TW201035128A - Radical-containing polymerization copolymer, activation energy curable resins composition using it and process for preparing radical-containing polymerization copolymer - Google Patents

Abstract

The present invention is to provide a fluoro-containing radical polymerization copolymer which is obtained by reacting compound (B) with part or full reactive groups contained in copolymer (A), wherein the said copolymer (A) is obtained by copolymerization of necessary monomer components which comprises a radical polymerization unsaturated monomer (a1) containing C1-6 fluoroalkyl group (the said alkyl group also comprises that has a ether bond by means of oxygen atom), and a radical polymerization unsaturated monomer (a2) having reactive group. The said compound (B) comprises a functional group which a bond can be formed by reacting with the said reactive group, and a radical polymerization unsaturated group. It is characterized in that the ratio of weight average molecular weight (Mw) and number average molecular weight (Mn), i.e. dispersity (Mw/Mn) is 1.5 or less. The said fluoro-containing radical polymerization copolymer can be used as a surface modifier having high performances of water-repellent and oil-repellent.

Description

[Technical Field] The present invention relates to a fluorine-containing radical polymerizable copolymer having water repellency and oil repellency and a method for producing the same. Also related to an active energy ray-curable resin composition containing the copolymer. [Prior Art] A compound having a fluoroalkyl group has both water repellency and oil repellency, and thus water repellency and oil repellency can be imparted after application on the surface of the article. Therefore, \ ) a compound having a fluoroalkyl group is used for imparting antifouling properties to a liquid crystal display (hereinafter referred to as "LCD") or a film of the outermost surface of a plasma display. A compound having a fluoroalkyl group is a fluoroalkyl group having a low surface tension property. Therefore, for a composition having no fluoroalkyl group, a fluoroalkyl group is moved during the coating of the composition by adding a small amount of a surface modifying agent. The surface allows the composition to exert water and oil repellency. 〇 In particular, in the hard coat layer for a polarizing plate of an LCD, a surface modifier which is required to have an antifouling property, and a case where a fluorine-containing surface modifier having a radical polymerizable property is added, in a hard coat layer In the coating film, the surface modifying agent is covalently bonded to greatly improve the durability (for example, see Patent Document 1). Recently, in the manufacture of color filters for LCDs, an ink jet method for producing a lower cost manufacturing method has been developed in comparison with the conventional lithography method. In the inkjet method, first, a black matrix (hereinafter abbreviated as "BM") is formed on the substrate by a lithography method, and then the ink in the frame formed by the BM is injected into the frame by the inkjet method so that the ink 201035128 does not overflow. Ink. At this time, in order to prevent the ink from adhering to the upper surface of Bm (the surface parallel to the substrate), that is, in order to prevent the ink from overflowing from the inside of the frame, it is necessary to impart water repellency to the BM to eject the ink. Necessary. As a method of imparting the liquid repellency, a method of imparting liquid repellency by forming a BM by a lithography method and reacting a fluorine-based gas on the surface of the BM by a plasma method can be employed. However, in this method, in addition to the upper surface of the BM which is required to have a liquid repellency of 0, the side of the BM is liquefied, thereby causing a problem that the ink cannot adhere to the wall surface of the BM. Thus, the thickness of the ink layer in the vicinity of the BM wall surface becomes extremely thin compared to the center portion of the frame, and there is a problem that color unevenness occurs due to the difference in the thickness of the ink in the frame. Here, the method for solving this problem is to add a radically polymerizable fluorine-based surface modifier to the BM photoresist solution before the formation of the BM by the negative lithography method, and the fluorine-based surface modifier is The effect of surface segregation is to first impart liquid repellency to the top surface of the BM before hardening, and to fix the liquid-repellent agent by radical polymerization by ultraviolet irradiation, and then to perform etching treatment by a developing solution on the wall surface. Form a BM that is not liquid-repellent. As a result, since the ink can also adhere to the wall surface of the BM, the thickness of the ink layer in the vicinity of the BM wall surface can be made the same as that of the center portion, and the ink is liquefied on the B Μ surface, so that the ink can be prevented from overflowing. In such a radically polymerizable fluorine-based surface modifier, a polymer comprising a polymerized unit having at least one alkyl group having at least one hydrogen atom substituted with a fluorine atom and having 20 or less carbon atoms, and a polymer unit having an ethylenic double bond is proposed. The printing ink of 201035128 is prepared (for example, refer to Patent Document 1). However, 'generally, the more the number of carbon atoms of the fluoroalkyl group, the higher the water repellency and the oil repellency, and the dial ink is, for example, a (meth)acrylic acid having a fluoroalkyl group having 8 or more carbon atoms. When the monomer is used as a raw material, it has sufficient liquid repellency. When a (meth)acrylic monomer having a fluoroalkyl group having 6 or less carbon atoms is used, the liquid repellency is insufficient. Here, in recent years, it has been found that a compound having a perfluoroindenyl group having 8 carbon atoms is decomposed to produce perfluorooctane sulfonic acid (PFOS) or perfluorooctanoic acid having high environmental and bioaccumulating properties ( PFOA). Further, it is understood that a compound having a perfluoroalkyl group having a larger number of carbon atoms of 8 produces a compound having higher environmental and bioaccumulation properties. Therefore, in the market, it is desired to use only a compound which is structurally incapable of producing a compound having a fluoroalkyl group having 6 or less carbon atoms, and to obtain a compound having as few carbon atoms as possible. However, when the number of carbon atoms of the fluoroalkyl group is small, it is not possible to exhibit sufficient water repellency and oil repellency, and it is contained in a fluorene radical polymerizable fluorine-based surface modifier having a fluoroalkyl group having 6 or less carbon atoms. The water repellency and oil repellency of the radical polymerizable fluorine-based surface modifier having a fluoroalkyl group having 8 or more carbon atoms are not exhibited. [PRIOR ART DOCUMENT] Patent Document 1 Patent Publication No. 2007-246696 Patent Document 2 International Publication No. WO2004/042474 SUMMARY OF INVENTION Technical Problem The subject to be solved by the present invention is to provide a The fluorine radical polymerizable copolymer and the method for producing the same, wherein the fluorine-containing radically polymerizable copolymer can be used as a surface modifying agent having a fluoroalkyl group having 6 or less carbon atoms, and can be used as a carbon atom. A water-repellent and oil-repellent surface modifier having a surface modification agent of 8 or more fluoroalkyl groups or higher. Further, an active energy ray-hardening resin composition using the fluorine-containing radical polymerizable copolymer is provided. Means for Solving the Problem As a result of intensive studies by the present inventors, it has been found that a radically polymerizable unsaturated monomer having a fluoroalkyl group having 6 or less carbon atoms and a radical polymerizable group having a reactive group are found. A copolymer obtained by copolymerizing an unsaturated monomer as a necessary monomer component, which is a copolymer having a specific molecular weight and a degree of dispersion, and a fluorine-containing free radical obtained by introducing a radically polymerizable unsaturated double bond by using the above-mentioned reactive group The base polymerizable copolymer is a surface modifier which is excellent in antifouling property and liquid repellency, and has completed the present invention. That is, the present invention relates to a fluorine-containing radically polymerizable copolymer by using a fluoroalkyl group having 1 to 6 carbon atoms (except that the above alkyl group also contains an ether bond via an oxygen atom) a copolymer (A) obtained by copolymerizing a radically polymerizable unsaturated monomer (a1) with a radically polymerizable unsaturated monomer (a2) having a reactive group as a necessary monomer component to have a reaction with the above The compound (B) which forms a bonded functional group and a radically polymerizable unsaturated group, and the reactive group which is a part or all of the copolymer (A), which is obtained by the reaction of 201035128, is characterized by The ratio of the weight average molecular weight (M w ) to the number average molecular weight (Μη), that is, the degree of dispersion (Mw/Mn) is 1 _5 or less. Furthermore, the present invention relates to a method for producing a fluorine-containing radically polymerizable copolymer, and further relates to an active energy ray-curable resin composition containing the fluorine-containing radical polymerizable copolymer and a cured product thereof. Advantageous Effects of Invention The fluorine-containing radically polymerizable copolymer of the present invention does not produce a carbon atom number of a compound having high environmental and bioaccumulative properties such as perfluorooctane sulfonic acid (PFOS) or perfluorooctanoic acid (PFOA). The above fluoroalkyl group is thus a safe product having low environmental and biological effects. Further, under the use of the fluorine-containing radical polymerizable copolymer of the present invention, water repellency and oil repellency as surface modifiers can be imparted to all articles. Further, the active energy ray-curable resin composition containing the fluorine-containing radically polymerizable copolymer of the present invention can be used for a protective film requiring antifouling properties, or used in a plane such as a liquid crystal display, a plasma display, or an organic EL display. D display anti-reflection film, anti-glare film, etc. A coating material for a protective film for a polarizing plate of a liquid crystal display represented by a triacetyl cellulose (TAC) film; a coating material for BM used for a filter of a liquid crystal display, an ink or a black photoresist; Hard coating materials such as control panels, mobile phone frames, liquid crystal displays for mobile phones, optical components such as optical fiber cladding materials, optical lenses, and optical waveguides. In particular, in the negative resist liquid of the material for forming the BM of the filter for LCD manufactured by the ink jet method, the fluorine-containing radical polymerizable 201035128 copolymer of the present invention is formulated as a surface modifier. The surface segregation action of the fluorine-containing radical polymerizable copolymer allows the fluorine-containing radical polymerizable copolymer to be partially deposited on the surface of the coating film, that is, the BM, and the liquid-repellent property is imparted only to the BM, and the BM wall surface is not imparted. The liquid repellency can be used as a surface on which the ink can be well adhered, and thus a color filter for LCD having uniform pixels which prevents ink from overflowing and having no color unevenness can be produced by the ink jet method. [Embodiment] The copolymer (A) used in the present invention is a radical polymerizable unsaturated monomer (a1) having a fluoroalkyl group having 1 to 6 carbon atoms and a radical polymerization having a reactive group. The unsaturated monomer (a2) is obtained as a copolymerization of a necessary monomer component. Among them, a fluoroalkyl group is one in which one or three fluorine atoms are bonded to one or two or more of the linked functional groups. Further, those in which the carbon atom in the fluoroalkyl group is an unsaturated bond are also included in the so-called fluoroalkyl group of the present invention. Further, a carbon atom in the fluoroalkyl group is bonded via an ether bond of an oxygen atom, and is also included in the fluoroalkyl group referred to in the present invention.

Q Examples of the monomer (al) include a monomer represented by the following formula (1).

