TW202208502A - Fluorine-containing polymerizable resin, active energy ray-curable composition, cured coating film, and article - Google Patents

Abstract

Provided is a fluorine-containing polymerizable resin capable of forming a low refractive index layer having excellent slipperiness and scratch resistance. Specifically, provided is a fluorine-containing polymerizable resin that is a product of a reaction between: a polymer (P), which is a copolymer of a compound (A) having a weight average molecular weight of 5000 or more and having a poly(perfluoroalkylene ether) chain and a styryl group at both chain terminals and a polymerizable unsaturated monomer (B) having a functional group (b); and a compound (C) having a polymerizable unsaturated group and a functional group (c) able to react with the functional group (b).

Description

Fluoropolymer resins, active energy ray curable compositions, cured coatings and articles

The present invention relates to a fluoropolymer resin, an active energy ray curable composition, a cured coating film, and an article.

Flat panel displays, such as liquid crystal displays and organic EL displays, are composed of laminates of a plurality of functional layers, and are required to display images with higher quality and thinner thicknesses.

For example, a low-refractive-index layer (Low-Reflection layer) is provided on the outermost surface of a polarizer, which is one of the components constituting a liquid crystal display, in order to increase the quality of the displayed image. The low-refractive index layer is required to have scratch resistance in addition to anti-glare properties or anti-reflection properties for improving visibility.

It is important in performance that the constituent materials of the low-refractive index layer are all low-refractive-index materials, but generally, materials with low-refractive index have poor scratch resistance. In addition, the LR layer is also a layer that is not resistant to scratches when the film thickness is about 100 nm.

For the above-mentioned problems, it has been proposed to add a fluoropolymer resin having a perfluoropolyether chain, a siloxy group and a polymerizable unsaturated group to a coating composition for a low refractive index layer to improve the surface resistance of the LR layer. Scratch property (for example, Patent Document 1). [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2012-72296

[The problem to be solved by the invention]

The film thickness of the low-refractive-index layer is usually about 100 nm, but the low-refractive-index material containing the fluoropolymer resin disclosed in Patent Document 1 generally has low slidability, and when the film thickness is about 100 nm, the slidability is insufficient, The problem of reduced scratch resistance.

The problem to be solved by the present invention is to provide a fluoropolymer resin capable of forming a low refractive index layer excellent in sliding properties and scratch resistance. [means to solve the problem]

The inventors of the present invention, as a result of intensive studies to solve the above-mentioned problems, found that sliding properties and scratch resistance are improved by a fluoropolymeric resin containing a poly(perfluoroalkylene ether) chain having a weight average molecular weight of 5,000 or more. , the present invention has been completed.

That is, the present invention relates to a fluoropolymer resin which is a reaction product of a polymer (P) and a compound (C), wherein the polymer (P) has a weight average molecular weight of 5,000 or more A copolymer of a poly(perfluoroalkylene ether) chain with a styrene group at both ends of the compound (A) and a polymerizable unsaturated monomer (B) having a functional group (b), and the compound ( C) having a functional group (c) reactive with the aforementioned functional group (b) and a polymerizable unsaturated group, and the aforementioned polymerizable unsaturated monomer (B) is selected from the group consisting of hydroxyl groups, isocyanate groups, epoxy groups, A polymerizable unsaturated monomer having at least one functional group (b) of the group of a carboxyl group, an acid anhydride group and a carboxylic acid halide group, wherein the compound (C) is selected from the group consisting of a hydroxyl group, an isocyanate group, an epoxy group A compound of at least one functional group (c) and a polymerizable unsaturated group of the group of a group, a carboxyl group, an acid anhydride group, and a halogenated halide group. [Effect of invention]

According to the present invention, a fluoropolymer resin capable of forming a low-refractive-index layer excellent in sliding properties and scratch resistance can be provided.

[Form for carrying out the invention]

Hereinafter, an embodiment of the present invention will be described. The present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within a range that does not impair the effects of the present invention. In the present specification, "(meth)acryloyl" refers to one or both of acryl and methacryloyl. In addition, "(meth)acrylate" mentioned later means one or both of methacrylate and acrylate.

[Fluoropolymer resin] The fluoropolymeric resin of the present invention is a reaction product of a polymer (P) and a compound (C), wherein the polymer (P) is a poly(perfluoroalkylene ether) chain having a weight average molecular weight of 5,000 or more and a A copolymer of compound (A) having styryl groups at both ends and a polymerizable unsaturated monomer (B) having functional group (b), and compound (C) having reactivity with the aforementioned functional group (b) The functional group (c) and the polymerizable unsaturated group. Hereinafter, each constituent unit of the fluorinated polymer resin of the present invention will be described.

The polymer (P) is a compound (A) having a poly(perfluoroalkylene ether) chain having a weight average molecular weight of 5,000 or more and styryl groups at both ends thereof, and a polymerizable unsaturated polymer having a functional group (b) A copolymer of monomer (B). The polymerization form of the aforementioned copolymer is not particularly limited, and may be a random copolymer of the compound (A) and the polymerizable unsaturated monomer (B), or may be the compound (A) and the polymerizable unsaturated monomer (B). ) block copolymers.

The poly(perfluoroalkylene ether) chain possessed by the compound (A) includes, for example, a linking group having a structure in which a divalent fluorinated hydrocarbon group having 1 to 3 carbon atoms and an oxygen atom are alternately linked. Preferably, it is a linking group represented by the following formula (X-1).

(前述式(X-1)中， 複數個X各自獨立地為全氟伸烷基。 亦可於複數個X中，無規地或嵌段狀地存在2種以上的全氟伸烷基。 n為重複數。n為例如3～60的範圍，較佳為6～40的範圍。)

(In the aforementioned formula (X-1), a plurality of Xs are each independently a perfluoroalkylene group. In the plurality of Xs, two or more types of perfluoroalkylene groups may be present randomly or in blocks. n is the number of repetitions. n is, for example, in the range of 3 to 60, preferably in the range of 6 to 40.)

As the perfluoroalkylene group of X, the following perfluoroalkylene groups (Y-1) to (Y-6) can be exemplified.

X is preferably a perfluoromethylene group or a perfluoroethylidene group independently of each other, and it is more preferable that a perfluoromethylene group and a perfluoroethylidene group coexist as long as the point of industrial availability is also included. In the case where the aforementioned perfluoromethylene group (a) and perfluoroethylene group (b) coexist, the presence ratio (a/b) (number ratio) is preferably 1/10 to 10/1, more preferably 3/10～10/3.

The fluorine atoms contained in one poly(perfluoroalkylene ether) chain are preferably in the range of 18 to 850 in total, and more preferably in the range of 30 to 300.

The poly(perfluoroalkylene ether) chain possessed by the compound (A) may have a weight average molecular weight of 5,000 or more, preferably 5,500 or more. The upper limit of the weight average molecular weight of the poly(perfluoroalkylene ether) chain possessed by the compound (A) is not particularly limited, but is, for example, 10,000, preferably 8,000 or less, and more preferably 7,500 or less. The weight average molecular weight of the poly(perfluoroalkylene ether) chain possessed by the compound (A) was measured by the method described in the examples.

The compound (A) is a compound having a styryl group at both ends, and is preferably a compound represented by the following general formula (a-1).

(前述通式(a-1)中， L₁ 及L₂ 各自獨立地為碳原子數1～6的伸烷基或碳原子數1～6的伸烷基醚基， PFPE為前述式(X-1)所表示的連結基。)

(In the aforementioned general formula (a-1), L ₁ and L ₂ are each independently an alkylene group having 1 to 6 carbon atoms or an alkylene ether group having 1 to 6 carbon atoms, and PFPE is the aforementioned formula (X -1) The linking group represented.)

In addition, the alkylene ether group refers to a divalent group including one or more alkylene groups and one or more ether bonds (-O-).

Specific examples of the compound represented by the aforementioned general formula (a-1) include the following.

Compound (A) can be produced by a known method, for example, by combining a compound having a poly(perfluoroalkylene ether) chain and hydroxyl groups at both ends thereof, and a compound having a halogenated alkyl group, an isocyanate group, and the like. It is produced by reacting styrene having a functional group reactive with a hydroxyl group.

