Classifications

• • 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
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
  • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
• • 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
  • 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
• • 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
  • 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
  • C08F220/22—Esters containing halogen
  • C08F220/24—Esters containing halogen containing perhaloalkyl radicals
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
  • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/02—Emulsion paints including aerosols
  • C09D5/022—Emulsions, e.g. oil in water
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere

Definitions

• the present disclosure relates to an aqueous emulsion, its use and its manufacturing method.
• Patent Document 2 a radically polymerizable monomer containing a perfluoroalkyl group having 1 to 6 carbon atoms and having no functional group, and a radically polymerizable monomer having no functional group
• An object of the present disclosure is to provide a novel aqueous emulsion that can be used as a release agent that has a low load force at the time of release, excellent release retention, and excellent product stability. .
• Section 1 (A) a fluoro(meth)acrylate monomer having a fluoroalkyl group having 1 to 6 carbon atoms; An aqueous emulsion containing (B) an alkyl (meth)acrylate monomer; and (C) polymer particles obtainable by emulsion polymerization of a fluorinated oil having no hydrogen atoms.
• Section 2. Item 2. The aqueous emulsion according to item 1, wherein the fluorine-based oil (C) is a perfluoropolyether.
• Item 3. Item 3. The aqueous emulsion according to Item 1 or 2, wherein the fluorine-based oil (C) has a number average molecular weight of 10,000 or less.
• R 3 is a linear monovalent aliphatic hydrocarbon group having 10 to 30 carbon atoms
• R 4 is a hydrogen atom or a methyl group.
• Item 6. Item 6. The aqueous emulsion according to any one of Items 1 to 5, wherein the portion derived from the alkyl (meth)acrylate monomer (B) accounts for 1% by weight or less of the solid content.
• Item 7. Item 7. The aqueous emulsion according to item 6, wherein in the alkyl (meth)acrylate monomer (B), R 3 is a linear monovalent aliphatic hydrocarbon group having 10 to 30 carbon atoms.
• Item 8. Item 8.
• Item 9. Item 9. A release agent containing the aqueous emulsion according to any one of items 1 to 8.
• Item 9. Use of the aqueous emulsion according to any one of Items 1 to 8 as a release agent.
• Item 11. A method for producing an aqueous emulsion, (A) a fluoro(meth)acrylate monomer having a fluoroalkyl group having 1 to 6 carbon atoms; A method comprising the step of emulsion-polymerizing (B) an alkyl (meth)acrylate monomer and (C) a fluorinated oil having no hydrogen atom to obtain polymer particles.
• a method for forming a release agent coating comprising the step of applying the aqueous emulsion according to any one of items 1 to 8 to the inner surface of a mold to form a release agent coating.
• Item 13 (1) A step of applying the aqueous emulsion according to items 1 to 8 to the inner surface of a mold to form a release agent coating; (2) a step of filling a molding composition into a mold having a release agent film formed in step (1) to mold a molding material; and (3) the molding material molded in step (2) A method for producing a molded molding material, including the step of releasing the mold from the mold.
• (meth)acrylate is used as a generic term for acrylate and methacrylate.
• Aqueous Emulsion The aqueous emulsion of the present disclosure comprises: (A) a fluoro(meth)acrylate monomer having a fluoroalkyl group having 1 to 6 carbon atoms; It is an aqueous emulsion containing (B) an alkyl (meth)acrylate monomer; and (C) polymer particles obtained by emulsion polymerization of a fluorinated oil having no hydrogen atoms.
• Fluoro (meth) acrylate monomer (A) The fluoro(meth)acrylate monomer (A) is not particularly limited as long as it has a fluoroalkyl group having 1 to 6 carbon atoms.
• the fluoro(meth)acrylate monomer (A) is preferably one containing a perfluoroalkyl group.
• the fluoroalkyl group of the fluoro(meth)acrylate monomer (A) may be linear or branched. A straight-chain fluoroalkyl group is preferred.
• the fluoroalkyl group is not particularly limited, but is preferably a fluoroalkyl group having 2, 4 or 6 carbon atoms from the viewpoint of ease of industrial production.
• the fluoroalkyl group is preferably a fluoroalkyl group having 1 to 6 carbon atoms, more preferably a fluoroalkyl group having 2 to 6 carbon atoms, from the viewpoint that better releasability can be imparted to the release agent.
• a fluoroalkyl group of 6 is more preferred.
• a perfluoroalkyl group having 6 carbon atoms is particularly preferred.
• the fluoro(meth)acrylate monomer (A) has at least a fluoroalkyl group and a (meth)acrylate group.
• the partial structure of the fluoro(meth)acrylate monomer (A), excluding the fluoroalkyl group and the (meth)acrylate group, can be selected from a wide range as long as the effects of the present disclosure are not impaired.
