TW201040233A - Fluorine-containing polymeric polymer and active energy ray-curable composition using the same - Google Patents

Abstract

This invention provides a fluorine-containing polymeric polymer and an active energy ray-curable composition using the same. The polymer is obtained by the following method: polymerizing a monomer constituent as a necessary polymeric unsaturated monomer (B) containing at least one reactive group selected from hydroxyl, isocyanate, epoxy, carboxyl, halogenated carboxylic acid and acid anhydride as an essential constituent with the two ends of a compound (A) having functional groups capable of producing radical groups at the two ends of poly(perfluoroalkyleneether) to obtain a polymer (C), and reacting a partial or all of the reactive groups of the polymer (C) with a compound (D) having at least one functional group selected from hydroxyl, isocyanate, epoxy, carboxyl, halogenated carboxylic acid and acid anhydride, and polymeric unsaturated groups that would react with the reactive groups to form bonds. The cured coating film using the fluorine-containing radical polymeric polymer has excellent antifouling property and has high resistance with respect to saponification resistance (strong base) treatment to restrain decreasing the antifouling property.

Description

[Technical Field] The present invention relates to a fluorine-containing polymerizable polymerization having antifouling properties, and an active energy ray-curable composition containing the polymer. [Prior Art]

The disordered compound has both hydrophobicity and oleophobicity, and its hydrophobicity and oleophobicity can be imparted by coating on the surface of the article. Therefore, the fluorine-containing compound is used for the purpose of imparting antifouling properties to a liquid crystal display (hereinafter referred to as "LCD") and a film on the outermost surface of an electric discharge display. For example, in the field of a coating material for a protective film such as a cellulose triacetate film in a polarizing plate for a liquid crystal display device, in order to impart antifouling properties to the surface of the film to the surface of the film, the coating is applied to the surface of the protective sheet. A fluorine-curable hard coat material such as a fluorine-based 曰 interface: a sex agent is added. However, in the case of the protective film, it is necessary to add a saponification treatment (strength treatment) to the opposite side to which the side of the hard coating material is applied, and the saponification liquid is inevitably brought into contact with the hard coating surface. The fluorine-based surfactant or the like present in the surface layer is decomposed by a strong alkali, and there is a problem that the antifouling property is lowered. Recently, in the manufacture of color filters for LCDs, an inkjet method has been developed as a manufacturing method for further reducing the cost compared with conventional photolithography. In the inkjet method, 'a black matrix (hereinafter referred to as "BM") is first formed on a substrate by photolithography, and then inkjet method is used without overflowing the ink from the depressed portion frame formed by the BM. Inject ink. At this time, in order not to adhere the ink to the upper surface of the BM (the surface parallel to the substrate), 3 201040233 means that in order not to make the ink from the inside of the frame, ... θ / benefit, it is necessary to give the ΒΜ The lyophobicity of the ink. However, when the yttrium is formed by photolithography, after hardening by ultraviolet irradiation, a heat hardening treatment is applied at 230 t x 30 minutes & 丄 ^ ^ 鬲 , , , 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟 氟,appear

The lyophobicity of the surface is degraded, or the problem of contamination of other parts and production lines by Bodhi a U.

Here, it is a gas-containing compound and A and S' are due to the fluorination present in the compound.

The functional group such as a burn group has a low surface chess M surface tension property, and therefore, a composition which does not contain a fluorinated alkyl group or the like is added in a small amount as a surface modifying agent, whereby the fluorinated alkyl group is coated. In the process of the object, it will be transferred to the surface and it can exert antifouling properties. As an active compound which exhibits such antifouling properties, an active energy ray-curable composition containing a fluorine compound having a poly(perfluoroalkylene ether) introduced therein and used for antifouling has been proposed. A polymerizable group having an improved sustainability is as described in 'Patent Documents 1 and 2'. In Patent Document i, as a fluorine-containing compound, a poly(perfluorostrand) which is formed by reacting a monomer having a poly(all (tetra) (tetra) bond) of (4) and a monomer having a reduced (tetra) fluorenyl group with polyisocyanate is proposed. Amino acid ester acrylate of alkyl ether) chain. Further, in Patent Document 2, as a fluorine-containing compound, it has been proposed to react a poly(perfluoroalkylene ether) having a hydroxyl group and a monomer having a hydroxyl group and an acryloyl group with a triisocyanate which is a trimer of a diisocyanate. An amino phthalate acrylate having a poly(perfluoroalkyl ether) chain formed. However, in the case of the urethane acrylate having a poly(perfluoroalkylene ether) chain described in the above patent documents 丨 and 2, it is not easy to produce poly(perfluoro) having a hydroxyl group in 201040233. The alkylene ether) and the acrylic monomer having a hydroxyl group are reacted with the triisocyanate compound in an appropriate ratio, thereby producing a compound having only an acrylonitrile group as a by-product and having only a poly(perfluoroalkylene ether) chain. The compound does not give a compound having both a poly(perfluoroalkylene ether) chain and an acryloyl group in the molecule, which is a problem. Further, a compound having only a poly(perfluoroalkylene ether) bond has a high molecular weight, and when used in an active energy ray-curable composition, it has low compatibility with other components, and thus the active energy ray-curable composition is formed. There are also problems such as white turbidity when the film is coated. Moreover, 'this urethane acrylate having a poly(perfluoroalkylamino) chain has low compatibility with a compound having only a poly(perfluoroalkylene ether) chain and a compound having only an acryl fluorenyl group. There are also problems such as phase separation. CITATION LIST Patent Literature Patent Literature 1: JP-A-2001-019736 (Patent Document 2) International Publication No. WO2003/002628 SUMMARY OF INVENTION Technical Problem The problem to be solved by the present invention is to provide a The fluorine-containing polymerizable polymer which is excellent in the compatibility of the components, is excellent in the antifouling property of the hardened coating when the cured coating film is formed, and can suppress the deterioration of the antifouling property even when the saponification treatment is performed. Further, an active energy ray-curable composition obtained by using the fluoropolymerizable polymer and having a cured coating film having excellent antifouling properties, and a cured product of 5 201040233 and an article having a cured coating film are also provided. In order to solve the problem, the present inventors have conducted intensive studies and found that the fluorine-containing polymerizable polymer obtained by the following method is excellent in compatibility with other components and excellent in antifouling property: a specific reaction is allowed a polymer obtained by polymerizing a polymerizable unsaturated monomer with a compound having a functional group capable of generating a radical at both ends of a poly(perfluoroalkylene ether) chain, and The reactive group is reacted to form a specific functional group bonded to the polymerizable unsaturated group, and a compound having a polymerizable unsaturated group is reacted to obtain a fluorine-containing polymerizable polymer. Thus, the present invention has been completed. That is, the present invention relates to a fluorine-containing polymerizable polymer characterized in that it is obtained by having at least one reactivity selected from the group consisting of a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a toothed carboxylic acid, and an acid anhydride. The polymerizable unsaturated monomer (B) is a monomer component which is an essential component and is polymerized at both ends of the compound (a) having a functional group capable of generating a radical at both ends of the poly(perfluoroalkyl ether) chain. And obtaining a polymer, and then partially or wholly of the reactive group of the polymer (c) and a group selected from a hydroxyl group and an isocyanate group which react with the reactive group to form a bond. The epoxy group, the carboxyl group, the i-carboxylic acid, and at least one functional group of the acid group and the polymerizable unsaturated group (D) are reacted. Further, the present invention relates to an active energy ray-curable composition containing the above-mentioned fluorine-containing polymerizable polymer, a cured product thereof, and an article having a cured coating film having the resin composition. Effect of the Invention 201040233 In the case of the fluoropolymer of the present invention, the above compound having a poly(all-equivalent alkyl ether) chain as a fluorine-containing moiety is used as a starter for polymerization'. Therefore, it is used together with a fluorine-containing monomer. Since the polymerization reaction is carried out differently, since the homopolymer of the fluorine-containing monomer is not produced, the polymer does not contain a component having low compatibility with other components. Therefore, it is excellent when it is blended in the active energy ray-curable composition. Compatibility. Further, the fluorine-containing polymerizable polymer of the present invention has a polymerizable unsaturated group 0, which has curability. Therefore, by forming a hard coating film on a substrate alone, it is possible to impart antifouling properties to the surface of the substrate. Further, after the dirt adhering to the surface of the cured coating film is removed, excellent antifouling properties with high stability can be exhibited. Further, when the active energy ray-curable composition containing the fluorine-containing polymerizable polymer as a fluorine-based surfactant is applied to a substrate, the fluorine atom and the other atoms have different polarities. The polymerizable polymer is segregated on the surface of the coating film, and surface modification imparting only the surface of the coating film to the antifouling property can be achieved. In addition, since the fluorine-containing polymerizable polymer has curability, it can be polymerized with other curable components in the active energy ray-curable composition. Therefore, in the cured coating film, the gas-containing hardenability of the present invention The resin is immobilized by cattle. Therefore, even if a heat treatment or the like is applied to the cured coating film, the fluorine-containing curable resin or the decomposed product thereof can be prevented from volatilizing and detaching from the surface of the cured coating film, and thus the surface of the substrate can be imparted with excellent antifouling properties with high durability. Further, the cured coating film of the fluorine-containing polymerizable polymer of the present invention has high resistance to treatment, and can suppress the fall of the antifouling property even after the saponification treatment. Therefore, the active energy I-line-curable composition using the fluorine-containing polymerizable polymer of the present invention is used as a TAc for a liquid crystal display polarizing plate which is required to impart antifouling properties and is subjected to saponification treatment by 201040233. Hard coating materials for films are extremely useful. [Embodiment] The fluorine-containing polymerizable polymer of the present invention is obtained by: polymerizing unsaturated monomer (B) having a selected from the group consisting of a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, and a halogenated citric acid. The monomer component having at least one reactive group in the acid anhydride) is polymerized at both ends of the compound (A) having a functional group capable of generating a radical at both ends of the poly(perfluoroalkyl ether) chain. The polymer (C) is further or partially reacted with the compound (D) of the above-mentioned reactive group of the polymer (C) (having a hydroxyl group, an isocyanate group, and a reaction with the reactive group to form a bond, The epoxy group, the carboxyl group, the functionalized acid, at least one functional group in the acid anhydride, and the polymerizable unsaturated group are reacted. The compound (A) having a functional group capable of generating a radical at both ends of a poly(perfluoroalkylene ether) chain used as a raw material of the fluorine-containing polymerizable polymer of the present invention is represented by the following formula (1) The poly(perfluoroalkylene ether) chain has a compound having a functional group capable of generating a radical at both ends.