The compound (A) constituting the polymer (P) may be used alone or in combination of two or more.

The polymerizable unsaturated monomer (B) is a polymerizable unsaturated monomer having at least one functional group (b) selected from the group consisting of a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, an acid anhydride group and a halide group . The polymerizable unsaturated monomer (B) may be a carboxylic acid halide having a polymerizable unsaturated group or a carboxylic acid anhydride. The polymerizable unsaturated group contained in the polymerizable unsaturated monomer (B) may be, for example, a vinyl group-containing group, and examples thereof include (meth)acryloyl group, (meth)acryloyloxy group, and benzene. A vinyl group, a maleimide group, etc., preferably a (meth)acryloyl group.

The polymerizable unsaturated monomer (B) is preferably a polymerizable unsaturated monomer represented by the following general formula (b-1).

(前述通式(b-1)中， R^b1 為氫原子或碳原子數1～6的烷基， R^b2 為碳原子數1～10的伸烷基、碳原子數6～18的伸芳基、或由選自碳原子數1～10的伸烷基、碳原子數6～18的伸芳基及醚鍵(-O-)之2種以上的組合而成的2價之連結基， R^b3 為羥基、異氰酸酯基、環氧基或羧基。)

(In the aforementioned general formula (b-1), R ^b1 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ^b2 is an alkylene group having 1 to 10 carbon atoms, and an arylene group having 6 to 18 carbon atoms. group, or a bivalent linking group consisting of a combination of two or more kinds selected from the group consisting of alkylene groups having 1 to 10 carbon atoms, aryl groups having 6 to 18 carbon atoms, and ether bonds (-O-). R ^b3 is a hydroxyl group, an isocyanate group, an epoxy group or a carboxyl group.)

The C1-C10 alkylene group of R ^b1 may be linear, branched, or cyclic. The arylidene group having 6 to 18 carbon atoms of R ^b2 may be a monocyclic ring or a condensed ring. Specific examples of the arylidene group having 6 to 18 carbon atoms in R ^b2 include a phenylene group, a naphthylene group, and the like. The alkyl-extended group and the aryl-extended group of R ^b2 may further have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a halogen atom, and the like. R ^b3 corresponds to the functional group (b) of the polymerizable unsaturated monomer (B).

Specific examples of the polymerizable unsaturated monomer (B) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-hydroxy (meth)acrylate. Propyl ester, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, N-(2-hydroxyethyl) ) (meth)acrylamide, glycerol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, 2-hydroxy-3 (meth)acrylate -Phenoxypropyl ester, 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalate, lactone-modified (meth)acrylate having a hydroxyl group at the terminal, etc. Saturated monomers; 2-(meth)acryloyloxyethyl isocyanate, 2-(2-(meth)acrylooxyethoxy)ethyl isocyanate, 1,1-isocyanate Unsaturated monomers with isocyanate groups such as bis((meth)acrylooxymethyl)ethyl ester; glycidyl (meth)acrylate, glycidyl (meth)acrylate 4-hydroxybutyl Unsaturated monomers with epoxy groups such as ethers; (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl phthalate, Unsaturated monomers with carboxyl groups such as lactic acid and itaconic acid; unsaturated monomers with acid anhydride groups such as maleic anhydride and itaconic anhydride; (meth)acrylic acid chloride, (meth)acrylic acid bromide, etc. The unsaturated monomers with halogenated halide groups, etc.

The polymerizable unsaturated monomer (B) constituting the polymer (P) may be one type alone, or two or more types may be used.

The polymer (P) may be a copolymer of the compound (A) and the polymerizable unsaturated monomer (B), and may contain the compound (A) and the polymerizable unsaturated monomer within the range that does not impair the effects of the present invention. Constituent units of polymerizable unsaturated monomers other than (B). The polymer (P) is preferably a copolymer composed of only the compound (A) and the polymerizable unsaturated monomer (B).

烷、甲苯、二甲苯、1,3-雙(三氟甲基)苯、1,4-雙(三氟甲基)苯等。此等有機溶媒的選擇，係考慮沸點、與原料或聚合物的相溶性、聚合性而適當選擇。化合物(A)由於尤其與有機溶媒的相溶性優良，所以大致可溶解於上述之有機溶媒中。The method for producing the polymer (P) includes copolymerizing the compound (A), the monomer (B), and, if necessary, other polymerizable unsaturated monomers in an organic solvent in the presence of a radical polymerization initiator. Methods. The organic solvents used here are preferably ketones, esters, amides, sulfites, ethers, hydrocarbons, and fluorine-based solvents, and specifically, acetone, methylethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, Dimethyl sulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, diethyl ether

alkane, toluene, xylene, 1,3-bis(trifluoromethyl)benzene, 1,4-bis(trifluoromethyl)benzene, etc. The selection of these organic solvents is appropriately selected in consideration of boiling point, compatibility with raw materials or polymers, and polymerizability. Since the compound (A) is particularly excellent in compatibility with an organic solvent, it is almost soluble in the above-mentioned organic solvent.

Examples of the above-mentioned radical polymerization initiators used in the production of the polymer (P) include acetyl peroxide, cumyl peroxide, tertiary butyl peroxide, propylene peroxide, Gasified benzyl, 2-chlorobenzyl peroxide, 3-chlorobenzyl peroxide, 4-chlorobenzyl peroxide, 2,4-dichlorobenzyl peroxide, 4-bromo peroxide methyl benzyl, lauryl peroxide, diisopropyl peroxycarbonate, tetralin peroxide, 1-phenyl-2-methylpropyl-1-hydroperoxide, triphenylacetate tertiary butyl ester, tertiary butyl hydroperoxide, tertiary butyl performate, tertiary butyl peracetate, tertiary butyl peroxybenzoate, tertiary butyl per-2-ethylhexanoate, perbenzene Peroxides such as tertiary butyl acetate, tertiary butyl per-4-methoxyacetate, etc.; 2,2'-dichloro-2,2'-azobispropane, 1,1'-azo( Methylethyl) diacetate, 2,2'-azobis(2-carboxamidinopropane) nitrate, 2,2'-azobisisobutane, 2,2'-azobisiso Butamide, 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylpropionate, 2,2'-dichloro-2,2'-azobis Butane, 2,2'-azobis-2-methylbutyronitrile, 2,2'-azobisisobutyric acid dimethyl ester, 2-(4-methylphenylazo)-2-methyl Malononitrile, 4,4'-azobis-4-cyanovaleric acid, 3,5-dihydroxymethylphenylazo-2-methylmalononitrile, 1,1'-azobis -1-Cyclohexanecarbonitrile, 1,1'-azobis-1-phenylethane, 1,1'-azobiscumene, ethyl 4-nitrophenylazobenzylcyanoacetate Esters, Phenylazodiphenylmethane, Phenylazotriphenylmethane, 4-Nitrotriphenylazotriphenylmethane, 1,1'-azobis-1,2-diphenyl Azo compounds such as ethane. Chain transfer agents such as lauryl mercaptan, 2-mercaptoethanol, thioglycerol, ethyl thioglycolate, and octyl thioglycolate can also be used as required.

The compound (C) is a compound having at least one functional group (c) and a polymerizable unsaturated group selected from the group consisting of a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, an acid anhydride group, and a halide group. The compound (C) may be a carboxylic acid halide or a carboxylic acid anhydride having a polymerizable unsaturated group. The polymerizable unsaturated group possessed by the compound (C) may be, for example, a vinyl group-containing group, and examples thereof include (meth)acryloyl group, (meth)acryloyloxy group, styryl group, and maleic group. An imino group or the like is preferably a (meth)acryloyl group.

When the functional group (b) is a hydroxyl group, the functional group (c) includes an isocyanate group, an epoxy group, a carboxyl group, an acid anhydride group, and a halide group, and when the functional group (b) is an isocyanate group. In the case, the functional group (c) includes a hydroxyl group, and when the functional group (b) is an epoxy group, the functional group (c) includes a hydroxyl group, a carboxyl group, and an acid anhydride group. When the group (b) is a carboxyl group, the functional group (c) includes a hydroxyl group and an epoxy group, and when the functional group (b) is a halide group, a hydroxyl group is used as the functional group (c). .

