JP2012072232A - Polymerizable fluorine-based compound, active energy ray-curable composition using the same, and cured product of the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerizable fluorine-based compound imparting excellent antifouling property to a coating film surface, and to provide an active energy ray-curable composition, a cured product of the composition and an article having the cured coating film of the compound or of the composition which maintain excellent antifouling property even when the coating film surface is abraded.SOLUTION: A polymerizable fluorine-based compound expressed by general formula (1) is used. In the formula, R, R, R, Rand Reach independently represent a hydrogen atom or a methyl group; at least one in R, Rand Rrepresents a group having a (meth)acryloyloxy skeleton and the rest represents a hydroxyl group; Xand Xeach independently represent an organic group; PFPE represents a poly(perfluoroalkylene ether) chain; and n represents a number ranging from 0 to 10 in average.

Description

  The present invention relates to a fluorine-containing surfactant capable of imparting excellent antifouling properties to a cured coating film surface, and a polymerizable fluorine-based compound used as a fluorine-containing surface modifier. The present invention also relates to an active energy ray-curable composition using the polymerizable fluorine-based compound, a cured product thereof, and an article having the cured coating film.

  Conventionally, a front protective plate is further provided on a polarizing plate which is the outermost surface of a liquid crystal display. As the front protective plate, a transparent resin plate (acrylic (PMMA) sheet, polycarbonate (PC) sheet, PMMA / PC composite type sheet) or glass is used. Since the resin sheet has a thickness of 0.3 mm to 2 mm and is softer than glass and is likely to be scratched by scratching, a hard coat layer is provided on the surface to provide scratch resistance.

  As a method for improving the scratch resistance by providing the above hard coat layer, a cured coating film obtained by curing a hard coat material containing a polyfunctional monomer such as polyfunctional (meth) acrylate is used as a base material surface. The method of forming is known. However, the conventional cured coating film has a problem in that when dirt such as fingerprints, sebum, sweat, and cosmetics adheres, the dirt is conspicuous and the screen display is difficult to see. In addition, in order to make the screen display easier to see, it is not easy to remove the dirt.

  Therefore, in order to prevent the adhesion of dirt, and to impart antifouling properties that can easily remove the attached dirt, the hard coat material may be combined with a fluorine-containing surfactant or fluorine-containing surface modifier (hereinafter, these are also combined). Studies have been made to simply add “fluorinated surfactant”) as an additive. In particular, in order to maintain antifouling properties, a monoacrylate having a polymerizable group, a monoacrylate having a fluorinated alkyl group designed to be immobilized by a covalent bond in a cured coating film, and an acrylic monomer having active hydrogen. A polymerizable fluorine-containing surfactant having an unsaturated group obtained by copolymerizing with a monomer and then reacting the obtained polymer with an acrylic monomer having an isocyanate group has been proposed (for example, , See Patent Document 1). This polymerization type fluorine-containing surfactant has a polymerizable group, and when used as an additive to a hard coat material, it is bonded to the polymerization component in the composition by a covalent bond and fixed to the coating film. The However, there has been a problem that the antifouling property is lowered when the surface of the cured coating film of the hard coat material is repeatedly wiped many times to wear the coating film surface.

  In addition, a poly (perfluoroalkylene ether) chain produced from a compound having a (perfluoroalkylene ether) chain and having di (meth) acryloyl groups at both ends thereof, and a polymerizable fluorine-containing group having an unsaturated group A surfactant has been proposed (for example, see Patent Document 2). Similar to the one described in Patent Document 1, this polymerization type fluorine-containing surfactant has a problem that the antifouling property after wear is greatly reduced.

  Therefore, in order to wipe off the repeatedly adhered dirt, there is a demand for a material that maintains antifouling properties even when the coating film surface is worn.

JP 2007-246696 A International Publication WO2009 / 133770

  The problem to be solved by the present invention is to provide a polymerizable fluorine-based compound capable of imparting excellent antifouling properties to the coating film surface. Moreover, the active energy ray-curable composition that can maintain excellent antifouling properties even if the surface of the coating film is worn by repeatedly wiping off the dirt adhering to the surface of the coating film, its cured product, and an article having the cured coating film Is to provide.

