KR101624976B1 - Fluorine-containing polymerizable polymer and active energy ray-curable composition using the same - Google Patents

Abstract

Is selected from the group consisting of a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide and an acid anhydride at both ends of a compound (A) having a radical-generating functional group at both terminals of the poly (perfluoroalkylene ether) (C) obtained by polymerizing a monomer component essentially comprising a polymerizable unsaturated monomer (B) having at least one reactive group which is reactive with the reactive group to form a bond with the reactive group (D) having at least one functional group and a polymerizable unsaturated group selected from the group consisting of an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide and an acid anhydride, and an activity using the fluorine-containing polymer Energy ray curable composition. The cured coating film using the fluorine radical polymerizable copolymer has excellent antifouling properties and has high resistance to saponification (strong alkali treatment), and can suppress the deterioration of the antifouling property.

Description

TECHNICAL FIELD The present invention relates to a fluorinated polymerizable polymer and an active energy ray curable composition using the fluorinated polymerizable polymer.

The present invention relates to a fluorine-containing polymer having an antifouling property. The present invention also relates to an active energy ray curable composition containing the polymer.

The fluorine compound combines water repellency and oil repellency and can be imparted with water repellency and oil repellency by coating on the surface of an article. Therefore, fluorinated compounds are used for the purpose of imparting antifouling properties to a liquid crystal display (hereinafter referred to as "LCD") or a film on the outermost surface of a plasma display.

For example, in the field of a coating material of a protective film such as a triacetyl cellulose (TAC) film in a polarizing plate for a liquid crystal display, in order to impart antifouling properties to fingerprints and contamination on the surface of the film, ultraviolet rays A curing type hard coating material is coated on the surface of the protective film. However, in the protective film, a saponification treatment (strong alkali treatment) is carried out on the opposite side of the side coated with the hard coating material for the purpose of improving the adhesiveness, and the contact of the saponified liquid to the hard coating side can not be avoided, There is a problem that the fluorine surfactant or the like existing in the surface layer is decomposed into strong alkali and the antifouling property is lowered.

In recent years, an ink jet method has been developed as a manufacturing method which can be lowered in cost as compared with the conventional photolithography method in manufacturing a color filter of an LCD. In the inkjet method, first, a black matrix (hereinafter, referred to as "BM") is formed on a substrate by photolithography, and then ink is injected by an ink-jet method so that the ink does not overflow from the inside of the recessed portion formed by the BM . At this time, in order to prevent ink from adhering to the upper surface (plane parallel to the substrate) of the BM, that is, to prevent the ink from overflowing from the inside of the frame, it is necessary to impart lyophobicity to the BM . However, when BM is formed by photolithography, since the heat setting treatment is performed at a high temperature condition of 230 DEG C x 30 minutes after curing by ultraviolet ray irradiation, a part of the component of the fluorine based surfactant is volatilized from the surface, The volatilization of the volatile matters causes contamination of other parts or production lines.

Here, since the functional group such as the fluorinated alkyl group present in the compound has the property of low surface tension, the fluorinated compound is coated with the composition by adding a small amount as a surface modifier to a composition having no fluorinated alkyl group The fluorinated alkyl group migrates to the surface in the process, and the antifouling property can be exerted.

As an active fluorine compound effective to exert this antifouling property, an active energy ray curable composition containing a poly (perfluoroalkylene ether) and a fluorine compound having a polymerizable group introduced into the molecule for the purpose of improving the durability of the antifouling property is proposed (See, for example, Patent Documents 1 and 2). Patent Document 1 discloses a fluorine compound having a poly (perfluoroalkylene ether) chain in which a polyisocyanate is reacted with a poly (perfluoroalkylene ether) having a hydroxyl group, a monomer having an hydroxyl group and an acyl group, Urethane acrylate has been proposed.

Further, in Patent Document 2, as a fluorine compound, a poly (perfluoro (meth) acrylate) obtained by reacting a triisocyanate which is a trimer of a diisocyanate with a poly (perfluoroalkylene ether) having a hydroxyl group and a monomer having a hydroxyl group and an acyl group (Meth) acrylate) has been proposed.

However, the urethane acrylates having the poly (perfluoroalkylene ether) chain described in the above Patent Documents 1 and 2 are produced in the production of a poly (perfluoroalkylene ether) having a hydroxyl group and a hydroxyl group per triisocyanate compound It is difficult to react the acrylic monomer at an appropriate ratio, so that a compound having only an acyl group or a compound having only a poly (perfluoroalkylene ether) chain is produced as a byproduct, and a poly (perfluoroalkylene ether) chain And a compound having both acyl groups can not be obtained.

Further, the compound having only a poly (perfluoroalkylene ether) chain often has a high molecular weight, and when used in an active energy ray curable composition, compatibility with other components is low. Therefore, the active energy ray curable composition There was also a problem such as opacity when it made a coating film. The urethane acrylate having such a poly (perfluoroalkylene ether) chain has poor compatibility with a compound having only a poly (perfluoroalkylene ether) chain and a compound having only an acryloyl group, And so on.

Japanese Patent Application Laid-Open No. 2001-019736 International Publication WO2003 / 002628

A problem to be solved by the present invention is to provide a fluoropolymerizable polymer which is excellent in compatibility with other components and which is excellent in antifouling property of the cured coating film when it is formed into a cured coating film and can suppress the deterioration of antifouling property even if subjected to saponification treatment It is on. Also disclosed is an active energy ray curable composition which can obtain a cured coating film excellent in antifouling property using the fluoropolymerizable polymer, a cured product thereof, and an article having the cured coating film.

As a result of intensive studies, the present inventors have found that a polymer obtained by polymerizing a polymerizable unsaturated monomer having a specific reactive group at both terminals of a compound having a radical-generating functional group at both terminals of the poly (perfluoroalkylene ether) , It was found out that the fluoropolymerizable polymer obtained by reacting the reactive functional group with a compound having a specific functional group and a polymerizable unsaturated group which forms a bond is excellent in compatibility with other components and is excellent in antifouling property , Thereby completing the present invention.

That is, the present invention relates to a process for producing a poly (perfluoroalkylene ether) polymer, which comprises reacting at both ends of a compound (A) having a radical-generating functional group at both terminals of the poly (perfluoroalkylene ether) chain a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, (C) obtained by polymerizing a monomer component comprising at least one polymerizable unsaturated monomer (B) having at least one reactive group selected from the group consisting of an anhydride and a reactive group, with respect to a part or all of the reactive groups (D) having at least one functional group and at least one polymerizable unsaturated group selected from the group consisting of a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide and an acid anhydride forming a bond, To a polymerizable polymer.

The present invention also relates to an active energy ray curable composition containing the fluoropolymerizable polymer, a cured product thereof, and an article having a cured coating film of the resin composition.

Since the fluorine-containing polymer of the present invention is used as the initiator of the polymerization reaction, the compound (A) having a fluorine-containing poly (perfluoroalkylene ether) chain is used as a polymerization initiator. Otherwise, since homopolymers of only fluorine monomers are not produced, they do not have components that are not compatible with other components in the polymer, and therefore have very good compatibility when incorporated into the active energy ray curable composition.

In addition, since the fluorine-containing polymerizable polymer of the present invention has a polymerizable unsaturated group and has a curing property, it is possible to impart antifouling properties to the surface of the substrate by coating it on a substrate alone to form a cured coating film. In addition, it exhibits excellent antifouling property since it has high stability even after the contamination adhering to the surface of the cured coating film is removed. The active energy ray curable composition containing the fluorine-containing polymer as a fluorine-containing surfactant is a fluorine-containing surfactant which, when applied to a substrate, has a polarity different from that of other atoms of the fluorine atom, Segregation, and surface modification that imparts antifouling properties to only the surface of the coating film is possible. Further, since the fluoropolymerizable polymer has curability, the fluorinated curable resin of the present invention can be firmly immobilized in the cured coating film, since the active energy ray curable composition can be polymerized with other curable components. Therefore, even if the cured coating film is subjected to heat treatment or the like, the fluorine-curable resin or its decomposition product can be prevented from volatilization or tearing off from the surface of the cured coating film, so that the surface of the substrate has high durability and excellent antifouling properties can be imparted.