(In the above formula (1), R represents a hydrogen atom, a fluorine atom, a methyl group, a cyano group, a phenyl group, a phenyl group or a -CnH2n-Rf' (n represents an integer of 1 to 8, and Rf represents the following formula) (Rf-Ι) to (Rf-7), R' represents a group of any one of the following formulae (R'q) to (R'-ΙΟ), and Rf represents the following formula ( (ff - Ι) to (Rf_7) base); 201035128 - OCnH2n - (R, -1> - och2ch2och2 - (R, -2) 0 - 0CH2CH2NHC0 - CnH2n - (R' -3) OH | OCH2CHCH2O-CnH2n-(R'-4) GH 1 OCH2CH*~CnH2n- (Rs -5) 0 CH2OCnH2flRr —OCh^CHsNHC^O - CHCH2〇CnH2n—(R* -6) CH2OCnH2nRr —〇-CHCH2OCnH2n— (R' -7) CnH2n+1 -〇CmH2mNS02- (R* -8) ^η^2η+1 (R' -9) 〒nH2n+1 -OCmH2mNCO- (R' -10) Table m 6) (The above formula (R η in '-l), (R'-3), (R'-5), (R'-6), and (R'-7) indicates an integer from 1 to 8, above formula (R'-8) , (R'-9) and (R'-10) represent an integer from 1 to 8, η represents an integer from 0 to 8, and Rf'' in the above formula (R' and (R'-7)) (Rf-Ι) to (Rf-7) ); -10-201035128

—C„F2n+1 (Rf-l) —C„F2nH (Rf-2) ^n^2n-1 (Rf-3) —Cnp2n-3 (R f -4) CmF 2m〇CnF2n^F3 (R f -5) CmP2m〇CnF2nOCpF2pCF3 (Rf-6) - CF2OC2F4OC2F4OCF3 (Rf-7) (n in the above formulas (Rf-1) and (Rf-2) represents an integer from i to 6, in the above formula (Rf-3) The η is not an integer of 2 to 6, and η in the above formula (Rf_4) represents an integer of 4 to 6, wherein m in the above formula (Rf-5) represents an integer of 1 to 5, and η represents an integer of 〇 to 4 'And the sum of 1 and η is 1 to 5, m in the above formula (Rf-6) represents an integer from 0 to 4, η represents an integer from 1 to 4, and P is an integer from 〇❹ to 4' and 111, The sum of 11 and 1) is 1 to 5). Among the monomers represented by the above formula (1), those having a fluoroalkyl group having 4 to 6 carbon atoms are preferred because they have excellent liquid repellency. More specific examples of the preferred monomer (al) include, for example, (al-Ι) to (al-15). -11- II CH2=C—C—o—CH2CH2-(CF2)3-CFj CH, [a 1 — 1) II CH2=(j:—c—〇-CH2CH2-(CF2)s-CF; ch3 3 -2) ^ 0 CH2〇-CH2CH2-(CF2)3-CF3 CH2=C—C—OCH2CH2NHC〇-CHCH2〇-CH2CH2-(CF2)3-CF3 iH3 (a 1 — 3) 0 CH2〇-CH2CH2-( CF2)5-CF3 CH2=C—c—OCHzCHzNHCO-CHCHaO-CHaCHa-iCFzis-CFa (a 1 -4) CHj 〒3h7 CH2=C—C-0CH2CH2NS02—<CF2)3-CF3 (a 1-5) Ch3

\\ II CH2=C—C—OCH2CH2NHC〇-CH2CH2-(CF2)n-CF3 (a 1-6) CH3

Ϊ H CH2=C—C—OCH2CHCH20—CH2CH2—(CF2)n-CF3 (a 1 - 7) CH, sCH—C— Ό—CH2CH2-(CF2}a-CF3 (a 1-8) CH2=CH —c—o—CH2CH2-(CF2)5-CF3 (a 1-9) 〇0 CH2〇-CH2CH2-(CF2)3-CF3 CH2=CH—fi—0CH2CH2NH&0-CHCH2〇-CH2CH2-(CF2h- CF3 (a 1 - 1 0) (j) O CH2〇-CH2CH2-(CF2)6-CF3 CH2=CH—C—OCH2CH2NHci〇-iHCH20-CH2CH2-{CF2)5-CF3 (a 1-1 1) ( a 1 - 1 2)

II CH2=CH-C—OCH2CH2NHC〇-CH2CH2-(CF2)n-CF3 (a 1-1 3)