(In the above formula (1), X is any one of the following formulas (a) to (e), and all of X in the formula (1) may be the same group 'or a plurality of groups may be absent There are rules or embedded segments. In addition, η indicates the number of repeating units and is a number of 1 or more.) 201040233

—CFjj. A CF2CF2—Cb) —CF2CF2CF2—(c)—CF2OF—(d)—CFCF2 is as polymerized as above (the full-surface extension group (4) bond has a carbon number of 1 to 2 fluorocarbon group and an oxygen atom. The structure in which the carbon atoms are 3 may be a type or a mixture of a plurality of types. In the poly(perfluoroalkylene group) chain, a coating film excellent in antifouling property is obtained. In view of the above, it is preferred that the total gas-extended methyl structure represented by the above formula (4) and the perfluoroextended ethyl structure represented by the above formula (4) are the total gas methyl structure represented by the above formula (4) and the above formula (b) The ratio of the total gas-extended ethyl group represented by the molar ratio is 1/10 to 10/1 of the molar ratio (a)/(b). Further, the η value in the above formula (1) is preferably 3 to 1 Torr. The range is more preferably in the range of 6 to 7 Å. Further, 'for the poly(perfluoroalkyl ether) chain, the dirt is removed from the dirt; the bones are g, and the non-fluorine-based curable resin is improved. The solubility of the composition is in the range of 18 to 200, and the phosphorus contained in the poly(perfluoroalkylene ether) chain is preferably in the range of 18 to 200. The range of 25 to 丨5 ^ ^ 乍 is the radical 9 which is capable of generating a radical of the above-mentioned compound (A). The base of the group of the above-mentioned compound (A) is, for example, an organic group having a halogen atom, an organic group having a hoof group, and An organic group of a dithioacetate group, an organic group having a peroxy group, an organic group having an azo group, etc. Here, a monomer component having the above monomer (B) as an essential component is formed by living radical polymerization. The lamp polymerization % is carried out at both ends of the compound (4) having a functional group having a polymerization initiation ability at both the poly(perfluoroalkylene group) chain, and as the functional group capable of generating a radical, a functional atom can be used. The organic group, the organic group having an alkane group, and the organic group having a dithioester group are preferably ruthenium from the viewpoints of easiness of synthesis, ease of polymerization control, and diversity of applicable polymerizable unsaturated monomers. The organic group of the oxime is a ruthenium or an organic group having a tooth atom, and examples thereof include 2% methyl propyl fluorenyloxy group, 2 propyl propyl oxy group, and a gas-based benzyl methoxy group. In order to have the above-mentioned function of the atom The base is introduced into both ends of the poly(perfluoroalkylene ether) chain, and a method of reacting the compound (al) with the compound (a2) can be cited. The compound (al) has the ability to react with poly(perfluoroalkyl ether). The two ends of the chain react to form a bonded functional group, and the compound (a2) has a functional group capable of reacting with the functional group to form a bond and has a dentate r organic group. Specifically, as the above compound (al) Examples of the functional group at both ends include a hydroxyl group, an isocyanate group, an epoxy group 'carboxy group, a halogenated carboxylic acid, an acid anhydride, etc. Examples of the compound (a) which has these g groups can be exemplified. In the following formulas (4) to (al_6), '(al-l)' (al-3) and (al-6) are easy to react in the following formulas (aM) to (4)·6). Further, PFPE" in the formula represents a poly(perfluoroalkylene ether) chain. 201040233 HO—CHz—PFPE—CH2-OH (a 1 — 1 ) (a 1 -2) HO—C—PFPE~*C—OH O 0 HO—CH2CH2—PFPE—CH2CH2~OH (a 1 - 3)

1-4)

HO—C—CHa-PFFE-CHj-C—OH

II II

1-5)

OCN-PFPE-NCO H2€^pH-CH2~O- , CH2-PFPE-CH2--CH2-CH-CH,

On the other hand, as the functional group which can be bonded to the functional group which is present at both ends of the above compound (a), and the bond formed by the above-mentioned compound (a2), the following group can be mentioned. For example, when the functional group at both terminals of the above compound (al) is a hydroxyl group, the functional group other than the organic group containing a tooth atom of the compound (a2) is preferably an isocyanate group or a toothed carboxylic acid. Further, as another method, an acid anhydride may be first reacted with a hydroxyl group of the above compound (al) to form a carboxyl group, and a compound having an epoxy group and an organic group containing a functional group may be used as the above compound (a2). The reaction is carried out to introduce an organic group having a halogen atom at both ends of the above compound (al). When the functional group at both terminals of the above compound (al) is an isocyanate group, the functional group of the (4)-containing ketone group of the compound (a2) is preferably a 201040233 hydroxy group. Further, when the functional group at both terminals of the above compound (al) is an epoxy group, the functional group other than the halogen atom-containing organic group of the compound (a2) is preferably a fluorenyl group. When the functional group at both terminals of the above compound (al) is a carboxyl group, the functional group other than the halogen atom-containing organic group of the compound (a2) is preferably an epoxy group. Further, when the functional group at both terminals of the above compound (al) is an acid anhydride, the functional group other than the halogen atom-containing organic group of the compound (a2) is preferably a hydroxyl group. In the combination of the functional group at both ends of the above compound (al) and the functional group other than the organic group containing a tooth atom of the compound (a2), the functional group at both terminals of the compound (al) is a hydroxyl group, and the above compound It is preferred that the functional group other than the organic group containing a tooth atom is a combination of a toothed tickic acid because the reaction is easy. As the reaction conditions in the case of the combination, the following conditions can be mentioned. As a specific method for introducing the above-mentioned organic group containing an atom into a poly(terminal) chain, when the functional group at both terminals of the above compound (4)) is a trans group, the above compound (a2) is a functional group containing a group. In the case of the acid retardation, a compound having a functional group having a polymerization initiation ability at both ends of the poly(perfluoroalkylene group) bond can be obtained by carrying out the reaction under dehydration and acetification conditions. Further, when the functional group at both terminals of the above compound (8) is a trans group and the compound (4) is a dentate group-containing dentate citric acid, the same can be obtained by reacting (8) and (d) in a benzoic acid and a tetrahydrogen solvent. The compound H having a functional group having a polymerization initiation ability can be used as needed in the reaction. Further, 'the functional group at both terminals of the above compound (al) is an isocyanate group, 12 201040233 when the above compound (a2) has a halogen group and a hydroxyl group as a functional group capable of reacting with the isocyanate group, 'by a touch such as tin octylate In the presence of a medium, (al) and oxime 2) are reacted to obtain a compound having a functional group having a polymerization initiation ability. Further, when the functional group at both terminals of the compound (a1) is an epoxy group, and the compound (a2) has a halogen group and a carboxyl group which is a functional group capable of reacting with the epoxy group, the triphenylphosphine and In the presence of a basic catalyst such as a tertiary amine, (al) and (a2) are reacted to obtain a compound having a functional group having a polymerization initiation ability. Poly(perfluoroalkylene ether) obtained by a combination of a functional group having a hydroxyl group at the both terminal of the compound (al) and a functional group other than a halogen atom-containing organic group of the compound (a2) Specific examples of the compound (A) having a functional group having a polymerization initiation ability at both ends of the chain include compounds represented by the following formulas (A-1) to (A-3).