The functional group (b) possessed by the polymerizable unsaturated monomer (B) and the functional group (c) possessed by the compound (C), for example, the fluoropolymer resin of the present invention contains a urethane bond. It is better to choose the method. Since the fluorine-containing polymeric resin of the present invention contains urethane bonds, the solubility is improved, and it can be dissolved in general-purpose solvents other than fluorine-based solvents.

The compound (C) is preferably a compound represented by the following general formula (c-1).

(前述通式(c-1)中， R^c1 為氫原子或碳原子數1～6的烷基， R^c2 為碳原子數1～10的伸烷基、碳原子數6～18的伸芳基、或由選自碳原子數1～10的伸烷基、碳原子數6～18的伸芳基及醚鍵(-O-)之2種以上的組合而成的2價之連結基， R^c3 為羥基、異氰酸酯基、環氧基或羧基。)

(In the aforementioned general formula (c-1), R ^c1 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ^c2 is an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 18 carbon atoms group, or a bivalent linking group consisting of a combination of two or more kinds selected from the group consisting of alkylene groups having 1 to 10 carbon atoms, aryl groups having 6 to 18 carbon atoms, and ether bonds (-O-). R ^c3 is a hydroxyl group, an isocyanate group, an epoxy group or a carboxyl group.)

The C1-C10 alkylene group of R ^c1 may be linear, branched, or cyclic. The arylidene group having 6 to 18 carbon atoms of R ^c2 may be a monocyclic ring or a condensed ring. Specific examples of the arylidene group having 6 to 18 carbon atoms in R ^c2 include a phenylene group, a naphthylene group, and the like. The alkyl-extended group and the aryl-extended group of R ^c2 may further have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a halogen atom, and the like. R ^c3 corresponds to the functional group (c) of the compound (C).

Specific examples of the compound (C) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (meth)acrylate base) 2-hydroxybutyl acrylate, 4-hydroxybutyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, N-(2-hydroxyethyl)(methyl) Acrylamide, glycerol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate Unsaturated monomers with hydroxyl groups such as esters, 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalate, lactone-modified (meth)acrylates with hydroxyl groups at the terminals, etc.; iso 2-(meth)acryloyloxyethyl cyanate, 2-(2-(meth)acryloyloxyethoxy)ethyl isocyanate, 1,1-bis((methyl) isocyanate ) Unsaturated monomers with isocyanate groups such as acryloxymethyl) ethyl ester; Oxygenated unsaturated monomers; (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl phthalate, maleic acid, Ikon Unsaturated monomers with carboxyl groups such as acids; unsaturated monomers with acid anhydride groups such as maleic anhydride, itaconic anhydride, etc.; (meth)acrylic acid chlorides, (meth)acrylic acid bromides, etc. of unsaturated monomers, etc. In addition, 2-hydroxy-3-propenyloxypropyl methacrylate, neopentaerythritol triacrylate, dipivalerythritol pentaacrylate, etc. having a hydroxyl group and a plurality of polymerizable unsaturated groups can also be used of unsaturated monomers.

From the standpoint of the excellent polymerization curability under ultraviolet irradiation, among these, preferred are: 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, and 2-hydroxybutyl acrylate , 4-hydroxybutyl acrylate, 1,4-cyclohexanedimethanol monoacrylate, N-(2-hydroxyethyl) acrylamide, 2-(meth)acryloyloxyethyl isocyanate, 4-Hydroxybutyl acrylate glycidyl ether, acrylic acid.

When the polymerizable unsaturated monomer (B) is a polymerizable unsaturated monomer represented by the aforementioned general formula (b-1), and the compound (C) is a compound represented by the aforementioned general formula (c-1), if Preferably, R ^b3 is a hydroxyl group, and R ^c3 is an isocyanate group.

When the polymer (P) has two or more functional groups (b), the compound (C) may have at least one functional group reactive with at least one of the two or more functional groups (b). Moreover, as long as it is reactive with the functional group (b) which a polymer (P) has, you may use 2 or more types of compound (C).

The resin obtained by reacting the functional group (c) of the fluorinated polymerizable resin compound (C) of the present invention with the functional group (b) of the polymer (P) has insufficient polymerizability due to the compound (C). Saturated groups and the polymerizability of the fluoropolymer resin of the present invention are ensured.

The method of reacting the compound (C) with the polymer (P) may be carried out under the conditions that the polymerizable unsaturated group in the compound (C) does not polymerize, and it is preferable to adjust the temperature condition to, for example, 30 to 120 The reaction was carried out in the range of °C. This reaction is preferably carried out in the presence of an organic solvent, if necessary, in the presence of a catalyst or a polymerization inhibitor.

For example, when the functional group (b) is a hydroxyl group and the functional group (c) is an isocyanate group, or when the functional group (b) is an isocyanate group and the functional group (c) is a hydroxyl group, it is preferable to use p-methoxyphenol. , hydroquinone, 2,6-di-tertiary butyl-4-methylphenol, etc. as polymerization inhibitors, and dibutyltin dilaurate, dibutyltin diacetate, tin octoate, zinc octoate, etc. are used as carbamic acid The esterification reaction catalyst is a method in which the reaction temperature is in the range of 20 to 150°C, particularly in the range of 40 to 120°C. In addition, when the functional group (b) is an epoxy group and the functional group (c) is a carboxyl group, or when the functional group (b) is a carboxyl group and the functional group (c) is an epoxy group, it is preferable to use p-methyl Oxyphenol, hydroquinone, 2,6-di-tertiary-butyl-4-methylphenol, etc. are used as polymerization inhibitors, and tertiary amines such as triethylamine and quaternary amines such as tetramethylammonium chloride are used Ammoniums, tertiary phosphines such as triphenylphosphine, and quaternary phosphoniums such as tetrabutylphosphonium chloride are used as catalysts for esterification, and the reaction is carried out at a reaction temperature of 80 to 130°C, especially 100 to 120°C.

烷、甲苯、二甲苯、1,3-雙(三氟甲基)苯、1,4-雙(三氟甲基)苯等。此等只要考慮沸點、相溶性而適當選擇即可。The organic solvent used in the above reaction is preferably ketones, esters, amides, sulfites, ethers, hydrocarbons, and fluorine-based solvents, and specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone , dimethyl sulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, diethyl ether

alkane, toluene, xylene, 1,3-bis(trifluoromethyl)benzene, 1,4-bis(trifluoromethyl)benzene, etc. These may be appropriately selected in consideration of the boiling point and compatibility.

The number average molecular weight (Mn) of the fluoropolymer resin of the present invention is preferably in the range of 1,000 to 20,000, more preferably in the range of 1,500 to 10,000. The weight average molecular weight (Mw) of the fluoropolymer resin of the present invention is preferably in the range of 3,000 to 80,000, more preferably in the range of 4,000 to 50,000. The number-average molecular weight and the weight-average molecular weight of the fluoropolymeric resin of the present invention were measured by the methods described in Examples.

The fluorine content of the fluorine-containing polymer resin of the present invention is preferably in the range of 2 to 50 mass %, more preferably 5 to 45 mass %, from the viewpoint of achieving both antifouling properties and compatibility with other components. The range is more preferably in the range of 10 to 40 mass %. The fluorine content of the fluorine-containing polymer resin of the present invention is a value calculated from the mass ratio of fluorine atoms to the total amount of raw materials used.

[active energy ray curable composition] The fluorine-containing polymer resin of the present invention can use itself as the main ingredient of the active energy ray-curable composition. Moreover, since the fluorine-containing polymer resin of the present invention has extremely excellent surface modification performance, by using the fluorine-containing surfactant added to the active energy ray-curable composition, it is possible to impart an excellent quality to the cured coating film. Stain resistance.

The active energy ray-curable composition of the present invention contains the fluorinated polymer resin of the present invention. As the main component, an active energy ray-curable resin (D) or an active energy ray-curable monomer (E) is contained. Moreover, in the active-energy-ray-curable composition of the present invention, the active-energy-ray-curable resin (D) and the active-energy-ray-curable monomer (E) may be used independently, but may be used in combination. Moreover, the fluorine-containing polymerizable resin of the present invention is preferably used as a fluorine-containing surfactant in the active energy ray-curable composition.

