WO2018193926A1 - 含フッ素共重合体 - Google Patents
含フッ素共重合体 Download PDFInfo
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- WO2018193926A1 WO2018193926A1 PCT/JP2018/015167 JP2018015167W WO2018193926A1 WO 2018193926 A1 WO2018193926 A1 WO 2018193926A1 JP 2018015167 W JP2018015167 W JP 2018015167W WO 2018193926 A1 WO2018193926 A1 WO 2018193926A1
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- monomer
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- containing copolymer
- monomers
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- 0 *OC(N(*N=C=O)C(**N=C=O)=O)=O Chemical compound *OC(N(*N=C=O)C(**N=C=O)=O)=O 0.000 description 1
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- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/20—Vinyl fluoride
- C08F214/205—Vinyl fluoride with non-fluorinated comonomers
- C08F214/207—Vinyl fluoride with non-fluorinated comonomers with non-fluorinated vinyl ethers
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- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
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- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/26—Tetrafluoroethene
- C08F214/265—Tetrafluoroethene with non-fluorinated comonomers
- C08F214/267—Tetrafluoroethene with non-fluorinated comonomers with non-fluorinated vinyl ethers
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- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
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- C08F218/02—Esters of monocarboxylic acids
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- 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
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/068—Polysiloxanes
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- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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- C08G18/3206—Polyhydroxy compounds aliphatic
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- C08G18/6279—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds containing fluorine atoms
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- C08G18/6295—Polymers of silicium containing compounds having carbon-to-carbon double bonds
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/7806—Nitrogen containing -N-C=0 groups
- C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
- C08G18/7837—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing allophanate groups
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
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- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
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- 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
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- C09D151/085—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 on to polysiloxanes
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Definitions
- the present invention relates to a fluorine-containing copolymer, a method for producing a fluorine-containing copolymer, a film composition, a method for producing a film composition, a coated article, and a method for forming a film.
- a fluorine-containing copolymer having a dimethylsiloxane structure in the side chain or main chain skeleton not only provides weather resistance and chemical resistance, but also can provide excellent stain resistance, water and oil repellency, slipperiness, and the like. Although it has been used effectively in a wide range of fields, improvement in scratch resistance has been demanded.
- a curing agent having a reactive functional group is contained as an essential component, and a) component is 50 to 95% by weight and b) component is 5 to 50% by weight based on the total of component a) and component b).
- Coating composition according to claim Rukoto is disclosed.
- Japanese Patent Application Laid-Open No. 2013-177535 discloses (a) a fluorine-containing monomer as a fluorine-containing copolymer capable of forming a coating film excellent in self-repairability against scratches and a coating composition using the same.
- a polymer unit based on a monomer (b) a polymer unit based on vinyl ether or vinyl ester (excluding those having a hydroxyl group and a carboxyl group) that gives a homopolymer having a glass transition temperature of 25 ° C.
- a solvent-soluble fluorine-containing copolymer containing 8.0 to 40.0 mol% of polymerized units (b) based on the total polymerized units, and a coating composition using the same.
- JP 2012-107101 A discloses acrylic resin (A), polyisocyanate (B), and additive (C).
- the acrylic resin (A) has a glass transition point of ⁇ 20 to 30 ° C. and a hydroxyl value per acrylic resin solid content of 40 to 100 mgKOH / g.
- the polyisocyanate (B) is an aliphatic organic diisocyanate (b1) and a polycarbonate diol (b2) having a number average molecular weight of 250 to 750; Self-healing type formation characterized in that it is an allophanate group-containing polyisocyanate having an average number of functional groups of 4 to 6 obtained by the reaction, and the additive (C) is a polydimethylsiloxane modified product having at least one hydroxyl group A functional coating composition is disclosed.
- International Publication No. 2016/152631 has (a) a coat layer using a silicon-containing fluororesin and an isocyanate-based crosslinking agent, (b) a urethane layer, and (c) an adhesive layer.
- a coating protective film is disclosed.
- JP-A-2000-313725 and JP-A-2001-163927 disclose fluorine-containing copolymers each containing a fluoroolefin and a predetermined organosilicon compound as polymerization units in a predetermined ratio. Yes.
- the present invention is excellent in film properties such as chemical resistance, weather resistance, water and oil repellency, stain resistance, repeated decontamination and slipperiness, and can form a film excellent in self-healing property against scratches.
- a fluorine-containing copolymer a coating composition using the same, a coated article, and a method for forming a coating.
- the present invention significantly reduces the weather resistance and chemical resistance as a function of the original fluororesin by reducing the glass transition temperature to room temperature or lower in the conventionally used dimethylsilicone-containing fluorine-containing copolymer. It was introduced without.
- the present invention relates to (A) fluoroolefin (hereinafter referred to as monomer (A)) in a constituent monomer of 15 to 85 mol%, (B) Consists of one or more organosilicon compounds [hereinafter referred to as monomer (B)] selected from the compound represented by the following general formula (1) and the compound represented by the following general formula (2) 0.001 to 10 mol% in the monomer, (C) a monomer selected from vinyl ether, vinyl ester, methacrylic acid ester and acrylic acid ester, having no curing reactive group, having an aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms, One or more monomers selected from monomers having a glass transition temperature of less than 0 ° C.
- monomer (C) of the homopolymer of the monomer (hereinafter referred to as monomer (C)) are 5 to 40 in the constituent monomers.
- a fluorine-containing copolymer comprising: The glass transition temperature is ⁇ 30 ° C.
- the present invention relates to a fluorine-containing copolymer.
- R 1 is an alkyl group having 1 to 6 carbon atoms, — (CH 2 ) r —OOC (CH 3 ) C ⁇ CH 2 , — (CH 2 ) r —OOC—HC ⁇ CH 2 or —CH ⁇ Represents CH 2 , R 2 represents — (CH 2 ) r —OOC (CH 3 ) C ⁇ CH 2 , — (CH 2 ) r —OOC—HC ⁇ CH 2 or —CH ⁇ CH 2 , and n represents 1 R represents a number from 1 to 6. ]
- the present invention also relates to a process for producing the fluorine-containing copolymer of the present invention, wherein (A) is used in the monomer for the reaction at 15 to 85 mol%, and (B) is used in the monomer for the reaction. 0.001 to 10 mol%, (C) is reacted in a proportion of 5 to 40 mol% in the monomer used for the reaction, and (D) is reacted in a proportion of 1 to 25 mol% in the monomer used in the reaction.
- the present invention relates to a method for producing a polymer.
- the present invention also includes the fluorine-containing copolymer of the present invention, a fluorine-containing copolymer, and a curing agent of the fluorine-containing copolymer, wherein the curing agent is an adduct-modified product or allophanate of a polyvalent isocyanate compound.
- the present invention relates to a coating composition which is a modified body.
- the present invention also relates to a method for producing the coating composition of the present invention, wherein the fluorine-containing copolymer and the curing agent are mixed.
- the present invention also relates to a coated article having a base material and a cured film of the coating composition of the present invention formed on the base material.
- the present invention also relates to a method for forming a cured film, wherein a coating film is formed by applying the coating composition of the present invention to a substrate, and the cured film is formed by curing the coating film.
- a film excellent in self-healing property against scratches can be obtained.
- a fluorine-containing copolymer a film composition using the same, a coated article, and a method for forming a film.
- the present invention can be suitably used for forming a film in a wide range of applications.
- the present invention can be used, for example, for automobile exterior films, marking films, window films and the like that are used outdoors for a long period of time.
- the present invention can be used to form a coating in a kitchen or bathroom where high water repellency, oil repellency, stain resistance and a smooth hand feeling are required indoors.
- the present invention can be used for forming a film in a housing of a home appliance, an electronic device, or the like.
- the fluorine-containing copolymer of the present invention contains 15 to 85 mol% of the fluoroolefin, which is the monomer (A), as a polymer unit.
- the coating formed from the fluorine-containing copolymer exhibits sufficient contamination resistance.
- the monomer (A) is 85 mol% or less in the constituent monomers because the solubility of the fluorinated copolymer in various solvents does not decrease.
- the proportion of the fluoroolefin is more preferably 30 to 80 mol% in the constituent monomers.
- Examples of the monomer (A) fluoroolefin include olefins having one or more fluorine atoms in the molecule.
- olefins having one or more fluorine atoms in the molecule For example, vinylidene fluoride, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene and the like are suitable. These fluoroolefins may be used alone or in combination of two or more, but a combination of vinylidene fluoride and tetrafluoroethylene is particularly preferable.
- Tetrafluoroethylene is preferred in that it lowers the Tg of the fluorine-containing copolymer of the present invention, and a film using the fluorine-containing copolymer of the present invention exhibits effective self-healing properties at room temperature or higher.
- VDF vinylidene fluoride
- TFE tetrafluoroethylene
- the mass ratio of the two is VDF / TFE, preferably 0.05 / 1 to 2.0 / 1, preferably 0.1 / 1 to 1.5 / 1 is more preferable.
- the fluorine-containing copolymer of the present invention has at least one selected from a compound represented by the following general formula (1) and a compound represented by (2), which is a monomer (B) as a polymerization unit.
- 0.001 to 10 mol% preferably 0.005 to 5 mol%, more preferably 0.005 to 3 mol%, still more preferably 0.005 to 2 mol%, More preferably, it is contained in an amount of 0.008 to 2 mol%, still more preferably 0.01 to 2 mol%, still more preferably 0.01 to 1 mol%, and still more preferably 0.05 to 1 mol%.
- R 1 is an alkyl group having 1 to 6 carbon atoms, — (CH 2 ) r —OOC (CH 3 ) C ⁇ CH 2 , — (CH 2 ) r —OOC—HC ⁇ CH 2 or —CH ⁇ Represents CH 2 , R 2 represents — (CH 2 ) r —OOC (CH 3 ) C ⁇ CH 2 , — (CH 2 ) r —OOC—HC ⁇ CH 2 or —CH ⁇ CH 2 , and n represents 1 R represents a number from 1 to 6. ]
- the film formed from the fluorine-containing copolymer has a sufficient water-repellent property over a long period of time. Oil, antifouling, slipperiness, and scratch relief based on slipperiness can be obtained. Moreover, if the monomer (B) is 10 mol% or less in the constituent monomers, sufficient chemical resistance, weather resistance and self-repairing property can be obtained for the film formed from the fluorine-containing copolymer.
- the monomers (B) when a compound having a large molecular weight, for example, a monomer having n of 200 to 400 in the general formula (1) is used, from the viewpoint of ease of polymerization, the proportion of the body is preferably 0.005 to 5 mol% in the constituent monomers.
- the monomer (B) is preferably polydimethylsiloxane with one end being methacryl-modified, polydimethylsiloxane with one end being acrylic-modified, polydimethylsiloxane having both ends methacryl-modified.
- These reactive silicone oils may be used alone or in combination of two or more.
- the number average molecular weight of these reactive silicone oils is preferably 200 to 30,000.
- polydimethylsiloxane with one end being methacryl-modified polydimethylsiloxane with one end being acrylic-modified
- polydimethylsiloxane having both ends methacryl-modified are suitable.