Next, the polymerizable unsaturated monomer (B) having a reactive group used in the present invention will be described. The reactive group of the above monomer (B) is at least one reactive group selected from the group consisting of an antelope group, an isocyanate group, an epoxy group, a carboxyl group, a halogenated carboxylic acid, and an acid anhydride. Further, the above-mentioned monomer (B) has a polymerization of 13 201040233. The unsaturation group is preferably a carbon-carbon unsaturated double bond having a radical polymerizable property, and more specifically, 'vinyl group, (meth) Acryl sulfhydryl, maleinium imino group, and the like. Among these groups, from the viewpoint of easiness of production of the polymer (c) to be described later, the (meth)acrylonyl group is preferred. Specific examples of the monomer (B) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and (methyl). ) 2 - hydroxybutyl acrylate ' hydroxybutyl methacrylate, 1,4-cyclohexane dimethanol mono (meth) acrylate, N_(2 hydroxy acetoxime) (methyl) propyl hydrazine Amine, glycerol mono(methyl)propionate, polyethylene glycol mono(mercapto) acrylate, polypropylene glycol mono(meth)acrylate, 2-hydroxy-3-phenyloxypropyl (methyl) a monomer having a hydroxyl group such as an acrylate, 2-(meth)acryloyloxyethyl-2-hydroxyethyl phthalate, a terminal hydroxyl group-containing lactone-modified (mercapto) acrylate; -(fluorenyl) propylene oxiranyl ethyl isocyanate, 2 (2-(meth) propylene methoxy ethoxy) ethyl isocyanate, etc., having an isocyanate group, glycidyl methacrylate, 4-hydroxybutyl An epoxy group-containing monomer such as acrylate glycidyl ether; (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-( Yl) oxyethyl Bing Xixi phthalic acid, and itaconic acid monomers having a carboxyl group; (meth) Bing Xixi gas _ carboxylic acid monomer and the like; acid anhydride monomers such as maleic anhydride. In the present invention, "(indenyl)acrylic acid" means one or both of methacrylic acid and acrylic acid, and "(indenyl)acrylic acid radical" means one of a methacrylic acid group and an acrylylene group. Or both, "(fluorenyl) acrylate" means one or both of methacrylate and acrylate. In the above polymerizable unsaturated monomer (B), 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate (meth) acrylate ^ 201040233, propyl acetonate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, N-(2-hydroxyethyl)(meth)acrylamide, glycerol mono(meth)acrylate, 2- Hydroxy_3_phenoxypropyl (meth) acrylate, 2-(meth) propylene oxiranyl ethyl isocyanate, glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether, (fluorenyl) Acrylic acid is effective because it can introduce a polymerizable unsaturated group into the obtained polymer (C), and the obtained resin is excellent in moisture resistance and chemical resistance after curing. Among them, a monomer containing a methacryl fluorenyl group is particularly excellent in terms of living radical polymerizability. In addition, the polymerizable unsaturated monomer (B) may be used in combination of two or more kinds, if it is a combination which does not affect the reactivity. Further, in the monomer which is the raw material of the polymer (c), in addition to the above monomer (B), another monomer which can be copolymerized with the monomer (e) may be used as the monomer (8), and for example, Methyl)methacrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl acrylate (meth)acrylate, (meth)acrylic acid Valeric vinegar, (meth)acrylic acid hexanoic acid, hydrazine (methyl) acrylic acid n-glycolic acid, (meth)acrylic acid octyl alcohol, (methyl) acrylic acid 2-ethylhexyl vinegar, (A Acrylic vinegar vinegar '(methyl) acrylate 癸 κ methyl) acrylic acid, dialkyl ketone, (meth) acrylic acid cyclohexyl amide, (meth) isopropyl isobornyl ester, etc. Alkyl methacrylate; aromatic styrene, methyl maleimide, ethyl horse, such as styrene, mercaptostyrene, p-methylstyrene, p-methoxystyrene醯 imine, propyl maleimide, butyl maleimine, hexylmaline, octyl maleimide, ten: burned: maleic imine, hard Lipid-based maleimide, stupid maleimide, earthworm, S-amine, etc., maleimide, 3_(dimethoxy, succinyl), C, 15 201040233, (meth) propyl hydrazine Acid (S), 3-((triethoxymethyl sulphate) propyl (methyl) propyl 曰 曰 曰 ( 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有 含有Body, flat _ Tian A "Into a soil yew-burning chain and other (meth) acrylic acid vinegar monolithic _ β / flat body temple. These early bodies (a3) may be used singly or in combination of two or more. In the method for producing the polymer (C), the above-mentioned compound (A) is used as a radical polymerization initiator to carry out living radical polymerization of the above monomer (8) and the above-mentioned monomer (8) to be used. method. Usually, in a living radical polymerization, a dormant species in which a living polymerization terminal is protected by an atom or a radical reversibly generates a radical ' reacts with a monomer, whereby a polymer having an extremely narrow molecular weight distribution can be obtained. Examples of such living radical polymerization include atomic mobile radical polymerization (ATRp), reversible addition-fragmentation radical polymerization (RAFT), and organic polymerization via nitrogen oxide radical polymerization (NMP). Free radical polymerization of hydrazine. For example, by living radical polymerization to produce the above polymer (〇, a copolymer having a very narrow molecular weight distribution can be obtained, which is preferable. Any of these methods is not particularly limited, but from the viewpoint of ease of control, etc. In view of the above, ATRP is preferred. In the ATRP, an organic compound or a cryptic compound or the like is used as a starter, and a metal complex composed of a transition metal compound and a ligand is used as a catalyst for polymerization. The transition metal compound is a compound represented by Μη+χη. The ΜΠ+ of the transition metal may be selected from Cu+, cu2+, Fe2+,

Fe3+, Ru2+, Ru3+, Cr2+, Cr3+, M〇. , M〇+, m〇2+, m:3+, w2+, f ' Rh\ Rh”, co+, c〇2+, Re2+, w+, Ni+, 16 201040233