H CH2=CH—c—OCH2CHCH2〇-CH2CH2-(CF2)n-CF3 (al — l 4) 〇(CH2)3CH3 a 1-1 5) CH2=CH-C—N—CH2CH2-(CF2) n-CF3 201035128 (n in the above formulas (al-6), (al-7), (ai-i3), (al-14), and (al-13) represents 3 or 5). Among the above-exemplified monomers (al), a monomer containing a methacryl group is preferred because it is excellent in living radical polymerizability. Further, it is also particularly preferable to (al-Ι) to (al-4). Further, the monomer (al) may be used singly or in combination of two or more. Further, in the monomer (ai) exemplified above, when a monomer having a reactive group such as a hydroxyl group such as a monomer (a 1-7) or (al-14) is used, the monomer described later can also be used ( A2) At this time, the polymer of the present invention can also be obtained without using the monomer (a2). Examples of the radically polymerizable unsaturated monomer (a2) having the above reactive group include a radical polymerizable unsaturated monomer having a reactive group such as a hydroxyl group, an isocyanate group, an epoxy group or a carboxyl group; A carboxylic acid halide or a carboxylic acid anhydride having a radical polymerizable unsaturated group. Specific examples of the monomer (a2) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and (methyl). 2-hydroxybutyl acrylate, 4-hydroxybutyl (meth) acrylate, 1,4-cyclohexane dimethanol 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 Ethyl ester, 2-(methyl) propylene oxime oxyethyl 2- hydroxyethyl phthalate, terminal hydroxyl group-containing lactone modified (meth) acrylate and other monomers having a hydroxyl group; 2-(methyl) propylene a monomer having an isocyanato group such as a methoxyethyl isocyanate or a 2-(2-(methyl) propylene oxyethoxy)ethyl isocyanate; a glycidyl (meth) acrylate, 4-hydroxybutyl acrylate Ester glycidyl ether, etc.-13- 201035128 Monomer having epoxy group; (meth)acrylic acid, 2-(methyl)propyl styrene ethyl succinate, 2-(methyl) propylene oxime Ethyl ester A monomer having a carboxyl group such as itaconic acid; a monomer of a carboxylic acid halide such as (meth)acrylic acid chloride; a monomer of a carboxylic anhydride such as maleic anhydride. In the present invention, "(meth)acrylic acid" means one or both of methacrylic acid and acrylic acid, and "(meth)acrylylene" means one or both of a methacryl fluorenyl group and an acryl fluorenyl group. "(Meth)acrylate" means either or both of methacrylate and acrylate. q In the monomer (a2) exemplified above, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (methyl) 2-hydroxybutyl acrylate, 4-hydroxybutyl (meth)acrylate, N-(2-hydroxyethyl)(meth)acrylamide, glycerol mono(meth)acrylate, (meth)acrylic acid 2 -Hydroxy-3-phenoxypropyl ester, 2-(meth)acryloyloxyethyl isocyanate, glyceryl methacrylate, 4-hydroxybutyl acrylate glycidyl ether, (meth)acrylic acid It is preferred that the radically polymerizable group is efficiently introduced into the obtained copolymer and the obtained resin is excellent in moisture resistance and chemical resistance after curing. Among them, the monomer containing a methacryl group is particularly preferable in that it is excellent in living radical polymerizability. Further, the monomer (a2) may be used alone or in combination of two or more kinds as long as the reactivity is not inhibited. In the monomer which is a raw material of the copolymer (A), in addition to the above monomer (a1) and monomer (a2), another monomer (a3) copolymerizable with the monomers may be used. Examples of the monomer (a3) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, and (methyl). Isobutyl acrylate, n-amyl (meth)acrylate, (methyl) -14- 201035128 n-hexyl acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, (meth) acrylate 2 -ethylhexyl ester, decyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate And other alkyl (meth)acrylates: styrene, α-methylstyrene, p-methylphenylethyl, p-methoxyphene, etc., aromatic vinyls: maleimide, A Kamalimide, ethyl maleimide, propyl maleimide, butyl maleimide, hexylmalamine, octyl maleimide, dodecane Kamalimide, stearyl imidamine, phenyl maleimide, cyclohexylmaleimine, etc., maleimide, 3-(trimethoprim) a (meth) acrylate monomer containing a methoxyalkyl group or an ethoxylated alkyl group such as an alkyl)propyl (meth) acrylate or a 3-(triethoxy decyl) propyl (meth) acrylate; A (meth) acrylate monomer containing a polyoxycarbonyl chain such as a polydimethyl siloxane chain. These monomers (a3) may be used singly or in combination of two or more. Here, the method for producing the copolymer (A) may, for example, be a method of subjecting the above monomeric bodies (al) to (a3) to living radical polymerization. Generally, in living-radical polymerization, a dormant species (d 〇rmantspecies) which protects the living polymerization end by atom or atomic group generates reversible free radicals and reacts with the monomer into fT, thereby obtaining a polymer having a very narrow molecular weight distribution. . Examples of the living radical polymerization include, for example, atomic mobile radical polymerization (hereinafter abbreviated as "ATRP"), reversible addition-cleavage type radical polymerization (RAFT), and free radical polymerization (NMP) with a nitric oxide. , using free radical polymerization (TERP) of organic hydrazine. When the above copolymer (A) -15 to 201035128 is produced by the living radical polymerization, a copolymer having an extremely narrow molecular weight distribution can be obtained. Among these methods, there is no particular limitation on the method to be used, and the above-mentioned ATRP is preferable in terms of ease of control and the like. The ATRP is polymerized by using an organic halide or a sulfonium halide as a starting agent and using a metal complex composed of a transition metal compound and a ligand as a catalyst. As the polymerization initiator used in the above ATRP, an organic halide can be used. Specifically, for example, 1-phenylethyl chloride, 1-phenylethyl bromide, chloroform, carbon tetrachloride, 2-chloropropionitrile, α, "'-dichloroxylene, α, α '- 〇 dibromo xylene, ter (α-bromomethyl) benzene, 2- to halogenated carboxylic acid having 1 to 6 carbon atoms (eg 2-chloropropionic acid, 2-bromopropionic acid, 2-chloroisobutyric acid) 2 -Bromoisobutyric acid, etc.) A compound having 1 to 6 carbon atoms: a base ester or the like. Among these, it is preferable that the 2-halogenated carboxylic acid having 1 to 6 carbon atoms has a carbon number of 1 to 6, and specific examples thereof include methyl 2-chloropropionate and 2 - Ethyl chloropropionate, methyl 2-bromopropionate, ethyl 2-bromoisobutyrate, etc. The transition metal compound used in the above ATRP is represented by Mn + X η. The Mn + of the transition metal may be selected from From Cu+ 'Cu2+ 'Fe2+, F e3 +, Ru 2 + , Ru3+, Cr2 " ' Cr3 + ' Mo° ' Mo+, Mo2+, Mo3 + , W2+, W3 ; + , 1 R.h3+ ' Rh4 +, Co f , Co2+, Re2+, Re3 + , Ni0 - * Ni+ > Mr 13H Bu, Mn4+, V2 +, V3 +, Zn+, Zn2+, Au+ 'Au2+, Ag+ and Ag; Further, X may be selected from a halogen atom, an alkoxy group having 1 to 6 carbon atoms, (S〇4)l/2, (P〇4)l/3, (HP〇4)l/2, ( Η2ΡΟ4), trifluoromethanesulfonate, hexafluorosulfonate, methanesulfonate, arylsulfonate (benzenesulfonate, toluenesulfonate, etc.), SeR1, CN and R2COOH -16- 201035128 &群" where 'R1 represents an aryl group, a linear or branched alkyl group having from 1 to 20 carbon atoms, preferably an alkyl group having from 1 to 1 Å; R2 represents a hydrogen atom; A linear or branched alkyl group having 1 to 6 carbon atoms (preferably a methyl group) substituted 1 to 5 times (preferably 1 or 3 times by fluorine or chlorine substitution). Tired and 'η denotes the formal charge on the metal, which is an integer from 0 to 7. The transition metal is not particularly limited, and preferred examples thereof include transition metals of Groups 7, 8, 9, 10, and 11, and more preferably, for example, copper of valence, copper of 1 valence, and 2 valence钌, 2 price iron, 2 price nickel. The compound which can be coordinately bonded to the above transition metal may, for example, be a compound having one or more nitrogen atoms, oxygen atoms, phosphorus atoms or sulfur atoms which can be coordinated with a transition metal via a sigma bond; a compound having two or more carbon atoms coordinated by a 7-position bond; a compound which can be coordinated to a transition metal via a μ bond or a bond. Specific examples of the compound capable of coordinating with the above transition metal are those in which the transition metal is monovalent copper, and examples thereof include 2,2'-bipyridine and a derivative thereof, 1,10-morpholine and A polyamine such as a derivative, tetramethylethylenediamine, pentamethyldiethylenetriamine or hexamethylgin(2-aminoethyl)amine. When the above transition metal is a divalent ruthenium, for example, triphenylphosphine, tributylphosphine, tricyclohexylphosphine, cyclooctadiene, benzene, anthracene-cymene, norbornadiene, 2, 2 may be mentioned. '-bibipyridine, 1,1 〇-morpholine and the like. Further, when the transition metal is a divalent iron, examples thereof include triphenylphosphine and triazacyclononane. In the production of the above copolymer (Α), it is preferred to use a solvent. Examples of the solvent to be used include ester solvents such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether B-17-201035128 acid ester, diisopropyl ether, dimethoxyethane, and diethylene glycol. An ether-based solvent such as methyl ether; a halogen-based solvent such as dichloromethane or dichloroethane; an aromatic solvent such as toluene or xylene; methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; A ketone solvent; an alcohol solvent such as methanol, ethanol or isopropyl alcohol; an aprotic polar solvent such as dimethylformamide or dimethyl sulfoxide. Further, the above-mentioned solvent may be used singly or in combination of two or more kinds. The polymerization temperature of the above copolymer (A) at the time of production is preferably in the range of from 20 ° C to 100 ° C. The above copolymer (A) can be produced as a random copolymer or a block copolymer by a production method. When the random copolymer is formed, the monomer (a1) and the monomer (a2) may be carried out in the presence of a polymerization initiator, a transition metal compound, a compound capable of coordinating bonding with the transition metal, and a solvent. Obtained by living radical polymerization. On the other hand, when the block copolymer is formed, the above monomer (a1) or the above monomer (a2) may be used alone in a polymerization initiator, a transition metal compound, a compound which can coordinately bond with the transition metal. And in the presence of a solvent, after the living radical polymerization is carried out, addition of another monomer different from the previously living radically polymerized monomer is carried out, followed by living radical polymerization. Further, when a block copolymer is obtained, if a monomer which has been previously polymerized by living radicals is used as the monomer (a2), the controllability of the molecular weight distribution is high. When the above copolymer (A) is used as a random copolymer, the mass ratio of the above-mentioned monomer (al) relative to the total mass of the copolymer (A) is the point of balance between liquid repellency and compatibility -18 - 201035128 In particular, it is preferably from 20 to 90% by mass, particularly preferably from 30 to 70% by mass. Further, the mass ratio of the above monomer (a2) with respect to the total mass of the copolymer (A) is preferably from 10 to 80% by mass in terms of a balance between liquid repellency and durability. 0 to 70% by mass is particularly good. When the copolymer (A) is used as a block copolymer, the mass ratio of the monomer (a1) of the total mass of the copolymer (A) is proportional to the point of balance between liquid repellency and compatibility. 10 to 80% by mass is preferred, and 20 to 60% by mass is particularly preferred. Further, the mass ratio of the above monomer (a2) with respect to the total mass of the copolymer (A) is preferably from 20 to 90% by mass, and from 40 to 80 in terms of the balance between liquid repellency and durability. The mass % is particularly good. In order to obtain the fluorine-containing radically polymerizable copolymer of the present invention, a part or all of the reactive groups of the copolymer (A) produced by the above method are used, and a functional group having a bond with the above reactive group is formed. And the radically polymerizable unsaturated group (B), the radically polymerizable unsaturated group is introduced into the copolymer (A). The functional group other than the radically polymerizable unsaturated group of the compound (B) can be selected in accordance with the reactive group of the copolymer (A). For example, when the reactive group of the copolymer (A) is a hydroxyl group, the above compound (B) is halogenated with a compound having an isocyanato group and a radical polymerizable unsaturated group or a carboxylic acid having a radical polymerizable unsaturated group. Preferably, the compound is preferably a compound having an isocyanate group and a radical polymerizable unsaturated group for the reason that the release is not required to be removed. Further, when the reactive group of the copolymer (A) is a hydroxyl group, first, a hydroxyl group of the copolymer (A) is reacted with a carboxylic acid anhydride to form a carboxyl group, and the carboxyl group has an epoxy group and a radical polymerizable unsaturated group. The compound -19-201035128 is further reacted as the compound (B), whereby a radical polymerizable unsaturated group can be introduced into the copolymer (A). When the reactive group of the copolymer (A) is an isocyanate group, the compound (B) is preferably a compound having a hydroxyl group and a radical polymerizable unsaturated group. When the reactive group of the copolymer (A) is an epoxy group, the compound (B) is preferably a compound having a carboxyl group and a radical polymerizable unsaturated group. Further, a compound having an isocyanato group and a radical polymerizable unsaturated group or a radical is formed on the secondary hydroxyl group formed by the reaction of the compound having a carboxyl group and a radical polymerizable unsaturated group. The reaction of the carboxylic acid halide of the polymerizable unsaturated group or the radically polymerizable unsaturated group can be further introduced into the copolymer (A). In addition, when the reactive group of the copolymer (A) is an epoxy group, a compound having no radically polymerizable unsaturated group, for example, a functional group having an addition reactivity with an epoxy group such as a carboxyl group a compound which forms a secondary hydroxyl group by reacting an epoxy group of the copolymer (A), and has a compound having an isocyanato group and a radical polymerizable unsaturated group or having a radical ❹ polymerizable property. The carboxylic acid halide of a saturated group is further reacted as the above compound (B), and a radical polymerizable unsaturated group can also be introduced into the copolymer (A). When the reactive group of the copolymer (A) is a carboxyl group, the compound (B) is preferably a compound having an epoxy group and a radical polymerizable unsaturated group. Further, a compound having an isocyanato group and a radical polymerizable unsaturated group or a free radical is formed on the secondary hydroxyl group formed after the reaction of the compound having an epoxy group and a radical polymerizable unsaturated group The carboxylic acid halide of the radically polymerizable unsaturated group is allowed to react as the above compound (B), and the radical poly-20-201035128 hydrophilic unsaturated group can be further introduced into the copolymer (A). Further, when the reactive group of the copolymer (A) is a carboxyl group, even a compound having no radical polymerizable unsaturated group, such as a compound containing an epoxy group, is formed by reacting a carboxyl group of the copolymer (A). a secondary hydroxyl group, and a compound having an isocyanato group and a radical polymerizable unsaturated group or a carboxylic acid halide having a radical polymerizable unsaturated group is reacted as the above compound (B). A radical polymerizable unsaturated group can also be introduced into the copolymer (A). When the copolymer (A) is obtained by using a carboxylic acid anhydride having a radical polymerizable unsaturated group as the radically polymerizable unsaturated monomer (a2) having the above reactive group, the above compound (B) has a hydroxyl group. A compound having a radical polymerizable unsaturated group is preferred. Further, after reacting the compound having a hydroxyl group and a radical polymerizable unsaturated group in the copolymer (A), the resulting carboxyl group is reacted with a compound having an epoxy group and a radical polymerizable unsaturated group. 'The radically polymerizable unsaturated group can also be introduced into the copolymer (A) and the radical polymerizable unsaturated monomer U2 having the above reactive group, if used, has no radical polymerizability. When the copolymer (A) is obtained by a carboxylic acid anhydride having a saturated group, even if the compound which does not have a radical polymerizable unsaturated group is a compound containing a hydroxyl group, the copolymer (A) is reacted to form a carboxyl group, and the hydroxyl group is formed. The compound having an epoxy group and a radical polymerizable unsaturated group is further reacted as the above compound (B), and a radical polymerizable unsaturated group can also be introduced into the copolymer (A). The above compound (B) can be used in the same manner as the above monomer (a2). And -21 to 201035128, in combination, the reactive group of the copolymer (A) is a hydroxyl group (the monomer having a hydroxyl group as the raw material monomer (a2)) and the compound (B) A compound having an isocyanato group and a radical polymerizable unsaturated group is preferred. In particular, a copolymer (A) produced by using 2-hydroxyethyl (meth)acrylate on the monomer (a2) is used as a reaction product of 2-propenyloxyethyl isocyanate as the compound (B). It is better. The amount of the compound (B) to be used is a monovalent (a2) l molar which is a raw material of the above copolymer (A), and it is preferably 0.5 to 1.1, and a radical polymerizable group can be introduced. The point and the point at which the unreacted (B) residue is not made to be 0.9 to 1.0 mol are particularly preferable. When the reactive group of the copolymer (A) is a hydroxyl group, and the compound (B) is a compound having an isocyanato group and a radically polymerizable unsaturated group, the reaction system is a solvent-free reaction. When a solvent can be used, it is preferred that the solvent is used to improve the fluidity of the reaction liquid. Examples of the solvent include ester solvents such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and the like; and ethers such as diisopropyl ether, dimethoxyethane, and diethylene glycol dimethyl ether. a solvent; a halogen-based solvent such as dichloromethane or dichloroethane; an aromatic solvent such as toluene or xylene; a ketone solvent such as methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; An aprotic polar solvent such as methylmethamine or dimethyl sulfoxide. Among these, an ester solvent, a ketone solvent, or an ether solvent is preferred. When the reactive group of the copolymer (A) is a hydroxyl group, when the compound (B) is a compound having an isocyanato group and a radical polymerizable unsaturated group, the copolymer (A) is promoted for -22-201035128. The reaction of the compound (B) is preferably carried out in the presence of a urethanization catalyst. Examples of the urethane-based catalyst include amines such as pyridine, pyrolipid, triethylamine, diethylamine, and dibutylamine; and phosphines such as triphenylphosphine and triethylphosphine; An organic tin compound such as dibutyltin laurate, octyltin trilaurate, octyltin diacetate, dibutyltin diacetate or tin octylate; an organometallic compound such as zinc octylate or the like. Further, when an organotin compound is used in combination with an amine, the urethanization is preferably carried out smoothly. The number average molecular weight (??) and the weight average molecular weight (Mw) of the fluorine-containing radically polymerizable copolymer of the present invention are preferably 3,000 or more in order to provide excellent water repellency and oil repellency, and are used for water repellency and oil repellency. More preferably, both Μη and Mw are preferably in the range of 5,000 to 100,000, and more preferably in the range of 10,000 to 50,000. Further, the range of the range of from 1. 〇 to 1.3 is preferably that the degree of dispersion of the fluorinated radically polymerizable copolymer (Mw/Mn) is 1.5 or less, and is particularly preferably excellent in water repellency and oil repellency. The range from 1.0 to 〇 1.2 is better. Further, the number average molecular weights are measured by a gel layering method (hereinafter abbreviated as "GPC") under the following measurement conditions. [Measurement of the number average molecular weight, the weight average molecular weight, and the dispersity] In the present invention, the number average molecular weight (??), the weight average molecular weight (Mw), and the degree of dispersion are determined by gel chromatography (GPC) under the following conditions. . At the same time, the number average molecular weight (??) and the weight average molecular weight (Mw) are in terms of standard polystyrene. Measuring device: "HLC-8220 GPC" manufactured by Tosoh Corporation -23- 201035128 Pipe column: Protection tube "HHR-H" manufactured by Tosoh (stock) (6.0mmI.Dx 4cm) + Tosoh (share) "TSK-GELGMHHR-N" (7_8mmI.D_x 30cm) manufactured by Tosoh Corporation (TSK-GELGMHHR-N) (7.8mmI.Dx 30cm) + "TSK-GELGMHHR-made by Tosoh Corporation" N" (7.8mmI_D.x 30cm) + "TSK-GEL GMHHR_N" manufactured by Tosoh Corporation (7.8mmI.D. x 3 0cm) Detector: ELSD ("ELSD2000" manufactured by Ott) Processing: "GPC-8020 Model II Data Analysis 0 Type 4.30" manufactured by Tosoh Corporation