- the organosilicon compounds represented by the general formula (1) or (2) may be used alone or in combination of two or more.
- the number average molecular weight of the organosilicon compound represented by the general formula (1) or (2) is preferably 200 to 30,000.
- Examples of the monomer (B) include at least one organosilicon compound selected from compounds represented by the following formulas (3), (4), (5) and (6).
- CH 2 C (CH 3 ) -COO-C 3 H 6 -Si (CH 3 ) 2- [O-Si (CH 3 ) 2 ] m -R 3 (3)
- R 3 represents an alkyl group having 1 to 6 carbon atoms, and m represents 1 to 250, preferably 5 to 200.
- CH 2 CH-COO-C 3 H 6 -Si (CH 3 ) 2- [OS i (CH 3 ) 2 ] p -R 4 (4)
- R 4 represents an alkyl group having 1 to 6 carbon atoms, and p represents 1 to 250, preferably 5 to 200.
- R 5 represents —OOC
- the fluorine-containing copolymer of the present invention is a monomer selected from vinyl ether, vinyl ester, methacrylic acid ester and acrylic acid ester, which is monomer (C), as a polymerization unit, and has a curing reactive group. And one or more monomers selected from monomers having an aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms and a homopolymer Tg of less than 0 ° C. 5 to 40 mol% in the monomer.
- the aliphatic saturated hydrocarbon group that the monomer (C) has may be either a straight chain or a branched chain. Examples of the monomer (C) include a monomer having neither a hydroxyl group nor an epoxy group.
- Monomer (C) has the effect of reducing the Tg of the fluorinated copolymer of the present invention, and the coating using the fluorinated copolymer of the present invention exhibits effective self-healing properties at room temperature or higher.
- the fluorine-containing copolymer of the present invention When the monomer (C) is incorporated into the fluorine-containing copolymer of the present invention because the Tg of the homopolymer of the monomer (C) is less than 0 ° C., the fluorine-containing copolymer is used. Effective self-repairing property can be imparted to the coated film.
- the Tg of the homopolymer of monomer (C) is, for example, that a film using a fluorinated copolymer exhibits effective self-healing properties even at 0 to 2 ° C., the average temperature in Japan in winter. -5 ° C. or lower is preferable.
- the Tg of the monomer (C) homopolymer is a value obtained by measurement with a differential scanning calorimeter (DSC). Specifically, it is measured by the same method as that of Tg of the fluorine-containing copolymer of the examples (however, the temperature range to be measured is changed).
- the vinyl ether examples include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, n-pentyl vinyl ether, isopentyl vinyl ether, and tarsha.
- the vinyl ether is preferably a vinyl ether having an alkyl group having 1 to 20 carbon atoms.
- vinyl esters include vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristylate, vinyl palmitate, vinyl stearate, etc. Is mentioned.
- methacrylic acid ester examples include n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-heptyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, n-decyl methacrylate, n-undecyl methacrylate, n-dodecyl methacrylate, n-tridecyl methacrylate, n-tetradecyl methacrylate, n-pentadecyl methacrylate, n-hexadecyl methacrylate, n-heptadecyl methacrylate, n-octadecyl methacrylate, n-nonadecyl Examples thereof include methacrylate and n-icosyl methacrylate.
- the acrylic ester specifically, ethyl acrylate, 2,2,2-trifluoroethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, isopentyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-heptyl acrylate, n-octyl acrylate, n-nonyl acrylate, n-decyl acrylate, n-undecyl acrylate, n-dodecyl acrylate, etc. Is mentioned.
- the monomer (C) is a monomer selected from vinyl ethers, has no curing reactive group, has an aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms, and is homogenous to the monomer.
- One or more monomers selected from monomers having a glass transition temperature of the polymer of less than 0 ° C. are preferred.
- the proportion of the monomer (C) is 5 to 40 mol% in the constituent monomers.
- the proportion of the monomer (C) is 5 mol% or more in the constituent monomers, the Tg of the fluorine-containing copolymer of the present invention can be effectively reduced, and the fluorine-containing copolymer was used. The self-repairing property of the film is easily developed.
- the proportion of the monomer (C) is 40 mol% or less in the constituent monomers, sufficient chemical resistance and weather resistance of the coating using the fluorine-containing copolymer can be obtained.
- the proportion of the monomer (C) is preferably 5 to 35 mol% in the constituent monomers.
- the fluorine-containing copolymer of the present invention is a monomer selected from vinyl ether, vinyl ester, allyl ether, methacrylic acid ester and acrylic acid ester, which is a monomer (D) as a polymerization unit, and a curing reaction 1 to 25 mol% of one or more monomers selected from monomers having a functional group are contained in the constituent monomers.
- the fluorine-containing copolymer of the present invention preferably has a curing reactive group such as a hydroxyl group or an epoxy group, and thereby becomes curable.
- the fluorine-containing copolymer of the present invention becomes a curable fluorine-containing copolymer by using, for example, a monomer having a hydroxyl group or an epoxy group as the monomer (D).
- the fluorine-containing copolymer of the present invention may be a thermosetting fluorine-containing copolymer.
- the monomer (D) preferably has at least one hydroxyl group or epoxy group as a curing reactive group.
- the monomer (D) is a repeating unit having an aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms, an alicyclic saturated hydrocarbon group having 1 to 20 carbon atoms, and an alkylene group having 1 to 20 carbon atoms. It may have a group selected from alkylene glycol groups having a number of 1 to 10.
- the monomer (D) further comprises an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms and an aliphatic hydrocarbon having 1 to 10 carbon atoms having an alicyclic saturated hydrocarbon group having 1 to 10 carbon atoms in its structure. And a group selected from an alkylene glycol group having 1 to 6 carbon atoms and 1 to 10 repeating units in the alkylene group.
- the number of carbon atoms of the aliphatic saturated hydrocarbon group is preferably 2 to 9, more preferably 4 to 6.
- the alicyclic saturated hydrocarbon group preferably has 3 to 8 carbon atoms, more preferably 5 to 7 carbon atoms.
- the aliphatic hydrocarbon containing the alicyclic saturated hydrocarbon structure preferably has 1 carbon atom. To 9, more preferably 2 to 6.
- the alkylene group of the alkylene glycol group preferably has 1 to 4 carbon atoms, more preferably 2 to 3 carbon atoms.
- the number of repeating units is preferably 1 to 5, more preferably 2 to 3.
- vinyl ether examples include glycidyl vinyl ether, glycidyloxymethyl vinyl ether, glycidyloxyethyl vinyl ether, glycidyloxybutyl vinyl ether, glycidyloxypentyl vinyl ether, glycidyloxycyclohexyl vinyl ether, hydroxymethyl vinyl ether, hydroxyethyl Vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxypentyl vinyl ether, hydroxyhexyl vinyl ether, hydroxyheptyl vinyl ether, hydroxyoctyl vinyl ether, hydroxynonyl vinyl ether, hydroxydecyl vinyl ether, hydroxyundecyl vinyl ether, hydroxydodecyl vinyl Ether, hydroxytridecyl vinyl ether, hydroxytetradecyl vinyl ether, hydroxypentadecyl vinyl ether, hydroxy
- vinyl esters include glycidyl vinyl ester, glycidyloxymethyl vinyl ester, glycidyloxyethyl vinyl ester, glycidyloxybutyl vinyl ester, glycidyloxypentyl vinyl ester, glycidyloxycyclohexyl vinyl ester.
- allyl ether examples include allyl glycidyl ether, 3-aroxy-1,2-propanediol, glycerol- ⁇ -monoallyl ether, ethylene glycol monoallyl ether, and the like.
- methacrylic acid esters include glycidyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2-hydroxypropyl methacrylate and the like.
- acrylic ester examples include 2-hydroxyethyl acrylate, 2-hydroxybutyl acrylate, and the like.
- the monomer (D) is a monomer selected from vinyl ethers, and preferably one or more monomers selected from monomers having a curing reactive group.
- the proportion of the monomer (D) is 1 to 25 mol% in the constituent monomers.
- the proportion of the monomer (D) is 1 mol% or more in the constituent monomers, good curing reactivity of the fluorinated copolymer can be obtained.
- the proportion of the monomer (D) is 25 mol% or less in the constituent monomers, sufficient chemical resistance, weather resistance, stain resistance, self-healing of the coating using the fluorine-containing copolymer Sex is obtained.
- the proportion of the monomer (D) is preferably 3 to 20 mol% in the constituent monomers. More preferably, it is 5 to 18 mol%.
- the fluorine-containing copolymer of the present invention is a monomer other than the monomers (A) to (D) as a polymerization unit within the range not impairing the effects of the present invention [hereinafter referred to as the monomer (E)]. Can be included.
- vinyl ethers such as cyclohexyl vinyl ether and 2- (perfluorohexyl) ethyl vinyl ether
- allyl ethers such as ethyl allyl ether, butyl allyl ether, cyclohexyl allyl ether, isobutyl allyl ether, n-propyl allyl ether
- methacrylics such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, dicyclopentanyl methacrylate, 2- (perfluorobutyl) ethyl methacrylate, 2- (perfluorohexyl) ethyl methacrylate
- Acid esters Other acrylic esters such as methyl acrylate, ethyl acrylate, t-butyl acrylate,
- the monomer (E) examples include olefins such as ethylene and propylene, and haloolefins such as vinyl chloride and vinylidene chloride.
- the proportion of the monomer (E) is preferably less than 20 mol%, more preferably 15 mol% or less in the constituent monomers.
- the total proportion of the monomers (A) to (D) is 80 mol% or more, further 85 mol% or more and 100 mol% or less in the constituent monomers. Preferably, it may be 100 mol%.
- the fluorine-containing copolymer of the present invention comprises 15 to 85 mol% in the monomer using the monomer (A) for the reaction, and 0.001 to 10 mol in the monomer using the monomer (B) for the reaction. %,
- the monomer (C) is reacted in a proportion of 5 to 40 mol% in the monomer used for the reaction, and the monomer (D) is reacted in a proportion of 1 to 25 mol% in the monomer used in the reaction. .
- a preferable value of this mol% is the same as the mol% in the constituent monomer.
- the fluorine-containing copolymer of the present invention can be produced, for example, by copolymerizing a predetermined proportion of a monomer mixture using a polymerization initiator.
- a polymerization initiator a water-soluble or oil-soluble one is appropriately used depending on the polymerization type and the type of solvent used as desired.
- oil-soluble initiators include peroxyester type peroxides such as t-butyl peroxyisobutyrate, t-butyl peroxyacetate, and t-butyl peroxypivalate; diisopropyl peroxydicarbonate, dinormalpropyl Dialkyl peroxydicarbonates such as peroxydicarbonate; benzoyl peroxide, azobisisobutyronitrile and the like are used.
- water-soluble initiator examples include a persulfate such as potassium persulfate, hydrogen peroxide, or a redox initiator composed of a combination of these with a reducing agent such as sodium bisulfite and sodium thiosulfate, and a small amount thereof.
- a persulfate such as potassium persulfate, hydrogen peroxide, or a redox initiator composed of a combination of these with a reducing agent such as sodium bisulfite and sodium thiosulfate, and a small amount thereof.