A group consisting of Mn3+, Mn4+, V2+, V3+, Zn+, Zn2+, Au+, Au2+, Ag+, and Ag2+. Further, X may be selected from a halogen atom, an alkoxy group having 1 to 6 carbon atoms, (S〇4)i/2, (Ρ〇4)ιη, (Ηϊ>〇4) 1/2, (H2P〇4). a group of trifluorosulfonate, hexafluorophosphate, sulfonium sulfonate, aryl sulfonate (preferably benzenesulfonate or benzenesulfonate), SeR1, CN and R2C〇〇 . Here, R1 represents an aryl group, a linear or branched alkyl group having a carbon number of 1 to 2 Å (preferably having 1 to 1 Å), and R2 represents a hydrogen atom and may be substituted by halogen. a straight or branched alkyl group having 1 to 6 carbon atoms (preferably a methyl group, and η represents a form charge on the metal, 5 times (preferably 1 or 3 times by fluorine or chlorine substitution). It is an integer of 〇~7. As the transition metal complex, 7 〇, y ' ιυ ' 11 valence copper, a divalent quinone transition metal complex, more preferably valence copper, valence iron or The complex of divalent nickel is a compound having a ligand capable of coordinate bonding with the above transition metal, and examples thereof include a ligand having at least one or more nitrogen capable of "coordination with a bond: 〇 = metal An atom, an oxygen atom, a phosphorus atom or a sulfur-containing compound, and a ligand having a ligand capable of being bonded to a transition gold by two or more carbon atoms, or a ligand having a bond or a bond? a compound in which a bond is coordinated with a transition metal. Specific examples of compounds in which a gold has a ligand, for example, Zhong Luolin and ί And 2,2'♦ than the bite and its derivatives, U0-phenanthrene, Hebi, tetramethylethylenediamine, pentamethyldi(2-aminoethyl)amine and other polyamines Mistakes, can be listed as two gas three (triphenyl, dichlorotris (three 17 201040233 Ding Lin) bismuth, dichloro (cyclooctyldiphenyl benzoquinone, two gas, one gas benzoquinone, dichloro-p-nickyl Isopropyl milk (norbornadiene) * Dichlorotris (1,10-phenanthroline, ·-milk (2,2'-bipyridyl;) oxime, misregistered as divalent iron, hydrogenated group Chlorotris(triphenylphosphine), etc., and a calcined complex, etc., may be exemplified by a solvent used in the production of the above polymer (c), such as a bistriphenyl scale complex or a triazacyclocycle. Preferably, a refrigerant is used. As jg ψ uu, an ether such as ethyl acetate, butyl acetate, propylene glycol, early methyl hydrazine acetate or the like, such as propyl-d-isopropyl ether or dimethoxyethyl dimethyl ether, is used. a solvent; a solvent such as dioxane, aerated gas, or a dentate; a solvent such as toluene, dimethyl-milk thereof, a mixture of methyl ethyl ketone, a second base, a cyclohexanone, or the like; Ethanol, isopropanol = (4) The above-mentioned solvent may be used singly or in combination of two or more kinds thereof. Further, the polymerization temperature at the time of producing the above polymer (c) It is preferably in the range of room temperature to 100° C. When the polymer (C) is a block-like portion composed of the monomer (B) and the monomer (8), the monomer (B) or the monomer (B) or The monomer (E) is separately subjected to living radical polymerization in the presence of the compound (A), a transition metal compound, a compound having a ligand capable of coordinate-bonding with the transition metal, and a solvent, and then added. A monomer different from the monomer which has been subjected to living radical polymerization first can be obtained by living radical polymerization. In order to obtain the fluorine-containing polymerizable polymer of the present invention, the use of the above-mentioned reactive group of the polymer (C) produced by the above method or the partial 18 201040233 is used to form a bond with the reactive group. a compound (1) selected from the group consisting of a p-isocyanate, an epoxy group, a phonophore, a functional acid, and a acid field, and a polymerizable unsaturated group (1)), in the polymer (C) A polymerizable unsaturated group is introduced therein. The above functional group which the above compound (〇) has can be selected depending on the reactive group of the polymer (C). Further, the polymerizable unsaturated group possessed by the above monomer (D) is preferably a carbon-carbon unsaturated double bond having a radical polymerizable property, and more specifically, a vinyl group, ^(methyl) acrylonitrile Base, Malay, and the like. In the case of adding the fluoropolymer polymer of the present invention to the active energy ray-curable composition, the polymerizable monomer (F) and polymerizable property described later are preferable. Resin (G) or the like has high hardenability. For example, when the reactive group of the polymer (C) is a hydroxyl group, the functional group of the compound (D) is preferably an isocyanate group, a carboxyl group or a carboxylic acid, and it is not necessary to remove the removed material. More isocyanate groups. When the reactive group of the polymer (C) is a hydroxyl group, first, a Q-acid anhydride is reacted with a hydroxyl group of the polymer (C) to form a carboxyl group. For the carboxyl group, an epoxy group and a polymerizable property are used. The compound of an unsaturated group is further reacted as the compound (B)', so that a polymerizable unsaturated group can also be introduced onto the polymer (c). When the reactive group of the polymer (c) is an isocyanate group, the above functional group of the compound (d) is preferably a trans group. When the reactive group of the polymer (C) is an epoxy group, the above functional group of the compound (D) is preferably a carboxyl group. Further, by reacting a compound having an isocyanate group or a toothed carboxylic acid and a polymerizable unsaturated group with a secondary hydroxyl group formed by the reaction of the above compound 201040233 (D), it is also possible to introduce a polymerization onto the polymer (c). Sexually unsaturated groups. In addition, when the reactive group of the polymer (c) is a bad oxy group, gpi is a compound having no polymerizable unsaturated group, but may be a ruthenium having a functional group capable of undergoing an addition reaction to an epoxy group such as a carboxyl group. Alternatively, a secondary hydroxyl group can be produced by reacting with an epoxy group of the polymer (C), and a compound having an isocyanate group or a deuterated carboxylic acid and a polymerizable unsaturated group can be used as the above compound (D). The hydroxyl group reacts to introduce a polymerizable unsaturated group into the polymer (C). When the reactive group of the polymer (C) is a carboxyl group, the group other than the polymerizable unsaturated group of the compound (D) is preferably an epoxy group. Further, a compound having an isocyanate group or a toothed carboxylic acid and a polymerizable unsaturated group is used as the compound (D)' to react with the second-order hydroxyl group formed after the reaction, so that it can be introduced into the polymer (C). Polymerizable unsaturated group. In addition, when the reactive group of the polymer (C) is a carboxyl group, even a compound having no polymerizable unsaturated group may be reacted with a carboxyl group of the polymer (C) as long as it is a compound having an epoxy group. Further, a secondary hydroxyl group is formed, and a compound having an isocyanate group or a ii-carboxylic acid and a polymerizable unsaturated group is used as the compound (D) to react with the hydroxyl group, and a polymerizable unsaturated group may be introduced into the polymer (c). When the reactive group of the polymer (C) is an acid anhydride, the functional group of the above compound (D) is preferably a hydroxyl group. More preferably, a compound having an epoxy group and a polymerizable unsaturated group is further reacted as the above compound (D) with a carboxyl group formed after the reaction. Further, when the reactive group of the polymer (C) is an acid anhydride, even if it does not have a polymerizable unsaturated group, as long as it is a compound having a hydroxyl group of 201040233, it can be reacted with an acid anhydride to form a carboxyl group, and has a ring. A compound having an oxy group and a polymerizable unsaturated group is reacted with the carboxyl group as the above compound, and a polymerizable unsaturated group may be introduced into the polymer (c). The combination of the reactive group of the above polymer (C) and the functional group of the above compound (D) may be a combination of a plurality of different kinds of functional groups as long as the reaction is not affected.

As the above compound (D), the same compound as the above monomer (B) can be used. Further, as a combination, a polymer having a reactive group of the polymer (c) which is a hydroxyl group (a compound obtained by using a compound having a hydroxyl group as a raw material monomer (B)) is preferred, and the polymerizable property of the compound (D) is not A combination of compounds in which the functional group other than the saturated group is an isocyanate group. It is particularly preferable to use 2_acryloyloxyethyl isocyanate as the compound (D)' to react with the polymer (C) produced by using 2-hydroxyethyl methacrylate as the monomer (B). In addition, the amount of the compound (D) to be used is preferably a monomer (aB) i mole which is a raw material of the polymer (C), and is preferably a polymerizable property. The aspect of the group and the aspect of the above-mentioned compound (D) which does not remain unreacted are particularly preferably 〇9 to 1 〇mol. When the reactive group of the polymer (c) is a hydroxyl group and the functional group other than the polymerizable unsaturated group of the compound (d) is an isocyanate group, these reactions may be carried out without a solvent, or may be carried out using a solvent. When the solvent is used, the fluidity of the reaction liquid is good, and therefore it is preferable. Examples of the solvent include ester solvents such as vinegar m acetic acid m monomethyl squaraine acetate; diisopropyl ether, dimethoxy ethane, diethylene glycol dimethyl ether, etc. (iv) solvent; 7. I-based solvent such as di-ethane hexane; benzene: 21 201040233 An aromatic solvent such as xylene; a ketone solvent such as ketone; a soil, methyl isobutyl ketone, or a polar solvent. Non-protonic properties such as guanamine, dimethyl sulfite, etc. The other two are: good ester solvents, ketone solvents, and coffee agents. Preferably, the reaction of the amine A formic acid st polymer (C) with the above compound (D) is carried out by comparing the presence of a catalytic catalyst. Examples of the amine phthalic acid catalyzed catalyst include „比定, _, triethylamine, diethylamine, and dibutylamine specific amines; triphenylphosphine, = lin-nu-ethylphosphine-specific phosphine; An organic tin compound such as dibutyltin laurate, octyltin dilaurate, octyltin diacetate, dibutyltin diacetate or tin octylate; or an organometallic compound such as zinc octylate. Further, if the organotin compound and the face are combined with the amine and the amine, the urethanization reaction can be carried out smoothly, and therefore it is preferred. The number average molecular weight ((iv) and weight average molecular weight (Mw) of the fluorine-containing polymerizable polymer of the present invention is preferably 3, or more, more preferably 5, -1 to 〇 '000. If the fluoropolymerizable block When the number average molecular weight of the polymer is in the "definite range", the hydrophobicity and the oleophobicity are particularly excellent. Further, these number average molecular weights and the like are measured by gel permeation chromatography (hereinafter referred to as Gpc). [GPC measurement conditions] Measurement equipment: "HLC-8220 GPC" manufactured by Tosoh Corporation, b column. Protective column (gUard column) manufactured by Tosoh Corporation "HHR-H" (6.0 mm IDx4cm) + East "TSK-GEL GMHHR-N" (7.8mm ID.x3〇cin) manufactured by Cao Co., Ltd. + "TSK-GEL GMHHR-N" manufactured by Tosoh Corporation (7.8mm 22 201040233 IDx30cm) + manufactured by Tosoh Corporation TSK-GEL GMHHR-N" (7.8mm IDx30cm) + "TSK-GEL GMHHR-N" manufactured by Tosoh Corporation (7.8mm IDx30cm) Detector: ELSD ("ELSD2000" by AUtech) Data processing: Tosoh Corporation Club system "GPC-8020 Type II data analysis 4.30 version" C) Measurement conditions: column temperature 4〇〇c Development solvent tetrahydrogen THF South (THF) Flow rate 1.0 ml/min Sample: The tetrachloropyrene solution in terms of resin@shape conversion is 丨.Q f%% filtered with a microfilter Sample (丨〇〇#丨). Ethylene