• the fluoro(meth)acrylate monomer (A) further contains one or more substituents such as an alkyl group and an alkylene group that are inert with respect to the reaction with the molding material, in addition to the fluoroalkyl group and the (meth)acrylate group. may have.
• the fluoro(meth)acrylate monomer (A) further has an ester bond inert with respect to reaction with the molding material between its substituents or between a substituent and a fluoroalkyl group or (meth)acrylate group.
• the first and other bonds may be inserted.
• fluoro(meth)acrylate monomer (A) examples include perfluoroalkyl group-containing (meth)acrylic acid esters represented by the following general formula (I).
• Rf is a perfluoroalkyl group having 1 to 6 carbon atoms
• R 1 is a linear or branched divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group or a divalent cyclic aliphatic hydrocarbon group
• R2 is a hydrogen atom, a chlorine atom or a methyl group.
• R 1 is a linear or branched divalent aliphatic hydrocarbon group, divalent aromatic hydrocarbon group or divalent cycloaliphatic hydrocarbon group.
• R 1 is preferably a linear or branched divalent aliphatic hydrocarbon group having 1 to 30 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms, or a divalent hydrocarbon group having 6 to 12 carbon atoms.
• R 1 is more preferably a linear or branched divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms, or 6 to 10 carbon atoms. is a divalent cycloaliphatic hydrocarbon group.
• linear or branched divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms is not particularly limited, but examples include an alkylene group having 1 to 10 carbon atoms.
• the alkylene group having 1 to 10 carbon atoms includes methylene group, ethylene group, trimethylene group, 2-methylethylene group, hexylene group and octylene group.
• alkylene groups having 1 to 10 carbon atoms alkylene groups having 1 to 6 carbon atoms are preferred, alkylene groups having 1 to 4 carbon atoms are more preferred, and alkylene groups having 1 to 2 carbon atoms are even more preferred.
• the divalent aromatic hydrocarbon group having 6 to 10 carbon atoms is not particularly limited, and examples thereof include a 1,4-phenylene group, a 1,4-bismethylenephenylene group and a 1,4-bisethylenephenylene group. mentioned.
• the divalent cycloaliphatic hydrocarbon group having 6 to 10 carbon atoms is not particularly limited, but examples thereof include 1,4-cyclohexylene group, 1,4-bismethylenecyclohexylene group and 1,4-bisethylenecyclohexylene group.
• a silene group and the like can be mentioned.
• perfluoroalkyl group-containing (meth)acrylic acid ester represented by the general formula (I) include the following.
• CH2 CH - COO - CH2-(CF2) 6F
• CH2 CH- COO- ( CH2 ) 2- ( CF2 )6F
• CH2 C( CH3 )-COO - CH2- ( CF2) 6F
• CH2 C( CH3 )-COO-( CH2 ) 2- ( CF2 ) 6F
• the aqueous emulsion of the present disclosure contains polymer particles obtained by emulsion polymerization of one of the fluoro(meth)acrylate monomers (A) described above with the alkyl(meth)acrylate monomer (B) and the fluorine-based oil (C). It may contain polymer particles obtained by emulsion polymerization of two or more of them with an alkyl (meth)acrylate monomer (B) and a fluorine-based oil (C).
• Alkyl (meth)acrylate monomer (B) The structure of the site of the alkyl (meth)acrylate monomer (B) excluding the alkyl group and the (meth)acrylate group can be selected from a wide range of structures as long as the effects of the present disclosure are not impaired.
• the monomer (B) may have a bond such as an ester bond inserted between the alkyl group and the (meth)acrylate group that is inert with respect to the reaction with the molding material.
• alkyl (meth)acrylate monomers (B) examples include (meth)acrylic acid esters represented by the following general formula (II).
• R 3 is a linear or branched monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group or a monovalent cyclic aliphatic hydrocarbon group
• R4 is a hydrogen atom or a methyl group.
• R 3 is a linear or branched monovalent aliphatic hydrocarbon group, monovalent aromatic hydrocarbon group or monovalent cycloaliphatic hydrocarbon group.
• R 3 is preferably a linear or branched monovalent aliphatic hydrocarbon group having 1 to 30 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms, or a monovalent C 6 to 12 cycloaliphatic hydrocarbon groups.
• the linear or branched monovalent aliphatic hydrocarbon group having 1 to 30 carbon atoms is not particularly limited, but examples thereof include alkyl groups having 1 to 30 carbon atoms, Alkyl groups of 25 are preferred, and alkyl groups of 1 to 22 carbon atoms are more preferred.
• R 3 in the general formula (II) is preferably 6 to 30, more preferably 8 to 28, and even more preferably 10 to 24. .
• alkyl groups having 1 to 22 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group and t-butyl group.