Further, the cured coating film using the fluorine-polymerizable polymer of the present invention has a high resistance to saponification treatment and can suppress the decrease in antifouling property even if it is saponified. Therefore, the active energy ray curable composition using the fluorine-polymerizable polymer of the present invention is extremely useful as a hard coating material for a TAC film used in a polarizing plate for a liquid crystal display to which antifouling properties are required and which is subjected to a saponification treatment with an alkali Do.

1 is a chart of the ¹ H-NMR spectrum of the fluoropolymerizable polymer prepared in Example 1. Fig.
2 is a chart of a GPC chart of the fluorine-containing polymerizable polymer prepared in Example 1. Fig.
3 is a chart of a ¹ H-NMR spectrum of the fluoropolymerizable polymer prepared in Example 2. Fig.
4 is a chart of GPC of the fluorine-containing polymer prepared in Example 2. Fig.

The fluorine-containing polymer of the present invention is a polymer obtained by reacting a compound (A) having both ends of a poly (perfluoroalkylene ether) chain with a compound having a radical-generating functional group at a terminal with a hydroxyl group, an isocyanate group, an epoxy group, (C) obtained by polymerizing a monomer component comprising a polymerizable unsaturated monomer (B) having at least one reactive group selected from the group consisting of halides and acid anhydrides, (D) having at least one functional group and a polymerizable unsaturated group selected from the group consisting of a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide and an acid anhydride which react with the reactive group to form a bond.

The compound (A) having functional groups having radical-generating ability at both terminals of the poly (perfluoroalkylene ether) chain used as a raw material for the fluorine-containing polymerizable polymer of the present invention is a poly (Perfluoroalkylene ether) chain having a radical-generating ability at both terminals thereof.

(In the above general formula (1), X is any one of the following formulas (a) to (e), all X in the general formula (1) may be the same, plural ones exist in a random phase or a block phase And n is one or more numbers representing repeating units)

As described above, the poly (perfluoroalkylene ether) chain has a structure in which divalent fluorocarbon groups having 1 to 3 carbon atoms and oxygen atoms are alternately connected. The divalent fluorocarbon group having 1 to 3 carbon atoms may be a single kind or a mixture of plural kinds.

The perfluoromethylene structure represented by the formula (a) and the perfluoroethylene structure represented by the formula (b) coexist in that a coating film having excellent antifouling property can be obtained from the poly (perfluoro alkylene ether) . The ratio of the perfluoromethylene structure represented by the formula (a) to the perfluoroethylene structure represented by the formula (b) is preferably 1/10 to 10/1, 1 < / RTI > The value of n in the general formula (1) is preferably in the range of 3 to 100, more preferably in the range of 6 to 70. [

In addition, the poly (perfluoroalkylene ether) chain is preferably a poly (perfluoroalkylene ether) chain in which the poly (perfluoroalkylene ether) chain is excellent in pollution wiping performance and activity and easy to improve solubility in a non- The total number of fluorine atoms contained in the ring is preferably in the range of 18 to 200, and particularly preferably in the range of 25 to 150.

Examples of the functional group having radical-generating ability of the compound (A) include organic groups having a halogen atom, organic groups having an alkyltoluide group, organic groups having a dithioester group, organic groups having a peroxide group, And the like. Here, by living radical polymerization, it is possible to obtain a monomer component (B) containing both of the monomers (B) at both ends of the compound (A) having a functional group having polymerization initiating ability at both terminals of the poly (perfluoroalkylene ether) An organic group having a halogen atom, an organic group having an alkyltelluril group, or an organic group having a dithioester group can be used as the functional group having the radical-generating ability, and particularly, the ease of synthesis, ease of polymerization control, application It is preferable to use an organic group having a halogen atom in the variety of polymerizable unsaturated monomers that can be used.

Examples of the organic group having a halogen atom include a 2-bromo-2-methylpropionyloxy group, a 2-bromo-propionyloxy group and a parachlorosulfonylbenzoyloxy group.

In order to introduce the organic group having a halogen atom at both terminals of the poly (perfluoroalkylene ether) chain, a functional group capable of forming a bond at both ends of the poly (perfluoroalkylene ether) And a compound (a2) having an organic group having a functional group capable of forming a bond by reacting with the functional group to react with the compound (a1). Specifically, the functional groups at both terminals of the compound (a1) include, for example, a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide and an acid anhydride. Specific examples of the compound (a1) having the functional groups at both ends thereof include the following formulas (a1-1) to (a1-6). Of the following formulas (a1-1) to (a1-6), (a1-1), (a1-3), and (a1-6) are preferred because the reaction is easy. In the formulas, " PFPE " represents a poly (perfluoroalkylene ether) chain.

On the other hand, as the functional group of the compound (a2) capable of forming a bond by reacting with the functional group at both terminals of the compound (a1), the following may be mentioned.

For example, when the functional group at both terminals of the compound (a1) is a hydroxyl group, the functional group other than the organic group having a halogen atom in the compound (a2) is preferably an isocyanate group or a carboxylic acid halide. As another method, a compound having a carboxyl group by reacting an acid anhydride with the hydroxyl group of the compound (a1) and having an organic group having an epoxy group and a halogen atom with respect to the carboxyl group is used as the compound (a2) It is also possible to introduce an organic group having a halogen atom at both terminals of the above-mentioned compound (a1).

When the functional group at both terminals of the compound (a1) is an isocyanate group, the functional group other than the organic group having a halogen atom in the compound (a2) is preferably a hydroxyl group. When the functional group at both terminals of the compound (a1) is an epoxy group, the functional group other than the organic group having a halogen atom contained in the compound (a2) is preferably a carboxyl group.

When the functional group at both terminals of the compound (a1) is a carboxyl group, the functional group other than the organic group having a halogen atom in the compound (a2) is preferably an epoxy group. When the functional groups at both terminals of the compound (a1) are acid anhydrides, the functional group other than the organic group having a halogen atom of the compound (a2) is preferably a hydroxyl group.

Among the combinations of the functional groups at both terminals of the compound (a1) and the functional groups other than the organic group having the halogen atom of the compound (a2), the functional groups at both terminals of the compound (a1) ) Having a halogen atom is a carboxylic acid halide is preferable because the reaction is easy. As the reaction conditions in the case of this combination, the following conditions may be mentioned.

As a specific method for introducing the organic group having a halogen atom at both terminals of the poly (perfluoroalkylene ether) chain, the functional groups at both terminals of the compound (a1) are hydroxyl groups and the compound (a2) In the case of a carboxylic acid, a compound having a functional group having polymerization initiating ability at both terminals of the poly (perfluoroalkylene ether) chain can be obtained by carrying out a reaction under dehydrated esterification conditions. (A1) and (a2) in a solvent such as toluene, tetrahydrofuran and the like in the case of a halide of a carboxylic acid in which the functional group at both terminals of the compound (a1) is a hydroxyl group and the compound (a2) A compound having a functional group having a polymerization initiating ability can be similarly obtained. In this reaction, a basic catalyst may be used if necessary.

(A1) in the presence of a catalyst such as tin octylate when the both terminal functional groups of the compound (a1) have an isocyanate group, the compound (a2) has a halogen group and a hydroxyl group as a functional group capable of reacting with the isocyanate group, And (a2), a compound having a functional group capable of initiating polymerization can be obtained.

When the two terminal functional groups of the compound (a1) have an epoxy group, the compound (a2) has a halogen group and a carboxyl group as a functional group capable of reacting with the epoxy group, a basic catalyst such as triphenylphosphine or a tertiary amine , A compound having a functional group having polymerization initiating ability can be obtained by reacting (a1) with (a2) in the presence of a base.

(Perfluoroalkylene ether) chain obtained by a combination in which the functional group at both terminals of the compound (a1) is a hydroxyl group and the functional group other than the organic group having a halogen atom of the compound (a2) is a carboxylic acid halide Specific examples of the compound (A) having a functional group having polymerization initiating ability at both terminals include compounds represented by the following formulas (A-1) to (A-3).

Next, the polymerizable unsaturated monomer (B) having a reactive group used in the present invention will be described. The reactive group of the monomer (B) is at least one reactive group selected from the group consisting of a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide and an acid anhydride. The polymerizable unsaturated group of the monomer (B) is preferably a carbon-carbon unsaturated double bond having a radical polymerizable property, and more specifically, a vinyl group, a (meth) acryloyl group, a maleimide group, . Among these, a (meth) acryloyl group is preferable in view of easy production of a polymer (C) to be described later.