- Inorganic initiators in which iron, ferrous salt, silver nitrate, and the like coexist, and dibasic acid organic initiators such as succinic acid peroxide, diglutaric acid peroxide, and monosuccinic acid peroxide are used.
- the amount of these polymerization initiators to be used is appropriately selected according to the type, copolymerization reaction conditions, and the like, but is usually 0.005 to 5% by mass, preferably 0.8%, based on the total amount of monomers used. It is in the range of 1 to 2% by mass.
- the polymerization method is not particularly limited, and for example, bulk polymerization method, suspension polymerization method, emulsion polymerization method, solution polymerization method and the like can be used.
- Ketones such as methyl ethyl ketone, carboxylic acid esters such as butyl acetate, hexane
- a solution polymerization method or an aqueous solvent using aliphatic saturated hydrocarbons such as xylene, aromatic hydrocarbons such as xylene, alcohols such as isopropyl alcohol, saturated halogenated hydrocarbons having one or more fluorine atoms, etc. as a solvent
- the emulsion polymerization method is preferred.
- preferred solvents for obtaining the fluorinated copolymer by a solution polymerization method include a solvent selected from ethyl acetate, butyl acetate, hexane, cyclohexane, heptane, xylene, toluene, isopropyl alcohol, and methyl ethyl ketone.
- a suspension or emulsifier is usually used as a dispersant, and a basic buffer is added to the pH of the reaction solution during polymerization. It is desirable that the value is 4 or more, preferably 6 or more.
- the reaction temperature in these copolymerization reactions is appropriately selected within the range of ⁇ 30 ° C. to 150 ° C. according to the type of the polymerization medium of the polymerization initiator. For example, when copolymerization is carried out in a solvent, it is usually in the range of 0 to 100 ° C., preferably 10 to 90 ° C.
- the reaction temperature refers to the maximum temperature during the reaction.
- the reaction pressure is not particularly limited, but is usually selected in the range of 0.1 to 10 MPa, preferably 0.1 to 5 MPa.
- copolymerization reaction can be performed by adding an appropriate chain transfer agent.
- the method for producing the fluorine-containing copolymer of the present invention 15 to 85 mol% in the monomer using the monomer (A) for the reaction, and 0% in the monomer using the monomer (B) for the reaction. 0.001 to 10 mol%, 5 to 40 mol% in the monomer using the monomer (C) for the reaction, and 1 to 25 mol% in the monomer using the monomer (D) for the reaction,
- a peroxyester type peroxide in a solvent selected from ethyl acetate, butyl acetate, hexane, cyclohexane, heptane, xylene, toluene, isopropyl alcohol, and methyl ethyl ketone, a reaction pressure of 0.1 to 5 MPa, a reaction temperature of 10 to The method of making it react at 90 degreeC is mentioned.
- the fluorine-containing copolymer of the present invention has a number average molecular weight of 2.0 ⁇ 10 4 to 7.0 ⁇ 10 4 .
- the number average molecular weight is preferably 2.5 ⁇ 10 4 to 6.9 ⁇ 10 4 , more preferably 2.7 ⁇ 10 4 to 6.8 ⁇ 10 4 .
- the fluorine-containing copolymer of the present invention has a weight average molecular weight of 1.0 ⁇ 10 5 to 3.0 ⁇ 10 5 .
- the weight average molecular weight is preferably 1.5 ⁇ 10 5 to 2.7 ⁇ 10 5 , more preferably 1.6 ⁇ 10 5 to 2.5 ⁇ 10 5 .
- the leveling of the coating composition containing the fluorinated copolymer is good.
- the strength of the coating film is high and an effective self-repairing property is obtained.
- the number average molecular weight of the fluorine-containing copolymer is 7.0 ⁇ 10 4 or less and the weight average molecular weight is 3.0 ⁇ 10 5 or less, the viscosity of the coating composition containing the fluorine-containing copolymer Becomes appropriate and the handling property is also improved.
- the number average molecular weight and the weight average molecular weight of the fluorine-containing copolymer are respectively measured by gel permeation chromatography under the following conditions.
- Measuring device HLC-8320GPC (Tosoh Corporation)
- Column TDgel SuperHZM-M (Tosoh Corporation)
- Detector RI (differential refractometer attached to the device)
- Reference material Polystyrene Data processing: EcoSEC-WS (Tosoh Corporation) Measurement conditions: column temperature (40 ° C.), solvent (tetrahydrofuran), flow rate (0.35 mL / min), sample concentration (0.14 wt%), sample injection amount (20 ⁇ L)
- the fluorine-containing copolymer of the present invention has a Tg of ⁇ 30 ° C. to 20 ° C.
- Tg is preferably ⁇ 25 ° C. to 15 ° C., more preferably ⁇ 20 ° C. to 12 ° C. If Tg is ⁇ 30 ° C. or higher, the toughness and chemical resistance of the coating using the fluorine-containing copolymer will be good. Moreover, if Tg is 20 degrees C or less, the effective self-repairing property at room temperature of the film using this fluorine-containing copolymer will be obtained.
- Tg of the fluorine-containing copolymer is a value obtained by measurement with a differential scanning calorimeter (DSC). Specifically, it was measured by the method of the example.
- the present invention provides a coating composition comprising the fluorine-containing copolymer of the present invention and a curing agent for the fluorine-containing copolymer, wherein the curing agent is an adduct-modified product or allophanate-modified product of a polyvalent isocyanate compound.
- the curing agent is an adduct-modified product or allophanate-modified product of a polyvalent isocyanate compound.
- the content of the fluorine-containing copolymer of the present invention in the coating composition of the present invention can be appropriately determined in consideration of the application and the object.
- the coating composition of the present invention preferably contains 0.5 to 90% by mass, more preferably 1 to 80% by mass of the fluorine-containing copolymer of the present invention.
- the film composition of the present invention contains a curing agent of the fluorine-containing copolymer of the present invention (hereinafter referred to as the curing agent of the present invention).
- the curing agent of the present invention is an adduct-modified product or allophanate-modified product of a polyvalent isocyanate compound from the viewpoint of self-healing properties of the coating.
- the curing agent of the present invention preferably has three or more functional groups.
- the curing agent of the present invention preferably has 3 or more NCO groups, and more preferably 3 to 5 NCO groups.
- Examples of adduct-modified products of polyisocyanates include adducts of polyisocyanates and polyhydric alcohols.
- the adduct-modified product of polyvalent isocyanate preferably has three or more functional groups.
- the adduct-modified product of polyvalent isocyanate preferably has 3 or more, more preferably 3 or more and 5 or less NCO groups. Specific examples include adducts of diisocyanates and polyhydric alcohols having 3 to 30 carbon atoms, and adducts of diisocyanates and trimethylolpropane.
- an adduct of a compound selected from hexamethylene diisocyanate, pentamethylene diisocyanate and isophorone diisocyanate and trimethylolpropane can be mentioned.
- the adduct-modified product of polyvalent isocyanate include compounds having a structure represented by the following formula (I).
- any polyvalent isocyanate-modified product having a structure classified as an adduct-modified product can be used as the curing agent of the present invention.
- R 1 to R 3 each independently represents an alkylene group having 5 or 6 carbon atoms, or an isophorone group.
- examples of the allophanate-modified product of polyvalent isocyanate include adducts of polyvalent isocyanate and monohydric alcohol.
- the allophanate-modified product of polyisocyanate preferably has three or more functional groups.
- the allophanate-modified product of polyisocyanate preferably has 3 or more, more preferably 3 or more and 5 or less NCO groups.
- Specific examples include adducts of diisocyanates and monohydric alcohols, and further adducts of diisocyanates and monohydric alcohols having 1 to 20 carbon atoms.
- a monohydric alcohol having a structure containing a compound selected from hexamethylene diisocyanate, pentamethylene diisocyanate, and isophorone diisocyanate, and an aliphatic or alicyclic saturated hydrocarbon group having 1 to 20 carbon atoms which may contain a branch. And adducts.
- an allophanate modified body of polyvalent isocyanate the compound which has a structure shown to following formula (II) is mentioned, for example.
- any polyvalent isocyanate-modified product containing a structure classified as an allophanate-modified product can be used as the curing agent of the present invention.
- R 1 is an alkylene group having 5 or 6 carbon atoms or an isophorone group
- R 2 is an aliphatic or alicyclic saturated hydrocarbon group having 1 to 20 carbon atoms which may contain a branch.
- the coating composition of the present invention can contain a curing agent other than the curing agent of the present invention (hereinafter referred to as other curing agent) as long as the effects of the present invention are not impaired.
- other curing agent a curing agent other than the curing agent of the present invention
- polyisocyanate compounds and modified compounds of polyisocyanate compounds that do not fall under the curing agent of the present invention can be used.
- melamine curing agents, urea resin curing agents, polybasic acid curing agents, and the like can also be used.
- the melamine curing agent include butylated melamine, methylated melamine, epoxy-modified melamine, and the like. Curing agents having various degrees of modification are appropriately used depending on the application, and the degree of self-condensation can be appropriately selected.
- the urea resin curing agent include methylated urea resin and butylated urea resin.
- polybasic acid curing agent include long-chain aliphatic dicarboxylic acids, aromatic polyvalent carboxylic acids, and acid anhydrides thereof.
- blocked polyvalent isocyanates can also be used as other curing agents.
- curing agent hardening can also be accelerated
- a curing agent used in a normal curable epoxy coating for example, an aliphatic such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, etc. Amines or modified products thereof, aromatic amines such as metaphenylenediamine, pp'-diaminodiphenylmethane, diaminophenylsulfone, or modified products thereof, phthalic anhydride, maleic anhydride, oxalic anhydride, hexahydrophthal A polyvalent carboxylic acid such as acid or pimelic acid or an anhydride thereof can be used.
- an aliphatic such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, etc.
- Amines or modified products thereof aromatic amines such as metaphenylenediamine, pp'-diaminodiphenylmethane, diaminophenylsulfone, or modified products thereof, phthalic anhydride, maleic an
- the coating composition of the present invention is a fluorine-containing copolymer in which the fluorine-containing copolymer has a hydroxyl group as a curing reactive group, and the curing agent is an adduct-modified product of a polyvalent isocyanate compound and an allophanate modification of a polyvalent isocyanate compound.
- a combination that is a curing agent selected from the body is preferred.
- the coating composition of the present invention is a fluorine-containing copolymer in which the fluorine-containing copolymer has a hydroxyl group as a curing reactive group, and the curing agent is an adduct-modified product of a polyvalent isocyanate compound having three NCO groups.
- a combination that is a curing agent selected from the compounds having the above and an allophanate-modified product of a polyvalent isocyanate compound and having three or more NCO groups is more preferable.
- the equivalent ratio of the hydroxyl group (OH) of the fluorinated copolymer to the NCO group of the curing agent is NCO / OH, preferably 0.3 to 2.0, more preferably 0.5 to 1.5.