• n-pentyl group neopentyl group, t-pentyl group, n-hexyl group, 2-ethylbutyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group, tridecyl group , tetradecyl group, cetyl group, stearyl group and behenyl group.
• examples of monovalent aromatic hydrocarbon groups having 6 to 12 carbon atoms include a phenyl group, a 2-ethylphenyl group, an indenyl group, a toluyl group and a benzyl group.
• the monovalent C 6-12 cycloaliphatic hydrocarbon group includes a cyclohexyl group, a norbornyl group, a norbornylmethyl group, an isobornyl group, a bornyl group, a menthyl group, an octahydroindenyl group, and an adamantyl group. and dimethyladamantyl groups.
• (meth)acrylic acid ester represented by the general formula (II) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and (meth)acrylic acid.
• the aqueous emulsion of the present disclosure contains polymer particles obtained by emulsion polymerization of one of the alkyl (meth)acrylate monomers (B) described above with the fluoro(meth)acrylate monomer (A) and the fluorine-based oil (C). It may contain polymer particles obtained by emulsion polymerization of two or more of them with a fluoro(meth)acrylate monomer (A) and a fluorine-based oil (C).
• the proportion of the portion derived from the alkyl (meth)acrylate monomer (B) in the solid content is preferably 3.5% by weight or less, and 2.0% by weight or less. is more preferably 0.5% by weight or less.
• the proportion of the portion derived from the alkyl (meth)acrylate monomer (B) in the solid content is preferably 3.5% by weight or less, and 2.0% by weight. % or less, more preferably 0.5% by weight or less.
• the ratio of fluoro(meth)acrylate monomer (A) to the total amount of fluoro(meth)acrylate monomer (A) and alkyl(meth)acrylate monomer (B) is preferably 75% by weight or more from the viewpoint of storage stability. , more preferably 93% by weight or more, and even more preferably 99% by weight or more.
• the ratio of the fluoro(meth)acrylate monomer (A) to the total amount of the fluoro(meth)acrylate monomer (A) and the alkyl(meth)acrylate monomer (B) is preferably 75% by weight or more in terms of releasability. , more preferably 93% by weight or more, and even more preferably 99% by weight or more.
• Fluorinated oil having no hydrogen atoms The fluorine-based oil (C) does not have hydrogen atoms and is liquid at room temperature.
• Examples of the fluorinated oil (C) include perfluorocarbons, perfluoropolyethers, oligomers of trifluoroethylene chloride, and the like.
• Perfluorocarbons include perfluorodecalin, perfluoromethyldecalin, perfluorotributylamine, perfluoropropylamine, perfluorohexane, and perfluorooctane.
• perfluoropolyethers include the following.
• n and m used in each compound are mutually independent integers.
• F ( CF ( CF3 ) CF2O ) nCF2CF3 (Krytox manufactured by Chemours) CF3O (CF ( CF3 ) CF2O ) n ( CF2O ) mCF3 (Fomblin Y manufactured by Solvay) CF3O ( CF2CF2O ) n ( CF2O ) mCF3 ( Fomblin Z manufactured by Solvay) F(CF 2 CF 2 CF 2 O) n CF 2 CF 3 (Demnum manufactured by Daikin Industries, Ltd.)
• the fluorine-based oil (C) preferably has a number average molecular weight of 10,000 or less, more preferably 7,000 or less, and further preferably 6,000 or less. Preferably, it is even more preferably 5000 or less.
• the fluorine-based oil (C) preferably has a number average molecular weight of 1,000 or more, more preferably 2,000 or more, and even more preferably 2,500 or more, from the standpoint of releasability.
• the fluorine-based oil (C) is a perfluoropolyether, it preferably has a number average molecular weight of 10000 or less, more preferably 7000 or less, from the viewpoint of storage stability of the aqueous emulsion of the present disclosure. , 6000 or less, and even more preferably 5000 or less.
• the fluorine-based oil (C) preferably has a number average molecular weight of 1,000 or more, more preferably 2,000 or more, and even more preferably 2,500 or more, from the standpoint of releasability.
• the aqueous emulsion of the present disclosure comprises: (A) a fluoro(meth)acrylate monomer having a fluoroalkyl group having 1 to 6 carbon atoms; (B) an alkyl (meth)acrylate monomer and (C) a fluorine-based oil having no hydrogen atom are subjected to emulsion polymerization to obtain polymer particles.
• the fluoro(meth)acrylate monomer (A), the alkyl(meth)acrylate monomer (B), and the fluorine-based oil (C) are as already described for the aqueous emulsion of the present disclosure.
• the emulsion polymerization is not particularly limited, it can be carried out, for example, as follows.
• Components (A) to (C) are emulsified in water in the presence of a polymerization initiator and an emulsifier, and after purging with nitrogen, the mixture is stirred at 50 to 80° C. for 1 to 10 hours for copolymerization.
