked products obtained using the acrylic rubbers obtained in Production Examples 8 to 13 were inferior in tensile strength (Production Examples 8 to 13 and Comparative Examples 1 to 6).
- Production Examples 14 to 18 in which an anti-aging agent was added to the monomer emulsion before emulsion polymerization, aggregates were generated in the obtained emulsion polymerization solution, and such aggregates were adhered. As a result, the inside of the agitation apparatus was contaminated due to (Production Examples 14 to 18, Comparative Examples 7 to 11).
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Abstract
Description
好ましくは、アクリルゴムは、老化防止剤の含有量が12,000重量ppm以下である。
本発明の製造方法において、前記老化防止剤添加工程における、前記老化防止剤の添加量を、前記乳化重合液中に含まれるアクリルゴム成分100重量部に対して、0.1~2重量部とすることが好ましい。
本発明の製造方法において、前記老化防止剤添加工程における、前記老化防止剤の添加量を、前記乳化重合液中に含まれるアクリルゴム成分100重量部に対して、0.2~1.2重量部とすることが好ましい。
本発明の製造方法において、前記老化防止剤が、硫黄原子を含有しないフェノール系老化防止剤、チオフェノール系老化防止剤、アミン系老化防止剤およびイミダゾール系老化防止剤から選択される少なくとも1種であることが好ましい。
本発明の製造方法において、前記老化防止剤が、3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオン酸ステアリル、2,4-ビス[(オクチルチオ)メチル]-6-メチルフェノール、4,4’―ビス(α,α-ジメチルベンジル)ジフェニルアミン、2-メルカプトベンズイミダゾール、およびモノ(又はジ、又はトリ)(α-メチルベンジル)フェノールから選択される少なくとも1種であることが好ましい。
本発明の製造方法において、前記老化防止剤が、3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオン酸ステアリルであることが好ましい。
本発明の製造方法において、前記老化防止剤を溶液または分散液の状態にて添加する際における、前記溶液または前記分散液中における老化防止剤の含有割合を、10~90重量%とすることが好ましい。
本発明の製造方法において、前記老化防止剤を溶液または分散液の状態にて添加する際における、前記溶液または前記分散液中における老化防止剤の含有割合を、20~60重量%とすることが好ましい。
本発明の製造方法において、前記含水クラムを、スクリュー型押出乾燥機または熱風乾燥機にて、150℃以上の温度で乾燥する乾燥工程をさらに備えることが好ましい。
本発明の製造方法において、前記単量体の乳化重合を、ノニオン性乳化剤およびアニオン性乳化剤の存在下で行うことが好ましい。
本発明の製造方法において、前記ノニオン性乳化剤およびアニオン性乳化剤の使用量を、ノニオン性乳化剤/アニオン性乳化剤の重量比で、50/50~75/25とすることが好ましい。
本発明の製造方法において、前記乳化重合工程において、前記アクリルゴムを形成するための単量体、重合開始剤および還元剤を、重合反応開始から任意の時間まで、重合反応系に連続的に滴下しながら乳化重合反応を行うことが好ましい。
本発明の製造方法において、前記アクリルゴムを形成するための単量体を、乳化剤および水と混合してなる単量体乳化液の状態にて、重合反応開始から任意の時間まで、重合反応系に連続的に滴下しながら乳化重合反応を行うことが好ましい。
さらに、本発明によれば、上記製造方法により得られるアクリルゴム組成物を架橋する工程を備えるゴム架橋物の製造方法が提供される。
まず、本発明の製造方法により製造されるアクリルゴムについて説明する。