Examples of the active energy ray-curable resin (D) include urethane (meth)acrylate resins, unsaturated polyester resins, epoxy (meth)acrylate resins, and polyester (meth)acrylate resins. ) acrylate resins, acrylic (meth)acrylate resins, resins having a maleimide group, etc., but in the present invention, urethane is particularly preferred from the viewpoint of transparency, low shrinkage, and the like Ester (meth)acrylate resin.

The urethane (meth)acrylate resin used here is obtained by reacting an aliphatic polyisocyanate compound or an aromatic polyisocyanate compound with a (meth)acrylate compound having a hydroxyl group. Resins with urethane linkages and (meth)acryloyl groups.

Examples of the aliphatic polyisocyanate compounds include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, Decamethylene diisocyanate, 2-methyl-1,5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate, dodecylene diisocyanate, 2-methylpentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, hydrogenated diisocyanate Phenylmethane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated tetramethyl xylene diisocyanate, cyclohexyl diisocyanate, etc., and aromatic polyisocyanate compounds include tolylene diisocyanate, 4 , 4'-diphenylmethane diisocyanate, xylene diisocyanate, 1,5-naphthalene diisocyanate, bis-tolidine diisocyanate, p-phenylene diisocyanate, etc.

On the other hand, as an acrylate compound having a hydroxyl group, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-(meth)acrylate Hydroxybutyl ester, 4-hydroxybutyl (meth)acrylate, 1,5-pentanediol mono(meth)acrylate, 1,6-hexanediol mono(meth)acrylate, neopentyl glycol monoacrylate Mono(meth)acrylates of dihydric alcohols such as (meth)acrylates, hydroxytrimethylacetate neopentyl glycol mono(meth)acrylates; trimethylolpropane di(meth)acrylates, Ethoxylated trimethylolpropane (meth)acrylate, propoxylated trimethylolpropane di(meth)acrylate, glycerol di(meth)acrylate, bis(2-(meth)acryloyloxy) Mono or di(meth)acrylates of trihydric alcohols such as ethyl) hydroxyethyl isocyanate, or those having hydroxyl groups obtained by modifying a part of these alcoholic hydroxyl groups with ε-caprolactone Mono and di(meth)acrylates; neopentaerythritol tri(meth)acrylate, di-trimethylolpropane tri(meth)acrylate, dipivaloerythritol penta(meth)acrylate, etc. A compound having a 1-functional hydroxyl group and a 3-functional or more (meth)acryloyl group, or a polyfunctional (meth)acrylate having a hydroxyl group obtained by further modifying the compound with ε-caprolactone; Dipropylene glycol mono(meth)acrylate, diethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, etc. with oxyalkylene Chain (meth)acrylate compounds; polyethylene glycol-polypropylene glycol mono(meth)acrylates, polyoxybutylene-polyoxypropylene mono(meth)acrylates, etc. with block structure oxanes (Meth)acrylate compound of base chain; poly(ethylene glycol-tetramethylene glycol) mono(meth)acrylate, poly(propylene glycol-tetramethylene glycol) mono(meth)acrylate Such as (meth)acrylate compounds having an oxyalkylene chain with a random structure, and the like.

The reaction of the above-mentioned aliphatic polyisocyanate compound or aromatic polyisocyanate compound and the acrylate compound having a hydroxyl group can be carried out by a routine method in the presence of a urethanization catalyst. The urethane catalyst that can be used here specifically includes amines such as pyridine, pyrrole, triethylamine, diethylamine, and dibutylamine, and triphenylphosphine, triethylphosphine, and the like. Phosphines, organotin compounds such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dibutyltin diacetate, tin octoate, etc., and organometallic compounds such as zinc octoate.

Among these urethane acrylate resins, it is particularly preferable to use an aliphatic polyisocyanate compound with It is obtained by the reaction of a (meth)acrylate compound having a hydroxyl group.

Secondly, unsaturated polyester resins are curable resins obtained by polycondensation of α,β-unsaturated diprotic acid or its anhydride, aromatic saturated diprotic acid or its anhydride, and diols. Maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chloromaleic acid, and these esters etc. are mentioned as (beta)-unsaturated diprotic acid or its acid anhydride. The aromatic saturated diprotic acid or its anhydride includes phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, halogenated Phthalic anhydride and esters of these, etc. The aliphatic or alicyclic saturated diprotic acid includes oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, and hexahydrophthalic anhydride and such esters, etc. The glycols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, and 2-methylpropane-1,3- Diol, neopentyl glycol, triethylene glycol, tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene glycol carbonate, 2 , 2-bis-(4-hydroxypropoxydiphenyl)propane, etc., and oxides such as ethylene oxide and propylene oxide can also be used in the same manner.

Next, epoxy vinyl ester resins include (meth)acrylic p-bisphenol A epoxy resins, bisphenol F epoxy resins, phenol novolak epoxy resins, and cresol novolacs. It is obtained by reacting the epoxy groups of epoxy resins such as epoxy resins.

Moreover, as resin which has a maleimide group, the bifunctional maleimide obtained by urethanizing N-hydroxyethylmaleimide and isophorone diisocyanate can be mentioned. Iminocarbamate compound, bifunctional maleimide ester compound obtained by esterification of maleiminoacetic acid and polytetramethylene glycol, maleiminohexanoic acid and new Four-functional maleimide ester compound obtained by esterification of tetraoxyethylene adduct of pentaerythritol, polyfunctional maleimide obtained by esterification of maleimide acetic acid and polyol compound ester compounds, etc. These active energy ray-curable resins (D) may be used alone or in combination of two or more.

As said active energy ray curable monomer (E), ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, for example base) acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate with a number average molecular weight in the range of 150 to 1,000 Meth)acrylate, polypropylene glycol di(meth)acrylate with number average molecular weight in the range of 150 to 1,000, neopentyl glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate Acrylates, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, hydroxytrimethylacetate, neopentyl glycol di(meth)acrylate Esters, Bisphenol A Di(meth)acrylate, Trimethylolpropane Tri(meth)acrylate, Neotaerythritol Tri(meth)acrylate, Dipivalerythritol Hex(meth)acrylate , Neopentaerythritol tetra(meth)acrylate, Trimethylolpropane di(meth)acrylate, Dinepentaerythritol penta(meth)acrylate, Dicyclopentenyl(meth)acrylate, Methyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, tertiary butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth)acrylate Octyl acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, octadecyl (meth)acrylate, isooctadecyl (meth)acrylate Aliphatic (meth)acrylic acid alkyl esters such as esters, glycerol (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, (meth)acrylate base) glycidyl acrylate, allyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-(diethylamino)ethyl (meth)acrylate, (meth)acrylic acid 2-(dimethylamino)ethyl ester, γ-(meth)acryloyloxypropyltrimethoxysilane, 2-methoxyethyl (meth)acrylate, methoxydiethylene glycol (methyl) ) acrylate, methoxydipropylene glycol (meth)acrylate, nonylphenoxy polyethylene glycol (meth)acrylate, nonylphenoxy polypropylene glycol (meth)acrylate, (meth)acrylate Phenoxyethyl acrylate, phenoxydipropylene glycol (meth)acrylate, phenoxypolypropylene glycol (meth)acrylate, polybutadiene (meth)acrylate, polyethylene glycol-polypropylene glycol ( Meth)acrylate, polyethylene glycol-polybutylene glycol (meth)acrylate, polystyrylethyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate , Dicyclopentyl (meth)acrylate, Dicyclopentenyl (meth)acrylate, Isobornyl (meth)acrylate, Cyclodecatriene (meth)acrylate, Benzene (meth)acrylate Esters; maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N- Hexylmaleimide, N-octylmaleimide, N-dodecyl Maleimide, N-octadecylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, 2-maleimideethyl-ethyl carbonate Ester, 2-maleimide ethyl-propyl carbonate, N-ethyl-2-maleimide ethyl carbamate, N,N-hexamethylenebismaleimide, polypropylene glycol - Maleimides such as bis(3-maleimidepropyl) ether, bis-2-maleimide ethyl carbonate, 1,4-dimaleimide cyclohexane, etc.