• the polymerization initiator is not particularly limited, but examples include benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, and acetyl peroxide.
• azobisisobutylamidine-dihydrochloride azobisisobutyronitrile
• sodium peroxide potassium persulfate and water-soluble polymerization initiators such as ammonium persulfate, and azobisisobutyronitrile
• benzoyl peroxide di- Oil-soluble polymerization initiators such as t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydicarbonate and azobismethyl propionate.
• the polymerization initiator is usually used in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the monomer.
• the monomers are placed in water using an emulsifying device capable of imparting strong crushing energy, such as a high-pressure homogenizer or an ultrasonic homogenizer. It is preferable to make fine particles and polymerize using an oil-soluble polymerization initiator.
• various anionic, cationic or nonionic emulsifiers can be used as emulsifiers.
• the emulsifier is usually used in the range of 0.5-20 parts by weight per 100 parts by weight of the monomer.
• a nonionic emulsifier or an anionic emulsifier is preferred as the emulsifier.
• nonionic emulsifiers include, but are not particularly limited to, polyoxyethylene alkyl ethers, sorbitan alkylates, sorbitan alkyl esters, and the like.
• polyoxyethylene alkyl ethers include, but are not particularly limited to, polyoxyethylene lauryl ether.
• Anionic emulsifiers include alkyl sulfates, alkyl sulfonates and alkyl phosphates.
• the alkyl sulfate ester is not particularly limited, but examples thereof include sodium alkyl sulfate.
• cationic emulsifiers examples include quaternary ammonium salts and alkylamine salts.
• the quaternary ammonium salt is not particularly limited, but includes lauryltrimethylammonium chloride and the like.
• a compatibilizing agent such as a water-soluble organic solvent or a low-molecular-weight monomer to make these monomers sufficiently compatible. Addition of a compatibilizer can improve emulsifiability and copolymerizability.
• the water-soluble organic solvent as a compatibilizer is not particularly limited, but examples include acetone, methyl ethyl ketone, ethyl acetate, glycol-based solvents and ethanol.
• a water-soluble organic solvent as a compatibilizer a glycol-based solvent is preferable.
• glycol-based solvents include propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, diethylene glycol diethyl ether and tripropylene glycol.
• the water-soluble organic solvent is usually used in the range of 1-50 parts by weight per 100 parts by weight of water.
• the water-soluble organic solvent is preferably used in an amount of 10 to 40 parts by weight per 100 parts by weight of water.
• a chain transfer agent may be used to adjust the molecular weight of the resulting polymer.
• chain transfer agents include, but are not limited to, lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, 2-ethylhexyl thioglycolate and 2,3-dimethylcapto-1-propanol.
• Chain transfer agents may be used alone or in combination of two or more.
• a chain transfer agent is usually used in the range of 0.001 to 7.0 parts by weight per 100 parts by weight of the monomer.
• solution polymerization is not particularly limited, it can be carried out, for example, as follows.
• a monomer is dissolved in an organic solvent in the presence of a polymerization initiator, and after purging with nitrogen, the mixture is heated and stirred at a temperature in the range of 30 to 120° C. for 1 to 10 hours.
• polymerization initiators include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate and diisopropyl peroxydicarbonate. mentioned.
• the polymerization initiator is usually used in the range of 0.01-20 parts by weight per 100 parts by weight of the monomer.
• the polymerization initiator is preferably used in the range of 0.01 to 10 parts by weight per 100 parts by weight of the monomer.
• the organic solvent is not particularly limited as long as it is inert to the monomers and dissolves them.
• organic solvents include acetone, chloroform, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate and butyl acetate and the like.
• the organic solvent is usually used in the range of 50 to 2000 parts by weight per 100 parts by weight of the total monomers.
• the organic solvent is preferably used in the range of 50 to 1000 parts by weight with respect to 100 parts by weight of the total monomers.
• release agent of the present disclosure is a release agent containing the water-based emulsion described above.
• the release agent of the present disclosure is not particularly limited, but preferably contains 0.5% to 50% by weight, more preferably 1.0% to 30% by weight, and still more preferably 1.5% by weight of the aqueous emulsion described above. % to 20% by weight.
• the release agent of the present disclosure may further contain a surfactant for the purpose of improving wettability to the mold.
• the surfactant is not particularly limited, but a fluorine-based or non-fluorine-based surfactant or the like can be used.
• Anionic surfactants, nonionic surfactants and cationic surfactants can be used as fluorine-based or non-fluorine-based surfactants.
• fluorine-based surfactants include fluorine-containing polyoxyethylene, sulfonates, carboxylates, and quaternary ammonium salts.
• non-fluorine-based anionic surfactants include alkyl sulfates, alkyl sulfonates, alkyl phosphates, and the like.
• the alkyl sulfate ester is not particularly limited, but examples thereof include sodium alkyl sulfate.