本発明の製造方法により製造されるアクリルゴムは、分子中に、主成分(本発明においては、ゴム全単量体単位中50重量%以上有するものを言う。)としての(メタ)アクリル酸エステル単量体〔アクリル酸エステル単量体および/またはメタクリル酸エステル単量体の意。以下、(メタ)アクリル酸メチルなど同様。〕単位を含有するゴム状の重合体である。
炭素数4~12のα,β-エチレン性不飽和ジカルボン酸の具体例としては、フマル酸、マレイン酸などのブテンジオン酸;イタコン酸;シトラコン酸;クロロマレイン酸;などが挙げられる。
炭素数4~12のα,β-エチレン性不飽和ジカルボン酸と炭素数1~8のアルカノールとのモノエステルの具体例としては、フマル酸モノメチル、フマル酸モノエチル、フマル酸モノn-ブチル、マレイン酸モノメチル、マレイン酸モノエチル、マレイン酸モノn-ブチルなどのブテンジオン酸モノ鎖状アルキルエステル;フマル酸モノシクロペンチル、フマル酸モノシクロヘキシル、フマル酸モノシクロヘキセニル、マレイン酸モノシクロペンチル、マレイン酸モノシクロヘキシル、マレイン酸モノシクロヘキセニルなどの脂環構造を有するブテンジオン酸モノエステル;イタコン酸モノメチル、イタコン酸モノエチル、イタコン酸モノn-ブチル、イタコン酸モノシクロヘキシルなどのイタコン酸モノエステル;などが挙げられる。
これらの中でも、炭素数4~12のα,β-エチレン性不飽和ジカルボン酸と炭素数1~8のアルカノールとのモノエステルが好ましく、ブテンジオン酸モノ鎖状アルキルエステル、または脂環構造を有するブテンジオン酸モノエステルがより好ましく、フマル酸モノn-ブチル、マレイン酸モノn-ブチル、フマル酸モノシクロヘキシル、およびマレイン酸モノシクロヘキシルがさらに好ましく、フマル酸モノn-ブチルが特に好ましい。これらのα,β-エチレン性不飽和カルボン酸単量体は、1種単独で、または2種以上を併せて使用することができる。なお、上記単量体のうち、ジカルボン酸には、無水物として存在しているものも含まれる。
(メタ)アクリル酸ハロアルキルエステルの具体例としては、(メタ)アクリル酸クロロメチル、(メタ)アクリル酸1-クロロエチル、(メタ)アクリル酸2-クロロエチル、(メタ)アクリル酸1,2-ジクロロエチル、(メタ)アクリル酸2-クロロプロピル、(メタ)アクリル酸3-クロロプロピル、および(メタ)アクリル酸2,3-ジクロロプロピルなどが挙げられる。
(メタ)アクリル酸ハロアシロキシアルキルエステルの具体例としては、(メタ)アクリル酸2-(クロロアセトキシ)エチル、(メタ)アクリル酸2-(クロロアセトキシ)プロピル、(メタ)アクリル酸3-(クロロアセトキシ)プロピル、および(メタ)アクリル酸3-(ヒドロキシクロロアセトキシ)プロピルなどが挙げられる。
(メタ)アクリル酸(ハロアセチルカルバモイルオキシ)アルキルエステルの具体例としては、(メタ)アクリル酸2-(クロロアセチルカルバモイルオキシ)エチル、および(メタ)アクリル酸3-(クロロアセチルカルバモイルオキシ)プロピルなどが挙げられる。
ハロゲン含有不飽和ケトンの具体例としては、2-クロロエチルビニルケトン、3-クロロプロピルビニルケトン、および2-クロロエチルアリルケトンなどが挙げられる。
ハロメチル基含有芳香族ビニル化合物の具体例としては、p-クロロメチルスチレン、m-クロロメチルスチレン、o-クロロメチルスチレン、およびp-クロロメチル-α-メチルスチレンなどが挙げられる。
ハロアセチル基含有不飽和単量体の具体例としては、3-(ヒドロキシクロロアセトキシ)プロピルアリルエーテル、p-ビニルベンジルクロロ酢酸エステルなどが挙げられる。
共役ジエン単量体の具体例としては、1,3-ブタジエン、イソプレン、およびピペリレンなどを挙げることができる。
非共役ジエン単量体の具体例としては、エチリデンノルボルネン、ジシクロペンタジエン、(メタ)アクリル酸ジシクロペンタジエニル、および(メタ)アクリル酸2-ジシクロペンタジエニルエチルなどを挙げることができる。
アクリルアミド系単量体としては、アクリルアミド、メタクリルアミドなどが挙げられる。
その他のオレフィン系単量体としては、エチレン、プロピレン、塩化ビニル、塩化ビニリデン、酢酸ビニル、エチルビニルエーテル、ブチルビニルエーテルなどが挙げられる。
次いで、本発明のアクリルゴムの製造方法について説明する。
本発明のアクリルゴムの製造方法は、
前記アクリルゴムを形成するための単量体を乳化重合することで、乳化重合液を得る乳化重合工程と、
前記乳化重合液に、老化防止剤を溶液または分散液の状態にて添加する老化防止剤添加工程と、
前記老化防止剤を添加した乳化重合液に、凝固剤を添加し、含水クラムを得る凝固工程と、を備える。
本発明の製造方法における、乳化重合工程は、アクリルゴムを形成するための単量体を乳化重合することで、乳化重合液を得る工程である。