Specific examples of the monomer (B) include, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) Cyclohexanedimethanol mono (meth) acrylate, N- (2-hydroxyethyl) (meth) acrylamide, glycerin mono (meth) acrylate, (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono Monomers having a hydroxyl group such as ethyl-2-hydroxyethyl phthalate and lactone-modified (meth) acrylate containing a terminal hydroxyl group; Monomers having an isocyanate group such as 2- (meth) acryloyloxyethyl isocyanate and 2- (2- (meth) acryloyloxyethoxy) ethyl isocyanate; Monomers having an epoxy group such as glycidyl methacrylate and 4-hydroxybutyl acrylate glycidyl ether; Monomers having a carboxyl group such as (meth) acrylic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylphthalic acid or itaconic acid; Monomers which are carboxylic acid halides such as (meth) acrylic acid chloride; And monomers which are acid anhydrides such as maleic anhydride. In the present invention, the term "(meth) acryl" refers to one or both of methacryl and acryl, "(meth) acryloyl" refers to either or both of methacryloyl and acryloyl, The term "(meth) acrylate" refers to one or both of methacrylate and acrylate.

Among the polymerizable unsaturated monomers (B) exemplified above, at least one monomer selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) (Meth) acrylate, glycerin mono (meth) acrylate, 2-hydroxy-3-phenoxy (Meth) acrylate, (meth) acryloyloxyethyl isocyanate, glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether, and (meth) The polymerizable unsaturated group can be introduced efficiently and the resulting resin is excellent in moisture resistance and chemical resistance after curing. Among them, the methacrylic group-containing monomer is particularly preferable in view of excellent living radical polymerization property. In addition, the polymerizable unsaturated monomer (B) may be used in combination of two or more, insofar as the polymerizable unsaturated monomer (B) is used alone, or in a combination in which reactivity does not interfere.

In addition to the monomer (B), other monomer (E) copolymerizable with the monomer may be used as the monomer to be a raw material of the polymer (C). Examples of the monomer (E) include monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n- butyl (meth) (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl Alkyl (meth) acrylates such as acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate and isobornyl (meth) acrylate; Aromatic vinyls such as styrene,? -Methylstyrene, p-methylstyrene, and p-methoxystyrene; Maleimides such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide and cyclohexylmaleimide, Methoxysilyl or ethoxysilyl group-containing (meth) acrylate monomers such as 3- (trimethoxysilyl) propyl (meth) acrylate and 3- (triethoxysilyl) propyl (meth) acrylate, polydimethyl (Meth) acrylate monomers containing a silicon chain such as a siloxane chain. These monomers (a3) may be used alone or in combination of two or more.

Here, as a production method of the polymer (C), a method of subjecting the monomer (B) and, if necessary, the monomer (E) to a living radical polymerization using the compound (A) as a radical polymerization initiator. Generally, in a living radical polymerization, a dormant species whose active polymerization terminal is protected by an atom or an atomic group reversibly reacts with a monomer by generating radicals, thereby obtaining a polymer having extremely narrow molecular weight distribution. Examples of such living radical polymerization include, but are not limited to, atom transfer radical polymerization (ATRP), reversible addition-cleavage type radical polymerization (RAFT), radical polymerization involving nitroxide (NMP) And radical polymerization (TERP) used. The production of the polymer (C) by the living radical polymerization is preferable because a copolymer having a very narrow molecular weight distribution can be obtained. No particular limitation is imposed on which method is used, but ATRP is preferable for ease of control and the like. ATRP is polymerized by using an organic halide, a halogenated sulfonyl compound or the like as a catalyst as a catalyst, a metal complex comprising an initiator, a transition metal compound and a ligand.

The transition metal compound used in the ATRP is represented by M ^{n +} X _n . The transition metal M ^{n +} is a transition metal selected from the group ^{consisting of} Cu ⁺ , Cu ²⁺ , Fe ²⁺ , Fe ³⁺ , Ru ²⁺ , Ru ³⁺ , Cr ²⁺ , Cr ³⁺ , Mo ⁰ , Mo ⁺ , Mo ²⁺ , Mo ^{3 +, W 2+, W 3+,} Rh 3+, Rh 4+, Co +, Co 2+, Re 2+, Re 3+, Ni 0, Ni +, Mn 3+, Mn 4+, V 2+ , V ³⁺ , Zn ⁺ , Zn ²⁺ , Au ⁺ , Au ²⁺ , Ag ⁺ and Ag ²⁺ . X represents a halogen atom, an alkoxy group having 1 to 6 carbon atoms, (SO ₄ ) _1/2 , (PO ₄ ) _1/3 , (HPO ₄ ) _1/2 , (H ₂ PO ₄ ) Plate, hexafluorophosphate, methanesulfonate, arylsulfonate (preferably benzene sulfonate or toluene sulfonate), SeR ¹ , CN and R ² COO. Here, R ¹ represents an alkyl group of 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) in the aryl, straight-chain or branched chain, and R ² represents a hydrogen atom, Represents an alkyl group (preferably a methyl group) having 1 to 6 carbon atoms in straight chain or branched chain which may be substituted) 1 to 3 times with fluorine or chlorine. Also, n represents a formal charge on the metal, and is an integer of 0 to 7.

The transition metal complex is preferably a transition metal complex of group 7, 8, 9, 10 or 11, more preferably a complex of zero valent copper, monovalent copper, divalent ruthenium, bivalent iron or divalent nickel.

Examples of the compound having a ligand capable of coordinating with the transition metal include compounds having a ligand containing at least one nitrogen atom, oxygen atom, phosphorus atom or sulfur atom capable of coordinating with a transition metal through a sigma bond, A compound having a ligand containing two or more carbon atoms that can be coordinated via a bond, and a compound having a ligand capable of coordinating to a transition metal through a mu-bond or an? -Bond.

Specific examples of the compound having the above-mentioned ligand include, for example, 2,2'-bipyridyl and its derivatives in the case where the central metal is copper, 1,10-phenanthroline and its derivatives, tetramethylethylenediamine, pentamethyl And polyamines such as diethylenetriamine, hexamethyltris (2-aminoethyl) amine, and the like. Examples of divalent ruthenium complexes include dichlorotris (triphenylphosphine) ruthenium, dichlorotris (tributylphosphine) ruthenium, dichloro (cyclooctadiene) ruthenium, dichlorobenzene ruthenium, dichloro p-cymene ruthenium, Ruthenium, cis-dichlorobis (2,2'-bipyridine) ruthenium, dichlorotris (1,10-phenanthroline) ruthenium and carbonylchlorohydride tris (triphenylphosphine) ruthenium . Examples of the divalent iron complexes include bistriphenylphosphine complexes and triazacyclononane complexes.

In the production of the polymer (C), a solvent is preferably used. Examples of the solvent to be used include ester solvents such as ethyl acetate, butyl acetate and propylene glycol monomethyl ether acetate; Ether solvents such as diisopropyl ether, dimethoxyethane and diethylene glycol dimethyl ether; Halogen-based solvents such as dichloromethane and dichloroethane; Aromatic solvents such as toluene and xylene; Ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Alcohol solvents such as methanol, ethanol and isopropanol; And non-protonic polar solvents such as dimethylformamide, dimethylsulfoxide and the like. The solvent may be used alone or in combination of two or more.

The polymerization temperature in the production of the polymer (C) is preferably in the range from room temperature to 100 캜.

When the copolymer portion composed of the monomer (B) and the monomer (E) in the polymer (C) is in the form of a block, the monomer (B) or the monomer (E) , A living radical polymerization in the presence of a transition metal compound, a compound having a ligand capable of coordinating with the transition metal and a solvent, and then adding a monomer different from the living radical polymerization monomer and further subjecting to living radical polymerization.

In order to obtain the fluorine-containing polymer of the present invention, it is preferable that a part or all of the reactive groups of the polymer (C) produced by the above-mentioned method has a hydroxyl group, isocyanate group, epoxy group, A polymerizable unsaturated group is introduced into the polymer (C) using the compound (D) having at least one functional group and a polymerizable unsaturated group selected from the group consisting of a carboxylic acid halide and an acid anhydride. The functional group of the compound (D) can be selected according to the reactive group of the polymer (C). The polymerizable unsaturated group of the monomer (D) is preferably a carbon-carbon unsaturated double bond having a radical polymerizable property, and more specifically, a vinyl group, a (meth) acryloyl group, a maleimide group, . Among them, when the fluorine-containing polymer of the present invention is added to the active energy ray-curable composition, since the polymerizable monomer (F) and the polymerizable resin (G) described later have high curability, .