Measuring temperature: column temperature 40 ° C development solvent tetrahydrofuran flow rate 1. 0ml/min Standard sample · According to the above "GPC-8020 Model II data analysis type 4. The measurement specification of 30" uses the following monodisperse polystyrene of a known molecular weight. (A-2 00) manufactured by Tosoh Co., Ltd. (A-1 00) manufactured by Tosoh Co., Ltd. (A-2500) manufactured by Tosoh Co., Ltd. "A-5000" manufactured by Cao (shares) "F-1" manufactured by Tosoh (shares) "F-2" manufactured by Tosoh (shares) "F-4" manufactured by Tosoh (shares) Tosoh ( "F-10" manufactured by Tosoh (shares) "F-40" manufactured by Tosoh (shares) "F-80" manufactured by Tosoh (shares) "F-128" manufactured by Cao Co., Ltd. "F-288" manufactured by Tosoh Co., Ltd. "F-5 50" manufactured by Tosoh Co., Ltd. Sample: Converting the solid content of the resin to 1. A 0% by mass solution of tetrahydrofuran was filtered with a Q microfilter (100/Z 1). In addition, the fluorine content of the fluorine-containing radically polymerizable copolymer of the present invention is excellent in water repellency and oil repellency, and the phase of the polymerizable monomer (C), the polymerizable resin (D), and the organic solvent to be described later is used. The solubility is good, preferably in the range of 1 to 50% by mass, more preferably in the range of 3 to 40% by mass, and particularly preferably in the range of 5 to 30% by mass. In particular, when a polymer of the above monomer (a1) and a polymer of the above monomer (a2) are used as a fluorine-containing radical polymerizable copolymer of a block copolymer, in order to have a fluoroalkyl group present adjacent thereto In the position, since the water repellency and the oil repellency are improved by the fluorinated alkyl group, sufficient water repellency and oil repellency can be exhibited even in the range of a low fluorine content of 1 to 20% by mass. In addition, the fluorine content in the fluorine-containing radically polymerizable copolymer of the present invention is calculated from the mass ratio of fluorine atoms to the total amount of the raw materials used. The active energy ray-curable resin composition of the present invention contains the above-described active energy ray-curable resin composition containing a fluororadical polymerizable copolymer. The blending amount of the fluorine-containing radical polymerizable copolymer is 0% by mass based on 100 parts by mass of the active energy ray-hardened resin composition. 01 to 10 -25- 201035128 The quality is better. In particular, since the coating film is effectively modified without impairing the physical properties such as the hardness of the coating film of the resin composition to be added, it is preferably from 0.05 to 3 parts by mass. The main component of the active energy ray-curable resin composition may, for example, be a polymerizable monomer (C) or a polymerizable resin (D). Examples of the monofunctional monomer in the above-mentioned polymerized ocean monomer (C) include, for example, fluorene-vinyl caprolactam, anthracene-vinylpyrrolidone, anthracene-vinylcarbazole, vinylpyridine, and propylene oxime. Amine, hydrazine, hydrazine-dimethyl(meth) acrylamide, isobutoxymethyl (meth) acrylamide, trioctyl (meth) acrylamide, diacetone (methyl) Acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate , propylene sulfhydryl porphyrin, (meth) acrylate lauryl ester, dicyclopentadiene (meth) acrylate, dicyclopentadienyloxyethyl (meth) acrylate, dicyclopentadiene (A) Acrylate, tetrahydrofuranmethyl (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, butoxyethyl (meth) acrylate, triethylene glycol monomethyl ether (methyl) Acryl phthalate, phenoxyethyl (meth) acrylate, and the like. These monofunctional monomers may be used singly or in combination of two or more. Examples of the polyfunctional monomer in the above polymerizable monomer (C) include, for example, trimethylolpropane tri(meth)acrylate, triethylene oxide modified trishydroxypropylpropane tris(methyl) ) acrylate, tripropylene oxide modified triglyceride (meth) acrylate, triethylene oxide modified glycerol tri (meth) acrylate, triepichlorohydrin modified glycerol tri (meth) acrylate, 1,3,5-tripropylene decyl hexahydro _s_ triple well, ginseng (propylene oxyethyl) trimeric isocyanate, pentaerythritol tris(methyl) propylene -26- 201035128 acid ester 'pentaerythritol tetra (a) Acrylate, tetraethylene oxide modified pentaerythritol tetra(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, diethylene oxide modified di-trimethylolpropane Tetrakis (meth) acrylate, alkyl modified dipentaerythritol pentaacrylate, alkyl modified dipentaerythritol tetraacrylate, ε-caprolactam modified dipentaerythritol hexa(meth) acrylate, dipentaerythritol five ( Methyl) acrylate, dipentaerythritol hexa(meth) acrylate, hexaepoxy Alkoxy modified sorbitol hexa (meth) acrylate, 0 hexa (meth Bing Xixi oxyethyl) cyclotriphosphazene like. These polyfunctional monomers may be used singly or in combination of two or more. The polymerizable monomer (D) may, for example, be a (meth)acrylic acid epoxy ester in which a (meth)acrylic acid is reacted in a compound having a plurality of epoxy groups, or an aliphatic polyisocyanate or an aromatic polyisocyanate. A urethane (meth) acrylate having a (meth) acrylate reaction of a hydroxyl group or the like. These polymerizable monomers (D) may be used alone or in combination of two or more. Examples of the above (meth)acrylic acid epoxy ester include, for example, bismuth (meth)acrylate in a bisphenol fluorene type epoxy resin, a bisphenol F type epoxy resin, a phenol novolak type epoxy resin, and a cresol novolac. Resin on epoxy resin such as varnish-type epoxy resin. Examples of the aliphatic polyvalent isocyanate used as a raw material of the above urethane (meth) acrylate include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, and VII. Methyl diisocyanate, octamethylene diisocyanate, decamethyl diisocyanate, 2-methyl-1,5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate, -27- 201035128 Dodecyl diisocyanate, 2-methylpentamethylene diisocyanate, 2,2,4·trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene Isocyanate, isophorone diisocyanate, norbornene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated benzyl diisocyanate, hydrogenated dimethyl diisocyanate, hydrogen tetramethyl phthalate Diisocyanate, cyclohexyl diisocyanate, and the like. Further, examples of the aromatic polyvalent isocyanate in which 0 is used as a raw material of the urethane (meth) acrylate include benzyl diisocyanate, 4,4'-diphenylmethane diisocyanate, and benzene. Methyl diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, and the like. On the other hand, examples of the (meth) acrylate having a hydroxyl group used as a raw material of the above urethane (meth) acrylate include hydroxyethyl (meth)acrylate and (meth)acrylic acid. Hydroxypropyl ester, hydroxybutyl (meth) acrylate, pentylene glycol mono(meth)acrylate, hexanediol mono(meth)acrylate, C) neopentyl glycol mono(meth)acrylate, hydroxyl Mono(meth) acrylate of a dihydric alcohol such as trimethylacetic acid neopentyl glycol mono (meth) acrylate; trimethylolpropane di(meth) acrylate, ethoxylated trimethylol Propane (meth) acrylate, propoxylated trimethylolpropane di(meth) acrylate, glycerol di(meth) acrylate, bis(2-(methyl) propylene methoxyethyl) hydroxy a mono- or di-(meth) acrylate of a trihydric alcohol such as ethyl tripolyisocyanate, or a part of the alcoholic hydroxy group modified with ε-caprolactam having a hydroxy group and a bis (methyl group) Acrylate; pentaerythritol tri(meth)acrylate, di-three-28- 201035128 hydroxymethyl a compound having one hydroxyl group and three or more (meth)acryl fluorenyl groups in one molecule such as an alkyl tris(meth)acrylate or dipentaerythritol penta(meth)acrylate, or the hydroxyl group of the compound is ε- Polyfunctional (meth) acrylate modified with caprolactam; dipropylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethyl b a (meth) acrylate compound having an oxygen alkyl group such as a diol mono(meth) acrylate; ^ polyethylene glycol polypropylene glycol mono(meth) acrylate, polyoxybutylene butyl-polyoxyethylene extension (meth) acrylate compound having a block structure of an alkylene chain such as mercaptopropyl (meth) acrylate; poly(ethylene glycol-tetramethylene glycol) mono(meth) acrylate A (meth) acrylate compound having a random structure of an aliphatic oxygen-extended alkyl chain such as poly(propylene glycol-tetramethylene glycol) mono(meth)acrylate. The reaction of the above aliphatic polyisocyanate or aromatic polyisocyanate with a hydroxyl group-containing (meth) acrylate can be carried out in the usual manner in the presence of a urethane catalyst. Examples of the urethane-catalyzed catalyst include amines such as pyridine, pyrrole, triethylamine, diethylamine, and dibutylamine; phosphines such as triphenylphosphine and triethylphosphine; and An organic tin compound such as dibutyltin acid, octyltin trilaurate, octyltin diacetate, dibutyltin diacetate or tin octylate; an organometallic compound such as zinc octylate or the like. Among these urethane (meth) acrylate resins, in particular, a reaction between an aliphatic polyisocyanate and a (meth) acrylate having a hydroxyl group is excellent in transparency and hardening of the cured coating film. The point of excellence is better. -29- 201035128 The active energy ray-curable resin composition of the present invention refers to a composition which is cured by irradiation and living with an energy ray. The active energy ray means ultraviolet rays such as ion beams of electron beams, alpha rays, xenon rays, and r rays. When ultraviolet rays are used as the active energy ray, a photopolymerization initiator (E) is added to the active energy ray-curable resin composition. Also, a photo sensitizer may be added if necessary. Further, when ionizing radiation of an electron beam, an α-ray, an X-ray, or an r-ray is used, even if the photopolymerization initiator or the photosensitizer 0 is not used, it can be rapidly hardened, so that it is not necessary to add it in particular. The photopolymerization initiator (E) may, for example, be an intramolecular splitting type photopolymerization initiator or a dehydrogenation type photopolymerization initiator. Examples of the intramolecular splitting type photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1·phenylpropan-1-one, and benzyldimethylketal. , 1-(4.cumyl)-2.hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-propyl)propyl, 1- Hydroxycyclohexyl-phenyl ketone, 2-methyl-2-sodium benzoyl (4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4) - acetophenone-based compound such as tyrosolinyl phenyl)-butanone; benzoin such as benzoin, benzoin methyl ether and benzoin isopropyl ether; 2,4,6-trimethyl a fluorenyl phosphine oxide compound such as bisphenylphosphine oxide or bis(2,4,6-trimethylphenylene) phenylphosphine oxide; benzophenone or tolyl acetaldehyde Ester and the like. On the other hand, examples of the dehydrogenation type photopolymerization initiator include benzophenone, o-benzonitrile benzoic acid methyl-4-phenylbenzophenone, and 4,4'-dichlorodiene. Benzophenone, hydroxybenzophenone, 4-benzylidene-4'-methyl-diphenyl sulfide, benzoated benzophenone, 3,3', 4,4'-tetra (third Base oxybenzoyl) diphenyl-30- 201035128 benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, etc.; 2-isopropylthioxanthone, 2 a thioxanthone compound such as 4-dimethylthioxanthone, 2,4-dione or 2,4-dichlorothioxanthone; an amine group such as rice bran diethylaminobenzophenone The photopolymerization initiator (E) such as the benzophenone-based compound-2-chloroacridone, 2-ethylhydrazine, 9,10-phenanthrenequinone or camphorquinone may be used singly or in combination of two or more. Further, examples of the photosensitizer include, for example, an amine such as an aliphatic amine amine; a urea such as o-tolylthiourea; diethyl sodium; s-benzylisothiourea-p-toluene; The amount of the photopolymerization initiator and the photo-sensitizer used for the sulfide of the sulfonate or the like, and the non-volatile content of the phase energy-hardening resin composition is 100% by mass. 01 to 20 parts by mass is preferred, with 0. More preferably, it is 3 to 10 parts by mass, and the purpose of the active energy ray-curable resin composition of the present invention is to adjust the viscosity and the refractive index or the color tone of the coating film in the range of the effect of the present invention without impairing the effect of the present invention. Various kinds of compounding materials for the purpose of adjusting the properties of the crucible or the coating film's organic solvent, acrylic resin, phenol resin, polyester resin, ester resin, urea resin, melamine resin, alkyd resin, cyclopolyamine resin, Polycarbonate resin, petroleum resin, fluororesin; various organic or inorganic particles such as PTFE (polytetrafluoroethylene), polyethylene, carbon, titanium oxide, copper, cerium oxide particles, etc.; polymerization polymerization inhibitor, antistatic agent, Defoamer, viscosity modifier, agent, weathering stabilizer, heat stabilizer, antioxidant, rust-proof ketone-based ethyl thioxanthone, 4,4,-; 10-butyl. These are aromatic dithiophosphoric acids and the like. For the active ingredients, each is used as a coating, and as a coating, it can be used as a coating of various amino carboxylic acid oxygen resins, various kinds of tree alumina, initiator, light stabilizer, slip agent, -31 - 201035128 wax, gloss A regulator, a mold release agent, a phase solvent, a conductivity adjuster, a pigment, a dye, a dispersant, a dispersion stabilizer, a decane-based system, a hydrocarbon-based surfactant, and the like. In the organic solvent in the above-mentioned compounding component, when the radically polymerizable copolymer of the present invention is used alone, the fluorine-containing radical polymerizable copolymer is used as an active energy ray-curable resin composition, and the substrate is used. The coating suitability is imparted, and thus a dilution solvent for viscosity adjustment can be used. Examples of the solvent to be diluted with 0 include aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, and isopropanol; and esters such as ethyl acetate and propylene glycol monomethyl ether acetate; Ketones such as ketone, methyl isobutyl ketone, and cyclohexanone, etc. These solvents may be used alone or in combination of two or more. When the active energy ray-curable resin composition of the present invention is used as a BM photoresist, a colorant is prepared in order to form black. The coloring agent is not particularly limited as long as it is black, and it is preferably a pigment such as carbon black, a metal oxide or a composite metal compound composed of two or more kinds of metal oxides. Further, 〇 may be a mixture of two or more kinds of organic pigments selected from pigments having a hue of red, blue, green, purple, yellow, cyan, and magenta, and a combination of blacks may be formed by color mixing. Examples of the above carbon black include lamp black, acetylene black, pyrolytic black, black, furnace black, and the like. The above metal oxides are, for example, titanium black obtained by oxidation of titanium or reduction of titanium dioxide. Usually, the titanium black is represented by a number of 1 or more. Further, the metal oxide is a metal oxide such as copper, iron, chromium, manganese or cobalt. Further, examples of the composite metal compound of -32 to 201035128 formed of two or more kinds of metal oxides include, for example, copper-chromium oxide, copper-chromium-manganese oxide, and copper-iron-manganese oxidation. Or cobalt-iron-manganese oxide or the like. On the other hand, examples of the organic pigments having a red hue include, for example, a quinacridone pigment, a perylene pigment, a pyrrolopyrrole pigment, an anthraquinone pigment, and the like; and a pigment having a cyan hue can be enumerated. For example, phthalocyanine pigments, indanthrene pigments, etc.; pigments having a green hue include, for example, halogenated phthalocyanine pigments; and pigments having a purple hue, such as dioxins, cultivating purple, and fast purple B. , methyl violet lake, indanthrene bright purple, etc.; pigments having a yellow hue include, for example, tetrachloroisoindolinone pigment, Hansa yellow pigment, benzidine yellow pigment, azo pigment, etc. The pigment having a cyan hue may be, for example, a metal-free phthalocyanine or a merocyanine; and a pigment having a magenta hue may, for example, be dimethylquinacridone or sulphur. In addition, the fluorine-containing radically polymerizable copolymer of the present invention may be appropriately formulated as an active energy ray-curable resin by appropriately mixing the photopolymerization initiator (E), an organic solvent, or the like with a polymerizable group. Use. Examples of the base material to which the fluorine-containing radically polymerizable copolymer of the present invention or the active energy ray-curable resin composition of the fluorine-containing radical polymerizable copolymer is applied may be, for example, a plastic substrate or a glass. Such as ceramic substrates; metal substrates such as iron, aluminum, etc., especially plastic substrates are useful. Examples of the material of the plastic substrate include polyester resins such as polyethylene terephthalate, polybutylene phthalate, and polyethylene naphthalate; polypropylene, polyethylene, and polymethylpentene. a polyolefin resin such as -1; a cellulose resin such as triethyl fluorenyl cellulose; a polystyrene resin, a polyamide resin, a polycarbonate resin, a flavonene resin, and a modified product. A borneol-based resin, a cyclic olefin copolymer, or the like. Further, it may be a laminate of two or more kinds of these resins. These plastic substrates can be in the form of a film or a sheet. Examples of the coating method of the fluorine-containing radically polymerizable copolymer of the present invention or the active energy ray-curable resin composition-coated substrate using the fluorine-containing radical polymerizable copolymer include gravure coating, roll coating, and teasing. Point scraper coating, air knife coating, conformal coating, spray coating, erection coating, immersion coating, spin coating, wheel coating, brush coating, screen printing coating, wire bar coating, fluid coating, and the like. Also, printing methods such as offset printing and letterpress printing. Among these, it is preferable that gravure coating, roll coating, squeegee coating, air knife coating, conformal coating, bar coating, and fluid coating can obtain a coating film having a more uniform thickness. The active energy ray which cures the fluorine-containing radically polymerizable copolymer of the present invention or the active energy ray-curable resin composition using the fluorine-containing radically polymerizable copolymer may, for example, be light, electron beam or radiation. Active energy enthalpy. Specific examples of the energy source or the curing device include a germicidal lamp, a fluorescent lamp for ultraviolet rays, a carbon arc lamp, a xenon lamp, a high-pressure mercury lamp for copying, a medium-pressure or high-pressure mercury lamp, an ultrahigh pressure mercury lamp, an electrodeless lamp, and a metal halide. A lamp, an ultraviolet ray having a natural light or the like as a light source, or an electron beam of a scanning type, a curtain type electron beam accelerator, or the like. Among these, it is preferable that the active energy ray is ultraviolet ray, and it is preferable to irradiate it in an inert gas atmosphere such as nitrogen at a point of polymerization efficiency. Moreover, a heat source of heat may be used as needed, and the heat treatment may be performed after the active energy ray-34-201035128 is hardened. The antifouling property (printing ink property, fingerprint resistance, etc.) can be imparted by using the fluorine-containing radically polymerizable copolymer of the present invention or the active energy ray-curable resin composition using the fluorine-containing radical polymerizable copolymer. The articles of the present invention include, for example, a film for a polarizing plate of a liquid crystal display (LCD) such as a TAC film; various display screens such as a plasma display (PDP) and an organic EL display: a touch-control version; a frame for a mobile phone or a mobile phone. Screens; optical recording media such as CD, DVD, Blu-ray Disc, etc.; transcription film for inlay molding (IMD, IMF); rubber rollers for OA machines such as photocopiers and printers; photocopiers, scanners, etc. The glass surface of the machine reading unit; the optical lens of the camera, video recorder, glasses, etc.; the windshield surface of the watch such as a watch; the window of various vehicles such as automobiles and electric cars; the various building materials such as makeup boards; the window glass of the house; Various plastic molded products such as artificial materials, artificial synthetic leather, and housings for home appliances, and FRP bathtubs. By applying the fluorinated curable resin or the active energy ray-curable resin composition of the present invention to the surface of the article, the cured coating film is formed by irradiating an active energy ray such as a violet ray or the like to impart antifouling property to the surface of the article. . Further, the fluorine-containing curable resin of the present invention is added to various coating materials suitable for each article, and the surface of the article can be provided with antifouling properties by coating and drying. In addition, the coating material to which the fluororesin-curable resin of