• non-fluorine-based nonionic surfactants include, but are not particularly limited to, polyoxyethylene alkyl ethers, sorbitan alkylates, sorbitan alkyl esters, and the like.
• polyoxyethylene alkyl ethers include, but are not particularly limited to, polyoxyethylene lauryl ether.
• non-fluorinated cationic surfactants include quaternary ammonium salts and alkylamine salts.
• the quaternary ammonium salt is not particularly limited, but includes lauryltrimethylammonium chloride and the like.
• the content in the release agent composition is not particularly limited, but is usually 0.01% by weight to 20% by weight, preferably 0.01% by weight. ⁇ 15% by weight, more preferably 0.01% to 10% by weight.
• the release agent of the present disclosure further contains at least one additive selected from the group consisting of silicone compounds, wax-based compounds, fluorine-based compounds, etc., for the purpose of improving releasability and/or finishing properties.
• at least one additive selected from the group consisting of silicone compounds, wax-based compounds, fluorine-based compounds, etc., for the purpose of improving releasability and/or finishing properties.
• silicone compound examples include, but are not limited to, dimethylsilicone oil, methylphenylsilicone oil, fluorosilicone oil, and silicone resin.
• the content in the release agent composition is not particularly limited, but is usually 0.01% by weight to 20% by weight, preferably 0.01% by weight to 20% by weight. 15% by weight.
• the wax-based compound is not particularly limited, but examples include polyethylene wax, paraffin wax and carnauba wax.
• the content in the release agent composition is not particularly limited, but is usually 0.01% by weight to 20% by weight, preferably 0.01% by weight. ⁇ 15% by weight.
• the fluorine-based compound is not particularly limited, but includes, for example, polytetrafluoroethylene, fluoropolyether, and fluorochloropolyether.
• the content in the release agent composition is not particularly limited, but is usually 0.01% by weight to 20% by weight, preferably 0.01% by weight. ⁇ 15% by weight.
• the release agent of the present disclosure contains, but is not particularly limited to, at least one emulsifier selected from the group consisting of nonionic emulsifiers, anionic emulsifiers and cationic emulsifiers.
• the emulsifier at least one emulsifier selected from the group consisting of nonionic emulsifiers and anionic emulsifiers is preferred.
• the nonionic emulsifier is not particularly limited as long as it can emulsify the release agent of the present disclosure and disperse it in an aqueous emulsion.
• examples include polyoxyethylene alkyl ether, sorbitan alkylate and sorbitan alkyl. Ester etc. are mentioned.
• polyoxyethylene alkyl ethers include, but are not particularly limited to, polyoxyethylene lauryl ether.
• Anionic emulsifiers include alkyl sulfates, alkyl sulfonates and alkyl phosphates.
• the alkyl sulfate ester is not particularly limited, but examples thereof include sodium alkyl sulfate.
• cationic emulsifiers examples include quaternary ammonium salts and alkylamine salts.
• the quaternary ammonium salt is not particularly limited, but includes lauryltrimethylammonium chloride and the like.
• the content ratio in the release agent composition is not particularly limited, but is usually 0.5% by weight to 25% by weight, preferably 1.0%, based on 100 parts by weight of the monomer. % to 20% by weight, more preferably 2.0% to 15% by weight.
• the release agent of the present disclosure is not particularly limited, but may further contain the additives described in the description of the emulsion polymerization, that is, a compatibilizer and/or a chain transfer agent.
• the release agent of the present disclosure is not particularly limited, but may further contain an organic solvent or the like described in the explanation of the solution polymerization above.
• the release agent of the present disclosure is not particularly limited, it is usually used as follows. After the mold release agent is applied to the inner surface of the mold and the solvent and dispersant are dried and removed, a mold release agent film is formed on the mold, and the mold is filled with the molding composition to release the molding material. After molding, the molding material is released from the mold.
• the mold for which the mold release agent of the present disclosure is used is not particularly limited, and examples thereof include molds made of aluminum, SUS, iron, epoxy resin, wood, etc., nickel electroformed molds or chromium-plated molds, and the like. mentioned.
• the molding material to be released using the release agent of the present disclosure is not particularly limited, but for example, urethane rubber, H-NBR, NBR, silicone rubber, EPDM, CR, NR, fluororubber, SBR, BR , IIR and IR, and thermosetting resins such as urethane foam, epoxy resin, phenol resin and FRP.
• the release agent of the present disclosure exhibits particularly excellent release properties for silicone rubber, and is therefore preferably used for releasing silicone rubber.