- the curing agent of the present invention is preferably 1 to 300 parts by mass, more preferably 2 to 250 parts by mass, and still more preferably 3 to 3 parts by mass with respect to 100 parts by mass of the fluorinated copolymer. Contains 200 parts by weight.
- the film composition of the present invention may contain a resin other than the fluorine-containing copolymer of the present invention.
- resins include acrylic resin, urethane resin, silicone resin, polyester resin, alkyd resin, melamine resin, epoxy resin, ketone resin, polycarbonate resin, polyolefin resin, polyvinyl chloride resin, and fluorine-containing copolymer of the present invention.
- a fluororesin other than a polymer may be used.
- These other resins may be in any form of powder, varnish, and dispersion.
- the coating composition of the present invention contains the above-mentioned other resins, from the viewpoint of not impairing the effects of the present invention, 0.1 to 500 parts by mass with respect to 100 parts by mass of the fluorinated copolymer of the present invention. The content of parts is preferred.
- the Tg of these other resins is also desirably in the range of ⁇ 30 ° C. to 20 ° C.
- the film composition of the present invention may contain a solvent.
- the solvent is preferably a solvent that dissolves the fluorine-containing copolymer of the present invention.
- the solvent is preferably an organic solvent. Examples of the organic solvent include esters, ketones, alcohols and aliphatic hydrocarbons.
- carboxylic acid esters such as ethyl acetate, propyl acetate, butyl acetate and amyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, methoxypropanol and ethoxypropanol
- alkanes such as n-pentane, i-pentane, n-hexane, i-hexane, cyclohexane, n-heptane, i-heptane and 2,2,4-trimethylpentane.
- the organic solvent known as Solvesso (brand name) and mineral spirit can also be used.
- ethers such as methyl cellosolve and ethylene glycol monomethyl ether can also be used.
- Aromatic hydrocarbons such as benzene, toluene and xylene can also be used.
- Pyrrolidone such as N-methylpyrrolidone can also be used.
- fluorine-type organic solvents such as Zeolola H (brand name), Novec7200 (brand name), and Novec7300 (brand name), can also be used.
- the said organic solvent can use 1 type (s) or 2 or more types.
- Water may be used as the solvent, but in that case, it is preferable to also contain an organic solvent.
- the mass ratio of water / (water + organic solvent) is preferably from 0.01 to 10.
- the coating composition of the present invention contains the above-mentioned solvent in the coating composition, preferably 5 to 99% by mass, more preferably 10 to 98% by mass, and still more preferably 20 to 95% by mass.
- the coating composition of the present invention can contain a curing catalyst.
- a curing catalyst there are known catalysts such as metal complexes including metal such as Sn, Zn, Zr, Ti, Bi, Al, Li, and Ca, metal salts, amines, organic acids, or acidic phosphates, and mixtures thereof. Can be mentioned.
- the film composition of the present invention can contain any component other than the fluorine-containing copolymer, the curing agent, the solvent, and the curing catalyst of the present invention as long as the effects of the present invention are not impaired.
- Optional ingredients include dispersants, matting agents, plasticizers, viscosity modifiers, antifoaming agents, anti-settling agents, leveling agents, antiseptics, antibacterial agents, antiviral agents, antifungal agents, antioxidants, anti-oxidants Oxidants, flame retardants, light stabilizers, UV absorbers, lubricants, antifreezing agents, film-forming aids, anti-coloring agents, pH adjusters, surfactants, anti-skinning agents, catalysts, hygroscopic agents, Examples thereof include pigments, deodorants, silane coupling agents, antistatic agents, water repellents, oil repellents, and hydrophilizing agents.
- the coating composition of the present invention can be produced by mixing the fluorine-containing copolymer of the present invention and the curing agent of the present invention.
- it can be produced by mixing the fluorine-containing copolymer of the present invention, the curing agent of the present invention, and a solvent.
- the mixing order of these components is not ask
- the fluorine-containing copolymer of the present invention and the curing agent of the present invention and the solvent are mixed in a ball mill, a bead mill, a paint shaker, a sand mill, a three-roll mill, It can carry out using various apparatuses used for normal paint preparation, such as a kneader. At this time, a pigment, a dispersant, a viscosity modifier, a leveling agent, an ultraviolet absorber and the like can be added as necessary.
- the film composition of the present invention may be prepared by mixing the fluorine-containing copolymer of the present invention and the curing agent of the present invention immediately before use.
- the present invention includes a first composition containing the fluorine-containing copolymer of the present invention and a curing agent for the fluorine-containing copolymer, wherein the curing agent is an adduct-modified product or allophanate of a polyvalent isocyanate compound.
- a coating composition kit comprising a second composition that is a modified body is provided. A solvent and arbitrary components can be suitably mix
- the coating composition of the present invention can be used as a varnish or a coating composition.
- a well-known component can be suitably mix
- the present invention provides a coated article having a substrate and a cured film of the coating composition of the present invention formed on the substrate.
- the matters described in the fluorine-containing copolymer and the coating composition of the present invention can be appropriately applied to the coated article of the present invention.
- Exterior applications include automotive exterior films such as automobile exterior paint, automobile exterior paint film, automobile paint protective film, automobile window film, and automobile marking film.
- automotive exterior films such as automobile exterior paint, automobile exterior paint film, automobile paint protective film, automobile window film, and automobile marking film.
- Specific examples include automobile exteriors and exterior parts such as automobile bodies, bumpers, spoilers, door knobs, headlamps, blinkers, side mirrors, radiator grills, and wheels.
- motorcycle exteriors and exterior parts such as motorcycle bodies, handles, saddles, gasoline tanks and the like can be mentioned.
- Other examples include exteriors of vehicles such as trains, exterior films, and exterior parts.
- window films, glass surface coats, marking films, protective films, paints and the like in vehicles such as automobiles, motorcycles and trains can be mentioned.
- examples of interior uses in vehicles such as automobiles include automobile interior seats, handles, meter panels, control panels, dashboards, door interiors, etc., and paints, protective films, design films, etc. in these applications.
- Applications other than these include, for example, cellular phones, smartphones, personal computers, televisions, portable terminals (including game consoles), electronic devices such as printers, televisions, air conditioners, microwave ovens, refrigerators, washing machines, air cleaners, vacuum cleaners , Home appliances such as ventilators, toys, shelves, bookshelves, beds, desks, chairs, sofas, interiors, ventilators, range hoods, kitchen panels, stainless steel sinks, bathtubs, toilets, etc., and paints in these applications , Protective films, and design films.
- the window film in a building, a glass surface coat, an outdoor marking film, a protective film for various articles, a coating for building materials, and the like can be given.
- the present invention is not limited to the above-mentioned application examples, and can be applied to various articles.
- the base material examples include iron, stainless steel, aluminum and the like, and surface treated metal, inorganic base material such as cement, lime, gypsum, ceramic, polyurethane, polyester, polyvinyl chloride, polyolefin, polycarbonate, ABS, Examples thereof include organic resin materials such as acrylic resins. Moreover, glass, wood, ceramics, etc. are mentioned. For example, these base materials may be prepared by adjusting the base with a sealer in advance according to the type of the base material. Moreover, the coating film may be formed in the surface by various coating materials other than the coating composition of this invention.
- the base material used in the present invention is not limited to the above-mentioned base materials.
- the base material examples include a film-like base material, a sheet-like base material, and a molded body having a shape other than these.
- the base material may be either a molded body processed for raw materials or a molded body processed for products.
- the film-like substrate examples include a polyurethane film, a vinyl chloride film, a PET film, and an acrylic film.
- the sheet-like base material examples include polyurethane sheets, polyvinyl chloride sheets, wet polyurethane synthetic leather sheets, dry polyurethane synthetic leather sheets, urethane rubber sheets, and vinyl chloride synthetic leather sheets.
- the molded body examples include an acrylic molded body, a polycarbonate molded body, an ABS molded body, an unsaturated polyester molded body, and glass having an arbitrary shape.
- the shape of the substrate used in the present invention is not limited to the shape of the substrate mentioned above.
- the thickness of the cured film is preferably 0.5 to 1000 ⁇ m, more preferably 1 to 1000 ⁇ m, still more preferably 1 to 200 ⁇ m, and still more preferably 5 to 100 ⁇ m.
- the present invention provides a method for forming a cured film, in which the coating composition of the present invention is applied to a substrate to form a coating film, and the coating film is cured to form a cured film.
- the matters described in the fluorine-containing copolymer, the coating composition and the coated article of the present invention can be appropriately applied.
- the base material may be either a molded body processed for raw materials or a molded body processed for products.
- a known method can be adopted depending on the shape and material of the substrate, for example, gravure coater, roll coater, reverse roll coater, comma coater, doctor Examples include knife coaters, bar coaters, kiss roll coaters, roller coating, spray coating, electrostatic spray coating, curtain coating, dip coating, rotary screen printing, and brush coating.
- the coating amount of the coating composition and the thickness of the coating film can be appropriately determined in consideration of the composition of the coating composition in consideration of the thickness of the target cured film.
- the coating film formed on the substrate is preferably heated to 30 to 250 ° C., more preferably 40 to 150 ° C., and cured as necessary.
- the present invention also provides a method for producing a coated article, in which the coating composition of the present invention is applied to a substrate to form a coating film, and the coating film is cured to form a cured coating film.
- the matters described in the method for forming a fluorine-containing copolymer, a coating composition, a coated article, and a cured coating of the present invention can be appropriately applied.
- the monomer (A) is 15 to 85 mol% in the constituent monomer
- the monomer (B) is 0.001 to 10 mol% in the constituent monomer
- the monomer (C) is A fluorine-containing copolymer containing 5 to 40 mol% of the constituent monomer and 1 to 25 mol% of the monomer (D) in the constituent monomer, and having a glass transition temperature of ⁇ 30 ° C. to 20 ° C.
- the present specification is such that the monomer (A) is 15 to 85 mol% in the constituent monomer, the monomer (B) is 0.001 to 10 mol% in the constituent monomer, A fluorine-containing copolymer comprising 5 to 40 mol% of the product (C) in the constituent monomer and 1 to 25 mol% of the monomer (D) in the constituent monomer, and having a glass transition temperature of ⁇ 30 A fluorine-containing copolymer having a number average molecular weight of 2.0 ⁇ 10 4 to 7.0 ⁇ 10 4 and a weight average molecular weight of 1.0 ⁇ 10 5 to 3.0 ⁇ 10 5.
- a fluorine-containing copolymer comprising: The glass transition temperature is ⁇ 30 ° C. to 20 ° C., The number average molecular weight is 2.0 ⁇ 10 4 to 7.0 ⁇ 10 4 , The weight average molecular weight is 1.0 ⁇ 10 5 to 3.0 ⁇ 10 5 , Fluorine-containing copolymer.
- R 1 is an alkyl group having 1 to 6 carbon atoms, — (CH 2 ) r —OOC (CH 3 ) C ⁇ CH 2 , — (CH 2 ) r —OOC—HC ⁇ CH 2 or —CH ⁇ Represents CH 2 , R 2 represents — (CH 2 ) r —OOC (CH 3 ) C ⁇ CH 2 , — (CH 2 ) r —OOC—HC ⁇ CH 2 or —CH ⁇ CH 2 , and n represents 1 R represents a number from 1 to 6. ]
- the monomer (D) is preferably a monomer having at least one group selected from a hydroxyl group and an epoxy group as a curing reactive group.
