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WO2024248159A1 - Polymère contenant du fluor, composition d'agent de démoulage, et procédé de démoulage - Google Patents

Polymère contenant du fluor, composition d'agent de démoulage, et procédé de démoulage Download PDF

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Publication number
WO2024248159A1
WO2024248159A1 PCT/JP2024/020156 JP2024020156W WO2024248159A1 WO 2024248159 A1 WO2024248159 A1 WO 2024248159A1 JP 2024020156 W JP2024020156 W JP 2024020156W WO 2024248159 A1 WO2024248159 A1 WO 2024248159A1
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Prior art keywords
fluorine
release agent
agent composition
group
containing polymer
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English (en)
Japanese (ja)
Inventor
大貴 石井
秀一 植畑
靖史 中前
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Daikin Industries Ltd
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Daikin Industries Ltd
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Priority to CN202480036539.4A priority Critical patent/CN121219333A/zh
Publication of WO2024248159A1 publication Critical patent/WO2024248159A1/fr
Anticipated expiration legal-status Critical
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
    • B29C33/60—Releasing, lubricating or separating agents
    • 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
    • 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

Definitions

  • This disclosure relates to a fluorine-containing polymer, a release agent composition, and a release method.
  • fluorine-based release agents have been used as release agents, in addition to wax-based and silicone-based release agents (Patent Documents 1 to 4).
  • the purpose of this disclosure is to provide a new release agent composition that has excellent release properties.
  • a fluorine-containing polymer which is a compound represented by the formula: [2]
  • Y 12 is a group represented by formula (I): -(Ar) a1 -(CFH) b1 -(CH 2 ) c1 -(O) d1 - (I)
  • Ar is a divalent aromatic group optionally substituted by a fluorine atom or R A ;
  • the fluorine-containing polymer according to any one of the above [1] to [3], wherein in the fluorine-containing monomer (A), X 11 is a hydrogen atom, a methyl group or a chlorine atom.
  • the radical polymerization reactive monomer (B) is represented by the formula (II): [Wherein, R3 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.
  • the fluorine-containing polymer according to any one of the above [1] to [4], wherein the alkyl (meth)acrylate is represented by the following formula: [6]
  • a release agent composition comprising: (1) the fluorine-containing polymer according to any one of the above [1] to [5]; and (2) a liquid medium which is at least one kind selected from water and an organic solvent.
  • the release agent composition according to the above [6] which is a solution or aerosol containing an organic solvent, or an aqueous emulsion containing water.
  • the release agent composition according to the above [6] or [7] wherein the content of the fluorine-containing polymer (1) is 0.1 to 50% by weight based on the weight of the release agent composition.
  • a method for forming a release agent coating comprising a step of applying the release agent composition according to any one of the above [6] to [8] to an inner surface of a molding die to form a coating of the release agent composition.
  • a step of applying the release agent composition according to any one of the above items [6] to [8] to the inner surface of a molding die to form a coating of the release agent composition (ii) filling a molding composition into a mold having a coating of the mold release agent composition to obtain a molded body; and (iii) removing the molded body from the mold.
  • the present disclosure provides a new release agent composition with excellent release properties.
  • the release agent composition is The composition comprises (1) a fluoropolymer, and (2) a liquid medium which is water and/or an organic solvent.
  • the fluorine-containing polymer functions as a release agent.
  • the release agent composition is preferably in the form of a solution or an aqueous emulsion.
  • Fluorine-Containing Polymer The fluorine-containing polymer is the active ingredient in the release agent composition, that is, the release agent.
  • the fluorine-containing polymer is The fluorine-containing polymer has (A) a repeating unit derived from a fluorine-containing monomer, and (B) a repeating unit derived from a radical-polymerizable monomer having no functional group.
  • the fluorine-containing polymer may have another repeating unit (C) (a repeating unit derived from another monomer (C)).
  • R A can be CF 3 O—.