• Example 1 Perfluorohexylethyl methacrylate (C6SFMA) 18.27 g, stearyl acrylate (StA) 1.38 g, Demnum S-20 (perfluoropolyether oil manufactured by Daikin Industries, average molecular weight 2700, structural formula F-(CF 2 CF 2 CF 2 O) n-CF 2 CF 3. ) 13.09 g, polyoxyethylene (20 mol) alkyl ether (nonionic emulsifier) 7.48 g, dipropylene glycol monomethyl ether 4.8 g, and pure water 70 g.
• C6SFMA Perfluorohexylethyl methacrylate
• StA stearyl acrylate
• Demnum S-20 perfluoropolyether oil manufactured by Daikin Industries, average molecular weight 2700, structural formula F-(CF 2 CF 2 CF 2 O) n-CF 2 CF 3.
• emulsification was performed with The obtained emulsified liquid was transferred to a 200 mL four-necked flask equipped with a reflux tube, a nitrogen inlet tube, a thermometer and a stirrer, added with 0.06 g of lauryl mercaptan and 0.13 g of ammonium persulfate, and stirred at 65°C under a stream of nitrogen. Reaction and polymerization were carried out for 3 hours. The solids concentration of the finished emulsion was 34.9%.
• Example 2 Instead of Demnum S-20, Demnum S-65 (Daikin Industries perfluoropolyether oil. Average molecular weight: 4500. Structural formula: F- ( CF2CF2CF2O ) n - CF2CF3 .) 13.09 g. Polymerization was carried out in the same manner as in Example 1, except that it was used. The finished emulsion solids content was 34.9%.
• Example 3 Polymerization was carried out in the same manner as in Example 1 except that 3.27 g of Demnum S-20 and 9.82 g of Demnum S-65 were used instead of Demnum S-20.
• the finished emulsion solids content was 34.9%.
• Example 4 Polymerization was carried out in the same manner as in Example 1, except that 6.54 g of Demnum S-20 and 6.55 g of Demnum S-65 were used instead of Demnum S-20.
• the finished emulsion solids content was 34.9%.
• Example 5 Polymerization was carried out in the same manner as in Example 1 except that 9.82 g of Demnum S-20 and 3.272 g of Demnum S-65 were used instead of Demnum S-20.
• the finished emulsion solids content was 34.9%.
• Example 6 Perfluorohexylethyl methacrylate (C6SFMA) 19.65g, Demnum S-20 13.09g, 7.48 g of polyoxyethylene (20 mol) alkyl ether (nonionic emulsifier), 4.8 g of dipropylene glycol monomethyl ether, and 70 g of pure water were sufficiently dissolved at 60° C. and emulsified with a high-pressure emulsifier.
• C6SFMA Perfluorohexylethyl methacrylate
• the obtained emulsified liquid was transferred to a 200 mL four-necked flask equipped with a reflux tube, a nitrogen inlet tube, a thermometer and a stirrer, added with 0.06 g of lauryl mercaptan and 0.13 g of ammonium persulfate, and stirred at 65°C under a stream of nitrogen. Reaction and polymerization were carried out for 3 hours. The solids concentration of the finished emulsion was 34.9%.
• Example 7 Polymerization was carried out in the same manner as in Example 6 except that Demnum S-65 was used instead of Demnum S-20.
• the finished emulsion solids content was 34.9%.
• Example 8 The same method as in Example 1, except that 18.27 g of perfluorohexylethyl methacrylate (C6SFMA) and 1.38 g of stearyl acrylate (StA) were changed to 19.45 g of perfluorohexylethyl methacrylate (C6SFMA) and 0.20 g of stearyl acrylate (StA). Polymerization was carried out at The final emulsion solids content was 34.8%.
• C6SFMA perfluorohexylethyl methacrylate
• StA stearyl acrylate
• Example 9 The same method as in Example 2, except that 18.27 g of perfluorohexylethyl methacrylate (C6SFMA) and 1.38 g of stearyl acrylate (StA) were changed to 19.45 g of perfluorohexylethyl methacrylate (C6SFMA) and 0.20 g of stearyl acrylate (StA). Polymerization was carried out at The finished emulsion solids content was 34.9%.
• C6SFMA perfluorohexylethyl methacrylate
• StA stearyl acrylate
• Example 10 The same method as in Example 3, except that 18.27 g of perfluorohexylethyl methacrylate (C6SFMA) and 1.38 g of stearyl acrylate (StA) were changed to 19.45 g of perfluorohexylethyl methacrylate (C6SFMA) and 0.20 g of stearyl acrylate (StA). Polymerization was carried out at The finished emulsion solids content was 34.9%.
• C6SFMA perfluorohexylethyl methacrylate
• StA stearyl acrylate
• Example 11 The same method as in Example 4, except that 18.27 g of perfluorohexylethyl methacrylate (C6SFMA) and 1.38 g of stearyl acrylate (StA) were changed to 19.45 g of perfluorohexylethyl methacrylate (C6SFMA) and 0.20 g of stearyl acrylate (StA). Polymerization was carried out at The finished emulsion solids content was 34.9%.