  As a result of intensive studies to solve the above problems, the present inventors have obtained a reaction between a compound having an epoxy group introduced at both ends of a poly (perfluoroalkylene ether) chain and (meth) acrylic acid. The active energy ray-curable composition containing a polymerizable fluorine-based compound that is polyfunctionalized by introducing a polymerizable group into a hydroxyl group present in the compound has excellent antifouling properties on the surface of the cured coating film. It was found that excellent antifouling properties could be maintained even when the surface of the coating film was worn by repeatedly wiping off the dirt adhering to the surface of the coating film.

  That is, the present invention relates to a polymerizable fluorine-based compound represented by the following general formula (1) and an active energy ray-curable composition containing the polymerizable fluorine-based compound.

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４及びＲ^５はそれぞれ独立に水素原子又はメチル基を表し、Ｒ^６、Ｒ^７及びＲ^８はそれぞれ独立に水酸基又は下記一般式（２）で表される基を表し、Ｘ^１及びＸ^２はそれぞれ独立に２価の有機基を表し、ＰＦＰＥはポリ（パーフルオロアルキレンエーテル）鎖を表す。ただし、Ｒ^６、Ｒ^７及びＲ^８のうち少なくとも１つは下記一般式（２）で表される基である。また、ｎは平均で０〜１０の範囲を表す。）

(In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or a methyl group, and R ⁶ , R ⁷ and R ⁸ each independently represent a hydroxyl group or the following general formula (2) X ¹ and X ² each independently represent a divalent organic group, and PFPE represents a poly (perfluoroalkylene ether) chain, provided that R ⁶ , R ⁷ and R ⁸ (At least one is a group represented by the following general formula (2), and n represents a range of 0 to 10 on average.)

（式中、Ｒ^９はそれぞれ独立に水素原子又はメチル基を表し、Ｘ^３はそれぞれ独立に単結合、２価又は３価の有機基を表す。また、ｍは１又は２を表す。）

(In the formula, each R ⁹ independently represents a hydrogen atom or a methyl group, each X ³ independently represents a single bond, a divalent or trivalent organic group, and m represents 1 or 2.)

  Furthermore, the present invention provides a cured product obtained by applying the polymerizable fluorine-based compound or the active energy ray-curable composition to a substrate and irradiating and curing the active energy ray, and the polymerizable fluorine-based compound or activity. The present invention relates to an article having a cured coating film of an energy beam curable composition.

  The polymerizable fluorine-based compound of the present invention can impart antifouling properties to the substrate surface by coating the substrate alone to form a cured coating film. Moreover, the active energy ray-curable composition containing the polymerizable fluorine-based compound as a fluorine-containing surfactant has an effect of minimizing the surface free energy peculiar to fluorine atoms when applied to a substrate. Thus, the polymerizable fluorine-based compound is segregated on the surface of the coating film, and surface modification that imparts antifouling property or the like only to the coating film surface is possible. Furthermore, since the polymerizable fluorine-based compound can be polymerized with other curable components in the active energy ray-curable composition, the polymerizable fluorine-based compound of the present invention is stronger in the cured coating film. Therefore, volatilization and desorption of the polymerizable fluorine-based compound or a decomposition product thereof can be suppressed from the surface of the cured coating film even if heat treatment, washing or the like is performed.

  Moreover, the cured coating film using the polymerizable fluorine-based compound of the present invention has excellent antifouling property on the surface, and repeatedly wipes off the dirt adhering to the cured surface to wear the coating film surface. In addition, since excellent antifouling property can be maintained, it is extremely useful as a hard coat layer for a front protective plate provided on the outermost surface of the liquid crystal display.

FIG. 1 is an IR spectrum chart of the polymerizable fluorine-based compound (1) obtained in Example 1. FIG. 2 is a chart of ¹ H-NMR spectrum of the polymerizable fluorine-based compound (1) obtained in Example 1. 3 is a chart of ¹³ C-NMR spectrum of the polymerizable fluorine-based compound (1) obtained in Example 1. FIG.