  • R A can be CF 3 NH-- or (CF 3 ) 2 N--, preferably CF 3 NH--.
  • X 11 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom).
  • X 11 is preferably a hydrogen atom, a methyl group, or a chlorine atom.
  • Y 11 is a direct bond, —O— or —NH—. Y 11 is preferably —O—. That is, the fluorine-containing monomer (A) is preferably an acrylate ester.
  • Y 12 is a direct bond or a divalent group.
  • Y 12 is preferably -(Ar) a1 -(CFH) b1 -(CH 2 ) c1 -(O) d1 -
  • Ar is a divalent aromatic group optionally substituted by a fluorine atom or R A ;
  • aromatic groups include aromatic rings containing only carbon as ring atoms (so-called arylenes), as well as aromatic rings containing nitrogen, oxygen or sulfur (so-called heteroarylenes), and groups having multiple aromatic rings.
  • the aromatic group preferably has a benzene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring, a tetracene ring, a pentacene ring, a benzopyrene ring, a chrysene ring, a pyrene ring, a triphenylene ring, a corannulene ring, an ovalene ring, an indole ring, a furan ring, a thiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a biphenyl ring, a terphenyl ring, a triphenylmethane ring, or a benzophenone ring.
  • the aromatic group preferably has a benzene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring, a tetracene ring, a pentacene ring, a benzopyrene ring, a chrysene ring, a pyrene ring, a triphenylene ring, a corannulene ring, or an ovalene ring, more preferably a benzene ring or a naphthalene ring, and even more preferably a benzene ring.
  • the aromatic group preferably has an indole ring, a furan ring, a thiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, or a pyrazine ring, more preferably an indole ring.
  • the aromatic group preferably has a biphenyl ring, a terphenyl ring, a triphenylmethane ring, or a benzophenone ring.
  • Ar is an unsubstituted divalent aromatic group.
  • Ar is a divalent aromatic group substituted with a fluorine atom or R 3 A.
  • Ar is a divalent aromatic group substituted by R 3 A.
  • Ar is a divalent aromatic group substituted with a fluorine atom.
  • the number of substituents on the aromatic group is not particularly limited, but may be, for example, 1 to 10, 1 to 5, 1 to 3, 1, 2, or 3. In one embodiment, the number of substituents on the aromatic group is 1 or more. In another embodiment, the aromatic group is fully substituted.
  • a1 is an integer from 0 to 10, preferably 0 or 1.
  • a1 is 0.
  • a1 is 1.
  • b1 is an integer from 0 to 200, preferably an integer from 0 to 6.
  • c1 is an integer between 0 and 200, preferably between 0 and 30.
  • d1 is an integer from 0 to 10, preferably an integer from 0 to 3.
  • Y 12 is -(CH 2 ) c1 -(O) d1 -(Ar) a1 -
  • Ar is a divalent aromatic group which may be substituted by a fluorine atom or R A , preferably an unsubstituted divalent aromatic group;
  • Y 12 is -(CH 2 ) c1 -
  • c1 is an integer from 1 to 36, preferably an integer from 1 to 30, and may be, for example, an integer from 1 to 9, or an integer from 1 to 3.
  • It is a group represented by the following formula:
  • Monomer (B) is a monomer that does not have a functional group. Since monomer (B) does not contain a functional group, it is possible to avoid a reaction between the release agent and the molding material during use.
  • Monomer (B) is a monomer that can be copolymerized with monomer (A).
  • Monomer (B) has a radical polymerization reactive site.
  • the radical polymerization reactive site is not particularly limited, but examples thereof include an acrylate group, a methacrylate group, a vinyl group, a vinylidene group, and an allyl group.
  • the radical polymerization reactive site is preferably an acrylate group or a methacrylate group.
  • the structure of the portion of monomer (B) other than the radical polymerization reactive portion can be selected from a wide range of structures as long as the effect of the present invention is not impaired.