For example, when the reactive group of the polymer (C) is a hydroxyl group, the functional group possessed by the compound (D) is preferably an isocyanate group, a carboxyl group or a carboxylic acid halide, and the isocyanate group is more preferable Do. When the reactive group of the polymer (C) is a hydroxyl group, a carboxylic group is first produced by reacting an acid anhydride with the hydroxyl group of the polymer (C), and a compound having an epoxy group and a polymerizable unsaturated group for the carboxyl group is reacted with the compound B), and further, a polymerizable unsaturated group can be introduced into the polymer (C).

When the reactive group of the polymer (C) is an isocyanate group, the functional group of the compound (D) is preferably a hydroxyl group.

When the reactive group of the polymer (C) is an epoxy group, the functional group of the compound (D) is preferably a carboxyl group. It is also possible to further introduce a polymerizable unsaturated group into the polymer (C) by reacting a secondary hydroxyl group formed after the reaction of the compound (D) with a compound having an isocyanate group or a carboxylic acid halide and a polymerizable unsaturated group. In the case where the reactive group possessed by the polymer (C) is an epoxy group, even a compound having no polymerizable unsaturated group may be a compound having a functional group having an addition reactivity to an epoxy group such as a carboxyl group, It is also possible to introduce a polymerizable unsaturated group into the polymer (C) by further reacting the compound (D) with a compound having a hydroxyl group and having an isocyanate group or a carboxylic acid halide and a radically polymerizable unsaturated group for the hydroxyl group .

When the reactive group of the polymer (C) is a carboxyl group, the functional group other than the polymerizable unsaturated group of the compound (D) is preferably an epoxy group. It is also possible to further introduce a polymerizable unsaturated group into the polymer (C) by reacting the compound (D) with a compound having an isocyanate group or a carboxylic acid halide and a polymerizable unsaturated group in the secondary hydroxyl group formed after the reaction. In the case where the reactive group possessed by the polymer (C) is a carboxyl group, a compound having an epoxy group, even if it is a compound having no polymerizable unsaturated group, may be reacted with a carboxyl group of the polymer (C) to produce a secondary hydroxyl group, It is also possible to introduce a polymerizable unsaturated group into the polymer (C) by further reacting a compound having an isocyanate group or a carboxylic acid halide and a polymerizable unsaturated group as the above compound (D).

When the reactive group of the polymer (C) is an acid anhydride, the functional group of the compound (D) is preferably a hydroxyl group. Further, it is more preferable to further react the compound having an epoxy group and a polymerizable unsaturated group as the compound (D) with respect to the carboxyl group formed after the reaction. In the case where the reactive group possessed by the polymer (C) is an acid anhydride, a compound having no polymerizable unsaturated group and a compound having a hydroxyl group may be reacted with an acid anhydride to produce a carboxyl group and an epoxy group and a polymerizable unsaturated group , The polymerizable unsaturated group can be introduced into the polymer (C) by further reacting the compound having the polymerizable unsaturated group as the compound (D).

The combination of the reactive group of the polymer (C) and the functional group of the compound (D) may be a combination of a plurality of different kinds of functional groups as long as the reaction does not interfere.

The compound (D) may be the same as the monomer (B). As the combination, it is preferable that the reactive group of the polymer (C) is a hydroxyl group (one having a hydroxyl group as a raw material monomer (B)) and one having a functional group other than a polymerizable unsaturated group contained in the compound (D) Combinations are preferred. Particularly, it is preferable to react 2-acryloyloxyethyl isocyanate as the compound (D) with the polymer (C) prepared by using 2-hydroxyethyl methacrylate in the monomer (B).

The amount of the compound (D) to be used is preferably from 0.5 to 1.1 based on 1 mol of the monomer (aB) as a raw material of the polymer (C) It is particularly preferable to set the amount of the compound (D) to 0.9 to 1.0 mole in view of not leaving the unreacted compound (D).

When the reactive group of the polymer (C) is a hydroxyl group and the functional group other than the polymerizable unsaturated group of the compound (D) is an isocyanate group, the reaction can be carried out without using a solvent or a solvent. This is preferable in that the fluidity of the reaction solution becomes good. Examples of the solvent include ester solvents such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; Ether solvents such as diisopropyl ether, dimethoxyethane and diethylene glycol dimethyl ether; Halogen-based solvents such as dichloromethane and dichloroethane; Aromatic solvents such as toluene and xylene; Ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; And aprotic polar solvents such as dimethylformamide and dimethylsulfoxide. Of these, ester solvents; Ketone solvents; Ether solvents are preferable.

In order to accelerate the reaction between the polymer (C) and the compound (D), the reaction is preferably carried out in the presence of an urethane formation catalyst. As the urethanization catalyst, for example, amines such as pyridine, pyrrole, triethylamine, diethylamine and dibutylamine; Phosphines such as triphenylphosphine and triethylphosphine; Organic tin compounds such as dibutyltin dilaurate, octyltin tribelaurate, octyltin diacetate, dibutyltin diacetate, and octanoic acid tin; And organic metal compounds such as zinc octanoate. Use of an organotin compound in combination with an amine is preferable because the urethanization reaction proceeds smoothly.

The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the fluoropolymerizable polymer of the present invention are preferably 3,000 or more, more preferably 5,000 to 200,000. When the number-average molecular weight of the fluorine-containing polymer block copolymer falls within this range, water repellency and oil repellency are particularly excellent. The number average molecular weight and the like are measured by gel permeation chromatography (hereinafter referred to as " GPC "), and the measurement conditions are as follows.

[Conditions for measuring GPC]

Measurement apparatus: "HLC-8220 GPC" manufactured by Tosoh Corporation,

Column: " HHR-H " (6.0 mm ID x 4 cm), manufactured by Tosoh Corporation,

&Quot; TSK-GEL GMHHR-N " (7.8 mm ID × 30 cm) manufactured by Tosoh Corporation,

&Quot; TSK-GEL GMHHR-N " (7.8 mm ID × 30 cm) manufactured by Tosoh Corporation,

&Quot; TSK-GEL GMHHR-N " (7.8 mm ID × 30 cm) manufactured by Tosoh Corporation,

&Quot; TSK-GEL GMHHR-N " (7.8 mm ID × 30 cm) manufactured by Tosoh Corporation,

Detector: ELSD (Ortech's "ELSD2000")

Data processing: "GPC-8020 Model II Data Interpretation Version 4.30" manufactured by Tosoh Corporation

Measurement conditions: Column temperature 40 캜

The developing solvent tetrahydrofuran (THF)

Flow rate 1.0 ml / min

Sample: A tetrahydrofuran solution of 1.0% by mass in terms of resin solid content was filtered with a microfilter (100 μl).

Standard samples: The following monodisperse polystyrenes with known molecular weights were used in accordance with the measurement manual of "GPC-8020 Model II Data Interpretation Version 4.30".

(Monodisperse polystyrene)

&Quot; A-500 " manufactured by Tosoh Corporation

&Quot; A-1000 " manufactured by Tosoh Corporation

Quot; A-2500 " manufactured by Tosoh Corporation

Quot; A-5000 " manufactured by Tosoh Corporation

Quot; F-1 " manufactured by Tosoh Corporation

Quot; F-2 " manufactured by Tosoh Corporation

Quot; F-4 " manufactured by Tosoh Corporation

Quot; F-10 " manufactured by Tosoh Corporation

Quot; F-20 " manufactured by Tosoh Corporation

Quot; F-40 " manufactured by Tosoh Corporation

Quot; F-80 " manufactured by Tosoh Corporation

&Quot; F-128 " manufactured by Tosoh Corporation

&Quot; F-288 " manufactured by Tosoh Corporation

Quot; F-550 " manufactured by Tosoh Corporation

The active energy ray curable composition of the present invention is an active energy ray curable composition containing the above fluoropolymerizable polymer. The blending amount of the fluorine-containing polymer is preferably 0.01 to 10% by mass in the non-volatile content of the active energy ray curable composition. Particularly, since the surface of the coating film can be efficiently modified without losing the physical properties such as the coating film hardness inherent to the resin composition to be added, it is preferably 0.05 to 3% by mass.