本発明の製造方法における、老化防止剤添加工程は、上記乳化重合工程において得られた、凝固を行う前の乳化重合液に、老化防止剤を溶液または分散液の状態にて添加する工程である。
本発明の製造方法における、凝固工程は、上記乳化重合工程により得られた乳化重合液に、凝固剤を添加することで、含水クラムを得る工程である。
また、本発明の製造方法においては、上記した凝固工程において得られた含水クラムに対して、洗浄を行う洗浄工程をさらに備えていることが好ましい。
また、上記製造方法においては、上記洗浄工程において洗浄を行った含水クラムに対し、乾燥を行う乾燥工程をさらに備えていてもよい。
本発明のアクリルゴム組成物は、上記した本発明の製造方法により得られるアクリルゴムに架橋剤を配合してなるものである。
本発明のゴム架橋物は、上述した本発明のアク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、本発明のアク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、および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、ゴム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、130~220℃、好ましくは150~190℃であり、架橋時間は、通常、2分~10時間、好ましくは3分~5時間である。加熱方法としては、プレス加熱、蒸気加熱、オーブン加熱、および熱風加熱などのゴムの架橋に用いられる方法を適宜選択すればよい。
各種の物性については、以下の方法に従って評価した。
アクリルゴムのムーニー粘度(ポリマームーニー)をJIS K6300に従って測定した。
乳化重合後の乳化重合液について、固形分の含有割合(乳化重合液全体を1とした時の割合)を測定し、次いで、乳化重合後の乳化重合液100gを精秤した後、重量既知の200メッシュのSUS製金網でろ過し、金網上の凝集物を数回水洗して、乳化重合液を除去した。これを、105℃で60分間、乾燥した後、その乾燥重量を測定し、下記式に基づいて凝集物含有割合(単位:重量%)を求めた。
凝集物含有率(重量%)={(α-β)/(γ×Δ)}×100
ここで、αは乾燥後の金網および乾燥凝集物の重量、βは金網の重量、γは乳化重合液の重量、Δは乳化重合液の固形分の含有割合をそれぞれ示す。
なお、乳化重合液の固形分の含有割合は、乳化重合液について乾燥を行い、乾燥前乳化重合液の重量と、乾燥後の重量とから下記式に基づいて求めた。
乳化重合液の固形分の含有割合(Δ)=乾燥後の重量/乾燥前乳化重合液の重量
アクリルゴムをテトラヒドロフランに溶解し、テトラヒドロフランを展開溶媒として、GPC測定を行うことにより、アクリルゴム中における、老化防止剤の含有量を測定した。具体的には、GPC測定により得られたチャートから、製造に使用した老化防止剤の分子量に対応するピークの積分値を求め、これらの積分値と、アクリルゴムのピークの積分値とを比較し、これらの積分値と対応する分子量から重量比率を求めることで、老化防止剤の含有量を算出した。
アクリルゴム中に含まれる灰分の量(重量%)を、JIS K6228に準拠して、測定した。
アクリルゴム組成物を、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分間プレスすることにより一次架橋し、次いで、得られた一次架橋物を、ギヤー式オーブンにて、さらに170℃、4時間の条件で加熱して二次架橋させることにより、シート状のゴム架橋物を得た。得られたゴム架橋物を3号形ダンベルで打ち抜いて試験片を作製した。次にこの試験片を用いて、JIS K6251に従い引張強度および伸びを測定した。
上記常態での引張強度および伸びの評価に用いた試験片と同様にして作製した試験片を、ギヤー式オーブン中で、温度175℃の環境下に504時間置いた後、引張強度および伸びを測定し、得られた結果と、上記方法にしたがって測定した常態での引張強度および伸びとを対比することにより、耐熱老化性の評価を行った。引張強度および伸びは、JIS K6251に従って測定した。
引張強度については、加熱後の試料の測定値が大きい方が耐熱性に優れる。伸びについては、熱老化させていない試料の測定値(常態での測定値)に対する加熱後の試料の測定値の変化率である伸び変化率(百分率)が0に近い方が耐熱性に優れる。