the present invention can improve the flatness and impart antifouling properties (printing ink property, fingerprint resistance, etc.) to the coating film can be, for example, a polarizing of an LCD such as a TAC film. Hard coat material for film for sheet; anti-glare (AG) coated material or anti-reflective (LR) coated material; plasma display, -35- 201035128 Organic EL display (PDP), etc. ; hard coating material for touch panel; color resist for each pixel of RGB used to form a color filter for liquid crystal display (hereinafter referred to as "CF"); ink, inkjet ink or paint; CF Black matrix with black photoresist, ink, inkjet ink or paint; resin composition for pixel separators such as plasma display (PDP), organic EL display; paint for wall frame of mobile phone or hard coat material; Hard-coated materials for mobile phones; hard-coated materials for optical recording media such as CD, DVD, and Blu-ray Disc 0; hard-coated materials for transcription film for insert molding (IMD, IMF); photocopiers, printers Coating material for rubber roller for OA machine Coating materials for glass for OA machine reading units such as photocopiers and scanners; coating materials for optical lenses for cameras, video recorders, and glasses; windshield and glass coating materials for watches such as watches; Coating materials for windows of various vehicles such as electric cars; printing inks or coatings for various building materials such as makeup boards; coating materials for window glass for residential buildings; woodworking coatings for furniture; coating materials for artificial and synthetic leather; The coatings or coating materials for various plastic moldings such as frame ϋ, FRP bathtub coatings or coating materials. Further, the fluororesin-curable resin or the active energy ray-curable resin composition of the present invention can be used to impart scratch resistance (scratch resistance) and antifouling properties, and examples thereof include a backlight member of an LCD. A lens sheet or a diffusion sheet or the like. Further, the fluorine-containing curable resin of the present invention is added to the coating material for a lens sheet or a diffusion sheet, in addition to improving the flat coating property of the coating material and imparting scratch resistance to the coating film of the coating material (scratch resistance) Injury) and antifouling properties. -36-201035128 The cured coating film of the fluorinated curable resin of the present invention has a low refractive index, and therefore, a low refractive index layer which is used in an antireflection layer which prevents reflection of a fluorescent lamp or the like on various display surfaces of an LCD or the like can be used. Use coating materials. Further, by adding the fluorinated curable resin 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, the low refractive index of the coating film can be maintained and the coating film can be applied. The surface imparts antifouling properties. Further, other uses of the fluorinated curable resin or the active energy ray-hardening resin composition of the present invention include, for example, an optical fiber cladding layer, an optical waveguide, a sealing material for a liquid crystal panel, and various optical sheets. , an optical adhesive, and the like. In particular, when the active energy ray-curable coating composition of the present invention is used as an anti-glare coating material in a coating material for a protective film for a polarizing plate for an LCD, cerium oxide particles and acrylic resin particles are used in each of the above-described compositions. The inorganic or organic fine particles such as polystyrene resin fine particles are blended so that the blending ratio becomes the total mass of the hardening component in the active energy ray-curable coating composition of the present invention.  1 to 〇.  If it is 5 times the amount, it is excellent in anti-glare property, and therefore it is preferable. [Examples] Hereinafter, the present invention will be described in more detail by way of examples and comparative examples. Further, the fluorine content in the fluorine-containing radically polymerizable copolymer is calculated from the mass ratio of fluorine atoms to the total amount of the raw materials used. (Example 1) 117 parts by mass of methyl ethyl ketone (hereinafter referred to as -37-201035128 "MEK"), 50 parts by mass of 2-propanol, 2, 2, - were placed in a reaction vessel substituted with nitrogen. Bipyridine. 69 parts by mass, cuprous chloride 1. 49 parts by mass, at 20. (: stirring for 30 minutes. Thereafter, adding 2-hydroxyethyl methacrylate (hereinafter referred to as "HEM A") 78. 1 part by mass of ethyl 2-bromoisobutyrate 2. 93 parts by mass, and reacted at 20 ° C for 16 hours under a nitrogen stream. Next, add MEK 45. 8 parts by mass, 2-propanol 19. 5 parts by mass of 40 parts by mass of 2-(nonafluorobutyl)ethyl methacrylate (hereinafter abbreviated as "NFMA"), and the temperature is raised to 0 to 60 ° C for 8 hours. Further, MEK is added. 91 . 6 parts by mass, 39 parts by mass of 2-propanol, and 80 parts by mass of NFMA were allowed to react for 26 hours. The reaction mixture was dissolved in methanol and reprecipitated by water/methanol to give a block polymer. 60 parts by mass of the block polymer was dissolved in 80 parts by mass of MEK, and a solution of tin 2-ethylhexanoate was added (0. 2% by mass of MEK solution) 1 part by mass, polymerization inhibitor (p-methoxyphenol) 0. 1 part by mass, and the temperature was raised to 60 °C. Into the liquid, while introducing dry air, a 50% by mass MEK solution of 2-propenyloxyethyl isocyanate (hereinafter abbreviated as "AOEI") was added dropwise. 1 part by mass was reacted for 1 hour, and further reacted at 80 ° C for 3 hours to obtain a solution of a fluorine-containing radical polymerizable copolymer of a block copolymer having a fluorine content of 20% by mass. The molecular weight of the fluorine-containing radically polymerizable copolymer was measured by Gpc, and the weight average molecular weight was 16,413, the number average molecular weight was 14,443, and the degree of dispersion (Mw/Mn) was 1. 14. Further, MEK was added to the obtained polymer solution to obtain a solution containing 20% by mass of the fluorine-containing radical polymerizable copolymer. 0 ch2=?—占〇-ch2ch2c4f9 ch3 -38- 201035128 (Example 2) Mixing ester 〇 〇 ) 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 装入 装入 装入 装入 装入 装入82 parts by mass of methanol, 5 parts by mass of 2,2 dibipyridine, cuprous chloride 1. 58 parts by mass, stirred at 20 ° C for 30 minutes. Thereafter, 104 parts by mass of HEMA and 2-bromoisobutyric acid B were added. 12 parts by mass, and reacted under nitrogen gas at 20 ° C for 5 hours. Next, NFMA 53 was added. One part by mass was allowed to react for 17 hours. The mixture was dissolved in methanol and reprecipitated by water/methanol to give a 0-stage polymer. 40 parts by mass of the block polymer was dissolved in the MEK 54 fraction, and a solution of tin 2-ethylhexanoate was added (0. 2% by mass of MEK solution parts by mass, polymerization inhibitor (p-methoxyphenol) 〇. 1 part by mass, heated to °C. 45 parts by mass of AOEI 50% by mass MEK solution was dropped into the liquid while introducing dry air, and reacted for 1 hour, and then allowed to stand at 80 ° C for 3 hours to obtain a block copolymer having a fluorine content of 8 mass%. A solution of a fluorine-containing self-polymerizable copolymer. The amount of the fluorine-containing radically polymerizable copolymer measured by GPC showed a weight average molecular weight of 1,6,447, a number average molecular weight of 14,527, and a degree of dispersion (Mw/Mn) of 1. 13. Further, MEK was added to the obtained polymer solution to obtain a solution containing 20% by mass of the fluorine-containing radical polymer. (Example 3) In a reaction vessel substituted with nitrogen, 160 parts by mass of methanol and 2, dibipyridine were charged. 69 parts by mass, cuprous chloride 1. 49 parts by mass, stirred at 20 ° C for 30 minutes. Thereafter, add HEMA 78. 1 part by mass of 2-bromoisobutylethyl ester 2. 93 parts by mass and reacted at 20 ° C under a nitrogen gas stream -39- 14 201035128 hours. Then, 52 parts by mass of methanol and 52 parts by mass of 2-(trifluorohexyl)ethyl methacrylate (hereinafter abbreviated as "TFMA") represented by the following formula were added, and the mixture was heated to 60 ° C to carry out a reaction for 11 hours. The reaction mixture was dissolved in methanol and reprecipitated with water/methanol to give a block polymer. 40 parts by mass of the block polymer was dissolved in 54 parts by mass of MEK, and a solution of tin 2-ethylhexanoate was added (0. 2% by mass of MEK solution) 8 parts by mass, polymerization inhibitor (p-methoxyphenol) 〇. 1 part by mass, heated to 60 °C. 45 parts by mass of 50 mass% MEK solution of AOEI was added to the liquid while introducing dry air, and the reaction was carried out for 1 hour, and then reacted at 80 ° C for 3 hours to obtain a block copolymer having a fluorine content of 14 mass%. A solution of a fluorine-containing radically polymerizable copolymer of the substance. The molecular weight of the fluorine-containing radically polymerizable copolymer was measured by GPC, and the weight average molecular weight was 13,548, the number average molecular weight was 12,151, and the degree of dispersion (Mw/Mn) was 1. 11. Further, MEK was added to the obtained polymer solution to obtain a solution containing 20% by mass of the fluorine-containing radical polymerizable copolymer. W ? W CH2 = C - CO - CH2CH2C6F13 ch3 (Example 4) In a reaction vessel substituted with nitrogen, 117 parts by mass of MEK, 50 parts by mass of 2-propanol, and 2,2'-bipyridine were charged. 69 parts by mass, cuprous chloride 1. 49 parts by mass, stirred at 20 ° C for 30 minutes. Thereafter, add HEM A 78. 1 part by mass of ethyl 2-bromoisobutyrate 2. 93 parts by mass, and reacted at 20 ° C for 16 hours under a nitrogen stream. Next, add MEK 45. 8 parts by mass, 2-propanol 19. 5 parts by mass, 40 parts by mass of NFMA, and raised to 60 ° C to make it anti-40-201035128 should be 8 hours. Further, add ΜΕΚ 91. 6 parts by mass, a mass fraction of 2-propanol 39, and 80 parts by mass of NFMA were allowed to react for 26 hours. The reaction mixture was dissolved in methanol and reprecipitated by water/methanol to give a block polymer. 50 parts by mass of the block polymer was dissolved in 65 parts by mass of ruthenium, and a solution of tin 2-ethylhexanoate was added (0. 2% by mass of bismuth solution) 8. 5 parts by mass, a polymerization inhibitor (p-methoxyphenol) 〇 · 1 part by mass, and the temperature was raised to 6 ° C. Into the liquid, while introducing dry air, 50% by mass of 2-methylpropenyloxyethyl isocyanate (hereinafter abbreviated as "AOEI") was dropped (1: solution 40. 6 parts by mass and reacted for 1 hour, and further reacted at 80 ° C for 3 hours to obtain a solution of a fluorine-containing radical polymerizable copolymer of a block copolymer having a fluorine content of 19% by mass. The molecular weight of the fluorine-containing radically polymerizable copolymer was measured by GpC, and the weight average molecular weight was 15,932, the number average molecular weight was 14,366, and the degree of dispersion (Mw/Mn) was 1. 11. Further, MEK was added to the obtained polymer solution to obtain a solution containing 20% by mass of the fluorine-containing radical polymerizable copolymer. 〇 (Example 5) 130 parts by mass of MEK and 2,2'-bipyridine were charged in a reaction vessel substituted with nitrogen. 72 parts by mass, cuprous chloride 0. 86 parts by mass, stirred at 20 ° C for 30 minutes. Thereafter, 54 parts by mass of HEMA and TFMA 87 were added. 6 parts by mass of ethyl 2-bromoisobutyrate 1. 66 parts by mass, and reacted at 60 ° C for 29 hours under a nitrogen stream. The reaction mixture was dissolved in methanol and reprecipitated by water/methanol to give a copolymer. 50 parts by mass of the copolymer was dissolved in MEK 66 parts by mass' and a solution of tin 2-ethylhexanoate was added -41 - 201035128 (0. 2% by mass of MEK solution) 8. 9 parts by mass, polymerization inhibitor (p-methoxyphenol) 〇.  1 part by mass, and the temperature was raised to 60 °C. The AOEI 50% by mass MEK solution was dropped into the liquid while introducing dry air. After 4 parts by mass and reacted for 1 hour, the mixture was further reacted at 80 ° C for 3 hours to obtain a solution of a fluorine-containing radical polymerizable copolymer having a fluorine content of 24% by mass. The molecular weight of the fluorine-containing radical polymerizable copolymer was measured by GPC, and the weight average molecular weight was 1, 6,034, the number average molecular weight was 14,696, and the degree of dispersion (Mw/Mn) was 1. 09. Further, MEK was added to the obtained polymer solution to obtain a solution containing 20% by mass of the fluorene-containing radically polymerizable copolymer. (Example 6) In a reaction vessel substituted with nitrogen, 142 parts by mass of THF, 2.72 parts by mass of 2,2'-bipyridine, and cuprous chloride 0 were charged. 86 parts by mass, stirred at 20 ° C for 30 minutes. Thereafter, 45 parts by mass of HEM A, a mass fraction of TFM A 94, and ethyl 2-bromoisobutyrate were added. 62 parts by mass, and reacted at 60 ° C for 27 hours under a nitrogen stream. The reaction mixture was dissolved in methanol and reprecipitated with water/methanol to give a copolymer. 50 parts by mass of the copolymer was dissolved in 66 parts by mass of MEK, and a solution of tin 2-ethylhexanoate was added (0. 2% by mass of MEK solution) 8 parts by mass, polymerization inhibitor (p-methoxyphenol) 0. 1 part by mass, and the temperature was raised to 60 °C. The AOEI 50% by mass MEK solution was dropped into the liquid while introducing dry air. After 8 parts by mass and reacted for 1 hour, the mixture was further reacted at 80 ° C for 3 hours to obtain a solution of a fluorine-containing radical polymerizable copolymer having a fluorine content of 29% by mass. The molecular weight of the fluorine-containing radically polymerizable copolymer was measured by GPC, and the weight average molecular weight was -42 - 201035128 1, 6,292, the number average molecular weight was 14,3, 39, and the degree of dispersion (Mw/Mn) was 1 · 1 4 . Further, MEK was added to the obtained polymer solution to obtain a solution containing 20% by mass of the fluorine-containing radical polymerizable copolymer. (Example 7) In a reaction vessel substituted with nitrogen, 137 parts by mass of MEK and 2,2'-bipyridine were charged. 72 parts by mass and 0. 86 parts by mass of cuprous chloride were stirred at 20 ° C for 30 minutes. Thereafter, add HEMA67. 4 parts by mass, TFMA75. 1 0 parts by mass of ethyl 2-bromoisobutyrate 1. 63 parts by mass, and reacted at 60 ° C for 29 hours under a nitrogen stream. The reaction mixture was dissolved in methanol and reprecipitated by water/methanol to give a copolymer. 50 parts by mass of the copolymer was dissolved in 66 parts by mass of MEK, and a solution of tin 2-ethylhexanoate was added (0. 2% by mass of MEK solution) 4 parts by mass, polymerization inhibitor (p-methoxyphenol) 0. 1 part by mass, heated to 60 °C. The AOEI 50% by mass MEK solution was dropped into the liquid while introducing dry air into the liquid. After 8 parts by mass and reacted for 1 hour, the mixture was further reacted at 80 ° C for 3 hours to obtain a solution of a fluorinated radical polymerizable copolymer having a fluorine content of 19% by mass. The molecular weight of the fluorine-containing radical polymerizable copolymer was measured by GPC, and the weight average molecular weight was 21,459, the number average molecular weight was 1,7,469, and the degree of dispersion (Mw/Mn) was 1. twenty three. Further, MEK was added to the obtained polymer solution to obtain a solution containing 20% by mass of the fluorine-containing radical polymerizable copolymer. (Comparative Example 1) Methyl isobutyl ketone (hereinafter abbreviated as "MIBK") was placed in a glass flask equipped with a stirring device, a thermometer, a cooling tube, and a drip device. 3 mass -43 - 201035128 parts 'The temperature was raised to 90 ° C while stirring under a nitrogen gas stream. Next, NFMA 3 8. 0 parts by mass and HEMA 29.7 parts by mass dissolved in MIBK 39. 8 parts by mass of the monomer solution, and a radical polymerization initiator (t-butylperoxy-2-ethylhexanoate) 4. 1 part by mass is dissolved in ΜΙΒΚ 4. 1 part by mass of the polymerization initiator solution, each of which was placed in a drip device, and the inside of the flask was maintained at 90 ° C while being dropped over 2 hours. After completion of the dropwise addition, the mixture was stirred at 90 ° C for 10 hours to obtain a copolymer solution. 0 Adding a polymerization inhibitor (p-methoxyphenol) to the copolymer solution obtained above. 1 part by mass, urethane catalyst (tin octoate) 〇. 〇3 parts, maintained at 60 °C while air AIR, while AOEI 32. 3 parts by mass was added dropwise at 1 hour. After the completion of the dropwise addition, the mixture was stirred at 60 ° C for 2 hours, and then heated to 80 ° C and stirred for 4 hours. Further, the end of the reaction was confirmed by IR spectrum measurement to the disappearance of absorption of the isocyanate group. Subsequently, a MIBK solution containing 20 parts by mass of a fluorine-containing radical polymerizable copolymer having a fluorine content of 20% by mass was obtained by dilution with MIBK. The fluorene molecular weight of the fluorine-containing radical polymerizable copolymer was measured by GPC, and the weight average molecular weight was 11,701, the number average molecular weight was 5,73 5, and the degree of dispersion (Mw/Mn) was 2. 04. (Comparative Example 2) In a glass flask equipped with a stirring device, a thermometer, a cooling tube, and a drip device, MIBK 50 was placed. 7 parts by mass, the temperature was raised to 90 ° C while stirring under a nitrogen gas stream. Next, NFMA25. 0 parts by mass and HEMA 36. 0 parts by mass dissolved in MIBK 34. 4 parts by mass of a monomer solution, and a radical polymerization initiator (t-butylperoxy-2-ethylhexanoate) 3. 7 parts by mass of -44-201035128 3,7 parts by mass of a polymerization initiator solution in MIBK, each of which was placed in a drip device, and was kept at 90 ° C while being dropped at 2 hours. After the completion of the dropwise addition, the mixture was stirred at 90 ° C for 10 hours to obtain a copolymer solution. A polymerization inhibitor (p-methoxyphenol) is added to the copolymer solution obtained above. 1 part by mass, urethane catalyst (tin octoate) 〇 · 〇 3 parts, maintained at 60 ° C under air flow while AOEI 39. 0 parts by mass was added dropwise at 1 hour. After completion of the dropwise addition, the mixture was stirred at 6 (TC for 2 hours, and then heated to 80 ° C for further 4 hours. Further, the end of the reaction was confirmed by IR spectrum measurement until the disappearance of the absorption of the isocyanate group. The MIBK solution containing 20 parts by mass of a fluorine-containing radically polymerizable copolymer having a fluorine content of 13% by mass was obtained by diluting with MIBK. The molecular weight of the fluorine-containing radically polymerizable copolymer was measured by GPC, and the weight average molecular weight was determined. It is 1 2,9 66, the number average molecular weight is 5,854, and the degree of dispersion (Mw/Mn) is 2-21. (Comparative Example 3) In a glass crucible bottle equipped with a stirring device, a thermometer, a cooling tube, and a drip device, it is loaded. MIBK 55. 0 parts by mass, the temperature was raised to 90 ° C while stirring under a nitrogen gas stream. Next, will TFMA35. 0 parts by mass and HEMA31. 2 parts by mass dissolved in MIBK 37. 3 parts by mass of a monomer solution, and a radical polymerization initiator (t-butylperoxy-2-ethylhexanoate) 4. 0 parts by mass dissolved in MIBK 4. Each of 0 parts by mass of the polymerization initiator solution was placed in a drip device, and the inside of the flask was maintained at 90 ° C while being dropped over 2 hours. After the completion of the dropwise addition, the mixture was stirred at 90 ° C for 10 hours to obtain a copolymer solution. To the copolymer solution obtained above, a polymerization inhibitor (p-methoxy-45-201035128 酣) 〇·1 part by mass, and a urethane catalyst (tin octoate) 0·03 parts were added under a stream of air. Maintained at 60. (: At the same time will be ΑΟΕΙ 33. 8 parts by mass was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 60 ° C for 2 hours, and then heated to 80 ° C and stirred for 4 hours. Further, the end of the reaction was confirmed by the disappearance of the absorption of the isocyanate group by the ir spectrum. Subsequently, a MIBK solution containing 20 parts by mass of a fluorine-containing radical polymerizable copolymer having a fluorine content of 20% by mass was obtained by dilution with MIBK. The molecular weight of the fluorine-containing radically polymerizable copolymer was measured by GPC, and the weight average molecular weight was 14,279, the number average molecular weight was 6,124, and the degree of dispersion (Mw/Mn) was 2. 33. (Comparative Example 4) 69 parts by mass of MIBK was placed in a glass flask equipped with a stirring device, a thermometer, a cooling tube, and a drip device, and the temperature was raised to 105 °C while stirring under a nitrogen gas stream. Next, 40 parts by mass of 2-(heptadecafluorooctyl)ethyl acrylate (hereinafter abbreviated as "HFA") and HEMA 28. 8 parts by mass dissolved in MIBK 69 parts by mass of monomer solution, starting with free radical polymerization