  The polymerizable fluorine-based compound of the present invention is a compound represented by the following general formula (1).

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４及びＲ^５はそれぞれ独立に水素原子又はメチル基を表し、Ｒ^６、Ｒ^７及びＲ^８はそれぞれ独立に水酸基又は下記一般式（２）で表される基を表し、Ｘ^１及びＸ^２はそれぞれ独立に２価の有機基を表し、ＰＦＰＥはポリ（パーフルオロアルキレンエーテル）鎖を表す。ただし、Ｒ^６、Ｒ^７及びＲ^８のうち少なくとも１つは下記一般式（２）で表される基である。また、ｎは平均で０〜１０の範囲を表す。）

(In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or a methyl group, and R ⁶ , R ⁷ and R ⁸ each independently represent a hydroxyl group or the following general formula (2) X ¹ and X ² each independently represent a divalent organic group, and PFPE represents a poly (perfluoroalkylene ether) chain, provided that R ⁶ , R ⁷ and R ⁸ (At least one is a group represented by the following general formula (2), and n represents a range of 0 to 10 on average.)

（式中、Ｒ^９はそれぞれ独立に水素原子又はメチル基を表し、Ｘ^３はそれぞれ独立に単結合、２価又は３価の有機基を表す。また、ｍは１又は２を表す。）

(In the formula, each R ⁹ independently represents a hydrogen atom or a methyl group, each X ³ independently represents a single bond, a divalent or trivalent organic group, and m represents 1 or 2.)

  The folded portion of the bond in the general formula (1) represents a single bond not involving a carbon atom. Moreover, the folding | returning part of the coupling | bonding in another formula is also synonymous.

R ¹ and R ² in the general formula (1) and R ⁹ in the general formula (2) are each independently a hydrogen atom or a methyl group, but the active energy ray-curable resin (B) and the activity described below are active. R ¹ , R ² and R ⁹ are preferably hydrogen atoms because of good polymerizability with the energy ray curable monomer (C).

X ¹ and X ² in the general formula (1) are each independently a divalent organic group. Specific examples of the divalent organic group include a methylene group, an ethylene group, a propylene group, and a butylene group. Etc.

X ³ in the general formula (2) is a single bond, a divalent or trivalent organic group. When X ³ is a single bond, m in the general formula (2) is 1. When X ³ , X ⁴ or X ⁵ is a divalent or trivalent organic group, m in the general formula (2) is 1 or 2. In the present invention, the term “single bond” means that they are directly bonded without any other atom.

Furthermore, since the divalent or trivalent organic group is a linking group formed by a reaction with a hydroxyl group of the compound (a4) described later, an organic group containing a urethane bond or an ester bond is preferable. Examples of such divalent or trivalent organic groups include the following organic groups. A (meth) acryloyl group surrounded by parentheses in the general formula (1) is bonded to Y ¹ , Y ² and Y ³ .

（式中、Ｙ^１、Ｙ^２及びＹ^３はそれぞれ独立にメチレン基、エチレン基、プロピレン基、ブチレン基等のアルキレン基を表し、Ｒ^１０は水素原子又はメチル基、エチル基、プロピル基等のアルキル基を表す。）

Wherein Y ¹ , Y ² and Y ³ each independently represent an alkylene group such as a methylene group, an ethylene group, a propylene group or a butylene group, and R ¹⁰ represents a hydrogen atom or a methyl group, an ethyl group or a propyl group. Represents an alkyl group.)

  The poly (perfluoroalkylene ether) chain represented by “PFPE” in the general formula (1) has a structure in which a divalent fluorocarbon group having 1 to 3 carbon atoms and oxygen atoms are alternately connected. The thing which has is mentioned. The divalent fluorocarbon group having 1 to 3 carbon atoms may be one kind or a mixture of a plurality of kinds, and specifically, those represented by the following structural formula (a1) Can be mentioned.