Among these, especially preferred are trimethylolpropane tri(meth)acrylate, neopentaerythritol tri(meth)acrylate, dipeoerythritol, in view of the excellent hardness of the cured coating film. Trifunctional or higher polyfunctional (meth)acrylates such as hexa(meth)acrylate and neotaerythritol tetra(meth)acrylate. These active energy ray-curable monomers (E) may be used alone or in combination of two or more.

In the active energy ray-curable composition of the present invention, when the fluorinated polymer resin of the present invention is used as a fluorine-containing surfactant, the usage amount thereof is relative to the active energy ray-curable resin (D) and the active energy ray. The total of 100 parts by mass of the curable monomer (E) is preferably in the range of 0.01 to 10 parts by mass, more preferably in the range of 0.1 to 5 parts by mass. When the amount of the fluorinated polymer resin of the present invention is within this range, leveling properties, water and oil repellency, and antifouling properties can be sufficient, and the hardness and transparency of the composition after curing can also be improved. become the full.

The fluoropolymer resin or active energy ray curable composition of the present invention can be applied to a substrate and then irradiated with active energy rays to form a cured coating film. The active energy rays refer to ionizing radiation such as ultraviolet rays, electron beams, alpha rays, beta rays, and gamma rays. When irradiating ultraviolet rays as active energy rays to form a cured coating film, it is preferable to add a photopolymerization initiator (F) to the fluoropolymer resin or the active energy ray curable composition to improve curability. In addition, if necessary, a photosensitizer may be further added to improve curability. On the other hand, in the case of using ionizing radiation such as electron beam, α-ray, β-ray, γ-ray, no photopolymerization initiator is particularly added since it hardens rapidly even if no photopolymerization initiator or photosensitizer is used. necessary for starter (F) or photosensitizer.

啉基(4-硫甲基苯基)丙烷-1-酮、2-苄基-2-二甲胺基-1-(4-

啉基苯基)丁酮等之苯乙酮系化合物；安息香、安息香甲基醚、安息香異丙基醚等之安息香類；2,4,6-三甲基安息香二苯基膦氧化物、雙(2,4,6-三甲基苯甲醯基)苯基膦氧化物等之醯基膦氧化物系化合物；二苯乙二酮、乙醛酸甲基苯酯等。As said photopolymerization initiator (F), an intramolecular cleavage type photopolymerization initiator and a hydrogen abstraction type photopolymerization initiator are mentioned. Intramolecular cleavage type photopolymerization initiators include, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylene Ketal, 1-(4-Isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl) ) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-

Lino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1-(4-

Acetophenone compounds such as aldolyl phenyl) butanone; benzoins such as benzoin, benzoin methyl ether, benzoin isopropyl ether, etc.; 2,4,6-trimethylbenzoin diphenylphosphine oxide, bis (2,4,6-trimethylbenzyl)phenylphosphine oxide and other acylphosphine oxide-based compounds; benzophenone, methylphenyl glyoxylate, and the like.

、2,4-二甲基氧硫𠮿

、2,4-二乙基氧硫𠮿

、2,4-二氯氧硫𠮿

等之氧硫𠮿

系化合物；米其勒酮、4,4’-二乙胺基二苯基酮等之胺基二苯基酮系化合物；10-丁基-2-氯吖啶酮、2-乙基蒽醌、9,10-菲醌、樟腦醌(camphor quinone)等。On the other hand, as a hydrogen abstraction type photopolymerization initiator, for example, diphenyl ketone, o-benzoylbenzoic acid methyl-4-phenyl diphenyl ketone, 4,4'- Dichlorobenzophenone, hydroxybenzophenone, 4-benzyl-4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,3',4,4'- Diphenyl ketone compounds such as tetrakis(tertiary butylperoxycarbonyl) benzophenone, 3,3'-dimethyl-4-methoxy benzophenone, etc.;

, 2,4-dimethyloxysulfide

, 2,4-Diethyloxysulfur

, 2,4-Dichloroxysulfur 𠮿

Waiting for oxygen sulfur 𠮿

Series compounds; Michler's ketone, 4,4'-diethylaminobenzophenone and other aminobenzophenone compounds; 10-butyl-2-chloroacridone, 2-ethylanthraquinone , 9,10-phenanthrenequinone, camphor quinone, etc.

Among the above-mentioned photopolymerization initiators (F), those having excellent compatibility with the above-mentioned active energy ray-curable resin (D) and active energy ray-curable monomer (E) in the active energy ray-curable composition are selected from the group consisting of: From this point of view, 1-hydroxycyclohexyl phenyl ketone and diphenyl ketone are also preferred, and 1-hydroxycyclohexyl phenyl ketone is particularly preferred. These photopolymerization initiators (F) may be used alone or in combination of two or more.

In addition, the aforementioned photosensitizers include, for example, amines such as aliphatic amines and aromatic amines, ureas such as o-toluenethiourea, sodium diethyldithiophosphate, and s-benzylisothiourea. Sulfur compounds such as p-toluenesulfonate, etc.

The usage-amount of these photopolymerization initiators and photosensitizers is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, with respect to 100 parts by mass of the nonvolatile components in the active energy ray-curable composition. parts, more preferably 0.3 to 7 parts by mass.

Furthermore, the active energy ray-curable composition of the present invention can be adapted to the purpose of use, characteristics, etc., within the range that does not impair the effects of the present invention, by adjusting the viscosity and refractive index, or adjusting the color tone of the coating film, etc. Various blending materials, such as various organic solvents, acrylic resins, phenol resins, polyester resins, polystyrene resins, urethane resins, urea Resins, melamine resins, alkyd resins, epoxy resins, polyamide resins, polycarbonate resins, petroleum resins, various resins such as fluororesins, PTFE (polytetrafluoroethylene), polyethylene, polypropylene, carbon, Various organic or inorganic particles such as titanium oxide, alumina, copper, and silica fine particles, polymerization initiators, polymerization inhibitors, antistatic agents, defoaming agents, viscosity modifiers, light-resistant stabilizers, weather-resistant stabilizers, heat-resistant Stabilizers, antioxidants, rust inhibitors, slipping agents, waxes, gloss modifiers, mold release agents, compatibilizers, conductivity modifiers, pigments, dyes, dispersants, dispersion stabilizers, polysiloxanes, Hydrocarbon-based surfactants, etc.

Among the above-mentioned blending components, the organic solvent is useful in appropriately adjusting the solution viscosity of the active energy ray-curable composition of the present invention, and in particular, it is easy to adjust the film thickness by performing thin film coating. Examples of organic solvents that can be used here include aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, isopropanol, and tertiary butanol; ethyl acetate and propylene glycol monomethyl ether. Esters such as acetate; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. These solvents may be used alone or in combination of two or more.

The amount of the organic solvent used here varies depending on the application, the intended film thickness and viscosity, but is preferably in the range of 0.5 to 4 times the mass based on the total mass of the hardening component.

The active energy rays for curing the active energy ray-curable composition of the present invention are, as described above, ionizing radiation such as ultraviolet rays, electron beams, alpha rays, beta rays, and gamma rays. Or a curing device, for example, a germicidal lamp, a fluorescent lamp for ultraviolet rays, a carbon arc, a xenon lamp, a high-pressure mercury lamp for photocopying, a medium-pressure or high-pressure mercury lamp, an ultra-high pressure mercury lamp, an electrodeless lamp, a metal halide lamp, a natural light Such as ultraviolet rays of the light source, or electron beams by scanning type, curtain type electron beam accelerators, and the like.

Among these, ultraviolet rays are particularly preferred, and ultraviolet rays are preferably irradiated under an inert gas atmosphere such as nitrogen in order to avoid inhibition of hardening by oxygen or the like. Moreover, you may heat-process after hardening with an ultraviolet-ray, using heat together as an energy source as needed.

The coating method of the active energy ray-curable composition of the present invention varies depending on the application, and examples thereof include the use of a gravure coater, a roll coater, a comma coater, and a knife coater. , air knife coater, curtain coater, kiss coater, curtain coater, wheel coater, spin coater, dipping, screen printing, spray, spreader, A coating method using a bar coater or the like, or a molding method using various molds, etc.