  • monomer (B) may further have one or more substituents, such as an alkyl group, which are inactive in reaction with the molding material.
  • Monomer (B) may further have bonds, such as an ester bond, which are inactive in reaction with the molding material, inserted between the substituents or between the substituent and the radical polymerization reactive portion.
  • the monomer (B) for example, a monomer represented by the following formula (II): [Wherein, R3 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.
  • (meth)acrylic acid esters include those represented by the following formula:
  • R3 is a linear or branched monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, or a monovalent cyclic aliphatic hydrocarbon group.
  • R3 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 cyclic aliphatic hydrocarbon group having 6 to 12 carbon atoms.
  • the linear or branched monovalent aliphatic hydrocarbon group having 1 to 30 carbon atoms is not particularly limited, but examples include alkyl groups having 1 to 30 carbon atoms, preferably alkyl groups having 1 to 22 carbon atoms, and more preferably alkyl groups having 10 to 22 carbon atoms.
  • alkyl groups having 1 to 22 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, neopentyl, t-pentyl, n-hexyl, 2-ethylbutyl, n-heptyl, n-octyl, 2-ethylhexyl, nonyl, decyl, dodecyl, tridecyl, tetradecyl, cetyl, stearyl, and behenyl.
  • monovalent aromatic hydrocarbon groups having 6 to 12 carbon atoms include phenyl, 2-ethylphenyl, indenyl, toluyl, and benzyl groups.
  • monovalent cyclic aliphatic hydrocarbon groups having 6 to 12 carbon atoms include cyclohexyl, norbornyl, norbornylmethyl, isobornyl, bornyl, menthyl, octahydroindenyl, adamantyl, and dimethyladamantyl groups.
  • (meth)acrylic acid esters represented by formula (II) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, neopentyl (meth)acrylate, t-pentyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acryl
  • the release agent of the present invention may be a release agent consisting of a fluoropolymer obtainable by copolymerizing one of the above-mentioned monomers (B) with monomer (A), or may be a release agent consisting of a fluoropolymer structure obtainable by copolymerizing two or more of the monomers (B) with monomer (A).
  • the fluorine-containing polymer may have a repeating unit derived from another monomer.
  • the fluorine-containing polymer preferably does not have a repeating unit derived from another monomer. That is, the fluorine-containing polymer is preferably composed of repeating units derived from monomers (A) and (B).
  • the other monomer (C) include silicon-containing monomers, such as modified silicone oils, such as amino-modified silicone oils and acrylic-modified silicone oils; and di(meth)acrylate monomers.
  • the other monomers include ethylene, vinyl acetate, acrylonitrile, styrene, polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, and vinyl alkyl ether.
  • Each of the monomers (A) to (C) may be a single type or a mixture of two or more types.
  • the number average molecular weight (Mn) of the fluorine-containing polymer may generally be 1,000 to 1,000,000, for example, 2,000 to 500,000, and particularly 3,000 to 200,000.
  • the number average molecular weight (Mn) of the fluorine-containing polymer is generally measured by GPC (gel permeation chromatography).
  • the liquid medium is at least one selected from water and an organic solvent.
  • the liquid medium may be an organic solvent alone.
  • the liquid medium may be an aqueous medium.
  • the aqueous medium may be water alone or a mixture of water and a (water-miscible) organic solvent.
  • the amount of the water-miscible organic solvent may be 30% by weight or less, for example 10% by weight or less (preferably 0.1% or more) relative to the liquid medium.
  • the amount of the liquid medium may be 30 to 99.1% by weight, particularly 50 to 99% by weight, based on the weight of the release agent composition.
  • composition may contain other components.
  • the release agent composition is an aqueous emulsion
  • the emulsifier may be at least one selected from a nonionic emulsifier, a cationic emulsifier, an anionic emulsifier, and an amphoteric emulsifier.
  • the release agent composition may contain additives as other components.