The oxime (t-butylperoxy-2-ethylhexanoate) 3 - 4 parts by mass of a polymerization initiator solution dissolved in 22.5 parts by mass of MIBK, each of which was placed in a drop device, was maintained at 105 while being in a flask. (:Instillation at the same time for 3 hours. After the end of the dropwise addition, the mixture was stirred at 10 ° C for 10 hours to obtain a copolymer solution. 0 ch2 = ch - co-ch2ch2c8f17 A polymerization inhibitor was added to the copolymer solution obtained above. (p-methoxyphenol) ο. 1 part by mass, urethane catalyst (tin octoate) 〇. 〇 5 parts 'under the air -46 - 201035128 gas flow while maintaining at 60 ° C while ΑΟΕΙ 3 1.2 parts by mass was added dropwise at 1 hour. After the completion of the dropwise addition, the mixture was stirred at 60 ° C for 1 hour, and then heated to 8 ° C for further 10 hours. Further, the end of the reaction was determined by IR spectroscopy to the isocyanate group. Then, the MIBK solution was diluted with MIBK to obtain a MIBK solution containing 20 parts by mass of a fluorine-containing radical polymerizable copolymer having a fluorine content of 25% by mass. The molecular weight of the fluorine-containing radically polymerizable copolymer was The result of GPC measurement was a weight average molecular weight of 7,065, q, a number average molecular weight of 2,991, and a degree of dispersion (Mw/Mn) of 2.36. [Measurement of number average molecular weight, weight average molecular weight, and dispersity] In the present invention, the number average molecular weight ( Μη), weight average molecular weight Mw) and the degree of dispersion are determined by gel chromatography (GPC) under the following conditions: The number average molecular weight (??) and the weight average molecular weight (Mw) are in terms of standard polystyrene. "HLC-8220 GPC" manufactured by Cao (share) Pipe column: Protection tube "HHR-H" manufactured by Tosoh Corporation (6.0mmI.Dx 4 cm) Ο + "TSK-GELGMHHR" manufactured by Tosoh Corporation -N"(7.8mmI.Dx 30cm) + "TSK-GELGMHHR-N" manufactured by Tosoh Corporation (7.8mmI.Dx 30cm) + "TSK-GELGMHHR-N" manufactured by Tosoh Corporation (7.8mmI) .Dx 30cm) + "TSK-GELGMHHR-N" (7.8mmI.Dx 30cm) manufactured by Tosoh Co., Ltd. Detector: ELSD ("ELSD2000" manufactured by Otto) Data Processing: Tosoh (share) "GPC-8020 Model II Data Analysis Type 4.30" manufactured by the company