- the monomer (D) includes an aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms, carbon, including the case where the monomer (D) has the curing reactive group.
- the production method of the fluorine-containing copolymer of these embodiments includes 15 to 85 mol% in the monomer using (A) for the reaction, 0.001 to 10 mol% in the monomer using (B) for the reaction, It can be produced by reacting (C) in a proportion of 5 to 40 mol% in the monomer used in the reaction and (D) in a proportion of 1 to 25 mol% in the monomer used in the reaction.
- a coating composition comprising the fluorine-containing copolymer of any one of the above aspects and a curing agent of the fluorine-containing copolymer, wherein the curing agent is an adduct-modified product or an allophanate-modified product of a polyvalent isocyanate compound.
- the monomer (D) of the fluorine-containing copolymer is a monomer having one or more groups selected from a hydroxyl group and an epoxy group as a curing reactive group. Is preferred.
- the curing agent is selected from hexamethylene diisocyanate, pentamethylene diisocyanate, and isophorone diisocyanate, including the case where the monomer (D) of the fluorine-containing copolymer is the monomer. It is preferably an adduct-modified product or allophanate-modified product of the polyvalent isocyanate compound.
- the curing agent is selected from hexamethylene diisocyanate, pentamethylene diisocyanate, and isophorone diisocyanate, including the case where the monomer (D) of the fluorine-containing copolymer is the monomer. More preferably, the adduct is a compound having three or more NCO groups or an allophanate modified compound having three or more NCO groups.
- the coating composition according to this aspect includes a curing agent including the case where the monomer (D) of the fluorine-containing copolymer is the monomer, and the case where the curing agent is the adduct-modified product or the allophanate-modified product. Is preferably 1 to 300 parts by mass, more preferably 2 to 250 parts by mass, and still more preferably 3 to 200 parts by mass with respect to 100 parts by mass of the fluorinated copolymer.
- a solvent preferably an organic solvent, including a case where it is contained in a range, is preferably contained in the coating composition in an amount of 5 to 99% by mass, more preferably 10 to 98% by mass, and still more preferably 20 to 95% by mass.
- the fluorinated copolymer of any of the above embodiments is preferably 0.5 to 90% by mass, more preferably 1 to 80% by mass
- the curing agent for the fluorinated copolymer is preferably 1 to 300 parts by weight, more preferably 2 to 250 parts by weight, still more preferably 3 to 200 parts by weight, with respect to 100 parts by weight of the fluorinated copolymer.
- Solvent preferably organic solvent, preferably 5 to 99% by mass, more preferably 10 to 98% by mass, and still more preferably 20 to 95% by mass.
- the monomer (D) of the fluorine-containing copolymer is a monomer having at least one group selected from a hydroxyl group and an epoxy group as a curing reactive group
- the curing agent is an adduct modification product of a polyvalent isocyanate compound selected from hexamethylene diisocyanate, pentamethylene diisocyanate, and isophorone diisocyanate, and is a compound or allophanate modification product having 3 or more, preferably 5 or less NCO groups.
- the coating composition of these embodiments can be produced by mixing the fluorine-containing copolymer and the curing agent.
- a coated article comprising: a base material; and a cured film of the coating composition according to any one of the aspects formed on the base material.
- the coated article of this aspect is preferably 0.5 to 1000 ⁇ m, more preferably 1 to 1000 ⁇ m, still more preferably 1 to 200 ⁇ m, and still more preferably 5 to 100 ⁇ m.
- a method for forming a cured coating comprising: applying a coating composition according to any one of the above aspects to a substrate to form a coating, and curing the coating to form a cured coating.
- the coating film is preferably cured at 30 to 250 ° C., more preferably at 40 to 150 ° C.
- Example Production Example and Comparative Production Example A curable fluorine-containing copolymer was prepared as follows. Tables 1 to 4 show the monomer composition of the copolymer.
- (Production Example 1) After degassing into an autoclave (withstand pressure of 10 MPa) with a stainless steel stirrer with an internal volume of 1 L, 96 g of vinylidene fluoride (hereinafter abbreviated as VDF), 84 g of tetrafluoroethylene (hereinafter abbreviated as TFE), normal butyl vinyl ether (hereinafter abbreviated as NBVE) , 36 g of homopolymer Tg: -55 ° C., 36 g of hydroxybutyl vinyl ether (hereinafter abbreviated as HBVE), 15 g of methacryl-modified silicone oil A (number average molecular weight of about 3500) represented by the following structural formula, 450 ml of butyl acetate, and t- 1.0 g of but
- Methacrylic modified silicone oil A CH 2 ⁇ C (CH 3 ) —COO—C 3 H 6 —Si (CH 3 ) 2 — [O—Si (CH 3 ) 2 ] 44 —OSi (CH 3 ) 3
- the obtained copolymer was isolated by drying under reduced pressure.
- the copolymer yield was 205 g and the monomer reaction rate was 77%.
- the hydroxyl value measured by the acetylation method with acetic anhydride of the obtained copolymer was 85 mg KOH / g resin, the fluorine content by the combustion method was 41% by mass, and the number average molecular weight measured by GPC (gel permeation chromatography) was It was 3.3 ⁇ 10 4 and the weight average molecular weight was 1.8 ⁇ 10 5 .
- This copolymer was dissolved in butyl acetate and used as a 20% strength by weight butyl acetate solution (varnish) for the preparation of the coating compositions of Examples 1, 2, 3 and Comparative Example 5.
- the obtained copolymer was isolated by drying under reduced pressure.
- the yield of the copolymer was 243 g, and the monomer reaction rate was 80%.
- the hydroxyl value measured by the acetylation method with acetic anhydride of the obtained copolymer was 72 mg KOH / g resin, the fluorine content by the combustion method was 35% by mass, and the number average molecular weight measured by GPC (gel permeation chromatography) was The weight average molecular weight was 3.0 ⁇ 10 4 and 1.6 ⁇ 10 5 .
- This copolymer was dissolved in butyl acetate and used as a 20% strength by weight butyl acetate solution (varnish) for the preparation of the coating compositions of Examples 4 and 5.
- the obtained copolymer was isolated by drying under reduced pressure.
- the copolymer yield was 164 g, and the monomer reaction rate was 60%.
- the hydroxyl value measured by the acetylation method with acetic anhydride of the obtained copolymer was 115 mg KOH / g resin, the fluorine content by the combustion method was 22% by mass, and the number average molecular weight measured by GPC (gel permeation chromatography) was It was 6.5 ⁇ 10 4 and the weight average molecular weight was 1.3 ⁇ 10 5 .
- This copolymer was dissolved in butyl acetate and used as a 20% strength by weight butyl acetate solution (varnish) in the preparation of the coating compositions of Examples 6 and 7.
- Methacrylic modified silicone oil B CH 2 ⁇ C (CH 3 ) —COO—C 3 H 6 —Si (CH 3 ) 2 — [O—Si (CH 3 ) 2 ] 140 —OSi (CH 3 ) 3
- the obtained copolymer was isolated by drying under reduced pressure.
- the copolymer yield was 208 g and the monomer reaction rate was 87%.
- the hydroxyl value measured by the acetylation method with acetic anhydride of the obtained copolymer was 67 mg KOH / g resin, the fluorine content by the combustion method was 39% by mass, and the number average molecular weight measured by GPC (gel permeation chromatography) was It was 3.4 ⁇ 10 4 and the weight average molecular weight was 2.3 ⁇ 10 5 .
- This copolymer was dissolved in butyl acetate and used as a 20% strength by weight butyl acetate solution (varnish) in the preparation of the coating compositions of Examples 8 and 9.
- the obtained copolymer was isolated by drying under reduced pressure.
- the yield of the copolymer was 204 g, and the monomer reaction rate was 87%.
- the hydroxyl value measured by the acetylation method with acetic anhydride of the obtained copolymer was 34 mg KOH / g resin, the fluorine content by the combustion method was 40% by mass, and the number average molecular weight measured by GPC (gel permeation chromatography) was It was 3.1 ⁇ 10 4 and the weight average molecular weight was 1.6 ⁇ 10 5 .
- This copolymer was dissolved in butyl acetate and used as a 20% strength by weight butyl acetate solution (varnish) in the preparation of the coating compositions of Examples 10 and 11.
- the obtained copolymer was isolated by drying under reduced pressure.
- the copolymer yield was 198 g and the monomer reaction rate was 78%.
- the hydroxyl value measured by the acetylation method with acetic anhydride of the obtained copolymer was 46 mg KOH / g resin, the fluorine content by the combustion method was 43% by mass, and the number average molecular weight measured by GPC (gel permeation chromatography) was The molecular weight was 2.1 ⁇ 10 4 and the weight average molecular weight was 1.1 ⁇ 10 5 .
- This copolymer was dissolved in butyl acetate and used as a 20% strength by weight butyl acetate solution (varnish) in the preparation of the coating compositions of Examples 12 and 13.
- the obtained copolymer was isolated by drying under reduced pressure.
- the copolymer yield was 190 g and the monomer reaction rate was 85%.
- the hydroxyl value measured by the acetylation method with acetic anhydride of the obtained copolymer was 73 mg KOH / g resin
- the fluorine content by the combustion method was 40% by mass
- the number average molecular weight measured by GPC (gel permeation chromatography) was It was 3.2 ⁇ 10 4 and the weight average molecular weight was 2.1 ⁇ 10 5 .
- This copolymer was dissolved in butyl acetate and used as a 20% strength by weight butyl acetate solution (varnish) in the preparation of the coating compositions of Comparative Examples 2-4.
- Tg measurement A butyl acetate solution (varnish) of the fluorinated copolymer was dried at 100 ° C. for 24 hours, and this was subjected to a nitrogen atmosphere using an input compensated double furnace differential scanning calorimeter DSC8000 (manufactured by PerkinElmer Co., Ltd.). Tg was measured at a heating rate of 10 ° C./min and a measurement range of ⁇ 50 ° C. to + 150 ° C. The results are shown in Tables 1 to 4.
- Substrate Thermoplastic polyester polyurethane (TPU) film in coating film protective film
- TPU Thermoplastic polyester polyurethane
- thermoplastic polyester polyurethane (TPU) film SHG2086-CR (6OPP), manufactured by Seadam Co., Ltd.
- TPU thermoplastic polyester polyurethane
- 6OPP thermoplastic polyester polyurethane
- the composition for coating was applied to a thermoplastic polyester polyurethane (TPU) film (SHG2086-CR (6OPP), manufactured by Seadam Co., Ltd.) having a thickness of 150 ⁇ m as a base material.
- surface of a TPU film was obtained
- the pressure-sensitive adhesive is coated on release paper (thickness 170 ⁇ m) using a knife coater so that the film thickness is about 20 ⁇ m after drying, and dried to form a pressure-sensitive adhesive layer on the release paper.
- the composite material (II) was obtained.