  • additives examples include silicon-containing compounds, waxes, and acrylic emulsions.
  • Other examples of additives include other fluorine-containing polymers, drying speed regulators, crosslinking agents, film-forming aids, compatibilizers, surfactants, antifreeze agents, viscosity modifiers, UV absorbers, antioxidants, pH adjusters, defoamers, texture adjusters, slip adjusters, antistatic agents, hydrophilizing agents, antibacterial agents, preservatives, insect repellents, fragrances, and flame retardants.
  • the amount of the other components may be 0.1 to 20% by weight, for example 0.5 to 10% by weight, based on the weight of the release agent composition.
  • the release agent of the present invention is The polymerizable composition can be produced by a method including a step of copolymerizing (A) a fluorine-containing monomer and (B) a radically polymerizable monomer having no functional group.
  • the copolymerization may be emulsion polymerization or solution polymerization.
  • Emulsion polymerization is not particularly limited, but can be carried out, for example, as follows: In the presence of a polymerization initiator and an emulsifier, various monomers are emulsified in water, and after nitrogen replacement, the mixture is copolymerized at 50 to 80°C for 1 to 10 hours while stirring.
  • the polymerization initiator is not particularly limited, but examples include water-soluble polymerization initiators such as benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexyl hydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine dihydrochloride, azobisisobutyronitrile, sodium peroxide, potassium persulfate, and ammonium persulfate, as well as oil-soluble polymerization initiators such as azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydicarbonate, and azobismethylpropionate.
  • water-soluble polymerization initiators such as benzoyl peroxide, lauroyl peroxide,
  • the polymerization initiator is usually used in the range of 0.01 to 10 parts by weight per 100 parts by weight of monomer.
  • emulsion polymerization in order to obtain an aqueous copolymer dispersion with excellent shelf stability, it is preferable to atomize the monomer in water using an emulsifying device capable of imparting strong crushing energy, such as a high-pressure homogenizer or ultrasonic homogenizer, and then polymerize using an oil-soluble polymerization initiator.
  • an emulsifying device capable of imparting strong crushing energy, such as a high-pressure homogenizer or ultrasonic homogenizer, and then polymerize using an oil-soluble polymerization initiator.
  • emulsifiers such as anionic, cationic or nonionic emulsifiers
  • the emulsifier is usually used in the range of 0.5 to 20 parts by weight per 100 parts by weight of monomer.
  • Nonionic or anionic emulsifiers are preferred as emulsifiers.
  • the nonionic emulsifier is not particularly limited, but examples thereof include polyoxyethylene alkyl ethers, sorbitan alkylates, and sorbitan alkyl esters.
  • the polyoxyethylene alkyl ether is not particularly limited, but examples thereof include polyethylene lauryl ether.
  • Anionic emulsifiers include alkyl sulfates, alkyl sulfonates, and alkyl phosphates.
  • alkyl sulfates include, but are not limited to, sodium alkyl sulfate.
  • Cationic emulsions include quaternary ammonium salts and alkylamine salts.
  • Quaternary ammonium salts are not particularly limited, but examples include lauryltrimethylammonium chloride.
  • a compatibilizer that makes the monomers sufficiently compatible, such as a water-soluble organic solvent or a low molecular weight monomer.
  • a compatibilizer can improve emulsifiability and copolymerizability.
  • Water-soluble organic solvents as compatibilizers are not particularly limited, but examples include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, diethylene glycol diethyl ether, tripropylene glycol, and ethanol.
  • the water-soluble organic solvent is usually used in the range of 1 to 50 parts by weight per 100 parts by weight of water.
  • the water-soluble organic solvent is preferably used in the range 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 are usually used in the range of 0.001 to 7.0 parts by weight per 100 parts by weight of monomer.
  • the solution polymerization can be carried out, for example, as follows, but is not limited to the above.
  • a polymerization initiator In the presence of a polymerization initiator, the monomer is dissolved in an organic solvent, and after nitrogen replacement, 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.