アクリルゴム組成物を、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分間プレスすることにより一次架橋し、次いで、得られた一次架橋物を、ギヤー式オーブンにて、さらに170℃、4時間の条件で加熱して二次架橋させることにより、シート状のゴム架橋物を得た。そして、得られたシート状のゴム架橋物から、3cm×2cm×0.2cmの試験片に切り取り、JIS K6258に準拠して、得られた試験片を温度80℃に調整した蒸留水中に72時間浸漬させる浸漬試験を行い、浸漬前後の試験片の体積変化率を下記式にしたがって、測定した。浸漬前後の体積変化率が小さいほど、水に対する膨潤が抑制されており、耐水性に優れると判断できる。
浸漬前後の体積変化率(%)=(浸漬後の試験片の体積-浸漬前の試験片の体積)÷浸漬前の試験片の体積×100
ホモミキサーを備えた混合容器に、純水46.294部、アクリル酸エチル49.3部、アクリル酸n-ブチル49.3部、フマル酸モノn-ブチル1.4部、アニオン性界面活性剤としてのラウリル硫酸ナトリウム(商品名「エマール 2FG」、花王社製)0.567部、およびノニオン性界面活性剤としてのポリオキシエチレンドデシルエーテル(商品名「エマルゲン 105」、重量平均分子量:約1500、花王社製)1.4部を仕込み、攪拌することで、単量体乳化液を得た。
製造例1と同様にして得られた乳化重合液を用い、製造例1と同様にして得られた乳化重合液100重量部に対する、老化防止剤としての3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオン酸ステアリルの50重量%水分散液の添加量を0.1部から0.3部(乳化重合液を製造する際に用いた仕込みの単量体の合計100部に対して、老化防止剤換算で0.5部)に変更した以外は、製造例1と同様にして、混合液の調製および凝固操作を行い、アクリルゴム(A2)の含水クラムを得た。
製造例1と同様にして得られた乳化重合液を用い、製造例1と同様にして得られた乳化重合液100重量部に対する、老化防止剤としての3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオン酸ステアリルの50重量%水分散液の添加量を0.1部から0.6部(乳化重合液を製造する際に用いた仕込みの単量体の合計100部に対して、老化防止剤換算で1部)に変更した以外は、製造例1と同様にして、混合液の調製および凝固操作を行い、アクリルゴム(A3)の含水クラムを得た。
製造例1と同様にして得られた乳化重合液を用い、製造例1と同様にして得られた乳化重合液100重量部に対し、老化防止剤として、3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオン酸ステアリルの50重量%水分散液に代えて、2,4-ビス[(オクチルチオ)メチル]-6-メチルフェノール(商品名「Irganox 1520L」、BASF社製)の50重量%水分散液(0.2重量%のラウリル硫酸ナトリウム(商品名「エマール 2FG」、花王社製)の水溶液50部に、2,4-ビス[(オクチルチオ)メチル]-6-メチルフェノール50部を添加・混合することにより調製)0.6部(乳化重合液を製造する際に用いた仕込みの単量体の合計100部に対して1部)を添加した以外は、製造例1と同様にして、混合液の調製および凝固操作を行い、アクリルゴム(A4)の含水クラムを得た。
製造例1と同様にして得られた乳化重合液を用い、製造例1と同様にして得られた乳化重合液100重量部に対し、老化防止剤として、3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオン酸ステアリルの50重量%水分散液に代えて、2-メルカプトベンズイミダゾール(商品名「ノクラック MB」、大内新興化学工業社製)の50重量%水分散液(0.2重量%のラウリル硫酸ナトリウム(商品名「エマール 2FG」、花王社製)の水溶液50部に、2-メルカプトベンズイミダゾール50部を添加・混合することにより調製)0.6部(乳化重合液を製造する際に用いた仕込みの単量体の合計100部に対して1部)を添加した以外は、製造例1と同様にして、混合液の調製および凝固操作を行い、アクリルゴム(A5)の含水クラムを得た。
製造例1と同様にして得られた乳化重合液を用い、製造例1と同様にして得られた乳化重合液100重量部に対し、老化防止剤として、3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオン酸ステアリルの50重量%水分散液に代えて、4, 4’-ビス(α,α-ジメチルベンジル)ジフェニルアミン(商品名「ノクラック CD」、大内新興化学工業社製)の50重量%水分散液(0.2重量%のラウリル硫酸ナトリウム(商品名「エマール 2FG」、花王社製)の水溶液50部に、4, 4’-ビス(α,α-ジメチルベンジル)ジフェニルアミン50部を添加・混合することにより調製)0.6部(乳化重合液を製造する際に用いた仕込みの単量体の合計100部に対して1部)を添加した以外は、混合液の調製および凝固操作を行い、製造例1と同様にして、アクリルゴム(A6)の含水クラムを得た。