• C6SFMA perfluorohexylethyl methacrylate
• StA stearyl acrylate
• Example 12 The same method as in Example 5, except that 18.27 g of perfluorohexylethyl methacrylate (C6SFMA) and 1.38 g of stearyl acrylate (StA) were changed to 19.45 g of perfluorohexylethyl methacrylate (C6SFMA) and 0.20 g of stearyl acrylate (StA). Polymerization was carried out at The finished emulsion solids content was 34.9%.
• C6SFMA perfluorohexylethyl methacrylate
• StA stearyl acrylate
• Example 13 Polymerization was carried out in the same manner as in Example 10, except that 0.20 g of lauryl acrylate (LA) was used instead of stearyl acrylate (StA). The final emulsion solids content was 34.8%.
• LA lauryl acrylate
• StA stearyl acrylate
• Example 14 Polymerization was carried out in the same manner as in Example 10, except that 0.20 g of behenyl acrylate (BA) was used instead of stearyl acrylate (StA). The final emulsion solids content was 34.8%. The finished emulsion solids content was 34.9%.
• BA behenyl acrylate
• StA stearyl acrylate
• Example 15 Demnum S-20 was replaced with Demnum S-200 (perfluoropolyether oil manufactured by Daikin Industries, average molecular weight 8400, structural formula F-(CF 2 CF 2 CF 2 O)n-CF 2 CF 3 ). Polymerization was carried out in the same manner as in Example 1, except for this. The finished emulsion solids content was 34.9%.
• Example 16 Instead of Demnum S-20, Fomblin M03 (perfluoropolyether oil from SOLVAY. Average molecular weight 3900. Polymerization was carried out in the same manner as in Example 1, except that the structural formula was changed to CF 3 O(CF 2 CF 2 O) n (CF 2 O) m CF 3 ). The finished emulsion solids content was 34.9%.
• Example 17 Instead of Demnum S-20, Fomblin M15 (perfluoropolyether oil from SOLVAY. Average molecular weight 9700. Polymerization was carried out in the same manner as in Example 1, except that the structural formula was changed to CF 3 O(CF 2 CF 2 O) n (CF 2 O) m CF 3 ). The finished emulsion solids content was 34.9%.
• Example 18 Example 1 except that Demnum S-20 was replaced with Krytox 1525 (Chemours perfluoroalkyl ether oil, average molecular weight 3470, structural formula F(CF(CF 3 )CF 2 O) n CF 2 CF 3 ) Polymerization was carried out in the same manner as The finished emulsion solids content was 34.9%.
• Comparative example 1 18.27 g of perfluorohexylethyl methacrylate (C6SFMA), 1.38 g of stearyl acrylate (StA), 4.49 g of polyoxyethylene (20 mol) alkyl ether (nonionic emulsifier), 2.88 g of dipropylene glycol monomethyl ether, and 42 g of pure water at 60°C After sufficiently dissolving in , emulsification was performed with a high-pressure emulsifier.
• C6SFMA perfluorohexylethyl methacrylate
• StA stearyl acrylate
• polyoxyethylene (20 mol) alkyl ether nonionic emulsifier
• dipropylene glycol monomethyl ether 2.88 g of dipropylene glycol monomethyl ether
• the obtained emulsified liquid was transferred to a 200 mL four-necked flask equipped with a reflux tube, a nitrogen inlet tube, a thermometer and a stirrer, added with 0.06 g of lauryl mercaptan and 0.13 g of ammonium persulfate, and stirred at 65°C under a stream of nitrogen. Reaction and polymerization were carried out for 3 hours. The solids concentration of the finished emulsion was 34.9%.
• Comparative example 2 14.54 g of perfluorohexylethyl methacrylate (C6SFMA), 5.11 g of stearyl acrylate (StA), 4.49 g of polyoxyethylene (20 mol) alkyl ether (nonionic emulsifier), 2.88 g of dipropylene glycol monomethyl ether, and 42 g of pure water at 60°C After sufficiently dissolving in , emulsification was performed with a high-pressure emulsifier.
• C6SFMA perfluorohexylethyl methacrylate
• StA stearyl acrylate
• polyoxyethylene (20 mol) alkyl ether nonionic emulsifier
• dipropylene glycol monomethyl ether 2.88 g of dipropylene glycol monomethyl ether
• the obtained emulsified liquid was transferred to a 200 mL four-necked flask equipped with a reflux tube, a nitrogen inlet tube, a thermometer and a stirrer, added with 0.06 g of lauryl mercaptan and 0.13 g of ammonium persulfate, and stirred at 65°C under a stream of nitrogen. Reaction and polymerization were carried out for 3 hours. The solids concentration of the finished emulsion was 34.9%.