Standard sample: According to the measurement manual of the above-mentioned "GPC-_II type data analysis 430 version", the following single-point (molecularly dispersed polystyrene) having a known molecular weight is used. "A-500" manufactured by Tosoh Corporation, Tosoh Corporation "A-1000" "A-2500" manufactured by Tosoh Corporation "A-5000" manufactured by Tosoh Corporation "F-factory made by Tosoh Corporation, "F-2" manufactured by Tosoh Corporation" Tosoh Corporation "F_4" "F-10" manufactured by Tosoh Corporation 23 Fukushima Co., Ltd. "F 2 〇," "F_4〇 made by Tosoh Corporation" F 8 〇,, Tosoh Corporation "F _ 12 8, manufactured by Tosoh Corporation", F _ 2 8 8 , manufactured by Tosoh Corporation, F _ 5 5 0, the active energy ray-curable composition of the present invention contains the above gas-containing gas. The active energy ray-curable composition of the polymer of 11.11. The blending amount of the fluorine-containing polymerizable polymer is preferably in the living, and the non-volatile component of the hardening type composition of the 绿 line green In the middle of 0.01 ~ 10 quality Jin. ΛΛ £ > „ Negative / 〇 特佳 is 0·05~3质量%, because this time The damage would have been added in the resin composition coating film physical properties such as hardness, and can be efficiently and modification of the coating film surface. The main component of the active energy ray-curable composition may be a polymerizable monomer (F) or a polymerizable resin (G). In the above polymerizable monomer (F), examples of the monofunctional monomer include N-vinyl caprolactam, N vinyl pyrrolidone, N-vinylcarbazole, vinyl pyridine, acrylamide, and N. N-Dimethyl(meth)acrylamide, isobutoxymethyl(fluorenyl)propenylamine' tert-octyl (meth) acrylamide, diacetone (decyl) decylamine, dimethyl Aminoethyl (indenyl) acrylate, diethylaminoethyl (meth) acrylic acid S曰7_amino-3,7-monomethyloctyl (methyl) propylene vinegar , acrylonitrile, fluorenyl laurate, dicyclopentadienyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate, dicyclopentanyl ( Methyl) acrylate, tetrahydrofurfuryl (meth) acrylate, ethyl diethylene glycol (meth) acrylate, butoxy ethyl (meth) acrylate, decyl triethyl Glycol (mercapto) propene 24 201040233 enoate, phenoxyethyl (meth) acrylate, and the like. These monofunctional monomers may be used singly or in combination of two or more. In the above polymerizable monomer (F), examples of the polyfunctional monomer include trimethylolpropane tris(f-) acrylate and triethylene oxide-modified trihydroxydecyl propane (meth) acrylate. , tripropylene oxide modified tris (meth) acrylate, triethylene oxide modified glycerol tri (meth) acrylate, tri epichlorohydrin modified glycerol tri (meth) acrylate, US tripropylene decyl hexahydrotriazine, bis(propionyloxyethyl)isocyanurate, pentaerythritol tri(meth)acrylate, bis(trihydroxydecylpropane)tetrakis(meth)acrylate, Diethylene oxide modified bis(trimethylolpropane)tetrakis(meth)acrylate, alkyl modified dipentaerythritol pentaacrylate, alkyl modified dipentaerythritol tetraacrylate, caprolactone modified dipentaerythritol Hexa(indenyl) acrylate, dipentaerythritol penta(indenyl) acrylate vinegar, dipentaerythritol hexa(meth) acrylate, hexaoxirane modified sorbitol hexa(meth) acrylate, hexamethyl Propylene oxiranyl ethyl) cyclotriphosphazene and the like. These polyfunctional monomers may be used singly or in combination of two or more. Examples of the polymerizable resin (G)' include an epoxy (meth) propionate formed by reacting a (meth) acrylate with a compound containing a plurality of epoxy groups, and an aliphatic polyisocyanate. Or a urethane (meth) acrylate such as an aromatic polyisocyanate and a light-based (f-) acetoacetate. These polymeric resins (G) may be used alone or in combination with an epoxy group of an epoxy resin such as J::r=, :=r= 25 201040233 epoxy resin or acetal epoxy resin. An epoxy (meth) acrylate formed by the reaction. For example, a tetramethyl isocyanurate, a pentamethyl diisocyanate, or a hexamethylene group can be used as a raw material for the raw material of the hydroxyacetic acid vinegar (meth) acrylate vinegar. Diisocyanate, heptamethyl diisocyanate, octamethyl diisocyanate, decyl methyl diisoacetate, 2·methyl-1,5-pentane diisocyanate, 3_A Base, 5 pentane diisocyanate vinegar, dodecyl methyl diisocyanate, 2-methyl pentamethyl diisocyanate, 2 2 4_ trimethyl hexamethylene diisocyanate Sour, 2,4, trimethylhexamethylene diisocyanate 2, isophorone diisocyanate, norbornane diisocyanate, hydrogenated monophenylmethane diisocyanate, hydrogenated methyl diisocyanate, Hydrogenated xylene diisocyanate, hydrogenated tetradecyl dimethyl benzene diisocyanate, cyclohexyl diisocyanate, and the like. Further, examples of the aromatic polyisocyanate used as a raw material of the above urethane (meth) acrylate include methyl phenyl diisocyanate, 4, 4, _ diphenylmethane diisocyanate, and diphenyl benzene diisocyanate. , 丨, 5-naphthalene diisocyanate δ, tolidine diisocyanate, p-diisocyanate, and the like. On the other hand, '(indenyl) acrylate having a hydroxyl group used as a raw material of the above-mentioned aminocarboxylic acid (meth) acrylate, for example, ethyl (meth) acrylate, ethyl hydroxy acrylate Ester, hydroxybutyl (meth) acrylate, pentyl mono(mercapto) acrylate, hexanediol mono(mercapto) acrylate, neopentyl glycol mono (meth) acrylate, hydroxypivalic acid new Mono(meth)acrylate of diol such as pentanediol mono(meth)acrylic acid vinegar; trihydroxymercaptopropane di(meth)acrylic acid vinegar, ethoxylated trihydroxydecylpropane (methyl) Acrylate, propoxylation 26 201040233 Dimethylolpropane di(meth)acrylate, glycerol di(meth)acrylate, bis((meth)acryloyloxyethyl)hydroxyethyltrimeric isocyanate a mono- or di(meth)acrylate of a trihydric alcohol, or a mono- and di-(meth)acrylate having a hydroxyl group formed by modifying a part of an alcoholic hydroxyl group with ε-caprolactone; pentaerythritol III ( Methyl) acrylate, bis(trimethylolpropane) III a compound having a hydroxyl group and three or more (f-group) propylene groups per molecule, such as methyl acrylate, dipentaerythritol penta (meth) acrylate, or the hydroxyl group of the compound is modified by ε_caprolactone And formed polyfunctional (meth) acrylate; dipropylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol single ( (meth)acrylic acid compound having an alkylene oxide chain such as methyl acrylate; polyethylene glycol-polypropylene glycol mono(meth)acrylate, polybutylene oxide-polypropylene oxide mono(fluorenyl) a (mercapto) acrylate compound having a block structure of an alkylene oxide chain such as an acrylate; poly(ethylene glycol monobutylene glycol) mono(meth)acrylate, poly(propylene glycol-butanediol) A (meth) acrylate compound having a random structure of an alkylene chain having a random structure such as a mono(f-) acrylate. The reaction of the above aliphatic polyisocyanate or aromatic polyisocyanate with a (meth) acrylate having a hydroxyl group can be carried out in the usual manner in the presence of a urethane catalyst. Examples of the amino phthalate-catalyzed catalyst include amines such as π, triethylamine, diethylamine, and dibutylamine; phosphines such as triphenylphosphine and triethylphosphine; and dibutyl laurate; Base kick, octyl kick of trilaurate, octyl tin diacetate, dibutyltin diacetate, tin octylate, etc.; organometallic compounds such as zinc octoate. In these urethane (meth) acrylate acid resin towels, a resin obtained by reacting an aliphatic poly 27 201040233 isocyanate with a hydroxyl group-containing (meth) acrylate, because of the excellent transparency and hardening of the cured coating film Excellent, so it is especially good. The active energy ray-curable combination of the present invention refers to a composition which hardens when irradiated with an active energy ray. The active energy ray means an ionizing ray such as an ultraviolet ray, an electron beam, an alpha ray, a P ray, or a 7 ray. When ultraviolet rays are used as the active energy ray, a photopolymerization initiator (Η) is added to the active energy ray-curable composition. Further, a photosensitizer may be further added as necessary. On the other hand, when an ionizing ray such as an electron beam, an α ray, a no ray or a τ ray is used, it can be hardened quickly without using a photopolymerization initiator and a photosensitizer, and therefore it is not necessary to add these substances in particular. As a photopolymerization initiator (Η), an intramolecular split type photopolymerization initiator and dehydrogenation are also mentioned, and Fei Ruru