製造例1と同様にして得られた乳化重合液を用い、製造例1と同様にして得られた乳化重合液100重量部に対し、老化防止剤として、3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオン酸ステアリルの50重量%水分散液に代えて、モノ(又はジ、又はトリ)(α-メチルベンジル)フェノール(商品名「ノクラック SP」、大内新興化学工業社製)の50重量%水分散液(0.2重量%のラウリル硫酸ナトリウム(商品名「エマール 2FG」、花王社製)の水溶液50部に、モノ(又はジ、又はトリ)(α-メチルベンジル)フェノール50部を添加・混合することにより調製)0.6部(乳化重合液を製造する際に用いた仕込みの単量体の合計100部に対して1部)を添加した以外は、混合液の調製および凝固操作を行い、製造例1と同様にして、アクリルゴム(A7)の含水クラムを得た。
製造例1と同様にして得られた乳化重合液を用い、製造例1と同様にして得られた乳化重合液100重量部に対し、老化防止剤としての3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオン酸ステアリル0.3部(乳化重合液を製造する際に用いた仕込みの単量体の合計100部に対して1部)を、水分散液の状態とせずに、そのまま添加した以外は、製造例1と同様にして、混合液の調製および凝固操作を行い、アクリルゴム(A8)の含水クラムを得た。
製造例1と同様にして得られた乳化重合液を用い、製造例1と同様にして得られた乳化重合液100重量部に対し、老化防止剤としての2,4-ビス[(オクチルチオ)メチル]-6-メチルフェノール0.3部(乳化重合液を製造する際に用いた仕込みの単量体の合計100部に対して1部)を、水分散液の状態とせずに、そのまま添加した以外は、製造例4と同様にして、混合液の調製および凝固操作を行い、アクリルゴム(A9)の含水クラムを得た。
製造例1と同様にして得られた乳化重合液を用い、製造例1と同様にして得られた乳化重合液100重量部に対し、老化防止剤としての2-メルカプトベンズイミダゾール0.3部(乳化重合液を製造する際に用いた仕込みの単量体の合計100部に対して1部)を、水分散液の状態とせずに、そのまま添加した以外は、混合液の調製および凝固操作を行い、製造例5と同様にして、アクリルゴム(A10)の含水クラムを得た。
製造例1と同様にして得られた乳化重合液を用い、製造例1と同様にして得られた乳化重合液100重量部に対し、老化防止剤としての4, 4’-ビス(α,α-ジメチルベンジル)ジフェニルアミン0.3部(乳化重合液を製造する際に用いた仕込みの単量体の合計100部に対して1部)を、水分散液の状態とせずに、そのまま添加した以外は、製造例6と同様にして、混合液の調製および凝固操作を行い、アクリルゴム(A11)の含水クラムを得た。
製造例1と同様にして得られた乳化重合液を用い、製造例1と同様にして得られた乳化重合液100重量部に対し、老化防止剤としてのモノ(又はジ、又はトリ)(α-メチルベンジル)フェノール0.3部(乳化重合液を製造する際に用いた仕込みの単量体の合計100部に対して1部)を、水分散液の状態とせずに、そのまま添加した以外は、製造例7と同様にして、混合液の調製および凝固操作を行い、アクリルゴム(A12)の含水クラムを得た。
製造例1と同様にして得られた乳化重合液を用い、製造例1と同様にして得られた乳化重合液100重量部に対し、老化防止剤としての3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオン酸ステアリル1部(乳化重合液を製造する際に用いた仕込みの単量体の合計100部に対して3.33部)を、水分散液の状態とせずに、そのまま添加した以外は、製造例1と同様にして、混合液の調製および凝固操作を行い、アクリルゴム(A13)の含水クラムを得た。
ホモミキサーを備えた混合容器に、純水46.294部、アクリル酸エチル49.3部、アクリル酸n-ブチル49.3部、フマル酸モノn-ブチル1.4部、アニオン性界面活性剤としてのラウリル硫酸ナトリウム(商品名「エマール 2FG」、花王社製)0.567部、ノニオン性界面活性剤としてのポリオキシエチレンドデシルエーテル(商品名「エマルゲン 105」、花王社製)1.4部、および老化防止剤としての3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオン酸ステアリル(商品名「Irganox 1076」、BASF社製)1部を仕込み、攪拌することで、単量体乳化液を得た。