Since the cured coating film of the fluoropolymer resin of the present invention has excellent antifouling properties (print resistance, fingerprint resistance, etc.), scratch resistance, etc., it can be coated and hardened on the surface of the article, so that the article can be cured. The surface imparts antifouling, scratch resistance, etc. In addition, since the fluorine-containing polymer resin of the present invention can also be added to the coating material as a fluorine-containing surfactant to impart leveling properties to the coating material, the active energy ray-curable composition of the present invention has High leveling.

Examples of articles that can be imparted with antifouling properties (print resistance, fingerprint resistance, etc.) using the fluorinated polymer resin or active energy ray-curable composition of the present invention include liquid crystal displays such as TAC films. (LCD) polarizer films; various display screens such as plasma displays (PDP) and organic EL displays; touch panels; casings or screens of electronic terminals such as mobile phones; color filters for liquid crystal displays (hereinafter referred to as Transparent protective film for "CF"); organic insulating film for liquid crystal TFT array; inkjet printing ink for electronic circuit formation; optical recording media such as CD, DVD, Blu-ray disc, etc.; Films; rubber rollers for OA machines such as copiers and printers; glass surfaces of reading parts of OA machines such as copiers, scanners, etc.; optical lenses for cameras, video cameras, glasses, etc.; windshields and glass surfaces of clocks such as watches ; Windows of various vehicles such as automobiles and railway vehicles; protective glass or film for solar cells; various building materials such as decorative panels; window glass of houses; Plastic moldings, FRP baths, etc. The surface of these articles can be coated with the active energy ray-curable composition of the present invention and irradiated with active energy rays such as ultraviolet rays to form a cured coating film, thereby imparting antifouling properties to the article surface. In addition, it is also possible to impart antifouling properties to the surface of an article by adding the fluorine-containing styrene compound of the present invention to various paints suitable for each article, and applying and drying.

In addition, in the case of a coating material that can improve leveling properties by adding the fluoropolymer resin of the present invention, and at the same time impart antifouling properties (anti-printing ink properties, fingerprint resistance, etc.) or chemical resistance to the coating film , can be cited: TAC film and other LCD polarizer film hardening coating material, anti-glare (AG: anti-glare) coating material or anti-reflection (LR) coating material; plasma display (PDP), Hard coating materials for various display screens such as organic EL displays; hard coating materials for touch panels; color photoresist, printing ink, inkjet printing ink or paint used to form each pixel of RGB used in CF ; Black photoresist, printing ink, ink jet printing ink or paint for black matrix of CF; resin composition for pixel barrier rib of plasma display (PDP), organic EL display, etc.; mobile phone, etc. Coatings or hard coating materials for electronic terminal casings; hard coating materials for mobile phone screens; coatings for transparent protective films to protect CF surfaces; coatings for organic insulating films of liquid crystal TFT arrays; inkjet printing inks for electronic circuit formation ; Hard coating materials for optical recording media such as CD, DVD, Blu-ray discs, etc.; Hard coating materials for transfer films for buried injection (IMD, IMF); Coating for OA machines for copiers, printers, etc. Layer materials; coating materials for glass of reading parts of OA machines such as copiers, scanners, etc.; coating materials for optical lenses of cameras, video cameras, glasses, etc.; coating materials for windshields and glass of watches, etc.; automobiles Window coating materials for various vehicles such as railway vehicles; coatings for anti-reflection films of protective glass or films for solar cells; printing inks or coatings for various building materials such as decorative panels; coating materials for residential window glass ; Woodworking coatings for furniture, etc.; Coating materials for artificial and synthetic leather; Coatings or coating materials for various plastic moldings such as housings of home appliances; Coatings or coating materials for FRP bath tubs, etc.

Furthermore, as an article that can be imparted with scratch resistance (scratch resistance) and antifouling properties using the fluoropolymeric resin or active energy ray-curable composition of the present invention, there is a backlight member for LCD. Diffusion plate or diffuser plate, etc. In addition, by adding the fluoropolymer resin of the present invention to the coating material for a fluoride sheet or a diffusion plate, the leveling property of the coating material can be improved, and at the same time, scratch resistance can be imparted to the coating film of the coating material ( scratch resistance) and stain resistance.

In addition, since the hardened coating film of the fluoropolymer resin of the present invention has a low refractive index, it can also be used as a coating for a low refractive index layer in an antireflection layer for preventing glare on the surface of various displays such as LCD by fluorescent lamps. cover material to use. In addition, the fluoropolymer resin of the present invention can also be added to the coating material for the antireflection layer, especially the coating material for the low refractive index layer in the antireflection layer, so as to maintain the low refractive index of the coating film and at the same time Provides antifouling properties to the surface of the coating film.

In addition, other applications in which the fluoropolymer resin or active energy ray curable composition of the present invention can be used include optical fiber sheath materials, waveguides, sealing materials for liquid crystal panels, and various optical sealing materials. , Optical adhesive, etc.

In particular, when the active energy ray-curable composition of the present invention is used as an anti-glare coating material in the application of a coating material for a protective film of an LCD polarizer, in each of the above-mentioned compositions, silica fine particles are , Inorganic or organic fine particles such as acrylic resin fine particles and polystyrene resin fine particles are blended in a ratio of 0.1 to 0.5 times the total mass of the hardening component in the active energy ray curable composition of the present invention to become Since it is excellent in anti-glare property, it is preferable.

In addition, when the fluorine-containing polymer resin or active energy ray-curable composition of the present invention is used as an anti-glare coating material for a protective film of a polarizer for LCD, a transfer method can also be applied, which is used to apply a coating method. Before the layer material is cured, it is brought into contact with a mold having an uneven surface shape, and then cured by irradiating active energy rays from the side opposite to the mold, and the surface of the coating layer is embossed to impart anti-glare properties. [Example]

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. In addition, this invention is not limited by the following Example.

The measurement conditions of the IR spectrum, ¹³ C-NMR spectrum, and GPC of the fluorine-containing resins obtained in the following Examples and Comparative Examples are as follows. [IR Spectrum Measurement Conditions] The resin solutions obtained in Examples were measured by the KBr method using the following apparatus. Device: "FT/IR-6100" manufactured by JASCO Corporation

[ ^13C -NMR spectrum measurement conditions] Apparatus: "JNM-ECA500" manufactured by JEOL Ltd. Solvent: Acetone-d ₆

[GPC measurement conditions] Measuring device: "HLC-8220 GPC" manufactured by Tosoh Corporation Column: Tosoh Corporation guard column "HHR-H" (6.0mmI.D.×4cm) + Tosoh Corporation "TSK-GEL GMHHR-N" (7.8mmI.D.×30cm) + Tosoh Corporation "TSK-GEL GMHHR-N" (7.8mmI.D.×30cm) + Tosoh Corporation "TSK-GEL GMHHR-N" (7.8mmI.D.×30cm) + Tosoh Corporation "TSK-GEL GMHHR-N" (7.8mmI.D.×30cm) Detector: Evaporative light scattering detector ("ELSD2000" manufactured by Alltech Japan Co., Ltd.) Data processing: "GPC-8020 Model II Data Analysis Version 4.30" manufactured by Tosoh Corporation Measurement conditions: column temperature 40°C Developing solvent: Tetrahydrofuran (THF) Flow rate 1.0ml/min Sample: A 1.0 mass % tetrahydrofuran solution in terms of solid content was filtered with a microfilter (5 μl). Standard sample: The following monodisperse polystyrene with known molecular weight was used according to the measurement manual of the aforementioned "GPC-8020 Model II Data Analysis Version 4.30".