Measurement temperature: column temperature 40 ° C -47 - 201035128 Development solvent tetrahydrofuran flow rate 1.0 ml / min Standard sample: According to the above "GPC-8020 model I1 data analysis type 4.3" measurement instructions, using the following molecular weights of known molecular weight Monodisperse polystyrene. (A-500) manufactured by Tosoh (shares) Q "A- 1 000" manufactured by Tosoh (shares) "A-25 00" manufactured by Tosoh Corporation "A-5000" manufactured by Cao (shares) "F-1" manufactured by Tosoh (shares) "F-2" manufactured by Tosoh (shares) "F-4" manufactured by Tosoh (shares) Tosoh ( "F-10" manufactured by Tosoh (shares) "F-40" manufactured by Tosoh (shares) "F_80" manufactured by Tosoh (shares) "T_80" manufactured by Tosoh (shares) "F-128" manufactured by Tosoh Corporation (F-2 8 8) "F-5 5 0" manufactured by Tosoh Co., Ltd. Sample: Conversion of 1.0% by mass of resin solid content to tetraammine The solution was filtered with a microfilter (100 # i). [Preparation of a UV-curable resin group containing a fluorine-containing radical polymerizable copolymer-48-201035128] 50 parts by mass of a non-yellowing type urethane acrylate, 50 parts of dipentaerythritol hexaacrylate 25 parts by weight of butyl acetate, photopolymerization initiator ("Irgacure 184" manufactured by Ciba Specialty Chemicals Co., Ltd.; 1-cyclohexyl benzophenone) 5 parts by mass, toluene 54 parts by mass, 2-propylene 28 parts by mass of the alcohol, 25 parts by mass of butyl acetate, and 2828 parts by mass of propylene glycol monomethyl ether were uniformly mixed to obtain an ultraviolet curable resin composition as a substrate. Next, phase 0.25 parts by mass of the ultraviolet curable resin composition to be used as the substrate, and a solution containing 20% by mass of the fluorine-containing radical polymerizable copolymer obtained in Examples 1 to 7 and Comparative Examples 1 to 4 were added. The ultraviolet curable resin composition containing a fluorine-containing radical polymerizable copolymer is obtained by uniformly mixing and mixing the mass parts. [Evaluation of the ultraviolet curable resin composition containing the fluorine-containing radical polymerizable copolymer] (Preparation of the sample for evaluation) Ο The above-mentioned obtained fluorine-containing radical polymerizable copolymer was obtained by a bar coater (No. 13). The ultraviolet curable resin composition was coated on a polyethylene terephthalate (PET) film (thickness 188; czm), placed in a drier at 60 ° C for 5 minutes to volatilize the solvent' and used an ultraviolet curing device (in an air environment) A high-pressure mercury lamp and an ultraviolet irradiation amount of 3.5 k J/m 2 were hardened to form a coating film. Further, in Comparative Example 5, the ultraviolet curable resin composition to which the fluorine-containing radical polymerizable copolymer was not added was subjected to the same operation to obtain a coating film. After the coating film was allowed to stand at 20 ° C for one day, the following contact angles were measured and evaluated, and the evaluation of the adhesion prevention property was evaluated. (Measurement and evaluation of contact angle) The contact angles of water, n-dodecane and diiodomethane on the coated surface of the coating film obtained above were measured, and the water repellency and oil repellency were evaluated. At the same time, the evaluation of the contact angle is based on the following criteria. (1) Water AA: The contact angle is 105° or more. 0 A : The contact angle is below 100° above 100°. B: The contact angle is lower than 100° above 95°. C: The contact angle is lower than 95°. (2) n-Dodecane AA: The contact angle is 65° or more. A: The contact angle is 60° or more and lower than 65°. B: The contact angle is 55° or more and less than 60°. C: The contact angle is lower than 5 5 °. 〇 (3) Diiodomethane AA: The contact angle is above 90°. A: The contact angle is below 85° below 90°. B: The contact angle is 80° or more and lower than 85°. C: The contact angle is lower than 80°. (Contamination-preventing property) The coated surface of the coating film obtained above is drawn with an oil-based pen ("Western Chemical Industry Co., Ltd." "Signature pen ink large blue"), and the naked eye is observed -50-201035128 The situation was opened, and the contamination prevention property was evaluated on the basis of the following criteria. A: The ink is bounced off. B: The ink is slightly bounced off. C: The ink does not bounce off. (Evaluation of the safety of the fluorine-containing radically polymerizable copolymer in the living body) The safety of the accumulation of the fluorine-containing radical polymerizable copolymer in the living body was evaluated based on the following criteria. A: Since it does not contain a fluoroalkyl group having 8 or more carbon atoms, it is less likely to accumulate in a living body, and therefore has high safety. B: Since it contains a fluoroalkyl group having 8 or more carbon atoms, it is highly likely to be accumulated in a living body, so safety is low. The contents and evaluation results of the fluorine-containing radically polymerizable copolymers obtained in Examples 1 to 7 and Comparative Examples 1 to 4 are shown in Table 1 and Table 2°.