The main components of the active energy ray curable composition include a polymerizable monomer (F) and a polymerizable resin (G). Examples of the monofunctional monomer in the polymerizable monomer (F) include N-vinylcaprolactam, N-vinylpyrrolidone, N-vinylcarbazole, vinylpyridine, acrylamide, N, (Meth) acrylate, isobutoxymethyl (meth) acrylamide, t-octyl (meth) acrylamide, diacetone (meth) acrylamide, dimethylaminoethyl Acrylate, dicyclopentadienyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, (Meth) acrylate, dicyclopentenyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethylenediethylene glycol (meth) acrylate, butoxyethyl , Phenoxyethyl (meth) acrylate And the like. These monofunctional monomers may be used alone or in combination of two or more.

Examples of the polyfunctional monomer in the polymerizable monomer (F) include trimethylolpropane tri (meth) acrylate, triethylene oxide modified trimethylolpropane tri (meth) acrylate, tripropylene oxide modified glycerin tri (meth) Acrylate, triethylene oxide-modified glycerin tri (meth) acrylate, triepichlorohydrin-modified glycerin tri (meth) acrylate, 1,3,5-triacrylohexahydro-s-triazine, tris (Meth) acrylate, pentaerythritol tetra (meth) acrylate, tetraethylene oxide modified pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra ) Acrylate, diethylene oxide-modified ditrimethylolpropane tetra (meth) acrylate, alkyl-modified dipentaerythritol (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol pentaacrylate, dipentaerythritol penta Acrylate, hexaethylene oxide-modified sorbitol hexa (meth) acrylate, hexakis (methacryloyloxyethyl) cyclotriphosphazene, and the like. These multifunctional monomers may be used alone or in combination of two or more.

Examples of the polymerizable resin (G) include urethane (meth) acrylate obtained by reacting a compound having a plurality of epoxy groups with (meth) acrylic acid, an aliphatic polyisocyanate or a reaction product of an aromatic polyisocyanate and a (meth) Methacrylate, and the like. These polymerizable resins (G) may be used alone or in combination of two or more.

Examples of the epoxy (meth) acrylate include (meth) acrylic acid such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin and cresol novolak type epoxy resin, .

Examples of the aliphatic polyisocyanate used as a raw material of the urethane (meth) acrylate include aliphatic polyisocyanates such as tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate Methyl-1,5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate, dodecamethylene diisocyanate, 2-methylpentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate , 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornadiisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tetramethylxsilyl Randy isocyanate, cyclohexane Di-isocyanate and the like.

Examples of the aromatic polyisocyanate used as a raw material of the urethane (meth) acrylate include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate , Tolylidine diisocyanate, p-phenylenediisocyanate, and the like.

On the other hand, examples of the (meth) acrylate having a hydroxyl group used as a raw material of urethane (meth) acrylate include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (Meth) acrylate, hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, and hydroxypivalic acid neopentyl glycol mono Of mono (meth) acrylate; (Meth) acrylates such as trimethylolpropane di (meth) acrylate, ethoxylated trimethylolpropane (meth) acrylate, propoxylated trimethylolpropane di (meth) acrylate, glycerin di Mono or di (meth) acrylates of trihydric alcohols such as hydroxyethyl isocyanurate, or mono- or di (meth) acrylates having hydroxyl groups in which some of these alcoholic hydroxyl groups are modified with? -Caprolactone, Acrylate; (Meth) acryloyl group having at least one hydroxyl group in one molecule such as pentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylol propane tri (meth) acrylate, dipentaerythritol penta A compound or a multifunctional (meth) acrylate obtained by modifying the hydroxyl group of the compound by? -Caprolactone; (Meth) acrylate having an oxyalkylene chain such as dipropylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and polyethylene glycol mono compound; (Meth) acrylate compounds having an oxyalkylene chain having a block structure such as polyethylene glycol-polypropylene glycol mono (meth) acrylate and polyoxybutylene-polyoxypropylene mono (meth) acrylate; A (meth) acrylate compound having a random oxyalkylene chain such as poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate and poly (propylene glycol-tetramethylene glycol) mono .

The reaction of the aliphatic polyisocyanate or aromatic polyisocyanate with the (meth) acrylate having a hydroxyl group can be carried out by a conventional method in the presence of an urethane-forming catalyst. As the urethanization catalyst, for example, amines such as pyridine, pyrrole, triethylamine, diethylamine and dibutylamine; Phosphines such as triphenylphosphine and triethylphosphine; Organic tin compounds such as dibutyltin dilaurate, octyltin tribelaurate, octyltin diacetate, dibutyltin diacetate, and octanoic acid tin; And organic metal compounds such as zinc octanoate.

Among these urethane (meth) acrylate resins, particularly those obtained by reaction with an aliphatic polyisocyanate and a (meth) acrylate having a hydroxyl group are preferable because of excellent transparency of the cured coating film and excellent curability.

The active energy ray curable composition of the present invention refers to a composition which is cured upon irradiation with active energy rays. This active energy ray refers to ionizing radiation such as ultraviolet ray, electron ray,? Ray,? Ray and? Ray. When ultraviolet rays are used as the active energy ray, a photopolymerization initiator (H) is added to the active energy ray curable composition. If necessary, a photosensitizer is further added. On the other hand, when ionizing radiation such as electron beams, alpha rays, beta rays, and gamma rays is used, it hardens quickly without using a photopolymerization initiator or photosensitizer.

Examples of the photopolymerization initiator (H) include an intramolecular-type photopolymerization initiator and a hydrogen-withdrawing photopolymerization initiator. Examples of the intramolecular isotactic photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 1- (4- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 2-methyl Acetophenone compounds such as 2-morpholino (4-thiomethylphenyl) propan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone; Benzoin such as benzoin, benzoin methyl ether, and benzoin isopropyl ether; Acylphosphine oxide-based compounds such as 2,4,6-trimethylbenzoindienylphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; Benzyl, methylphenylglyoxyester and the like.

Examples of the hydrogen-withdrawing photopolymerization initiator include benzophenone, methyl-4-phenylbenzophenone o-benzoylbenzoate, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl- Benzophenone based compounds such as diphenyl sulfide, acrylated benzophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone and 3,3'-dimethyl- compound; Thioxanthone compounds such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone and 2,4-dichlorothioxanthone; Aminobenzophenone compounds such as Michler's ketone and 4,4'-diethylaminobenzophenone; Butyl-2-chloroacridone, 2-ethyl anthraquinone, 9,10-phenanthrenequinone, camphorquinone, and the like. These photopolymerization initiators (E) may be used alone or in combination of two or more.

Examples of the photosensitizer include amines such as aliphatic amines and aromatic amines, ureas such as o-tolylthiourea, sodium diethyldithiophosphate, s-benzylisothiuronium-p-toluene sulfo And sulfur compounds such as nitrate.

The amount of the photopolymerization initiator and photosensitizer used is preferably 0.01 to 20 parts by mass, more preferably 0.3 to 10 parts by mass, per 100 parts by mass of the non-volatile component in the active energy ray curable composition.

The active energy ray curable composition of the present invention can be used for adjusting the viscosity or the refractive index or adjusting the color tone of a coating film or other coating properties Acrylic resin, phenol resin, polyester resin, urethane resin, urea resin, melamine resin, alkyd resin, epoxy resin, polyamide resin, urethane resin, urea resin, Various kinds of organic or inorganic particles such as PTFE (polytetrafluoroethylene), polyethylene, carbon, titanium oxide, alumina, copper and silica fine particles, a polymerization initiator, a polymerization inhibitor An antistatic agent, a defoaming agent, a viscosity adjusting agent, a light stabilizer, a weather stabilizer, a heat stabilizer, an antioxidant, a rust inhibitor, a sleeping agent, A release agent, a compatibilizing agent, a conductivity adjusting agent, a pigment, a dye, a dispersing agent, a dispersion stabilizer, a silicone system, and a hydrocarbon surfactant.

When the fluoropolymerizable polymer of the present invention is used singly, the organic solvent in the above-mentioned compounding component is used as an active energy ray-curable composition when the fluoropolymerizable polymer is blended to impart the coating property to the substrate , It is useful to use it as a diluting solvent for viscosity adjustment. Examples of the diluting solvent include aromatic hydrocarbons such as toluene and xylene; Alcohols such as methanol, ethanol and isopropyl alcohol; Esters such as ethyl acetate and propylene glycol monomethyl ether acetate; And ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. These solvents may be used alone or in combination of two or more.