- Substrate: Vinyl chloride (PVC) film in coating film protective film The same conditions as the above-mentioned coating film protective film using TPU, except that a non-phthalic acid-based vinyl chloride film having a thickness of 0.3 mm (Celeb 267 (hardness # 360), sold by Ishizuka Corporation) was used as the base material, As the same treatment, a coating film protective film was produced. A “scratch resistance test (brass brush)” described later was performed on the surface of the coating film in the coating film protective film. The results are shown in Tables 1 to 4.
- Substrate PET film in coating film protective film
- a coating film protective film is produced under the same conditions and treatment as the above-mentioned coating film protective film using TPU, except that a 125 ⁇ m thick easily-adhesive PET film (Cosmo Shine A4300, manufactured by Toyobo Co., Ltd.) is used as the base material. did.
- the 60 ° gloss value of the film after UV irradiation was measured by the same method as before irradiation, and the gloss retention was determined by the following formula.
- the example which did not perform an accelerated weathering test was described as "ND" in the table
- Gloss retention (%) ⁇ 60 ° gloss value (after irradiation) / 60 ° gloss value (before irradiation) ⁇ ⁇ 100
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Abstract
Description
従来、屋外で長期間暴露され、直射日光を受け、酸性雨や鳥糞、洗剤、日焼け止めクリーム等の種々の薬害を受けることになる各種用途、例えば、自動車外装フィルムや自動車塗装保護フィルム、ウィンドウフィルム、マーキングフィルムなど、主として樹脂を基体としたフィルム類、更に屋内外で使用される各種建材や物品に対し、耐候性と耐薬品性などを付与するために、有機溶剤に溶解された含フッ素樹脂を主成分とする塗料又は塗料組成物が塗布されることが行われてきた。特にジメチルシロキサン構造を側鎖あるいは主鎖骨格に有する含フッ素共重合体は、耐候性や耐薬品性を与えるだけでなく、優れた耐汚染性と撥水撥油性、すべり性等を付与できることから、広範な分野で有効に用いられてきたが、耐キズ性の向上が求められていた。
従来の自己修復性を与える含フッ素共重合体は、耐候性や耐薬品性と耐キズ性には優れるものの、ジメチルシロキサン構造を側鎖あるいは主鎖骨格に有する含フッ素共重合体にみられる高い耐汚染性や撥水撥油性、すべり性を有さないことから、当該特性が要求される用途への適用が困難であった。また、ポリジメチルシロキサン構造を有し、含フッ素共重合体を含まない自己修復性塗料組成物は、高いすべり性を発現するが、含フッ素共重合体を含んだ塗料組成物に比べて耐候性、耐や薬品性に劣るといった課題があった。
(B)下記の一般式(1)で表される化合物及び下記一般式(2)で表される化合物から選ばれる1種以上の有機ケイ素化合物〔以下、単量体(B)という〕を構成単量体中0.001~10モル%、
(C)ビニルエーテル、ビニルエステル、メタクリル酸エステル及びアクリル酸エステルから選ばれる単量体であって、硬化反応性基を有さず、炭素数1~20の脂肪族飽和炭化水素基を有し、該単量体のホモポリマーのガラス転移温度が0℃未満である単量体から選ばれる1種以上の単量体〔以下、単量体(C)という〕を構成単量体中5~40モル%、並びに
(D)ビニルエーテル、ビニルエステル、アリルエーテル、メタクリル酸エステル及びアクリル酸エステルから選ばれる単量体であって、硬化反応性基を有する単量体から選ばれる1種以上の単量体〔以下、単量体(D)という〕を構成単量体中1~25モル%
含む含フッ素共重合体であって、
ガラス転移温度が-30℃~20℃であり、
数平均分子量が2.0×104~7.0×104であり、
重量平均分子量が1.0×105~3.0×105である、
含フッ素共重合体に関する。
以下に本発明の詳細を説明する。
〔含フッ素共重合体及びその製造方法〕
本発明の含フッ素共重合体は、重合単位として、単量体(A)である、フルオロオレフィンを構成単量体中15~85モル%含む。
一般式(1)あるいは(2)で示される有機ケイ素化合物の数平均分子量は、200~30,000が好ましい。
CH2=C(CH3)-COO-C3H6-Si(CH3)2-〔O-Si(CH3)2〕m-R3 (3)
(ここで、R3は炭素数1~6のアルキル基を示し、mは1~250、好ましくは5~200を示す。)
CH2=CH-COO-C3H6-Si(CH3)2-〔O-Si(CH3)2〕p-R4 (4)
(ここで、R4は炭素数1~6のアルキル基を示し、pは1~250、好ましくは5~200を示す。)
R5-C3H6-Si(CH3)2-〔O-Si(CH3)2〕q-C3H6-R5 (5)
(ここで、R5は-OOC(CH3)C=CH2を示し、qは1~250、好ましくは5~200を示す。)
CH2=C(CH3)COO-C3H6Si〔O-Si(CH3)3〕3 (6)
単量体(E)としては、シクロヘキシルビニルエーテル、2-(パーフルオロヘキシル)エチルビニルエーテルなどの、その他のビニルエーテル、
エチルアリルエーテル、ブチルアリルエーテル、シクロヘキシルアリルエーテル、イソブチルアリルエーテル、n-プロピルアリルエーテルなどの、その他のアリルエーテル、
メチルメタクリレート、エチルメタクリレート、n-ブチルメタクリレート、t-ブチルメタクリレート、シクロヘキシルメタクリレート、ジシクロペンタニルメタクリレート、2-(パーフルオロブチル)エチルメタクリレート、2-(パーフルオロヘキシル)エチルメタクリレートなどの、その他のメタクリル酸エステル、
メチルアクリレート、エチルアクリレート、t-ブチルアクリレート、2-(パーフルオロブチル)エチルアクリレート、2-(パーフルオロヘキシル)エチルアクリレートなどの、その他のアクリル酸エステル、
が挙げられる。
また、単量体(E)としては、例えば、エチレン、プロピレン等のオレフィン、塩化ビニル、塩化ビニリデン等のハロオレフィンが挙げられる。
本発明の含フッ素共重合体は、単量体(E)の割合が構成単量体中20モル%未満、更に15モル%以下、であることが好ましい。
換樹脂等のイオン交換樹脂、炭酸水素ナトリウム、炭酸ナトリウム、炭酸水素カリウム、炭酸カリウム、リン酸ナトリウム等のアルカリ金属塩類又はアルカリ土類金属塩類、アルミナ、ジルコニア、チタニア等の金属酸化物、モレキュラーシーブス等のゼオライト類等を添加し、フッ化水素等の酸性物質を中和してもよい。添加のタイミングは重合前、重合中、重合後のいずれの場合でもよく、2回以上に分けてもよい。
また、本発明の含フッ素共重合体は、重量平均分子量が1.0×105~3.0×105である。この重量均分子量は、好ましくは1.5×105~2.7×105、より好ましくは1.6×105~2.5×105である。
含フッ素共重合体の数平均分子量が2.0×104以上、且つ重量平均分子量が1.0×105以上であれば、該含フッ素共重合体を含む被膜用組成物のレベリングが良好で、平滑な塗膜を得ることができると同時に被膜の強度も高く、有効な自己修復性が得られる。また、含フッ素共重合体の数平均分子量が7.0×104以下、且つ重量平均分子量が3.0×105以下であれば、該含フッ素共重合体を含む被膜用組成物の粘度が適切となり、ハンドリング性も良好となる。
ここで、含フッ素共重合体の数平均分子量及び重量平均分子量は、それぞれ、以下の条件でゲル パーミエーション クロマトグラフィーにより測定されたものである。
測定装置:HLC-8320GPC(東ソー株式会社)
カラム:TDgel SuperHZM-M(東ソー株式会社)
検出器:RI(装置付属の示差屈折計)
標準物質:ポリスチレン
データ処理:EcoSEC-WS(東ソー株式会社)
測定条件:カラム温度(40℃)、溶剤(テトラヒドロフラン)、流速(0.35mL/min)、試料濃度(0.14wt%)、試料注入量(20μL)
本発明は、本発明の含フッ素共重合体と、該含フッ素共重合体の硬化剤とを含有し、該硬化剤が多価イソシアネート化合物のアダクト変性体又はアロファネート変性体である、被膜用組成物を提供する。例えば、本発明の含フッ素共重合体を用いて、ワニスや塗料組成物を調製し、それらを用いて被膜を形成させることにより、自己修復性に優れた被膜を得ることができる。本発明の被膜用組成物に用いる含フッ素共重合体は、水酸基、エポキシ基のような硬化反応性基を有するものが好ましい。
また、その他の硬化剤として、メラミン硬化剤、尿素樹脂硬化剤、多基塩基酸硬化剤などを用いることもできる。該メラミン硬化剤としては、例えばブチル化メラミン、メチル化メラミン、エポキシ変性メラミン等が挙げられ、用途に応じて各種変性度の硬化剤が適宜用いられ、また自己縮合度も適宜選ぶことができる。尿素樹脂硬化剤としては、例えばメチル化尿素樹脂やブチル化尿素樹脂等が挙げられる。多基塩基酸硬化剤としては、例えば長鎖脂肪族ジカルボン酸、芳香族多価カルボン酸類及びこれらの酸無水物等が挙げられる。
本発明は、基材と、該基材上に形成された本発明の被膜用組成物の硬化被膜と、を有する塗装物品を提供する。本発明の塗装物品には、本発明の含フッ素共重合体及び被膜用組成物で述べた事項を適宜適用することができる。
これら以外の用途として、例えば、携帯電話、スマートフォン、パソコン、テレビ、ポータブル端末(ゲーム機を含む)、プリンター等の電子機器、テレビ、エアコン、電子レンジ、冷蔵庫、洗濯機、空気清浄機、掃除機、換気扇等の家電類、玩具類、棚、書棚、ベッド、机、椅子、ソファー等のインテリア類、換気扇、レンジフード、キッチンパネル、ステンレスシンク、浴槽、トイレ等の用途、及びこれらの用途における塗料、保護フィルム、意匠性フィルム等が挙げられる。また、建築物等におけるウィンドウフィルム、ガラス表面コート、屋外マーキングフィルム、各種物品の保護フィルム、建材用塗装等が挙げられる。