  • the polymerization initiator is usually used in the range of 0.01 to 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.
  • 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 per 100 parts by weight of the total monomers.
  • the form of the release agent composition can be appropriately selected depending on the purpose of use, and may be, for example, a solution, an emulsion, or an aerosol. It is preferable that the release agent composition is a solution or an aerosol containing an organic solvent, or an aqueous emulsion containing water.
  • the release agent composition preferably contains 0.5% to 50% by weight of the fluorine-containing polymer, more preferably 1.0% to 30% by weight, and particularly preferably 1.5% to 20% by weight, based on the weight of the release agent composition.
  • the release agent composition may further contain a surfactant (emulsifier) for the purpose of improving wettability to the mold.
  • a surfactant emulsifier
  • a fluorine-based or non-fluorine-based surfactant, etc. can be used.
  • an anionic surfactant, a nonionic surfactant, and a cationic surfactant can be used.
  • Fluorosurfactants include fluorine-containing polyoxyethylenes, sulfonates, carboxylates, and quaternary ammonium salts.
  • non-fluorinated anionic surfactants include alkyl sulfates, alkyl sulfonates, and alkyl phosphates.
  • alkyl sulfates include sodium alkyl sulfate.
  • non-fluorinated nonionic surfactants include polyoxyethylene alkyl ethers, sorbitan alkylates, and sorbitan alkyl esters.
  • polyoxyethylene alkyl ethers include polyoxyethylene lauryl ether.
  • Non-fluorinated cationic surfactants include quaternary ammonium salts and alkylamine salts.
  • quaternary ammonium salts examples include lauryltrimethylammonium chloride.
  • the amount of the surfactant may be 0.01% by weight to 20% by weight, preferably 0.01% by weight to 15% by weight, and more preferably 0.05% by weight to 10% by weight, based on the release agent composition.
  • the release agent composition may further contain at least one release enhancing additive selected from the group consisting of silicone compounds, wax-based compounds, fluorine-based compounds, etc., for the purpose of improving the release properties and/or finish.
  • at least one release enhancing additive selected from the group consisting of silicone compounds, wax-based compounds, fluorine-based compounds, etc., for the purpose of improving the release properties and/or finish.
  • silicone compounds include dimethyl silicone oil, methylphenyl silicone oil, modified silicone oil (e.g., amino-modified silicone oil), fluorosilicone oil, and silicone resin.
  • wax-based compounds include polyethylene wax, paraffin wax, and carnauba wax.
  • fluorine-based compounds include polytetrafluoroethylene, fluoropolyether, and fluorochloropolyether.
  • the amount of the release enhancer additive may be 0.01% to 20% by weight, preferably 0.02% to 15% by weight, based on the weight of the release agent composition.
  • the release agent composition is an aqueous emulsion
  • it preferably contains at least one emulsifier selected from the group consisting of nonionic emulsifiers, anionic emulsifiers, and cationic emulsifiers.
  • the nonionic emulsifier may be any that can emulsify the fluoropolymer of the present disclosure and disperse it in an aqueous emulsion, and examples of such an emulsifier include polyoxyethylene alkyl ethers, sorbitan alkylates, and sorbitan alkyl esters. Examples of polyoxyethylene alkyl ethers include polyoxyethylene lauryl ether.
  • Anionic emulsifiers include alkyl sulfates, alkyl sulfonates, and alkyl phosphates.
  • Alkyl sulfates include sodium alkyl sulfate.
  • Cationic emulsifiers include quaternary ammonium salts and alkylamine salts. Quaternary ammonium salts include lauryltrimethylammonium chloride.
  • the amount of emulsifier is usually 0.5 to 25 parts by weight, preferably 1.0 to 20 parts by weight, and more preferably 2.0 to 15 parts by weight, per 100 parts by weight of the fluoropolymer.
  • the release agent composition is a solution, it may further contain an organic solvent, etc.