When the active energy ray-curable composition of the present invention is used as a BM resist solution, a colorant is added to make it black. The colorant is not particularly limited as long as it is black, but a pigment such as carbon black, a metal oxide, and a composite metal compound comprising two or more kinds of metal oxides is preferable. Further, it may be a combination of two or more organic pigments selected from pigments having hue of red, blue, green, blue, yellow, cyan, magenta, and black by mixing.

Examples of the carbon black include lamp black, acetylene black, thermal black, channel black, furnace black, and the like. Examples of the metal oxide include titanium black obtained by oxidation of titanium or reduction of titanium dioxide. Usually, titanium black is represented by Ti _m O _2m-1 (m is a number of 1 or more). As the metal oxide, metal oxides such as copper, iron, chromium, manganese, and cobalt can also be used. Examples of the composite metal compound composed of two or more metal oxides include oxides of copper-chromium, oxides of copper-chromium-manganese, oxides of copper-iron-manganese, and oxides of cobalt-iron- .

Examples of the organic pigments include quinacridone pigments, perylenic pigments, pyrrolo pyrrole pigments, and anthraquinone pigments. Examples of the pigments having a red hue include quinacridone pigments, Examples of the pigments having a hue include phthalocyanine pigments and indanthrene pigments. Examples of pigments having a hue include halogenated phthalocyanine pigments and pigments having a purple color. Examples of the pigments having a color having a yellow hue include tetrachloroisoindolinone type pigments, Chinese yellow type pigments, benzidine yellow pigments, benzoin type pigments, Yellow pigments, and azo pigments. Examples of the pigments having a cyan color include nonmetal phthalocyanine, merocyanine, and the like, and pigments having a magenta color There may be mentioned dimethyl quinacridone, thioindigo.

Further, since the fluoropolymerizable polymer of the present invention has a polymerizable group, the photopolymerization initiator (H), an organic solvent and the like may be suitably blended and used alone as an active energy ray curable resin.

Examples of the substrate to which the fluorine-containing polymerizable polymer of the present invention or the active energy ray-curable composition using the fluorine-polymerizable polymer is applied include plastic substrates; A ceramic substrate such as glass; Iron, aluminum, and the like, and is particularly useful for a plastic substrate. As the material of the plastic substrate, for example, polyester resin such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; Polyolefin-based resins such as polypropylene, polyethylene, and polymethylpentene-1; Cellulose-based resins such as triacetylcellulose; Polystyrene resins, polyamide resins, polycarbonate resins, norbornene resins, modified norbornene resins, and cyclic olefin copolymers. Further, two or more types of substrates made of these resins may be bonded. These plastic substrates may be in the form of a film or a sheet.

Examples of the method of applying the fluorine-containing polymerizable polymer of the present invention or the active energy ray-curable composition using the fluorine-polymerizable polymer to the substrate include gravure coating, roll coating, comma coating, air knife coating, Dip coating, spinner coating, wheeler coating, brush coating, solid coating by silk screen, wire bar coating, flow coating, and the like. It is also possible to use a printing method such as offset printing and letterpress printing. Among them, gravure coating, roll coating, comma coating, air knife coating, kiss coating, wire bar coating and flow coating are preferable because a coating film with a more uniform thickness can be obtained.

Examples of the active energy ray for curing the fluorine-containing polymerizable polymer or the active energy ray-curable composition using the fluorine-containing polymer of the present invention include active energy rays such as light, electron beam and radiation. Specific examples of the energy source or curing device include sterilizing lamps, fluorescent lamps for ultraviolet rays, carbon arc lamps, xenon lamps, high pressure mercury lamps for copying, medium pressure or high pressure mercury lamps, ultra high pressure mercury lamps, electrodeless lamps, metal halide lamps, Ultraviolet rays generated by a curtain type electron beam accelerator, or an electron beam by a scanning type or curtain type electron beam accelerator.

Of these, the active energy ray is preferably ultraviolet ray, and it is more preferable to irradiate it in an inert gas atmosphere such as nitrogen gas from the viewpoint of polymerization efficiency. If necessary, heat may be used in combination as an energy source, irradiated with active energy rays, and cured, followed by heat treatment.

The cured coating film of the fluorine-polymerizable polymer of the present invention has excellent antifouling properties (foot printability, transparency and the like), scratch resistance and the like. Therefore, the surface of the article is coated and cured, Scratch resistance and the like can be given. Further, the fluorine-polymerizable polymer of the present invention can impart leveling properties to the porcelain by adding it as a fluorine-based surfactant to the porcelain (coating material). Therefore, the active energy ray- Respectively.

Examples of articles capable of imparting antifouling properties (ink repellency, transparency, and the like) by using the fluorine-polymerizable polymer or active energy ray-curable composition of the present invention include polarizing plate films of liquid crystal displays (LCD) such as TAC films; Various display screens such as a plasma display (PDP) and an organic EL display; Touch panel; A screen of a cellular phone housing or a cellular phone; Optical recording media such as CD, DVD, and Blu-ray disc; Transfer film for insert mold (IMD, IMF); Rubber rollers for office automation equipment such as copying machines and printers; A glass surface of a reading unit of an OA such as a copying machine or a scanner; An optical lens such as a camera, a video camera, and a spectacle; Windshield of watch such as wrist watch, glass surface; Windows of various vehicles such as automobiles and railway cars; Various construction materials such as lacquer plates; Window pane of a house; Woodworking materials such as furniture, artificial / synthetic leather, various plastic molded articles such as housings for home appliances, and FRP bathtubs. Antifouling properties can be imparted to the surface of the article by applying the fluorine-curing resin or active energy ray-curable composition of the present invention to the surfaces of these articles and irradiating active energy rays such as ultraviolet rays to form a cured coating film. It is also possible to impart the antifouling property to the surface of the article by adding the fluorine-curing resin of the present invention to various kinds of paints suitable for each article and applying and drying the same.

As a porcelain which can be imparted with antifouling properties (ink repellency, transparency, etc.) to the coating film while improving the leveling property by adding the fluorine-curing resin of the present invention, Anti-glare (AG) coatings or antireflective (LR) coatings; Hard coating materials for various display screens such as plasma display and organic EL display (PDP); Hard coating material for touch panels; A color resist, a printing ink, an ink jet ink or a coating material for forming RGB pixels used in a color filter for a liquid crystal display (hereinafter referred to as "CF"); Black resist for black matrix of CF, printing ink, ink jet ink or coating; A resin composition for a pixel barrier, such as a plasma display (PDP) or an organic EL display; A coating material for mobile phone housings or a hard coating material; Hard coating materials for screens of mobile phones; Hard coating materials for optical recording media such as CD, DVD, and Blu-ray disc; Hard coat material for transfer film for insert mold (IMD, IMF); Coating materials for rubber rollers for OA equipment such as copiers and printers; A glass coating material for a reading unit of an OA such as a copying machine or a scanner; Coating materials for optical lenses such as cameras, video cameras, and glasses; Windshield for watches such as wrist watches, glass coatings; Coating materials for windows of various vehicles such as automobiles and railroad cars; Printing inks or paints for various building materials such as painted surfaces; Coating materials for windowpanes of houses; Wood-based paints such as furniture; Artificial and synthetic leather coating materials; Paints or coating materials for various plastic molded articles such as housings of household appliances; A FRP bath coating material or a coating material.

Examples of articles that can impart scratch resistance (scratch resistance) and antifouling property by using the fluorine-curing resin or active energy ray-curable composition of the present invention include a prism sheet or a diffusion sheet which is a backlight member of an LCD . Further, by adding the fluorine-curing resin of the present invention to a coating material for a prism sheet or a diffusion sheet, it is possible to improve the leveling property of the coating material and to impart abrasion resistance (scratch resistance) and antifouling property to the coating film of the coating material .

Further, since the cured coating film of the fluorine-curing resin of the present invention has a low refractive index, it can also be used as a porcelain for a low refractive index layer in an antireflection layer for preventing glare such as fluorescent lamps on various display surfaces such as an LCD . Antifouling properties can also be imparted to the coating film surface while maintaining the low refractive index of the coating film by adding the fluorine-curing resin of the present invention to the porcelain for the antireflection layer, particularly the porcelain for low refractive index layer in the antireflection layer.

Examples of other applications in which the fluorine-curable resin or active energy ray-curable composition of the present invention can be used include optical fiber clad materials, waveguides, sealing materials for liquid crystal panels, various optical sealants, optical adhesives, and the like have.