本発明は、基材に前記本発明の被膜用組成物を塗布して塗膜を形成し、該塗膜を硬化させて硬化被膜を形成する、硬化被膜の形成方法を提供する。本発明の硬化被膜の形成方法には、本発明の含フッ素共重合体、被膜用組成物及び塗装物品で述べた事項を適宜適用することができる。
本明細書は、単量体(A)を構成単量体中15~85モル%、単量体(B)を構成単量体中0.001~10モル%、単量体(C)を構成単量体中5~40モル%、及び単量体(D)を構成単量体中1~25モル%含む含フッ素共重合体であって、ガラス転移温度が-30℃~20℃であり、数平均分子量が2.0×104~7.0×104であり、重量平均分子量が1.0×105~3.0×105である、含フッ素共重合体と、
該含フッ素共重合体の硬化剤とを含有し、
該硬化剤が多価イソシアネート化合物のアダクト変性体又はアロファネート変性体である、組成物の、被膜用組成物としての使用を開示する。
該含フッ素共重合体の硬化剤とを含有し、
該硬化剤が多価イソシアネート化合物のアダクト変性体又はアロファネート変性体である、被膜剤のための組成物を開示する。
(A)フルオロオレフィンを構成単量体中15~85モル%、
(B)下記の一般式(1)で表される化合物及び下記一般式(2)で表される化合物から選ばれる1種以上の有機ケイ素化合物を構成単量体中0.001~10モル%、
(C)ビニルエーテル、ビニルエステル、メタクリル酸エステル及びアクリル酸エステルから選ばれる単量体であって、硬化反応性基を有さず、炭素数1~20の脂肪族飽和炭化水素基を有し、該単量体のホモポリマーのガラス転移温度が0℃未満である単量体から選ばれる1種以上の単量体を構成単量体中5~40モル%、並びに
(D)ビニルエーテル、ビニルエステル、アリルエーテル、メタクリル酸エステル及びアクリル酸エステルから選ばれる単量体であって、硬化反応性基を有する単量体から選ばれる1種以上の単量体〔以下、単量体(D)という〕を構成単量体中1~25モル%
含む含フッ素共重合体であって、
ガラス転移温度が-30℃~20℃であり、
数平均分子量が2.0×104~7.0×104であり、
重量平均分子量が1.0×105~3.0×105である、
含フッ素共重合体。
前記いずれかの態様の含フッ素共重合体と、該含フッ素共重合体の硬化剤とを含有し、該硬化剤が多価イソシアネート化合物のアダクト変性体又はアロファネート変性体である、被膜用組成物。
前記いずれかの態様の含フッ素共重合体を、好ましくは0.5~90質量%、より好ましくは1~80質量%、
該含フッ素共重合体の硬化剤を、含フッ素共重合体100質量部に対して、好ましくは1~300質量部、より好ましくは2~250質量部、更に好ましくは3~200質量部、及び
溶剤、好ましくは有機溶剤を、好ましくは5~99質量%、より好ましくは10~98質量%、更に好ましくは20~95質量%
含有し、
前記含フッ素共重合体の単量体(D)が、硬化反応性基として、水酸基及びエポキシ基から選ばれる1種以上の基を有する単量体であり、
前記硬化剤が、ヘキサメチレンジイソシアネート、ペンタメチレンジイソシアネート、イソホロンジイソシアネートから選ばれる多価イソシアネート化合物のアダクト変性体であってNCO基を3つ以上、好ましくは5つ以下有する化合物又はアロファネート変性体であってNCO基を3つ以上、好ましくは5つ以下有する化合物である、
被膜用組成物。
基材と、該基材上に形成された前記いずれかの態様の被膜用組成物の硬化被膜と、を有する塗装物品。
基材に前記いずれかの態様の被膜用組成物を塗布して塗膜を形成し、該塗膜を硬化させて硬化被膜を形成する、硬化被膜の形成方法。
製造例及び比較製造例
硬化性含フッ素共重合体を、次のようにして調製した。表1~4に共重合体の単量体組成を示した。
(製造例1)
内容積1Lのステンレス製攪拌機付きオートクレーブ(耐圧10MPa)に、脱気したのち、フッ化ビニリデン(以下VDFと略す)96g、テトラフルオロエチレン(以下TFEと略す)84g、ノルマルブチルビニルエーテル(以下NBVEと略す、ホモポリマーのTg:-55℃)36g、ヒドロキシブチルビニルエーテル(以下HBVEと略す)36g、下記構造式で示されるメタクリル変性シリコーンオイルA(数平均分子量約3500)15g、酢酸ブチル450ml、及びt-ブチルパーオキシピバレート1.0gを入れ、攪拌しながら内温を60℃に昇温した。
メタクリル変性シリコーンオイルA:
CH2=C(CH3)-COO-C3H6-Si(CH3)2-〔O-Si(CH3)2〕44-OSi(CH3)3
内容積1Lのステンレス製攪拌機付きオートクレーブ(耐圧10MPa)に、脱気したのち、VDF96g、TFE84g、オクタデシルビニルエーテル(以下ODVEと略す、ホモポリマーのTg:-100℃未満)45g、HBVE36g、シクロヘキシルビニルエーテル(以下CHVEと略す)26g、実施例1と同様のメタクリル変性シリコーンオイルA(数平均分子量約3500)15g、酢酸ブチル450ml、及びt-ブチルパーオキシピバレート1.0gを入れ、攪拌しながら内温を60℃に昇温した。
内容積1Lのステンレス製攪拌機付きオートクレーブ(耐圧10MPa)に、脱気したのち、VDF80g、TFE70g、エチルビニルエーテル(以下EVEと略す、ホモポリマーのTg:-43℃)70g、HBVE39g、実施例1と同様のメタクリル変性シリコーンオイルA(数平均分子量約3500)15g、酢酸ブチル450ml、及びt-ブチルパーオキシピバレート1.0gを入れ、攪拌しながら内温を60℃に昇温した。
内容積1Lのステンレス製攪拌機付きオートクレーブ(耐圧10MPa)に、脱気したのち、VDF96g、TFE84g、NBVE36g、HBVE39g、下記構造式で示されるメタクリル変性シリコーンオイルB(数平均分子量約8000)16g、酢酸ブチル450ml、及びt-ブチルパーオキシピバレート1.0gを入れ、攪拌しながら内温を60℃に昇温した。
メタクリル変性シリコーンオイルB:
CH2=C(CH3)-COO-C3H6-Si(CH3)2-〔O-Si(CH3)2〕140-OSi(CH3)3
内容積1Lのステンレス製攪拌機付きオートクレーブ(耐圧10MPa)に、脱気したのち、VDF56g、TFE87g、NBVE49g、HBVE14g、CHVE13g、実施例1と同様のメタクリル変性シリコーンオイルA(数平均分子量約3500)15g、酢酸ブチル450ml、及びt-ブチルパーオキシピバレート1.0gを入れ、攪拌しながら内温を60℃に昇温した。
内容積1Lのステンレス製攪拌機付きオートクレーブ(耐圧10MPa)に、脱気したのち、VDF96g、TFE84g、NBVE60g、ヒドロキシエチルビニルエーテル(以下HEVEと略す)24g、実施例1と同様のメタクリル変性シリコーンオイルA(数平均分子量約3500)15g、酢酸ブチル450ml、及びt-ブチルパーオキシピバレート1.0gを入れ、攪拌しながら内温を60℃に昇温した。
内容積1Lのステンレス製攪拌機付きオートクレーブ(耐圧10MPa)に、脱気したのち、VDF56g、TFE87g、HBVE35g、CHVE53g、実施例1と同様のメタクリル変性シリコーンオイルA(数平均分子量約3500)15g、酢酸ブチル450ml、及びt-ブチルパーオキシピバレート1.0gを入れ、攪拌しながら内温を60℃に昇温した。
内容積1Lのステンレス製攪拌機付きオートクレーブ(耐圧10MPa)に、脱気したのち、VDF56g、TFE87g、NBVE28g、HBVE29g、CHVE25g、酢酸ブチル450ml、及びt-ブチルパーオキシピバレート1.0gを入れ、攪拌しながら内温を60℃に昇温した。
含フッ素共重合体の酢酸ブチル溶液(ワニス)を100℃-24時間の条件で乾燥させ、これを、入力補償型ダブルファーネス示差走査熱量測定装置DSC8000(PerkinElmer株式会社製)を用い、窒素雰囲気下、昇温速度10℃/min、測定範囲-50℃~+150℃にてTgを測定した。結果を表1~4に示した。
<被膜用組成物の調製>
[被膜用組成物の調製(1)]
製造例1~6及び比較製造例1~2の各含フッ素共重合体溶液に対し、硬化剤としてヘキサメチレンジイソシアネートのトリメチロールプロパンによるアダクト変性体(NCO含有量7%)(旭化成ケミカルズ株式会社製、デュラネートE402-80B)(3官能)をNCO/OH=1.1の割合で加え、酢酸ブチルにて溶液の固形分濃度が23%となるよう希釈し、被膜用組成物を調製した。ここで用いた硬化剤は、表中、「アダクト変性体」と示した。なお、含フッ素共重合体100質量部に対する硬化剤の量は12.8~34.0質量部の範囲であった。
製造例1~6及び比較製造例2の各含フッ素共重合体溶液に対し、硬化剤としてペンタメチレンジイソシアネートによるアロファネート変性体(NCO含有量16.2%)(東ソー株式会社製、コロネート2793)(5官能)をNCO/OH=1.1の割合で加え、酢酸ブチルにて溶液の固形分濃度が23%となるよう希釈し、被膜用組成物を調製した。ここで用いた硬化剤は、表中、「アロファネート変性体1」と示した。なお、含フッ素共重合体100質量部に対する硬化剤の量は5.6~14.8質量部の範囲であった。
製造例1の含フッ素共重合体溶液に対し、比較の硬化剤としてヘキサメチレンジイソシアネートのイソシアヌレート変性体(NCO含有量21%)(東ソー株式会社製、コロネートHX)(3官能)をNCO/OH=1.1の割合で加え、酢酸ブチルにて溶液の固形分濃度が23%となるよう希釈し、比較例5の被膜用組成物を調製した。ここで用いた硬化剤は、表中、「イソシアヌレート変性体」と示した。なお、含フッ素共重合体100質量部に対する硬化剤の量は10.8質量部であった。
製造例1の含フッ素共重合体溶液に対し、硬化剤としてヘキサメチレンジイソシアネートによるアロファネート変性体(NCO含有量19.5%)(旭化成ケミカルズ株式会社製、デュラネートD101)(2官能)をNCO/OH=1.1の割合で加え、酢酸ブチルにて溶液の固形分濃度が23%となるよう希釈し、実施例3の被膜用組成物を調製した。ここで用いた硬化剤は、表中、「アロファネート変性体2」と示した。なお、含フッ素共重合体100質量部に対する硬化剤の量は17.7質量部であった。
[基材:ガラス板]
被膜用組成物を、表面をアセトンで脱脂した厚さ2mmのガラス板に#20バーコーター(乾燥後膜厚の計算値:約10μm)を用いてハンド塗布し、100℃に加熱された乾燥機で4時間加熱硬化させ、実施例又は比較例の含フッ素共重合体とその硬化剤とからなる被膜が形成された塗装物品を得た。塗装物品の被膜について以下の評価を行った。結果を表1~4に示した。
被膜用組成物を、表面をイソプロピルアルコールで脱脂した厚さ1mmのポリエステル系ウレタンゴムフィルムに#10バーコーター(乾燥後膜厚の計算値:約5μm)を用いてハンド塗布し、120℃に加熱された乾燥機で3分加熱硬化させ、50℃で3日養生した。これにより、実施例又は比較例の含フッ素共重合体とその硬化剤とからなる被膜が形成された塗装物品を得た。この塗装物品の被膜について、後述の「耐擦傷試験(真鍮ブラシ)」を行った。結果を表1~4に示した。
剥離紙、粘着剤層、ウレタン層、並びに、含フッ素共重合体とその硬化剤とからなる被膜を有する塗膜保護フィルムを、以下の手順で作製した。
被膜用組成物を、基材である厚さ150μmの熱可塑性ポリエステル系ポリウレタン(TPU)フィルム(SHG2086-CR(6OPP)、シーダム株式会社製)に、#10バーコーター(乾燥後膜厚の計算値:約5μm)及び#20バーコーター(乾燥後膜厚の計算値:約10μm)を用いてハンド塗布し、120℃に加熱された乾燥機で1分加熱硬化させ、60℃で3日養生した。これにより、TPUフィルムの片面に、実施例又は比較例の含フッ素共重合体とその硬化剤とからなる被膜が形成された複合材(I)を得た。