単量体乳化液を調製する際に、老化防止剤として、3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオン酸ステアリルに代えて、2,4-ビス[(オクチルチオ)メチル]-6-メチルフェノール(商品名「Irganox 1520L」、BASF社製)1部を配合した以外は、製造例14と同様にして、単量体乳化液を得た。
単量体乳化液を調製する際に、老化防止剤として、3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオン酸ステアリルに代えて、2-メルカプトベンズイミダゾール(商品名「ノクラック MB」、大内新興化学工業社製)1部を配合した以外は、製造例14と同様にして、単量体乳化液を得た。
単量体乳化液を調製する際に、老化防止剤として、3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオン酸ステアリルに代えて、4, 4’-ビス(α,α-ジメチルベンジル)ジフェニルアミン(商品名「ノクラック CD」、大内新興化学工業社製)1部を配合した以外は、製造例14と同様にして、単量体乳化液を得た。
単量体乳化液を調製する際に、老化防止剤として、3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオン酸ステアリルに代えて、モノ(又はジ、又はトリ)(α-メチルベンジル)フェノール(商品名「ノクラック SP」、大内新興化学工業社製)1部を配合した以外は、製造例14と同様にして、単量体乳化液を得た。
単量体乳化液を調製する際に、老化防止剤としての3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオン酸ステアリルを配合しなかった以外は、製造例14と同様にして、単量体乳化液を得た。
バンバリーミキサーを用いて、製造例1で得られたアクリルゴム(A1)100部に、カーボンブラック(商品名「シーストSO」、東海カーボン社製)60部、ステアリン酸2部、エステル系ワックス(商品名「グレックG-8205」、大日本インキ化学社製)1部、および、4, 4’-ビス(α,α-ジメチルベンジル)ジフェニルアミン(商品名「ノクラック CD」、大内新興化学工業社製)2部を添加して、50℃で5分間混合した。次いで、得られた混合物を50℃のロールに移して、ヘキサメチレンジアミンカーバメート(商品名「Diak#1」、デュポンダウエラストマー社製、脂肪族多価アミン化合物)0.5部、および1,3-ジ-o-トリルグアニジン(商品名「ノクセラーDT」、大内新興化学工業社製、架橋促進剤)2部を配合して、混練することにより、アクリルゴム組成物を得た。
製造例1で得られたアクリルゴム(A1)に代えて、製造例2~7で得られたアクリルゴム(A2)~(A7)をそれぞれ使用した以外は、実施例1と同様にして、アクリルゴム組成物を得て、同様に測定・評価を行った結果を表2に示す。
製造例1で得られたアクリルゴム(A1)に代えて、製造例8~19で得られたアクリルゴム(A8)~(A19)をそれぞれ使用した以外は、実施例1と同様にして、アクリルゴム組成物を得て、同様に測定・評価を行った結果を表2に示す。
(*2)凝固前の乳化重合液に添加した配合剤の添加量は、乳化重合液100部に対する配合量で示した。
(*3)50重量%水分散液は、0.2重量%のラウリル硫酸ナトリウム(商品名「エマール 2FG」、花王社製)の水溶液50部に、老化防止剤50部を添加・混合することにより調製した。
また、乳化重合前の単量体乳化液に、老化防止剤を添加した製造例14~18においては、得られた乳化重合液中に凝集物が発生してしまい、このような凝集物の付着による攪拌装置内の汚れが発生してしまう結果となった(製造例14~18、比較例7~11)。
さらに、アクリルゴムの製造工程において、老化防止剤を添加しなかった製造例19においては、乾燥によりムーニー粘度の低下が発生し、また、製造例19により得られたアクリルゴムを用いて得られるゴム架橋物は、引張強度に劣るものであった(製造例19、比較例12)。
Claims (19)
- アクリルゴムを製造する方法であって、
前記アクリルゴムを形成するための単量体を乳化重合することで、乳化重合液を得る乳化重合工程と、
前記乳化重合液に、老化防止剤を溶液または分散液の状態にて添加する老化防止剤添加工程と、
前記老化防止剤を添加した乳化重合液に、凝固剤を添加し、含水クラムを得る凝固工程と、を備えるアクリルゴムの製造方法。 - アクリルゴム中の、老化防止剤の含有量が500重量ppm以上である請求項1に記載のアクリルゴムの製造方法。