• Comparative example 3 18.27 g of perfluorohexylethyl methacrylate (C6SFMA), 1.38 g of stearyl acrylate (StA), 7.48 g of polyoxyethylene (20 mol) alkyl ether (nonionic emulsifier), 4.8 g of dipropylene glycol monomethyl ether, and 70 g of pure water at 60°C After sufficiently dissolving in , emulsification was performed with a high-pressure emulsifier.
• C6SFMA perfluorohexylethyl methacrylate
• StA stearyl acrylate
• polyoxyethylene (20 mol) alkyl ether nonionic emulsifier
• 4.8 g of dipropylene glycol monomethyl ether 4.8 g of dipropylene glycol monomethyl ether
• the obtained emulsified liquid was transferred to a 200 mL four-necked flask equipped with a reflux tube, a nitrogen inlet tube, a thermometer and a stirrer, added with 0.06 g of lauryl mercaptan and 0.13 g of ammonium persulfate, and stirred at 65°C under a stream of nitrogen. Reaction and polymerization were carried out for 3 hours.
• the solids concentration of the finished emulsion was 26.5%. 3.27 g of Demnum S-20 and 9.82 g of Demnum S-65 were added to this emulsion, and after sufficient stirring at 60° C., high-pressure emulsification was performed.
• the resulting emulsion had a solid content concentration of 34.8%.
• Comparative example 4 3.27g of Demnum S-20, 9.82g of Demnum S-65, 3.0g of polyoxyethylene (20 mol) alkyl ether (nonionic emulsifier), 1.92g of dipropylene glycol monomethyl ether, and 28g of pure water are thoroughly dissolved at 60°C, Emulsification was performed using a high-pressure emulsifier. The solids concentration of the finished emulsion was 34.7%. 45.01 g of this Demnum emulsion and 69.21 g of the emulsion obtained in Comparative Example 1 were placed in a 200 CC beaker and mixed with stirring at 25°C. The resulting emulsion had a solid content concentration of 34.8%.
• Test method for mold release durability 1.
• the release agent compositions prepared in Example 1-18 and Comparative Example 1-4 were each diluted with water to 0.3 mass%, and the molds (three molds) were kept at 180°C under the same conditions using a spray gun. After application to the cylindrical medium-sized hole of the vinyl methyl silicone rubber (VQM) was injected into the hole. 2. After that, the above vinyl methyl silicone rubber was press-molded at 180° C. for 2 minutes at 15 MPa. 3. After press-molding, the resistance of the medium-sized cylindrical molding was measured with a pressure gauge (0 to 200 N). 4. Thereafter, the mold was molded without applying the release agent composition, and the resistance measurement in 2 was repeated.
• VQM vinyl methyl silicone rubber
• the resistance was measured with a pressure gauge, and it was defined as the releasing force. It was assumed that the larger the resistance, the larger the releasing force, and the smaller the resistance, the smaller the releasing force. That is, the evaluation method is such that excellent releasability has low resistance, and poor releasability has high resistance.
• the number of times that this resistance was maintained at 20 N or less was defined as the number of sustained times, and was defined as the release persistence.
• Test method for product stability The release agent compositions prepared in Examples 1-18 and Comparative Examples 1-4 were placed in a 100 cc glass bottle and left in a constant temperature bath at 40 ° C for 24 hours and 72 hours. The sedimentation state of the stencil composition was followed up. ⁇ indicates no sediment at all, ⁇ indicates a faint presence, ⁇ ⁇ indicates a faint presence, ⁇ indicates a circular shape, and ⁇ indicates a clear presence or two-layer separation. did.
• Table 1 shows the evaluation results. Obtained by emulsion polymerization of (A) a fluoro (meth) acrylate monomer having a fluoroalkyl group having 1 to 6 carbon atoms, (B) an alkyl (meth) acrylate monomer, and (C) a fluorine-based oil having no hydrogen atoms
• Aqueous emulsions containing polymer particles Examples 1 to 18
• aqueous emulsions containing polymer particles Comparative Examples 1 and 2 obtained by emulsion polymerization of components (A) and (B). Therefore, the load force at the time of release was lower and the release durability was better.
• aqueous emulsions (Examples 1 to 18) obtained by emulsion polymerization of the components (A) to (C) were added to the aqueous emulsions obtained by emulsion polymerization of the components (A) and (B). C) was added (Comparative Example 3), and a case where an aqueous emulsion obtained by emulsion polymerization of components (A) and (B) and an emulsion obtained by emulsifying component (C) were blended (Comparative Example 4 ), the load force at the time of releasing from the mold was lower, the releasing durability was superior, and the product stability was also superior.
• Example 8 to 13 in which the content of component (B) in the solid content was about 0.5%, the product stability tended to be better. This tendency was more pronounced in Examples 8 to 13, in which the alkyl group of component (B) had 12 or 18 carbon atoms.

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