  • the release agent composition When the release agent composition is an aerosol, it can be filled into an aerosol can using a propellant.
  • propellants include LPG, dimethyl ether, and carbon dioxide.
  • the amount of propellant is usually 10 to 95% by weight, preferably 20 to 90% by weight, and more preferably 30 to 90% by weight, based on the total amount of the release agent composition and the propellant. If the amount of propellant is 10% by weight or more, the spraying can be performed better and a more uniform coating tends to be obtained. Also, if the amount of propellant is 95% by weight or less, the coating does not tend to become too thin and the release properties do not tend to decrease too much.
  • the release agent composition can be used as an internal or external release agent. It is preferably used as an external release agent.
  • the release agent composition is usually used as follows: The release agent composition is applied to the inner surface of a mold. After the solvent and dispersant are dried and removed, a release agent coating (a fluoropolymer coating) is formed on the mold. The mold is filled with a molding composition to form a molding material, and the molding material is then removed from the mold.
  • a release agent coating a fluoropolymer coating
  • molds for which the release agent composition can be used include metal molds such as aluminum, SUS, and iron, epoxy resin and wooden molds, and nickel electroformed or chrome plated molds.
  • rubbers such as urethane rubber, H-NBR, NBR, silicone rubber, EPDM, CR, NR, fluororubber, SBR, BR, IIR and IR
  • thermosetting resins such as urethane foam, epoxy resin, phenolic resin and FRP (e.g., CFRP and GFRP), and thermoplastic resins such as ABS, polycarbonate and PBT.
  • Synthesis Example 3 The alcohol obtained in Synthesis Example 2 was reacted with methyl methacrylate in the presence of a basic catalyst (calcium hydroxide) to obtain a fluorine-containing methacrylate (compound 3).
  • a basic catalyst calcium hydroxide
  • the resulting emulsion was placed in a 300 ml four-neck flask equipped with a reflux condenser, a nitrogen inlet tube, a thermometer and a stirrer, and kept at 60°C for about 1 hour under a nitrogen stream.
  • 0.3 g of ammonium persulfate dissolved in 5 g of water was added as an initiator to initiate polymerization.
  • the mixture was heated and stirred at 60°C for 3 hours to prepare an aqueous copolymer emulsion, and the resulting aqueous emulsion was adjusted with ion-exchanged water so that the solid content concentration was 0.3% by mass.
  • Production Example 4 After thoroughly dissolving 23 g of the compound obtained in Synthesis Example 3: CF 3 O—CH 2 CH 2 —OCO—C(CH 3 ) ⁇ CH 2 and 50 g of stearyl methacrylate, an aqueous copolymer emulsion was prepared in the same manner as in Production Example 1, and the solids concentration was adjusted to 0.3 mass% with ion-exchanged water.
  • Production Example 5 After thoroughly dissolving 14 g of the compound obtained in Synthesis Example 3: CF 3 O—CH 2 CH 2 —OCO—C(CH 3 ) ⁇ CH 2 and 70 g of lauryl acrylate, an aqueous copolymer emulsion was prepared in the same manner as in Production Example 1, and the solids concentration was adjusted to 0.3 mass% with ion-exchanged water.
  • Production Example 6 After 50 g of glycidyl methacrylate was sufficiently dissolved, an aqueous copolymer emulsion was prepared in the same manner as in Production Example 1, and the solid content was adjusted to 0.3% by mass with ion-exchanged water.
  • Production Example 7 After 61 g of glycidyl methacrylate and 19 g of stearyl acrylate were sufficiently dissolved, an aqueous copolymer emulsion was prepared in the same manner as in Production Example 1, and the solid content was adjusted to 0.3% by mass with ion-exchanged water.
  • Production Example 8 After 10 g of hydroxybutyl acrylate and 50 g of stearyl acrylate were sufficiently dissolved, an aqueous copolymer emulsion was prepared in the same manner as in Production Example 1, and the solid content was adjusted to 0.3% by mass with ion-exchanged water.