Particularly, when the active energy ray-curable composition of the present invention is used as an anti-glare coating material in the coating material for a protective film of a polarizing plate for LCD, inorganic or organic materials such as silica fine particles, acrylic resin fine particles, and polystyrene resin fine particles, It is preferable to blend the organic fine particles at a ratio of 0.1 to 0.5 times the total mass of the curing component in the active energy ray curable composition of the present invention because the antifogging property is excellent.

When the fluorine-curing resin or the active energy ray-curable composition of the present invention is used for an anti-glare coating material for a protective film of a polarizing plate for LCD, the coating material is brought into contact with the mold having surface irregularities before curing, It is also applicable to a transfer method in which the surface of the coating layer is embossed by irradiating an active energy ray from the opposite side to harden it, thereby imparting antistatic properties.

[Example]

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The fluorine content of the fluorine-containing polymer is calculated from the mass ratio of fluorine atoms to the total amount of raw materials used.

(Synthesis Example 1) Synthesis of perfluoropolyether bromoisobutyric acid ester derivative

29 g of a dialcohol of perfluoropolyether represented by the following formula (A'-1), 4.6 g of triethylamine and 15 g of diisopropyl ether (hereinafter referred to as " IPE ") were charged into a reaction vessel and stirred, To give a homogeneous solution. To this solution, 10 g of 2-bromoisobutyric acid bromide was added dropwise over 75 minutes while being cooled so that the internal temperature did not exceed 30 占 폚. The mixture was stirred at room temperature for 3 hours and further stirred at 40 占 폚 for 15 hours. Subsequently, after diluting with 89 g of IPE, 100 g of 0.1 M hydrochloric acid was added and stirred. From the obtained reaction solution, the organic layer separated by liquid separation was washed with a saturated sodium hydrogencarbonate aqueous solution and saturated brine, and dried over anhydrous sodium sulfate. Thereafter, the obtained reaction solution was concentrated with an efferentiator to obtain 30.7 g of a perfluoropolyether bromoisobutyric acid ester derivative.

(Wherein X is a perfluoromethylene group and a perfluoroethylene group, an average of 7 perfluoromethylene groups per molecule and an average of 8 perfluoroethylene groups, and the average number of fluorine atoms is 46 , And the number average molecular weight by GPC is 1,500)

(Example 1)

8.2 g of methyl ethyl ketone (hereinafter referred to as " MEK "), 0.373 g of 2,2'-bipyridyl and 0.118 g of cuprous chloride were added to a reaction vessel purged with nitrogen, and the mixture was stirred at room temperature for 30 minutes. Subsequently, 6.25 g of 2-hydroxyethyl methacrylate and 1.98 g of the perfluoropolyether bromoisobutyric acid ester derivative obtained in Synthesis Example 1 were added and reacted at 50 DEG C for 21 hours under a nitrogen stream to obtain a polymer solution. The obtained polymer solution was diluted with methanol and purified by reprecipitation with water / methanol to obtain a white solid. 3.0 g of this solid was dissolved in 4.1 g of MEK, 2.1 g of a 2-ethylhexanoate tin solution (0.2 mass% MEK solution) was added, and the temperature was raised to 60 占 폚. 4.66 g of a MEK solution (50% by mass) of 2-acryloyloxyethyl isocyanate was added dropwise while introducing dry air into the solution. After reacting for 1 hour at 80 ° C for 4 hours, 1) having a molecular weight of 40% by mass. The molecular weight of the fluoropolymerizable polymer (1) was measured by GPC to find that the number average molecular weight was 9,100 and the weight average molecular weight was 10,500.

The ¹ H-NMR spectrum of the fluoropolymerizable polymer (1) obtained in Example 1 is shown in Fig. 1, and the GPC chart is shown in Fig. The peaks near 1.2 ppm and 2.1 ppm in the ¹ H-NMR spectrum are from residual solvents.

(Example 2)

7.6 g of MEK, 0.559 g of 2,2'-bipyridyl and 0.177 g of cuprous chloride were added to a reaction vessel purged with nitrogen, and the mixture was stirred at room temperature for 30 minutes. Then, 4.72 g of 2-hydroxyethyl methacrylate and 2.96 g of the perfluoropolyether bromoisobutyric acid ester derivative obtained in Synthesis Example 1 were added and reacted at 50 DEG C for 21 hours under a nitrogen stream to obtain a polymer solution. The obtained polymer solution was diluted with methanol and purified by reprecipitation with water / methanol to obtain a white solid. 3.0 g of this solid was dissolved in 4.0 g of MEK, 2.1 g of a 2-ethylhexanoate tin solution (0.2 wt% MEK solution) was added, and the temperature was raised to 60 占 폚. 3.74 g of a MEK solution (50 mass%) of 2-acryloyloxyethyl isocyanate was added dropwise while introducing dry air into the solution, reacted for 1 hour, reacted at 80 ° C for 4 hours, diluted with MEK, A 40% by mass MEK solution of the fluoropolymerizable polymer (2) was obtained. The molecular weight of this fluorine-containing polymer (2) was measured by GPC and found to be 6,200 in number average molecular weight and 7,700 in weight average molecular weight.

The ¹ H-NMR spectrum of the fluoropolymerizable polymer (2) obtained in Example 2 is shown in Fig. 3, and the GPC chart is shown in Fig. The peaks near 1.2 ppm and 2.1 ppm in the ¹ H-NMR spectrum are from residual solvents.

(Comparative Example 1)

69 parts by mass of methyl isobutyl ketone (hereinafter referred to as " MIBK ") as a solvent was charged into a glass flask equipped with a stirrer, a thermometer, a cooling tube, and a dropping device and heated to 105 DEG C while stirring under a nitrogen stream. Next, 137.8 parts by mass of a monomer solution obtained by mixing 40 parts by mass of an acrylate containing a fluorinated alkyl group represented by the following formula, 28.8 parts by mass of 2-hydroxyethyl methacrylate, and 69 parts by mass of MIBK, 100 parts by mass of a radical polymerization initiator (t- 2-ethylhexanoate) and 25.5 parts by mass of a polymerization initiator solution prepared by mixing 22.5 parts by mass of MIBK were set in a separate dripping apparatus, and while maintaining the inside of the flask at 105 ° C for 3 hours . After completion of dropwise addition, the mixture was stirred at 105 DEG C for 10 hours to obtain 232.7 parts of a polymer solution.

Then, 0.1 part by mass of p-methoxyphenol as a polymerization inhibitor and 0.05 part by mass of tin octylate as a urethanization catalyst were charged and 31.2 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise under air flow at 60 캜 for 1 hour did. After completion of the dropwise addition, the mixture was stirred at 60 占 폚 for 1 hour, elevated to 80 占 폚 and stirred for 10 hours, and as a result, disappearance of isocyanate groups was confirmed by IR spectroscopy. Subsequently, a part of the solvent was distilled off under reduced pressure to obtain a 40 mass% MIBK solution of the fluoropolymerizable polymer (3). When the molecular weight of the fluorine-containing polymer (3) was measured by GPC (polystyrene reduced molecular weight), the number average molecular weight was 3,000, the weight average molecular weight was 7,000, and the maximum molecular weight was 40,000.

[Measurement of number-average molecular weight and weight-average molecular weight]

In the present invention, the number average molecular weight (Mn), the weight average molecular weight (Mw) and the degree of dispersion were measured by GPC under the following conditions. The number average molecular weight (Mn) and the weight average molecular weight (Mw) are values in terms of standard polystyrene.

Measurement apparatus: "HLC-8220 GPC" manufactured by Tosoh Corporation,

Column: " HHR-H " (6.0 mm ID x 4 cm), manufactured by Tosoh Corporation,

&Quot; TSK-GEL GMHHR-N " (7.8 mm ID × 30 cm) manufactured by Tosoh Corporation,

&Quot; TSK-GEL GMHHR-N " (7.8 mm ID × 30 cm) manufactured by Tosoh Corporation,

&Quot; TSK-GEL GMHHR-N " (7.8 mm ID × 30 cm) manufactured by Tosoh Corporation,

&Quot; TSK-GEL GMHHR-N " (7.8 mm ID × 30 cm) manufactured by Tosoh Corporation,

Detector: ELSD (Ortech's "ELSD2000")

Data processing: "GPC-8020 Model II Data Interpretation Version 4.30" manufactured by Tosoh Corporation

Measurement conditions: Column temperature 40 캜

The developing solvent tetrahydrofuran (THF)

Flow rate 1.0 ml / min

Sample: A tetrahydrofuran solution of 1.0% by mass in terms of resin solid content was filtered with a microfilter (100 μl).