還流器及び攪拌機を備えたフラスコに、アクリル酸ブチル95質量部、アクリル酸5質量部、過酸化物系開始剤及びトルエン(溶剤)を混合し、窒素雰囲気下で加温、撹拌し、重合反応によりアクリル系ポリマーを得た(重量平均分子量=500,000)。
前記アクリル系ポリマー100質量部(固形分換算)、及びエポキシ系架橋剤(商品名:TETRAD-X、三菱ガス化学株式会社製)0.01質量部を混合して粘着剤を得た。
前記粘着剤を剥離紙(厚さ170μm)にナイフコーターを用いて乾燥後膜厚が約20μmとなるように塗工し、乾燥して粘着剤層を剥離紙上に形成し、粘着剤と剥離紙の複合材(II)を得た。
前記複合材(I)の、TPU基材の含フッ素共重合体とその硬化剤とからなる被膜がコートされた面の逆側にあたるコートされていない面に対して、前記複合材(II)の粘着剤層を貼付して、塗膜保護フィルムを作製した。
基材として厚さ0.3mmの非フタル酸系塩化ビニルフィルム(セレブ 267(硬度#360)、石塚株式会社が販売)を用いた以外は、上記TPUを用いた塗膜保護フィルムと同条件、同処理として、塗膜保護フィルムを作製した。この塗膜保護フィルムにおける前記被膜の面を対象として、後述の「耐擦傷試験(真鍮ブラシ)」を行った。結果を表1~4に示した。
基材として厚さ125μmの易接着PETフィルム(コスモシャイン A4300、東洋紡株式会社製)を用いた以外は、上記TPUを用いた塗膜保護フィルムと同条件、同処理として、塗膜保護フィルムを作製した。この塗膜保護フィルムにおける前記被膜の面を対象として、後述の「耐擦傷試験(真鍮ブラシ)」を行った。結果を表1~4に示した。
JIS-K5400 8.5.2(1990)(碁盤目テープ試験)により以下の2通りの方法で測定した。
・被膜表面をそのまま測定に供する(表中、未処理と標記)。
・被膜表面を塗膜が剥離しない程度に軽くサンドペーパー(粒度1200)で処理して測定に供する(表中、サンドペーパー処理と標記)。
10%HCl溶液による24時間スポットテスト後の被膜外観を目視観察し、以下の基準で判定した。
◎:異状なし
○:ほとんど変化なし
△:やや侵される
×:侵される
10%NaOH溶液による24時間スポットテスト後の被膜外観を目視観察し、以下の基準で判定した。
◎:異状なし
○:ほとんど変化なし
△:やや侵される
×:侵される
キシレンによる30分スポットテスト後の被膜外観を目視観察し、以下の基準で判定した。
◎:異状なし
○:ほとんど変化なし
△:やや侵される
×:侵される
油性フェルトペン(黒色)により被膜表面を塗りつぶし、室温で1時間放置後、乾拭きによりインクを除去した。その際の被膜表面のインクの除去性を以下の基準で評価した。なお、黒色油性フェルトペンはマジックインキ(商品名)、寺西化学工業株式会社製を用いた。
◎:全く跡が付かない
○:ごくわずか跡が付く
△:かなり跡が付く
×:完全に跡が残る
被膜における純水及びオレイン酸の接触角(単位:度)を、Drop Master DM300(協和界面化学株式会社製)を用い、気温20℃、湿度40%RHの条件下にて、滴下量10μLにて測定した。
被膜の60°光沢値を、GLOSS CHECKER IG-330(株式会社堀場製作所)を用いてn=3の水準で測定した。その後、超促進耐候性試験機メタルウェザーKW-R7TP(ダイプラ・ウィンテス株式会社製)を用い、紫外線強度65mW/cm2、ブラックパネル温度53℃、相対湿度50%の条件で、被膜に対して紫外線を20時間照射後、ブラックパネル温度30℃、相対湿度98%の条件で4時間無照射状態にするサイクルを計8サイクル行うことにより、耐候性促進試験を行った。紫外線照射後の被膜の60°光沢値を照射前と同様の方法で測定し、光沢保持率を、以下の式で求めた。なお、促進耐候性試験を行わなかった例は、表中、「ND」と記載した。
光沢保持率(%)={60°光沢値(照射後)/60°光沢値(照射前)}×100
気温20℃環境下にて、180mm真鍮ブラシ(エスコ)に200g荷重を取り付け、被膜上をこれで20往復(移動幅40mm、移動速度80mm/秒)し、傷が修復するまでの時間を最大2分まで計測した。
Claims (12)
- (A)フルオロオレフィンを構成単量体中15~85モル%、
(B)下記の一般式(1)で表される化合物及び下記一般式(2)で表される化合物から選ばれる1種以上の有機ケイ素化合物を構成単量体中0.001~10モル%、
(C)ビニルエーテル、ビニルエステル、メタクリル酸エステル及びアクリル酸エステルから選ばれる単量体であって、硬化反応性基を有さず、炭素数1~20の脂肪族飽和炭化水素基を有し、該単量体のホモポリマーのガラス転移温度が0℃未満である単量体から選ばれる1種以上の単量体を構成単量体中5~40モル%、並びに
(D)ビニルエーテル、ビニルエステル、アリルエーテル、メタクリル酸エステル及びアクリル酸エステルから選ばれる単量体であって、硬化反応性基を有する単量体から選ばれる1種以上の単量体〔以下、単量体(D)という〕を構成単量体中1~25モル%
含む含フッ素共重合体であって、
ガラス転移温度が-30℃~20℃であり、
数平均分子量が2.0×104~7.0×104であり、
重量平均分子量が1.0×105~3.0×105である、
含フッ素共重合体。
- 単量体(D)が、硬化反応性基として、水酸基及びエポキシ基から選ばれる1種以上の基を有する、請求項1に記載の含フッ素共重合体。
- 単量体(D)が、炭素数1~20の脂肪族飽和炭化水素基、炭素数1~20の脂環式飽和炭化水素基、及びアルキレン基の炭素数が1~20で繰り返し単位数が1~10であるアルキレングリコール基から選ばれる基を有する、請求項1又は2に記載の含フッ素共重合体。
- 請求項1~3の何れか1項に記載の含フッ素共重合体の製造方法であって、(A)を反応に用いる単量体中15~85モル%、(B)を反応に用いる単量体中0.001~10モル%、(C)を反応に用いる単量体中5~40モル%、(D)を反応に用いる単量体中1~25モル%の割合で反応させる、含フッ素共重合体の製造方法。
- 請求項1~3の何れか1項に記載の含フッ素共重合体と、該含フッ素共重合体の硬化剤とを含有し、該硬化剤が多価イソシアネート化合物のアダクト変性体又はアロファネート変性体である、被膜用組成物。
- 前記硬化剤が、ヘキサメチレンジイソシアネート、ペンタメチレンジイソシアネート、イソホロンジイソシアネートから選ばれる多価イソシアネート化合物のアダクト変性体又はアロファネート変性体である、請求項5記載の被膜用組成物。
- 硬化剤を、含フッ素共重合体100質量部に対して、1~300質量部含有する、請求項5又は6に記載の被膜用組成物。
- 請求項5~7の何れか1項に記載の被膜用組成物の製造方法であって、前記含フッ素共重合体と前記硬化剤とを混合する、被膜用組成物の製造方法。
- 基材と、該基材上に形成された請求項5~7の何れか1項に記載の被膜用組成物の硬化被膜と、を有する塗装物品。
- 硬化被膜の膜厚が0.5~1000μmである、請求項9に記載の塗装物品。
- 基材に請求項5~7の何れか1項に記載の被膜用組成物を塗布して塗膜を形成し、該塗膜を硬化させて硬化被膜を形成する、硬化被膜の形成方法。
- 前記塗膜を、30~250℃で硬化させる、請求項11に記載の硬化被膜の形成方法。
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JP2019513572A JP7060586B2 (ja) | 2017-04-17 | 2018-04-11 | 含フッ素共重合体 |
US16/605,111 US20200157372A1 (en) | 2017-04-17 | 2018-04-11 | Fluorine-containing copolymer |
KR1020197026249A KR102490295B1 (ko) | 2017-04-17 | 2018-04-11 | 함불소 공중합체 |
EP18788317.8A EP3597675B1 (en) | 2017-04-17 | 2018-04-11 | Fluorine-containing copolymer |
CN201880025605.2A CN110494459B (zh) | 2017-04-17 | 2018-04-11 | 含氟共聚物 |
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WO2019230598A1 (ja) * | 2018-05-30 | 2019-12-05 | Agc株式会社 | 組成物および物品 |
JP2021504518A (ja) * | 2017-11-24 | 2021-02-15 | ダイキン・フルオロケミカルズ・(チャイナ)・カンパニー・リミテッドDaikin Fluorochemicals (China) Co., Ltd. | 組成物、塗料、塗膜、太陽電池モジュールのバックシート、及び、太陽電池モジュール |
WO2021045030A1 (ja) * | 2019-09-02 | 2021-03-11 | 関東電化工業株式会社 | 耐摩耗性の優れた塗料組成物 |
WO2021172322A1 (ja) * | 2020-02-25 | 2021-09-02 | 関東電化工業株式会社 | 含フッ素共重合体組成物 |
US11584836B2 (en) * | 2018-06-13 | 2023-02-21 | AGC Inc. | Decorative film, composition, method for producing decorative film, and method for producing three-dimensional molded product provided with decorative film |
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EP3786238A1 (en) * | 2015-11-20 | 2021-03-03 | Honeywell International Inc. | Gloss retentive fluorocopolymers for coating applications |
CN116376420B (zh) * | 2023-04-19 | 2024-05-24 | 湖南中能新材料技术有限公司 | 一种含氟涂料及其制备方法与应用 |
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CN110494459B (zh) | 2022-01-28 |
EP3597675B1 (en) | 2022-04-27 |
US20200157372A1 (en) | 2020-05-21 |
TW201900700A (zh) | 2019-01-01 |
EP3597675A4 (en) | 2021-01-27 |
JP7060586B2 (ja) | 2022-04-26 |
KR102490295B1 (ko) | 2023-01-20 |
EP3597675A1 (en) | 2020-01-22 |
KR20190132367A (ko) | 2019-11-27 |
TWI755519B (zh) | 2022-02-21 |
JPWO2018193926A1 (ja) | 2020-03-05 |
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