(monodisperse polystyrene) "A-500" manufactured by Tosoh Corporation "A-1000" manufactured by Tosoh Corporation "A-2500" manufactured by Tosoh Corporation "A-5000" manufactured by Tosoh Corporation "F-1" manufactured by Tosoh Corporation "F-2" manufactured by Tosoh Corporation "F-4" manufactured by Tosoh Corporation "F-10" manufactured by Tosoh Corporation "F-20" manufactured by Tosoh Corporation "F-40" manufactured by Tosoh Corporation "F-80" manufactured by Tosoh Corporation "F-128" manufactured by Tosoh Corporation "F-288" manufactured by Tosoh Corporation "F-550" manufactured by Tosoh Corporation

[Synthesis of compounds containing poly(perfluoroalkylene ether) chains] (Synthesis Example 1) Into a glass flask equipped with a stirring device, a thermometer, a cooling tube, and a dripping device, 150 parts by mass of a perfluoropolyether compound having hydroxyl groups at both ends represented by the following formula (a-1), p-chloromethyl group was charged. 68 parts by mass of styrene, 0.05 part by mass of p-methoxyphenol as a polymerization inhibitor, 44 parts by mass of a 50 mass part aqueous solution of benzyltriethylammonium chloride as a phase transfer catalyst, and 0.12 part by mass of potassium iodide. Next, stirring was started under air flow, the temperature in the flask was raised to 45° C., and 1.3 parts by mass of a 49 mass % aqueous solution of sodium hydroxide was added dropwise over 2 hours. After completion of the dropping, the temperature was raised to 60° C. and stirred for 1 hour. After that, 11.5 parts by mass of a 49 mass % aqueous solution of sodium hydroxide was added dropwise over 4 hours, and then the reaction was further performed for 15 hours.

(前述式(a-1)中， 複數個X₁ 各自獨立地為全氟亞甲基或全氟伸乙基，每1分子中有全氟亞甲基平均19個、全氟伸乙基平均19個存在，氟原子之數量係平均為114。 根據GPC的重量平均分子量為4,000。)

(In the aforementioned formula (a-1), a plurality of X ₁ are each independently a perfluoromethylene group or a perfluoroethylene group, and there are an average of 19 perfluoromethylene groups and an average perfluoroethylene group per molecule. 19 exist, and the number of fluorine atoms is 114 on average. The weight-average molecular weight according to GPC is 4,000.)

After completion of the reaction, the generated salt was filtered off, the filtrate was allowed to stand, and the supernatant was removed. Further, 500 mL of water was added, and washing with water was performed three times. After washing with water, it was further washed three times with 500 mL of methanol. Then, 0.06 parts by mass of p-methoxyphenol and 0.2 parts by mass of 3,5-di-tert-butyl-4-hydroxytoluene were added to the solution as polymerization inhibitors, and then a water bath set at 45° C. was used and a rotary Methanol was distilled off while concentrating in an evaporator to obtain a compound represented by the following formula (A-1) having a poly(perfluoroalkylene ether) chain and styryl groups at both ends thereof (hereinafter abbreviated as "Compound (A-1)").

(前述式(A-1)中， 複數個X₁ 各自獨立地為全氟亞甲基或全氟伸乙基，每1分子中有全氟亞甲基平均19個、全氟伸乙基平均19個存在，氟原子之數量係平均為114。)

(In the aforementioned formula (A-1), a plurality of X ₁ are each independently a perfluoromethylene group or a perfluoroethylidene group, and there are an average of 19 perfluoromethylene groups and an average perfluoroethylidene group per molecule. 19 exist, and the number of fluorine atoms is 114 on average.)

(Synthesis example 2) Into a glass flask equipped with a stirring device, a thermometer, a cooling tube, and a dropping device, 200 parts by mass of a perfluoropolyether compound having hydroxyl groups at both ends represented by the following formula (a-2), p-chloromethyl group was charged. 70.7 parts by mass of styrene, 0.04 parts by mass of p-methoxyphenol as a polymerization inhibitor, 2.7 parts by mass of a 50 mass part aqueous solution of benzyltriethylammonium chloride as a neutralizing agent, and 0.22 parts by mass of potassium iodide. Next, stirring was started under an air flow, the temperature in the flask was raised to 45° C., and 3.3 parts by mass of a 49 mass % aqueous solution of sodium hydroxide was added dropwise over 2 hours. After completion of the dropping, the temperature was raised to 60° C. and stirred for 1 hour. After that, 9.3 parts by mass of a 49 mass % aqueous solution of sodium hydroxide was added dropwise for 1 hour, and then the reaction was further performed for 10 hours.

(前述式(a-2)中， 複數個X₂ 各自獨立地為全氟亞甲基或全氟伸乙基，每1分子中有全氟亞甲基平均35個、全氟伸乙基平均35個存在，氟原子之數量係平均為210。 根據GPC的重量平均分子量為6,000。)

(In the aforementioned formula (a-2), a plurality of X ₂ are each independently a perfluoromethylene group or a perfluoroethylene group, and there are an average of 35 perfluoromethylene groups and an average perfluoroethylene group per molecule. 35 exist, the number of fluorine atoms is 210 on average. The weight average molecular weight according to GPC is 6,000.)

After completion of the reaction, the generated salt was filtered off, the filtrate was allowed to stand, and the supernatant was removed. 250 parts by mass of 1,3-bis(trifluoromethyl)benzene and 250 parts by mass of methanol were added and washed. After washing three times with a mixed solution of 150 parts by mass of methanol and 50 parts by mass of water, washing was further conducted two times with 200 parts by mass of methanol. Then, 0.04 parts by mass of p-methoxyphenol and 0.4 parts by mass of 3,5-di-tert-butyl-4-hydroxytoluene were added to the solution as polymerization inhibitors, and then a water bath set at 45° C. was used and a rotary The evaporator was azeotroped with 1,3-bis(trifluoromethyl)benzene, and methanol was distilled off while concentrating to obtain poly(perfluoroalkylene ether) represented by the following formula (A-2). ) chain and a compound of styryl groups at both ends thereof (hereinafter abbreviated as "compound (A-2)").

(前述式(A-2)中， 複數個X₂ 各自獨立地為全氟亞甲基或全氟伸乙基，每1分子中有全氟亞甲基平均35個、全氟伸乙基平均35個存在，氟原子之數量係平均為210。)

(In the aforementioned formula (A-2), a plurality of X ₂ are each independently a perfluoromethylene group or a perfluoroethylene group, and there are an average of 35 perfluoromethylene groups and an average perfluoroethylene group per molecule. 35 exist, and the number of fluorine atoms is 210 on average.)

[Synthesis of Fluorine Resin] (Comparative Example 1) Into a glass flask equipped with a stirring device, a thermometer, a cooling tube, and a dropping device, 73.1 parts by mass of 1,3-bis(trifluoromethyl)benzene was charged as a solvent, and the temperature was raised to 105°C while stirring under a nitrogen stream. Next, 41.8 parts by mass of compound (A-1) obtained in Synthesis Example 1, 80 parts by mass of 2-hydroxyethyl methacrylate, and 153.1 parts by mass of 1,3-bis(trifluoromethyl)benzene were dissolved Three kinds of droplets of the polymerization initiator solution prepared from 18.3 parts by mass of tertiary butylperoxy-2-ethyl hexanoate as a radical polymerization initiator were installed in separate dropping devices, respectively. While keeping the inside of the flask at 105°C, it was dripped over 2 hours at the same time. After completion of the dropping, the solution of the polymer (P-1) was obtained by stirring at 105°C for 10 hours.

In the solution of the above-obtained polymer (P-1), 0.08 parts by mass of p-methoxyphenol as a polymerization inhibitor and 0.06 parts by mass of tin octoate as a urethane catalyst were charged, and the mixture was heated in air. While stirring was started under air flow, 85 parts by mass of 2-(meth)acryloyloxyethyl isocyanate was added dropwise over 1 hour while maintaining the temperature at 60°C. After completion of the dropwise addition, the mixture was stirred at 60° C. for 1 hour, and then the temperature was raised to 80° C., and the mixture was stirred for 5 hours and reacted. After the completion of the reaction, the disappearance of the absorption peak of the isocyanate group was confirmed by IR spectrum measurement. Next, after removing the solid matter generated in the reaction solution by filtration, a part of the solvent was distilled off under reduced pressure to obtain a polymerizable fluororesin (1).