Methylphenyl acetate or the like. As a dehydrogenation type photopolymerization initiator, o-benzhydryl-benzoic acid f-ester-4-phenyldione, trans-dioxadolone, 4-benzylidene group, for example, diphenyl steel, Benzophenone, 4,4,-dichlorodibenzoyl-4-methyl-monophenylsulfide, acetonitrile 28 201040233 A ketone, 3,3, '4,4,·tetra (tert-butyl) a benzophenone compound such as a peroxymethyl group, a benzophenone, a 3,3,-monomethyl-4-decyloxybenzophenone; an isopropyl siaton, a 2,4-didecyl group; Thioxanthene 2,4-diethylthioxanthone, 2,4-dichloro-sexy, etc. (iv) ketone compounds; Michler's ketone, 4,4, _diethylaminobenzhydrazide, etc. Aminobenzophenone compound; 10-butyl-2-chloro. Hey. Ding _, 2_ B 醌 9' 1 〇 醌 醌 醌, 樟 醌 。. These photopolymerization initiators (e) may be used singly or in combination of two or more kinds. Further, examples of the photosensitizer include an amine such as an aliphatic amine or an aromatic amine, a urea such as o-trithiourea, sodium diethyl disulfide, and s-benzylisothiourea-p-toluenesulfonate. Sulfur compounds, etc. The amount of the photopolymerization initiator and the photosensitizer used is a part by weight relative to the nonvolatile component of the active energy ray-curable composition. Don't ~2. The quality is better. .3~1〇 parts by mass. It is preferable that the active energy ray-curable composition of the present invention can be used for the purpose of adjusting the viscosity and the refractive index, or for adjusting the coating, in accordance with the purpose of use, characteristics, and the like, without impairing the effects of the present invention. The color tone of the film and the adjustment of other coating properties or film properties, and are used simultaneously as various compounding materials, such as various organic solvents, acrylic resins, phenolic resins, polyester resin, urea resin, melamine resin, alkyd resin, ring Various resins such as oxygen resin, polyamide resin, polycarbonate resin, petroleum resin, fluororesin, etc., various kinds of PTFE (polytetrafluoroethylene), polyethylene, carbon, titanium oxide, oxidized, copper, and cerium oxide particles Organic or inorganic particles, polymerization initiators, polymerization inhibitors, antistatic agents, defoamers, viscosity modifiers: light stabilizers, stabilizers, heat stabilizers, antioxidants, anti-recording agents, 29 201040233 Lubricants , wax, brightening agent, release agent pigment, dye, dispersant, dispersion stabilizer: two-lead paste ^ active agent. "Embedded emulsion, hydrocarbon-based interfacial polymerization = two =: organic solvent in the fraction, in the case of the fluorine-containing polymerization of the present invention and the preparation of the fluorine-containing polymerizable polymer, in order to impart coating properties to the substrate It is effective as a dilute solvent for adjusting the (four) degree. Examples of the dilute agent include aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, ethyl, and isopropanol; ethyl acetate and the like; Methyl ethyl net, methyl A, isobutyl 3, and acetic acid 3 can be used alone. These solvents can be used alone or in addition to the four or the other. When the active energy ray hardening is known to be an agent liquid, in order to form black, it is necessary to match =: the product is as long as it is black, and it is particularly suitable for the coloring agent. As the coloring agent, oxides are used in two or more types. Metal oxides are preferably carbon black, metal pigments. In addition, 'may also be selected from the group consisting of red, blue, greenish purple, magenta-colored pigments, ... organic two 22:,,: two to form a black combination . ^丁—This color, as the above carbon black, for example, black, channel black, furnace black, and the like. For B fast black, pyrolytic carbon, by titanium oxidation or # 4 metal emulsion, titanium black can be used: reduction of titanium black. In general, the compound is represented by a metal oxide of M, and it is represented by a metal oxide of M. Composite metal compounding 30 201040233 =, for example, copper-chromium oxide, steel_chromium_short oxide, copper_iron-manganese oxide or cobalt-iron-manganese oxide, etc., as an organic pigment Examples of the pigment-based pigments and flower-based pigments having a red hue, and the pigments and onions: = pigments having a blue hue, such as phthalocyanine pigments, indan- lins, and pigments, and examples of pigments having a green color are exemplified. The heart color pigments Ο color two to one color pigment can be listed as two. Evil purple, solid purple " base purple:: indanthrene bright purple, etc., yellow pigments can be cited four gas = phase pigment , Hansa yellow pigment, benzidine yellow pigment, even = pigment, etc., the pigment having a cyan color can be exemplified by a metal-free propanol, a part 2, etc., and a pigment having a magenta color can be exemplified by dimethyl hydrazine _, Sulfur blue special. In addition, as the present invention The conjugated polymer may be used as an active energy ray-curable resin by appropriately mixing the above-mentioned photopolymerization initiator (8) and organic solvent, and coating the above-mentioned fluoropolymerizable polymer of the present invention. Or coating a substrate using an active energy ray-curable composition of 1: fluoropolymerizable polymer, y to exemplify a plastic substrate; a ceramic I substrate such as glass; an iron, a metal such as a metal, etc., a plastic base It is particularly useful as a material for a plastic knee substrate, and examples thereof include polyester resins such as polyethylene terephthalate vinegar, polybutylene terephthalate, and polyethylene naphthalate. Polypropylene, polystyrene & 1·戍埽 and other poly-smoke-based resins; cellulose triacetate and other fiber drop: Shuyue 曰 'polystyrene resin, & guanamine resin, polycarbonate resin, sheet A olefinic tree, a modified norbornene resin, a cyclic olefin copolymer 31 201040233, etc. Further, a base material formed by laminating two or more kinds of base materials composed of these resins may be used. The material may be in the form of a film or a sheet. The method of applying the above-mentioned fluorine-containing polymerizable polymer of the present invention or the active energy ray-curable composition using the fluorine-containing polymerizable polymer to the material may, for example, be gravure coating, roll coating or comma coating. , air knife coating, kiss coating, spray coating, cross coating, dip coating 'spin coating' wheeler coating, brush coating, dense coating with screen printing, bar coating: Flow coating, etc. In addition, it can also be a printing method such as flexographic printing or typography. Among these methods, gravure coating, roll coating, comma coating, air knife coating, coating, and wire rod Coating and flow coating can obtain a coating film having a constant thickness, which is preferable. As the gas-containing polymerizable polymer of the present invention or the #-energy-hardening type composition using the gas-containing polymer The hardened active energy rays may include active energy rays such as light, electron enthalpy, and radiation. As a specific energy source or hardening 奘罟, for example, a sterilization lamp, an ultraviolet fluorescent lamp, a carbon arc lamp, a xenon lamp, a 斿e > a copying mercury lamp, a medium pressure or a high pressure mercury lamp, and a super璧 Mercury lamp, I Ray anti-heat electrode lamp, metal halide lamp, ultraviolet ray with natural light, etc., 4b 扪H line 4, an electron beam formed by a scanning type, curtain type electron beam accelerator, and the like. Among these rays, the active energy ray of Y is better than ultraviolet rays. From the viewpoint of polymerization efficiency, it is better to store it in an inert gas atmosphere such as a rat. Further, heat may be simultaneously used as an energy source as needed, and after heat treatment by irradiation with an active energy ray, heat treatment is performed. 32 201040233 The cured coating film of the fluorine-containing polymerizable polymer of the present invention has excellent antifouling properties (ink repellency, fingerprint resistance, etc.), scratch resistance, and the like, and therefore can be applied to the surface of the article and cured. The surface of the article is imparted with antifouling properties, scratch resistance, and the like. Further, since the fluorine-containing polymerizable polymer of the present invention is added as a gas-based surfactant to the coating material, the coating material can be imparted with uniformity, and thus the active energy ray-curable composition of the present invention has high Both are flat. ° 0 As an article which can impart antifouling properties (ink repellency, fingerprint resistance, etc.) to the fluorinated polymerizable polymer or the active energy ray-curable composition of the present invention, a liquid crystal display (LCD) such as a TAC film can be used. Film for polarizing plate; various display screens such as plasma display (PDP), organic EL display; touch panel; portable telephone case or portable telephone screen; optical recording medium such as CD, Dvd, Blu-ray disc; Transfer film for molding (IMD, IFD); rubber roller for 〇A equipment such as photocopiers, printers, etc.; glass surface for reading parts of 〇A equipment such as photocopiers, scanners, etc.; cameras, cameras, glasses, etc. 〇Optical lens; windshield surface of watches and other watches; windows of various vehicles such as automobiles and railway vehicles; various building materials such as decorative panels; wood materials for residential window glass, furniture, artificial or synthetic leather, housings for home appliances, etc. forming. D, FRP bathtub, etc. By applying the 3 fluororesin resin or the active energy ray-curable composition of the present invention to the surface of these articles, the cured coating film is formed by irradiation with an active energy ray such as ultraviolet rays, whereby the surface of the article can be imparted with tamper resistance. Further, the gas-curable resin of the present invention can be applied to various coating materials, coated and dried to impart antifouling properties to the surface of the article. 33 201040233 ... As a coating material to which the fluorine-containing curable resin of the present invention is added and the coating film is provided with antifouling properties (ink repellency, fingerprint resistance, etc.), the TAC is exemplified. It is hard to use various materials such as H material, anti-glare (AG) coating material or anti-reflection (LR) coating material 'plasma display, organic EL display (pDp) for film for polarizing plate of liquid crystal display (LCD) such as film. Coating material 'hard coating material for touch panel; used to form various pixels used in color illuminators for liquid crystal displays (hereinafter referred to as "CF"): color etchants, printing inks, inkjet inks or Paint; resin composition for pixel partitions such as plasma display (PDP), organic EL display; coating or hard coating material for portable telephone housing; hard coating material for portable telephone screen, CD DVD, Blu-ray disc Hard coating materials for optical recording media, hard coating materials for transfer film 2 (IMD, IFD), coating materials for photocopying machines, printers, etc., sighs, coating materials for spare rubber rolls, photocopying machines, scanning materials Coating of the glass of the reading part of the 〇A device (4) Optical 2 coating for cameras, cameras, glasses, etc. (4); coating materials for windshields for hand-held watches, coating materials for windows, such as window coating materials for various vehicles, etc. Coatings for window glass for use in homes; materials; coatings for woodwork such as furniture; furniture or coatings for various plastic moldings such as shells for human or synthetic leather fabrics; FRP bath coatings or coatings Cloth materials, etc. Further, as an article which can impart scratch resistance and antifouling property by using the fluorine-containing curable resin or the energy ray-curable composition of the present invention, it is exemplified as the backing of the LCD from & A piece of enamel or a scattering sheet. Further, by adding the fluorine-containing curable resin of the present invention to the wafer or the scattering sheet, the coating film is improved in scratch resistance (scratch resistance) and prevention while improving the uniformity of the coating material at 34 201040233. Stained.料