-51- 201035128 [Table 1]

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Ugly raw material monomer (al) (carbon number of fluoroalkyl group) NFMA (4) NFMA (4) TFMA (6) NFMA (4) TFMA (6) TFMA (6) TFMA (6) monomer (a2) HEMA HEMA HEMA HEMA HEMA HEMA HEMA compound (B) AOEI AOEI AOEI MOEI AOEI AOEI AOEI Molecular weight Mw 16,413 16,447 13,548 15,932 16,034 16,292 21,459 Μη 14,443 14,527 12,151 14,366 14,696 14,339 17,469 Dispersity Mw/Mn 1.14 1.13 1.11 1.11 1.09 1.14 1.23 Fluorine content (mass t%) 20 8 14 19 24 29 19 Evaluation results Contact angle (.) Water 105 104 108 103 105 108 105 Positive ten Dioxane 61 60 67 60 65 66 64 Diiodomethane 91 87 91 85 89 89 90 Evaluation of the contact angle Water AA A AA A AA AA AA n-Dodecane AA A A A A A A A 2- A A A A A A A A A A A A A A A Angle Assessment AAAA 巳AB Accumulation Safety AAAAAAA

[Table 2] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 i Raw material monomer (al) (carbon number of fluoroalkyl group) NFMA (4) NFMA (4) TFMA (6) HFA ( 8) Unmatched monomer (32) HEMA HEMA HEMA HEMA compound (B) AOEI AOEI AOEI AOEI Molecular weight Mw 11,701 12,966 14,279 7,065 Μη 5,735 5,854 6,124 2,991 Dispersity Mw/Mn 2.04 2.21 2.33 2.36 Fluorine content (% by mass) 20 13 20 25 Evaluation results Contact angle (°) Water 94 87 102 106 57 n-Dodecane 55 49 62 65 17 Diiodomethane 78 75 87 89 39 Evaluation of contact angle Water CCA AA C n-Dodecane 巳 CA AA C Diiodine Methane CCAAC contact angle fl Η ancient c 巳 CAC safety in the accumulation body AAAB - From the evaluation results shown in Table 1, it is understood that the fluorine-containing radical polymerizable copolymer of the present invention of Examples 1 to 7 is water, positive ten Dioxane and diiodomethane have a high contact angle of -52 to 201035128 and are excellent in adhesion prevention. Further, since the fluorine-containing radically polymerizable copolymer of the present invention has only a fluoroalkyl group having 6 or less carbon atoms, the safety in the body is also high. On the other hand, from the evaluation results shown in Table 2, the fluorine-containing radical polymerizable copolymers of Comparative Examples 1 to 3 having a degree of dispersion (Mw/Mn) exceeding 1.5 were observed for water, n-dodecane and diiodide. The contact angle of methane is insufficient, and the prevention of contamination adhesion is also insufficient. Further, the fluorine-containing radically polymerizable copolymer of Comparative Example 4 produced by using a monomer (al) having a fluoroalkyl group having 8 carbon atoms has high contact with water, n-dodecane and diiodomethane. The angle is excellent also in the prevention of contamination adhesion. However, since it has a fluoroalkyl group having 8 carbon atoms, it has a problem of accumulating safety in the body. Further, in Comparative Example 5 in which the fluorine-containing radical polymerizable copolymer was not used, the contact angle with respect to water, n-dodecane and diiodomethane was extremely low, and there was no contamination preventing property. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an IR spectrum of a fluorine-containing radical polymerizable copolymer produced in Example 1. Fig. 2 is a W-NMR spectrum of the fluorine-containing radically polymerizable copolymer produced in Example 1. Fig. 3 is a GPC chart of the fluorine-containing radical polymerizable copolymer produced in Example 1. Fig. 4 is a GPC chart of the fluorine-containing radical polymerizable copolymer produced in Example 2. -53- 201035128 Fig. 5 is a GPC chart of the fluorine-containing radical polymerizable copolymer produced in Example 3. Fig. 6 is a GPC chart of the fluorine-containing radical polymerizable copolymer produced in Example 4. Fig. 7 is a GPC chart of the fluorine-containing radical polymerizable copolymer produced in Example 5. Fig. 8 is a GPC chart of the fluorine-containing radical polymerizable copolymer produced in Example 6. Fig. 9 is a GPC chart of the fluorine-containing radical polymerizable copolymer produced in Example 7. The first graph is a GPC chart of the fluorine-containing radical polymerizable copolymer produced in Comparative Example 1. Fig. 1 is a GPC chart of the fluorine-containing radical polymerizable copolymer produced in Comparative Example 2. Fig. 12 is a GPC chart of the fluorine-containing radical polymerizable copolymer produced in Comparative Example 3. [Main component symbol description] 4FFf: 〇 -54-

Claims (1)

201035128 VII. Patent application scope: 1. A fluorine-containing radical polymerizable copolymer which is obtained by having an ether bond for a fluoroalkyl group having 1 to 6 carbon atoms (only the above-mentioned hospital base also contains an oxygen atom) Copolymer (A) obtained by copolymerizing a radically polymerizable unsaturated monomer (ai) and a radically polymerizable unsaturated monomer (a2) having a reactive group as a necessary monomer component to have The reactive group reacts to form a bonded functional group and a radically polymerizable unsaturated group (B), and reacts to some or all of the reactive groups of the copolymer (A). The ratio of the weight average molecular weight (Mw) to the number average molecular weight (?η), that is, the degree of dispersion (Mw/Mn) is 1.5 or less. 2. The fluorine-containing radically polymerizable copolymer according to claim 1, wherein the monomer (a2) has at least one selected from the group consisting of a hydroxyl group, an isocyanate group, an epoxy group and a carboxyl group. a radically polymerizable unsaturated monomer in a reactive group, or a carboxylic acid halide or a carboxylic acid anhydride having a radical polymerizable unsaturated group; and the aforementioned compound (B) has at least one selected from the group consisting of hydroxyl groups and A functional group in which a cyanate group, an epoxy group, and a carboxyl group are grouped, a compound having a radical polymerizable unsaturated group, or a carboxylic acid halide or a carboxylic acid anhydride having a radical polymerizable unsaturated group. 3. The fluorine-containing radically polymerizable copolymer according to claim 1, wherein the monomer U2) is a radically polymerizable unsaturated monomer having a hydroxyl group; and the compound (B) has an isocyanate group. And a compound of a radical polymerizable unsaturated group. 4. The fluorine-containing radical polymerization-55-201035128 copolymer according to any one of claims 3 to 3, wherein the monomer (a1) is a monomer represented by the following formula (1) , Ο II ... CH2==C—C—R′—Rf (1) R (In the above formula (1), R represents a hydrogen atom, a fluorine atom, a methyl group, a cyano group, a phenyl group, a benzyl group or a group. CnH2n-Rf' (n represents an integer of 1 to 8, Rf' represents a group of any one of the following formulae (Rf-Ι) to (Rf-7)), and R' represents a formula (R, -l) Rf represents a group of any one of (R'-ΙΟ), Rf represents a group of any one of the following formulae (Rf-Ι) to 〇(Rf-7); -OCnH2n-(R'-1)~OCH2CH2OCH2 —(R' -2) Ο ~0CH2CH2NHC0-CnH2n—(R* -3) OH —0CH2CHCH20-CnH2n—(R′ -4) OH -〇CH2CH-CnH2n- (R,-5) O CH2〇CnH2nRf, — OCH2CH2NHCO-CHCH2OCnH2n~ (R* -6) CH2OC„H2nRr —〇-CHCH2〇C„H2n—(R5 -7) CnH2n+1 —OCmH2mNS〇2—(R,8) (R,- 9) CnH2n+1 —〇CmH2mNC〇- (R*-l〇) (in the above formulas (R,-l), (R'-3), (R'-5), (R'-6) and (R'-7) η -56- 201035128 An integer from 1 to 8, wherein m in the above formulae (R'-8), (r, _9), and (R,_1〇) represents an integer from 1 to 8 'n represents an integer from 〇 to 8, and the above g(R, Rf'' in _6) and (R'-7) means the base of (Rf-Ι) to (Rf_7); -C„F2n+i (R f - 1) —C„F2nH (Rf -2) —CnF2n-1 (Rf-3) 〇—CnF2n.3 (Rf-4) —〇mF2m〇CnF2nCF3 (R f -5) CmF2m〇CnF2n〇^pF2pCF3 (R f -6) —CF2OC2F4OC2F4OCF3 (Rf- 7) (η in the above formulas (Rf-Ι) and (Rf-2) represents an integer of 1 to 6, and η in the above formula (Rf-3) represents an integer of 2 to 6, and the above formula (Rf-4) η represents an integer from 4 to 6, and m in the above formula (Rf_5) represents an integer from 丨 to 5 'η represents an integer from 〇 to 4, and the sum of !1! and n is 1 to 5, and the above formula (Rf In -6), m represents an integer of 0 to 4, η represents an integer of 1 to 4, Ρ is an integer of 0 to 4, and the sum of m, η, and ρ is 1 to 5). 5. The fluorine-containing radically polymerizable copolymer according to any one of claims 1 to 4, wherein the copolymer (Α) is obtained by using the monomer (al) and the monomer (a2) as essential sheets. A copolymer which is a living radical polymerized. The fluorine-containing radically polymerizable copolymer according to any one of claims 1 to 4, wherein the copolymer (A) is active as the monomer (a2) as an essential monomer. After the radical polymerization, the above monomer (a1) is added, and then the living radical is polymerized, and the polymer of the above monomer (a1) is polymerized on the terminal of the polymer having the monomer (a2) as an essential monomer. Elongated copolymer. 7. The fluorine-containing radically polymerizable copolymer according to claim 5, wherein the living radical polymerization is a polymerization initiator, a transition metal D compound, and a compound capable of coordinating with the transition metal. Atom-moving radical polymerization carried out in the presence of. An active energy ray-curable resin composition, which is characterized by containing the fluorine-containing radical polymerizable copolymer according to any one of claims 1 to 7. A cured product characterized in that the active energy ray-curable resin composition of the eighth application of the patent application is coated on a substrate and irradiated with an active energy ray to harden it. □ 10. A method for producing a fluorine-containing radical polymerizable copolymer, comprising: a first step and a second step, wherein the first step: the freedom of a fluoroalkyl group having 1 to 6 carbon atoms a radically polymerizable unsaturated monomer (al) and a radically polymerizable unsaturated monomer (a2) having a reactive group, a polymerization initiator, a transition metal compound, and a compound capable of coordinating bonding with the transition metal and In the presence of a solvent, the living radical is polymerized to obtain a copolymer (A) of the above monomer (al) and the above monomer (a2); -58- 201035128. Step 2: reacting with the above reactive group to form The compound (B) having a bonded functional group and a radically polymerizable unsaturated group reacts with some or all of the reactive groups of the copolymer (A) to introduce a radical polymerizable unsaturated group. A method for producing a fluorine-containing radically polymerizable copolymer, comprising: a first step, a second step, and a third step, wherein the first step: unsaturated polymerizable unsaturated group having a reactive group The monomer U2) is subjected to living radical polymerization in the presence of a polymerization initiator, a transition metal compound, and a compound capable of coordinating with the transition metal, and a solvent; Step 2: In the reactant obtained in the first step A radically polymerizable unsaturated monomer (al) having a fluoroalkyl group having 1 to 6 carbon atoms is added, and then living radical polymerization is carried out to obtain a copolymer of the above monomer (al) and the above monomer (a2) ( A); the third step: a compound (B) having a functional group reactive with the above reactive group and forming a bond and a radical polymerizable unsaturated group, and a part or all of the copolymer (A) The reactive group is reacted to introduce a radical polymerizable unsaturated group. -59-