(Example 1) Into a glass flask equipped with a stirring device, a thermometer, a cooling tube, and a dropping device, 35.3 parts by mass of 1,3-bis(trifluoromethyl)benzene was charged as a solvent, and the temperature was raised to 105° C. while stirring under a nitrogen stream. Next, a mixed solution of 20.0 parts by mass of compound (A-2) obtained in Synthesis Example 2 and 20.0 parts by mass of 1,3-bis(trifluoromethyl)benzene, 38.8 parts by mass of 2-hydroxyethyl methacrylate and A mixed solution of 44.4 parts by mass of 1,3-bis(trifluoromethyl)benzene and 9.6 parts by mass of 1,3-bis(trifluoromethyl)benzene dissolved trihexanoic acid as a radical polymerization initiator The three types of dripping solutions of the polymerization initiator solutions prepared from 8.9 parts by mass of tertiary butyl peroxy-2-ethyl ester were installed in separate dripping devices, and the inside of the flask was kept at 105° C. It takes 2 hours to instill at the same time. After completion of the dropping, the solution of the polymer (P-2) was obtained by stirring at 105°C for 5 hours.

Next, in the solution of the polymer (P-2) obtained above, 0.04 parts by mass of p-methoxyphenol as a polymerization inhibitor and 0.03 parts by mass of tin octoate as a urethane catalyst were charged, and 41.2 parts by mass of 2-(meth)acryloyloxyethyl isocyanate was dropwise added over 1 hour while starting stirring under an air stream while maintaining the temperature at 60°C. After completion of the dropwise addition, the mixture was stirred at 60° C. for 1 hour, and then the temperature was raised to 80° C., and the mixture was stirred for 5 hours and reacted. After the completion of the reaction, the disappearance of the absorption peak of the isocyanate group was confirmed by IR spectrum measurement. Next, after removing the solid matter generated in the reaction solution by filtration, a part of the solvent was distilled off under reduced pressure to obtain a polymerizable fluororesin (2).

[Evaluation of Fluorine Resin] With respect to the fluorine-containing resins produced in each of Example 1 and Comparative Example 1, antireflection films were produced by the following methods, and their physical properties were evaluated.

<Preparation of composition for antireflection layer> 1.265 parts by mass of methyl isobutyl ketone dispersion liquid containing 20 mass % of hollow silica fine particles (average particle diameter: 60 nm), 0.207 parts by mass of neopentaerythritol triacrylate (PETA), and 2 of photopolymerization initiators were mixed -Hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one (manufactured by Ciba Japan K.K. " Irgacure 127") 0.01 mass part, 0.20 mass part of the fluorine-containing resin produced in Example 1 or Comparative Example 1, and methyl isobutyl ketone was further added as a solvent to obtain an antireflection layer adjusted to a nonvolatile content of 5% with composition.

<Preparation of composition for hard coating> Mixed urethane acrylate ("UV1700B" of The Nippon Synthetic Chemical Industry Co., Ltd.) 30 parts by mass, 25 parts by mass of butyl acetate, 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator (“Irgacure 184” manufactured by Ciba Specialty Chemicals) 1.2 parts by mass, 11.78 parts by mass of toluene as a solvent, 5.892 parts by mass of 2-propanol, 5.892 parts by mass of ethyl acetate, and 5.892 parts by mass of propylene glycol monomethyl ether were dissolved, Thus, a coating composition for a hard coat was obtained.

<Manufacture of antireflection film> The obtained coating composition for hard coating was applied to a PET film with a thickness of 188 μm using a bar coater No. 13, and then put in a dryer at 70° C. for 1 minute to volatilize the solvent, and then used It was cured by an ultraviolet curing device (in a nitrogen atmosphere, using a high-pressure mercury lamp, and an ultraviolet irradiation dose of 0.5 kJ/m ² ), and a cured coating film having a cured coating with a film thickness of 8 μm on one side was produced.

The anti-reflection coating composition was applied on the hard coat layer of the hard coat film obtained above by using a bar coater No. 2, and then put in a dryer at 50° C. for 1 minute and 30 seconds to volatilize the solvent, and UV light was applied. The hardening device (under nitrogen atmosphere, using a high pressure mercury lamp, ultraviolet irradiation dose of 2kJ/m ² ) was used to harden it, and an anti-reflection film with a film thickness of 0.1 μm and a hardened coating was produced on a hardened coating with a film thickness of 10 μm. . With respect to the antireflection layer of the obtained film, the coefficient of kinetic friction and scratch resistance were evaluated by the following methods. The results are shown in Table 1.

<Slidability evaluation> Using a kinetic friction coefficient measuring device (“TriboGear TYPE: 38” manufactured by Shinto Scientific Co., Ltd.), the kinetic friction coefficient of the hardened coating surface was measured with a φ10 mmSUS ball indenter, a load of 100 g, and a scanning speed of 300 mm/min. The measurement system was carried out three times, and the average value of the three times was taken as the dynamic friction coefficient of the surface of the hardened coating.

<Scratch resistance evaluation> Using a TriboGear surface performance tester TYPE: 38 manufactured by Shinto Scientific, a steel wool #0000 was placed on a 1 cm×1 cm indenter, and loads of 100 g, 300 g, and 500 g were applied to each, and it was made to go back and forth 10 times. The number of scratches adhering to the surface of the cured film after the test was calculated, and the case where the number of scratches was less than 3 was evaluated as "○", and the case where the number of scratches was 4 or more and less than 10 was evaluated as "△", and the case where the number of scratches was 10 or more was evaluated as "X".

[Table 1] Comparative Example 1 Example 1 coefficient of kinetic friction 0.171 0.083 scratch resistance Load 100g ○ ○ Load 300g × ○ Load 500g × △

From the results in Table 1, it can be seen that compared with the fluororesin (Comparative Example 1) containing a poly(perfluoroalkylene ether) chain with a weight average molecular weight of 5,000 or less, a poly(perfluoroalkylene ether) chain with a weight average molecular weight of 5,000 or more is contained. The fluorine-containing resin (Example 1) having a base ether chain can form a low-refractive index layer excellent in sliding property and scratch resistance.

without.

without.

without.

Claims (7)

A fluoropolymer resin which is a reaction product of a polymer (P) and a compound (C), wherein the polymer (P) is a poly(perfluoropolymer) having a weight average molecular weight of 5,000 or more A copolymer of an alkyl ether) chain with a styryl group at both ends of the compound (A) and a polymerizable unsaturated monomer (B) having a functional group (b), and the compound (C) has a functional The group (b) has a reactive functional group (c) and a polymerizable unsaturated group, The polymerizable unsaturated monomer (B) has at least one functional group (b) selected from the group consisting of a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, an acid anhydride group, and a carboxylic acid halide group. polymerizable unsaturated monomers, The compound (C) is a compound having at least one functional group (c) and a polymerizable unsaturated group selected from the group consisting of a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, an acid anhydride group, and a halide group. The fluorine-containing polymerizable resin according to claim 1, wherein the polymerizable unsaturated monomer (B) is a polymerizable unsaturated monomer represented by the following general formula (b-1):

(In this general formula (b-1), R ^b1 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ^b2 is an alkylene group having 1 to 10 carbon atoms, and an arylene group having 6 to 18 carbon atoms. group, or a bivalent linking group consisting of a combination of two or more kinds selected from the group consisting of alkylene groups having 1 to 10 carbon atoms, aryl groups having 6 to 18 carbon atoms, and ether bonds (-O-). R ^b3 is a hydroxyl group, an isocyanate group, an epoxy group or a carboxyl group). The fluorine-containing polymerizable resin according to claim 1 or 2, wherein the compound (C) is a compound represented by the following general formula (c-1):

(In this general formula (c-1), R ^c1 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ^c2 is an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 18 carbon atoms group, or a bivalent linking group consisting of a combination of two or more kinds selected from the group consisting of alkylene groups having 1 to 10 carbon atoms, aryl groups having 6 to 18 carbon atoms, and ether bonds (-O-). R ^c3 is hydroxyl, isocyanate, epoxy or carboxyl). The fluoropolymeric resin according to any one of claims 1 to 3, which has a urethane bond. An active energy ray-curable composition comprising the fluorine-containing polymerizable resin according to any one of claims 1 to 4, and an active energy ray-curable resin (D) or an active energy ray-curable monomer (E). A cured coating film, which is a cured coating film of the fluoropolymer resin according to any one of claims 1 to 4 or the active energy ray-curable composition according to claim 5. An article having the hardened coating film as claimed in claim 6.