Since the cured coating film containing the curable resin of the present invention has a low refractive index, it can also be used as a coating material for a low refractive index layer which prevents an antireflection layer such as a glory lamp from being mapped on various display surfaces such as an LCD. Further, by adding the fluorine-containing curable tree pond of the present invention to the coating material for an antireflection layer, particularly the coating material for a low refractive index layer in the antireflection layer, it is possible to maintain the low refractive index of the coating film. At the same time, the coated surface is imparted with antifouling properties. In addition, as another use of the fluorinated curable resin or the active energy ray-curable composition of the present invention, an optical fiber coating material, an optical waveguide, a sealing material for a liquid crystal panel, various optical sealing materials, and optical use can be used. Followers and so on. In particular, in the use of a coating material for a protective film for a polarizing plate for LCD, the active energy ray-curable composition of the present invention is used as an antiglare coating material or the like, and in the above respective compositions, by the present invention In the active energy ray-curable composition, the ratio of 〇1 to 〇5 times the total mass of the hardening component is combined with inorganic or organic fine particles such as cerium oxide particles, acrylic resin particles, and polystyrene resin particles to obtain excellent anti-glare. Sex, so it is better. When the fluorinated curable resin or the active energy ray-curable composition of the present invention is used as an antiglare coating material for a protective film for a polarizing plate for LCD, the following transfer method may be applied: hardening of the coating material. It is previously brought into contact with a metal mold having a concave-convex surface shape, and then hardened by irradiating an active energy ray from the side opposite to the metal mold, and embossing the surface of the coating to impart anti-glare property. EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples and comparative examples. Here, the gas content of the fluorine-containing polymerizable polymer is calculated as the mass ratio of the fluorine atom to the total amount of the raw materials used. (Synthesis Example 1) Synthesis of perfluoropolyether bromoisobutyrate derivative In the reaction container, 29 g of a perfluoropolyether diol represented by the following formula (A, _1}, and 4.6 g of triethylamine were added. Diisopropyl ether (hereinafter referred to as "ΙρΕ" is stirred to form a homogeneous solution. In this solution, the internal temperature is less than 30 while cooling. The above is added dropwise with 2_bromoisobutylate for 75 minutes.醯Bromo 1 〇g. Stir at room temperature for 3 hours, then stir for 5 hours at 4 (rc), then dilute with IPE 89g, then add 1 〇〇g of 〇1M hydrochloric acid and stir. The organic layer separated in the obtained reaction solution was washed with saturated aqueous sodium hydrogen carbonate and brine, and dried over anhydrous sodium sulfate. Isobutyrate derivative. ho-ch2-{x~.〇^x-CH2_〇h (α._ό (wherein, X is a perfluoromethyl group and a perfluoroethyl group, which is present per molecule) 7 perfluoromethyl groups with an average of 8 perfluoroextended ethyl groups with an average number of fluorine atoms of 46. The number average molecular weight obtained by the 'GPC method 1,500.) (Example 1) 8.2 g of methyl ethyl ketone (hereinafter referred to as MEK), 2.2,-bipyridinium.373 g, and 0.118 g of cuprous oxide were added to a reaction vessel which was replaced with helium gas. Give a drop of 30 minutes at the temperature. Then, add 2-hydroxyethyl methacrylate 36 201040233

6, by the synthesis example " found all gas (four) desert generation isobutyric acid derivative Jg' under a nitrogen stream, 5Gt reaction 2H, a polymer solution. The obtained polymer solution was diluted with methanol, and recrystallized with water/methanol to give a white solid. The solid 3. 〇g was dissolved in MEK4, and a 2% ethylhexanoic acid tin solution (0.2 g amount of MEK solution) was added 2 ig and heated to _. - While introducing dry air into the solution, 4.66 g of MEK solution (50% by mass) of 2% propylene ethyl ethyl isocyanate was added dropwise, and the reaction was carried out for 1 hour, and then diluted at 8 (TC reaction for 4 hours) and then diluted with MEK to obtain 40% by mass MEK solution of the fluoropolymerizable polymer (1). Here, when the molecular weight of the fluorine-containing polymerizable polymer (1) is measured by the 帛Gpc method, the number average molecular weight is 9,100' and the weight average molecular weight is ι〇5〇. Lβ The NMR spectrum of the fluorinated polymerizable polymer (1) obtained in Example 1 is shown in Fig. 2, and the GPC is shown in Fig. 2. Here, the peak near 1.2 ppm and 2. lppm of the lH_NMR spectrum is The peak of the residual solvent. (Example 2) C) In a reaction vessel purged with nitrogen, MEK 7.6 g, 2, 2, - 〇疋 0.559 g, and cuprous chloride 0177 g were added and allowed to stand at room temperature. % minutes off. Then, 2.76 g of 2-hydroxyethyl methacrylate was added to obtain 2.96 g of a wholly-depleted polyacid-polybutyric acid-derived derivative from the synthesis example, and reacted at 5 ° C for 21 hours under a nitrogen stream to obtain a polymer solution. . The obtained polymer solution was diluted with decyl alcohol and reprecipitated with water/methanol to give a white solid. 3.0 g of this solid was dissolved in MEK 4.0 g, and 2.1 g of a 2-ethylhexanoic acid tin solution (〇, 2 parts by weight of MEK solution) was added and the temperature was raised to 6 〇〇c. While introducing dry air into the solution, a MEK solution of 2-propenyloxyethyl isocyanate was added dropwise 37 201040233 (50% by mass) 3.74 g, and the reaction was carried out! Hour, further at 8 〇t: reaction for 4 hours, and then diluted with MEK to obtain 4 〇 mass of the fluoropolymerizable polymer (2); the molecular weight of the fluoropolymerizable polymer (7) was determined by the glutamine solution by the glutamine solution. The number average molecular weight was 6,200 and the weight average molecular weight was 7,7〇〇. The 1H-NMR chart of the fluorine-containing polymerizable polymer (2) obtained in Example 2 is shown in Fig. 3, and the GPC chart is shown in Fig. 4. Here, the peak near 1.2 ppm and 2.1 ppm of the 丨H_NMR chart reading is the peak of the residual solvent. (Comparative Example 1) 69 parts by mass of decyl isobutyl ketone (hereinafter referred to as MIBK) as a solvent was added to a glass flask equipped with a scrambler, a thermometer, a cooling tube, and a dropping device, while nitrogen gas was used. Mixing under the flow, while raising the temperature to 105 C, then, the mass of the sulphuric acid-containing S 曰 40 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 质量 质量 质量 质量 质量 质量 质量 质量 质量 质量 质量 质量 质量 质量 质量 质量 质量Part and operation κ 69 parts by mass of the monomer solution formed by mixing 137 parts by mass, from a radical polymerization initiator (t-butylperoxy-2-ethylhexanoic acid vinegar) 34 parts by mass and MIBK 22.5 negative s 9 parts by mass of the polymerization initiator solution formed by mixing were placed in separate dropping devices, and while maintaining the inside of the flask, the mixture was dropwise added over 3 hours. After the completion of the dropwise addition, 232.7 parts by mass of a polymer solution was obtained at ι〇5 (: 1 Torr). CH2=CH-(i〇-CH2CH2CeFl7, adding p-methoxyphenol as a polymerization inhibitor, As a carboxylic acid 81 catalyst, 5 parts by mass of tin octoate G.G., while maintaining 60 in the air stream. (:, while using], ★ Techno was added dropwise with 2-propene oxiranyl ether for 1 hour. Acid S is intended to be 3 1.2 parts by mass. Drips α *** 4, /&, after the summer slicing is added, "ot stir for 1 hour, then 38 201040233, then warm to 80 ° C and stir for 10 hours, thereby proceeding As a result, it was confirmed by the IR spectrum measurement that the isocyanate group disappeared. Then, a part of the solvent was distilled off under reduced pressure to obtain a 40% by mass MIBK solution of the fluorine-containing polymerizable polymer (3). Here, the fluorine-containing polymerization was measured by GPC. The molecular weight (polystyrene-converted molecular weight) of the polymer (3), the number average molecular weight was 3,000, the weight average molecular weight was 7,000, and the maximum molecular weight was 40,000. [Measurement of the number average molecular weight and the weight average molecular weight] In the present invention Medium average molecular weight (Μη) The weight average molecular weight (Mw) and the molecular weight distribution are measured by GPC under the following conditions: Further, the number average molecular weight (??) and the weight average molecular weight (Mw) are values in terms of standard polystyrene. "HLC-8220 GPC" manufactured by Cao Co., Ltd., Pipe column: "HHR-H" (6.0mm ID x4cm) made by Tosoh Corporation + "TSK-GEL GMHHR-N" manufactured by Tosoh Corporation (7.8mm IDx30cm) + "TSK-GEL GMHHR-N" (7.8mm IDx30cm) manufactured by Tosoh Corporation + "TSK-GEL GMHHR-N" (7.8mm IDx30cm) manufactured by Tosoh Corporation TSK-GEL GMHHR-N" (7.8mm IDx30cm) Detector: ELSD ("ELSD2000" by Alltech) Data processing: "GPC-8020 Type II data analysis 39 201040233 4.30 version" made by Tosoh Corporation