- アクリルゴム中の、老化防止剤の含有量が12,000重量ppm以下である請求項2に記載のアクリルゴムの製造方法。
- アクリルゴム中における、アクリルゴム成分の含有量が95重量%以上である請求項1~3のいずれかに記載のアクリルゴムの製造方法。
- 前記老化防止剤添加工程における、前記老化防止剤の添加量を、前記乳化重合液中に含まれるアクリルゴム成分100重量部に対して、0.1~2重量部とする請求項1~4のいずれかに記載のアクリルゴムの製造方法。
- 前記老化防止剤添加工程における、前記老化防止剤の添加量を、前記乳化重合液中に含まれるアクリルゴム成分100重量部に対して、0.2~1.2重量部とする請求項5に記載のアクリルゴムの製造方法。
- 前記老化防止剤が、硫黄原子を含有しないフェノール系老化防止剤、チオフェノール系老化防止剤、アミン系老化防止剤およびイミダゾール系老化防止剤から選択される少なくとも1種である請求項1~6のいずれかに記載のアクリルゴムの製造方法。
- 前記老化防止剤が、3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオン酸ステアリル、2,4-ビス[(オクチルチオ)メチル]-6-メチルフェノール、4,4’―ビス(α,α-ジメチルベンジル)ジフェニルアミン、2-メルカプトベンズイミダゾール、およびモノ(又はジ、又はトリ)(α-メチルベンジル)フェノールから選択される少なくとも1種である請求項7に記載のアクリルゴムの製造方法。
- 前記老化防止剤が、3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオン酸ステアリルである請求項8に記載のアクリルゴムの製造方法。
- 前記老化防止剤を水溶液または水分散液の状態にて添加する請求項1~9のいずれかに記載のアクリルゴムの製造方法。
- 前記老化防止剤を溶液または分散液の状態にて添加する際における、前記溶液または前記分散液中における老化防止剤の含有割合を、10~90重量%とする請求項1~10のいずれかに記載のアクリルゴムの製造方法。
- 前記老化防止剤を溶液または分散液の状態にて添加する際における、前記溶液または前記分散液中における老化防止剤の含有割合を、20~60重量%とする請求項11に記載のアクリルゴムの製造方法。
- 前記含水クラムを、スクリュー型押出乾燥機または熱風乾燥機にて、150℃以上の温度で乾燥する乾燥工程をさらに備える請求項1~12のいずれかに記載のアクリルゴムの製造方法。
- 前記単量体の乳化重合を、ノニオン性乳化剤およびアニオン性乳化剤の存在下で行う請求項1~13のいずれかに記載のアクリルゴムの製造方法。
- 前記ノニオン性乳化剤およびアニオン性乳化剤の使用量を、ノニオン性乳化剤/アニオン性乳化剤の重量比で、50/50~75/25とする請求項14に記載のアクリルゴムの製造方法。
- 前記乳化重合工程において、前記アクリルゴムを形成するための単量体、重合開始剤および還元剤を、重合反応開始から任意の時間まで、重合反応系に連続的に滴下しながら乳化重合反応を行う請求項1~15のいずれかに記載のアクリルゴムの製造方法。
- 前記アクリルゴムを形成するための単量体を、乳化剤および水と混合してなる単量体乳化液の状態にて、重合反応開始から任意の時間まで、重合反応系に連続的に滴下しながら乳化重合反応を行う請求項16に記載のアクリルゴムの製造方法。
- 請求項1~17のいずれかに記載の製造方法により得られるアクリルゴムに、架橋剤を配合する工程を備えるアクリルゴム組成物の製造方法。
- 請求項18に記載の製造方法により得られるアクリルゴム組成物を架橋する工程を備えるゴム架橋物の製造方法。
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CN110198971B (zh) | 2022-03-11 |
KR102524865B1 (ko) | 2023-04-21 |
CN110198971A (zh) | 2019-09-03 |
EP3575345B1 (en) | 2022-05-11 |
EP3575345A1 (en) | 2019-12-04 |
JPWO2018139466A1 (ja) | 2019-11-21 |
EP3575345A4 (en) | 2020-08-19 |
JP6760403B2 (ja) | 2020-09-23 |
KR20190104171A (ko) | 2019-09-06 |
SG11201906761PA (en) | 2019-08-27 |
TW201833145A (zh) | 2018-09-16 |
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