  • Production Example 9 A compound (control compound 2) prepared with reference to Example 1 of Japanese Patent No. 5664745 was adjusted with ion-exchanged water to a solid content concentration of 0.3% by mass.
  • Production Example 10 50 g of dimethyl silicone emulsion, SM67036EX (Comparative Compound 2, manufactured by Dow Toray Co., Ltd.) was adjusted with ion-exchanged water to a solids concentration of 0.3% by mass.
  • the coverage area of the compounded liquid when applied was measured and classified as follows: ⁇ : The coverage area of the release agent is 80% or more (the release agent has excellent wettability with respect to the molded product) ⁇ : The coverage area of the release agent is 60 to 80% or more (the release agent has good wettability with respect to the molded product) ⁇ : The coverage area of the release agent is 20 to 60% or more (the release agent has poor wettability with respect to the molded product) ⁇ : Coverage area rate of the release agent is less than 20% (wettability of the release agent to the molded product is very poor)
  • each abbreviation indicates the following compound.
  • STA stearyl acrylate
  • IBM isobornyl methacrylate
  • STMA stearyl methacrylate
  • LA lauryl acrylate
  • GMA glycidyl methacrylate
  • HBA hydroxybutyl acrylate
  • the release agent composition of the present disclosure can be used as an internal or external release agent.
  • the release agent composition of the present disclosure can be used in various moldings.
  • the release agent composition of the present disclosure is generally in the form of a coating material.
  • the release agent composition of the present disclosure can be used as a rust inhibitor, a moisture inhibitor, a waterproof agent, a water repellent, and an antifouling agent.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)

Abstract

L'invention concerne un polymère contenant du fluor possédant des unités récurrentes dérivées: (A) d'un monomère contenant du fluor; et (B) d'un monomère réagissant à la polymérisation radicalaire ne possédant pas de groupe fonctionnel. Le monomère contenant du fluor (A) est un composé représenté par la formule: CH2=C(-X11)-C(=O)-Y11-Y12-RA [Dans cette formule, chaque symbole est tel que défini dans la description].
PCT/JP2024/020156 2023-06-02 2024-06-03 Polymère contenant du fluor, composition d'agent de démoulage, et procédé de démoulage Pending WO2024248159A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202480036539.4A CN121219333A (zh) 2023-06-02 2024-06-03 含氟聚合物、脱模剂组合物和脱模方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2023091773A JP2024173390A (ja) 2023-06-02 2023-06-02 含フッ素重合体、離型剤組成物および離型方法
JP2023-091773 2023-06-02

Publications (1)

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WO2024248159A1 true WO2024248159A1 (fr) 2024-12-05

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Country Status (3)

Country Link
JP (1) JP2024173390A (fr)
CN (1) CN121219333A (fr)
WO (1) WO2024248159A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012011657A (ja) * 2010-06-30 2012-01-19 Teijin Dupont Films Japan Ltd インモールド転写材用粘着離型ポリエステルフィルム
JP2014117815A (ja) * 2012-12-13 2014-06-30 Teijin Dupont Films Japan Ltd 成形用離型ポリエステルフィルム
JP2014129517A (ja) * 2012-11-29 2014-07-10 Daikin Ind Ltd 離型剤、離型剤組成物及び離型剤の製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012011657A (ja) * 2010-06-30 2012-01-19 Teijin Dupont Films Japan Ltd インモールド転写材用粘着離型ポリエステルフィルム
JP2014129517A (ja) * 2012-11-29 2014-07-10 Daikin Ind Ltd 離型剤、離型剤組成物及び離型剤の製造方法
JP2014117815A (ja) * 2012-12-13 2014-06-30 Teijin Dupont Films Japan Ltd 成形用離型ポリエステルフィルム

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CN121219333A (zh) 2025-12-26

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