Measurement conditions: column temperature 40 ° C Development solvent Tetrahydrofuran (THF) Flow rate 1.0 ml / min Hydrogen. South sample: A sample (1 〇 〇 β 1) obtained by passing a microfilter into a four solution of 丨〇 mass % in terms of resin solids. Standard sample: According to the above-mentioned "GPC_8G2() π-type f-plate measurement manual, the following early-dispersed polystyrene (early-dispersed polystyrene) U having a known molecular weight of 4·3〇* is known. "Α-500" manufactured by Tosoh Corporation "“-500" manufactured by Tosoh Corporation "Α-2500" manufactured by Tosoh Corporation "Α_5〇〇〇" manufactured by Tosoh Corporation "Fj" manufactured by Tosoh Corporation "F-2" "F_4" manufactured by Tosoh Corporation, "F_1〇" manufactured by Tosoh Corporation "F-2" manufactured by Tosoh Corporation "F-40" manufactured by Tosoh Corporation Tosoh Corporation "F-80" "F-128", manufactured by Tosoh Corporation, "F-288" manufactured by Tosoh Corporation, "F-55", [containing fluorine-containing polymerizable polymer, / 201040233 Preparation of Performance Line Hardening Composition] (Examples 3 to 4, Comparative Examples 2 to 3)

5 parts by mass of a non-yellowing urethane acrylate, 5 parts by mass of pentaerythritol hexaacrylate, 25 parts by mass of butyl acetate, and a photopolymerization initiator (manufactured by Ciba Specialty Chemicals Co., Ltd.) 5 parts by mass of "IRGACURE 184,", hydroxycyclohexyl phenyl ketone), 54 parts by mass of toluene, 1 part of 2-propanol oxime, 25 parts by mass of ethyl acetate, and 28 parts by mass of propylene glycol monomethyl ether were uniformly homogenized. 'According to the active energy ray-curable composition as a matrix, 625 parts by mass of the active energy ray-curable composition as the matrix was added'. The content contained in Examples i to 2 and Comparative Example t was added: Polymerizable polymerization 2.5 parts by mass of a solution of 40% by mass of the product was uniformly mixed to obtain an active energy ray-curable composition containing a fluorinated polymerizable polymer = otherwise 'the gas-containing polymerization obtained by Example 丨 2 and Comparative Example i was used: The active energy ray-curable composition of the polymer was used as Comparative Example 2 as Example 34 and Comparative Example 3, respectively, in which an ultraviolet curable composition was prepared without adding a fluorine-containing polymerizable polymer and only a matrix. polymerization Evaluation of the compatibility of the polymer] The appearance of the active energy ray-curable composition as described above was visually observed to evaluate the compatibility of the fluorine-containing polymerizable polymer. A: Transparent B: turbidity C: Component separation was found. : Evaluation of active energy ray-cured warfare materials by polymerizable polymer] 201040233 (Production of sample for 5 parity) Using the above-mentioned active fluorene-containing polymerizable copolymer-containing active ceramsite-line-curable composition After coating on a polyethylene terephthalate (PET) film (thickness 188/m) with a bar coater (N〇.丨3), it was dried in a 6 〇 dryer. After allowing to stand for 5 minutes, the solvent was volatilized, and it was cured by using an ultraviolet curing device (high-pressure mercury lamp under a nitrogen atmosphere, ultraviolet irradiation amount: 〇kJ/m2) to prepare a coating film. Further, as Comparative Example 2, the content was not added. A coating film was prepared in the same manner as the active energy ray-curable composition of the fluoropolymerizable polymer. The coated film was allowed to stand at room temperature for one day, and then the following contact angle measurement and evaluation were carried out to prevent the adhesion of dirt. Sexual evaluation. On the coated surface of the coating film, a line was drawn with a felt pen (a large blue universal pen manufactured by Teishi Chemical Industry Co., Ltd.), and the adhesion state of the blue ink was observed to evaluate the antifouling property (anti-fouling adhesion, dirt). In addition, after ultraviolet curing, the film was subjected to a dipping treatment for 7 minutes in a strong aqueous alkali solution (2 m〇1/1 KOH aqueous solution) of 〇, and washed with pure water, and 100%. After drying at room temperature for X3 minutes, the film was allowed to cool at room temperature, and the anti-fouling property (anti-fouling adhesion and soil wiping property) was also evaluated using a felt pen on the film after cooling. In Table 1. Table contains IL polymerizable polymer (1) (2) Compatibility A: Evaluation result of antifouling adhesion VII> Evaluation result of scale and resolvability Strong film AA strong aqueous solution before aqueous solution treatment Membrane after treatment of membrane AA alkaloid aqueous solution after treatment A AA AA A A\ Δ _c_____ —c_____ —c_____ —___c B AA AB — c

Example 3 Example 4 - Comparative Example 2 Comparative Example 3 42 201040233 (Evaluation criteria for anti-fouling adhesion) AA: The antifouling property was the best, and the ink was separated into a spherical shape. A: The ink is not separated into a spherical shape to form a linear alienation (the line width is less than 50% of the width of the felt tip). B: The ink forms a linear detachment, and the line width is 50% or more and less than 100% of the width of the felt tip. C. / The ink element is not alienated' to form a clear depiction on the surface. (Evaluation Criteria for Dirt Erasing) 〇 "After the "anti-fouling adhesion" test, the cotton paper was used to wipe with a load of 1 kg according to the following criteria: A: - The ink was completely removed after the wiping. : 2~1 The ink was completely removed after the rubbing. C: The ink was not completely removed by one rubbing operation. From the evaluation results of Examples 3 and 4 shown in Table 1, it was found that the coating was used. The active energy ray-hardening composition of the fluorinated polymerizable polymers (1) and (2) of the invention has high antifouling adhesion and soil repellency on the surface of the film after ultraviolet curing. Even in the case of the treatment with the strong alkali water, the performance of the film was not lowered. On the other hand, in Comparative Example 2 in which the fluorine-containing polymerizable polymer was not used, it was found that the surface of the film after the active energy ray-curable composition was applied and ultraviolet curing was performed. Antifouling adhesion and soil release property are not. In addition, for Comparative Example 3 using a gas-containing polymerizable polymerization different from the gas-containing polymerizable polymer of the present invention, the prepared active energy Wire hardening There is a slight turbidity in the composition, and the compatibility is insufficient. Moreover, the surface of the film after the application of the active energy ray hardening residue 43 201040233 and ultraviolet curing is resistant to dirt adhesion, but the dirt removal property is insufficient. After the treatment with strong alkaline water, these properties are reduced. [Simplified illustration]

Fig. 1 is an iH-NMR chart of a fluorine-containing polymerizable polymer produced in Example 1. 2 is a Gpc chart of a fluorine-containing polymerizable polymer produced in Example 1. FIG. Fig. 3 is a chart of a fluorine-containing polymerizable polymer produced in Example 2. 4 is a Gpc diagram of a fluorine-containing polymerizable polymer produced in Example 2. FIG. [Main component symbol description] None 44

Claims (1)

201040233 VII. Patent application scope: 1. A fluorine-containing polymerizable polymer, which is obtained by the following method: having a carboxyl group selected from the group consisting of a trans group, an isocyanate group, an epoxy group, and a carboxyl group; The polymerizable unsaturated monomer (B) having at least one reactive group in the acid and the acid anhydride is a monomer component having an essential component and a compound having a functional group capable of generating a radical at both ends of the poly(perfluoroalkyl ether) chain The both ends of (A) are polymerized to obtain a polymer (C), and some or all of the reactive groups of the polymer (c) are reacted with the reactive group to form a bond C. The reaction of the compound (d) selected from the group consisting of a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a halogenated carboxylic acid, and an acid anhydride, and a polymerizable unsaturated group is carried out. A fluoropolymerizable polymer, wherein the functional group capable of generating a radical of the compound (A) is an organic group having a halogen atom, an organic group having an alkylhydrazine group, an organic group having a dithioester group, and having Oxyl An organic group, or of an organic group having an azo group. 3. The fluoropolymerizable polymer according to the first aspect of the patent application, in which ϋ' the compound (Α) has a radical-generating functional group having an organic group of a halogen atom and having an alkylene group. An organic radical or a dithioester group, and a polymerization method in which the monomer (B) is an essential monomer component and polymerized with the compound (A) is a living radical polymerization. 4. The fluoropolymerizable polymer according to claim 3, wherein the living radical polymerization is carried out by a polymerization initiator, a transition metal compound, and a ligand having a ligand and a transition metal compound. Atom-moving radical polymerization carried out in the presence of a compound of a substituent. The active energy ray-curable composition of the present invention is characterized in that it contains a fluorine-containing polymerizable polymer according to any one of claims 1 to 4. A hardened material which is formed by hardening an active energy ray-curable composition of claim No. 7. An article characterized by having a hardened coating film of the active energy line hardening composition of the patent application range. Eight, the pattern: (such as the next page) 46