Standard samples: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of "GPC-8020 Model II Data Interpretation Version 4.30".

(Monodisperse polystyrene)

&Quot; A-500 " manufactured by Tosoh Corporation

&Quot; A-1000 " manufactured by Tosoh Corporation

Quot; A-2500 " manufactured by Tosoh Corporation

Quot; A-5000 " manufactured by Tosoh Corporation

Quot; F-1 " manufactured by Tosoh Corporation

Quot; F-2 " manufactured by Tosoh Corporation

Quot; F-4 " manufactured by Tosoh Corporation

Quot; F-10 " manufactured by Tosoh Corporation

Quot; F-20 " manufactured by Tosoh Corporation

Quot; F-40 " manufactured by Tosoh Corporation

Quot; F-80 " manufactured by Tosoh Corporation

&Quot; F-128 " manufactured by Tosoh Corporation

&Quot; F-288 " manufactured by Tosoh Corporation

Quot; F-550 " manufactured by Tosoh Corporation

[Production of active energy ray-curable composition containing fluorine-containing polymerizable polymer]

(Examples 3 to 4 and Comparative Examples 2 to 3)

50 parts by mass of pentafunctional non-deformed urethane acrylate, 50 parts by mass of dipentaerythritol hexaacrylate, 25 parts by mass of butyl acetate, a photopolymerization initiator ("Irgacure 184" manufactured by Ciba Specialty Chemicals Inc.) Hydroxycyclohexyl phenyl ketone), 54 parts by mass of toluene, 28 parts by mass of 2-propanol, 25 parts by mass of ethyl acetate and 28 parts by mass of propylene glycol monomethyl ether were uniformly mixed to obtain an active energy ray curable composition ≪ / RTI > Subsequently, 2.5 parts by mass of a solution containing 40% by mass of the fluoropolymerizable polymer obtained in Examples 1 and 2 and Comparative Example 1 was added to 265 parts by mass of the active energy ray curable composition serving as the base, An active energy ray curable composition containing a fluorine polymerizable polymer was obtained. The active energy ray-curable compositions using the fluorine-polymerizable polymers obtained in Examples 1 and 2 and Comparative Example 1 were evaluated as Examples 3 to 4 and Comparative Example 3, respectively, and ultraviolet rays of the base A curable composition alone was also prepared and used as Comparative Example 2.

[Evaluation of Compatibility of Fluoropolymerizable Polymer]

The appearance of the active energy ray curable composition obtained above was visually observed to evaluate the compatibility of the fluoropolymerizable polymer.

A: transparent

B: There is turbidity

C: Separation of components is visible

[Evaluation of active energy ray curable composition containing fluorinated radically polymerizable polymer]

(Preparation of samples for evaluation)

The active energy ray curable composition containing the fluorine radical polymerizable copolymer obtained above was applied to a polyethylene terephthalate (PET) film (thickness 188 탆) using a bar coater (No. 13) And the solvent was volatilized and cured by using an ultraviolet curing apparatus (high-pressure mercury lamp under a nitrogen atmosphere, an ultraviolet irradiation amount of 2.0 kJ / m ² ) for 5 minutes to prepare a coated film. As Comparative Example 2, a coating film was similarly prepared for an active energy ray curable composition to which a fluoropolymerizable polymer was not added. The coated film was allowed to stand at room temperature for one day, and then the following contact angle was measured and evaluated, and the antifouling adhesion was evaluated.

The coated surface of the obtained coated film was polished with a felt pen (Magic Ink large blue, manufactured by Teranishy Kagaku Kogyo K.K.), and the adhered state of the blue ink was observed to measure the antifouling property (dirt adhesion preventing property, And evaluated.

After UV curing, the film was immersed in a strong alkaline aqueous solution (a KOH aqueous solution of 2 mol / l) at 70 캜 for 1 minute, washed with pure water, dried at 100 캜 for 3 minutes, (Antifouling property, stain resistance) by using a felt-tip pen was also evaluated. The evaluation results are shown in Table 1.

[Table 1]

(Evaluation Criteria of Anti-

AA: The best antifouling property, and the ink splashing on the beads

A: The ink is not splashed on the ball, and the line splashing occurs (the line width is less than 50% of the width of the pen tip of the felt pen).

B: The line of ink flew on the line, and the line width was 50% or more but less than 100% of the width of the pen tip of the felt pen

C: The ink is not fried at all and is clearly drawn on the surface.

(Evaluation Criteria of Pollution Wiping)

After the test of " prevention of contamination adherence ", the shape when wiped with tissue paper with a load of 1 kg was evaluated according to the following criteria.

A: I was able to completely remove the ink by wiping one time

B: Was able to completely remove the ink by wiping 2 to 10 times

C: The ink could not be completely removed by the wiping operation 10 times

In the evaluation results of Examples 3 and 4 shown in Table 1, the surface of the film coated with the active energy ray-curable composition using the fluorine-containing polymerizable polymers (1) and (2) of the present invention and cured by ultraviolet rays, And it was found that it had a preventive property and a pollution wiping property. It was also confirmed that these performances did not deteriorate even when treated with strong alkaline water.

On the other hand, in Comparative Example 2 in which the fluorine-polymerizable polymer was not used, it was found that the surface of the film coated with the active energy ray-curable composition and cured with ultraviolet rays had insufficient dirt adhesion and contamination wipe resistance. Further, in Comparative Example 3 using the fluorine-containing polymer (3) different from the fluorine-containing polymerizable polymer of the present invention, it was found that the prepared active energy ray-curable composition had a slight turbidity and the compatibility was insufficient. Further, it was found that the film surface coated with the active energy ray-curable composition and cured with ultraviolet rays had antifouling property, but the antifouling property was insufficient. It was also confirmed that these performances were lowered when treated with a strong alkaline water.

Claims (10)

An isocyanate group, an epoxy group, a carboxyl group, a carboxylate halide (hereinafter referred to as " carboxylic acid halide ") is added to both ends of a compound (A) having functional groups having radical-generating ability at both ends of a poly (perfluoroalkylene ether) chain represented by the following general formula (C) obtained by polymerizing a monomer component essentially comprising a polymerizable unsaturated monomer (B) having at least one reactive group selected from the group consisting of aliphatic, aromatic, (D) having at least one functional group and a polymerizable unsaturated group selected from the group consisting of a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide and an acid anhydride which react with a reactive group to form a bond, Containing fluorine-containing polymer.

(In the above general formula (1), X is any one of the following formulas (a) to (e), all X in the general formula (1) may be the same, plural ones exist in a random phase or a block phase And n is one or more numbers representing repeating units)

The method according to claim 1,
The perfluoroethylene structure represented by the formula (a) and the perfluoroethylene structure represented by the formula (b) coexist in the poly (perfluoroalkylene ether) chain represented by the general formula (1) Wherein the fluoropolymerizable polymer is a fluoropolymer. The method according to claim 1,
Wherein n in the general formula (1) is in the range of 3 to 100. The fluoropolymerizable polymer according to claim 1, The method according to claim 1,
Wherein n in the general formula (1) is in the range of 6 to 70. The fluoropolymerizable polymer according to claim 1, The method according to claim 1,
The radical-forming functional group of the compound (A) is preferably an organic group having a halogen atom, an organic group having an alkyltelluril group, an organic group having a dithioester group, an organic group having a peroxide group, or an organic group having an azo group Fluorinated polymer. The method according to claim 1,
(B) is contained in the compound (A) in the compound (A), the functional group having a radical-generating ability is an organic group having a halogen atom, an organic group having an alkyltelluril group or a dithioester group, Is a living radical polymerization, and the polymerization method in which the polymerization is carried out as a monomer component is a living radical polymerization. The method according to claim 6,
Wherein the living radical polymerization is carried out in the presence of a polymerization initiator, a transition metal compound and a compound having a ligand capable of coordinating with the transition metal. An active energy ray curable composition comprising the fluoropolymerizable polymer according to any one of claims 1 to 7. A cured product obtained by curing the active energy ray-curable composition according to claim 8. An article having a cured coating film of the active energy ray curable composition according to claim 8.

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