（上記構造式（ａ１）中、Ｘは下記構造式（ａ１−１）〜（ａ１−５）であり、構造式（ａ１）中の全てのＸが同一構造のものであってもよいし、また、複数の構造がランダムに又はブロック状に存在していてもよい。また、ｔは繰り返し単位数を表す１以上の整数である。）

(In the structural formula (a1), X is the following structural formulas (a1-1) to (a1-5), and all X in the structural formula (a1) may have the same structure, In addition, a plurality of structures may be present randomly or in a block shape, and t is an integer of 1 or more representing the number of repeating units.

  Among these, the perfluoromethylene structure represented by the structural formula (a1-1) and the structure in that the coating film surface has particularly good wiping properties and excellent antifouling properties. Those coexisting with the perfluoroethylene structure represented by the formula (a1-2) are particularly preferable. Here, the abundance ratio between the perfluoromethylene structure represented by the structural formula (a1-1) and the perfluoroethylene structure represented by the structural formula (a1-2) is a molar ratio [structure (a1- 1) / structure (a1-2)] is preferably 1/10 to 10/1 in terms of antifouling property, and the value of t in the structural formula (a1) is 3 to 100. The range of 6 to 70 is particularly preferable.

  In addition, the poly (perfluoroalkylene ether) chain is included in one poly (perfluoroalkylene ether) chain from the viewpoint of excellent antifouling property and easy improvement in solubility in a non-fluorinated curable resin composition. The total number of fluorine atoms is preferably in the range of 18 to 200, more preferably in the range of 25 to 150.

  Further, the number n of repeating units in the general formula (1) is in the range of 0 to 10 on average, but when the polymerizable fluorine-based compound of the present invention is used as a fluorine-based surfactant, The range of 0 to 5 is preferable on average because the compatibility with the components can be made better, and the range of 0 to 2 is more preferable on average.

The number n of repeating units in the general formula (1) can be calculated using the hydroxyl equivalent of the compound (a2) and the epoxy equivalent of the compound (a3) described later. For example, when the compound (a2) is reacted with epichlorohydrin and epoxidized to obtain the compound (a3), the number n of repeating units in the general formula (1) is obtained by the following formula (1). Can do. The hydroxyl equivalent of the compound (a2) is, for example, the compound (a2) represented by the following general formula (a2-1-1), measured by ¹⁹ F-NMR, and adjacent to the hydroxyl group and methylene. After determining the integral ratio of the chemical shift of the CF ₂ moiety, the chemical shift of the perfluoromethylene group (—CF ₂ —), the chemical shift of the perfluoroethylene group (—CF ₂ CF ₂ —), etc. The compound (a2) obtained from the results of obtaining the number of other perfluoromethylene groups, perfluoroethylene groups, etc. from the respective integral ratios, with the integral ratio of the chemical shift of the CF ₂ moiety adjacent thereto being 4 Can be obtained by dividing the molecular weight of 2 by 2. Moreover, the epoxy equivalent of a compound (a3) can be measured with the following method.

（式中、ｐ及びｑはそれぞれ独立に１以上の整数を表す。）

(In the formula, p and q each independently represents an integer of 1 or more.)

[Measurement method of epoxy equivalent]
Dissolve the sample (1 ± 0.3 mmol equivalent) in 20 ml of methyl ethyl ketone, add 5 ml of 20% by mass acetic acid solution (CTMAB) of cetyltrimethylammonium bromide, add 4-6 drops of crystal violet indicator (acetic acid solution), and stir with a stirrer. Titrate with 0.1 mol / l perchloric acid acetic acid solution (0.1 mol / l HClO ₄ ). One drop of 0.1 mol / l perchloric acid acetic acid solution is added to change the color from blue-violet to blue, and the titration is obtained with the blue color maintained for 1 minute as the end point. Further, since the volume expansion coefficient of the solvent needs to be corrected by temperature, the temperature of the perchloric acid acetic acid solution is recorded. At the same time, a blank test without using a sample is performed to measure the titration amount in the same manner, and the epoxy equivalent is determined according to the following formula (2) using the obtained titration amount.

Ｗ ：試料量（ｇ）
Ｖｓ：本試験に要する０．１ｍｏｌ／ｌ ＨＣｌＯ_４の適定量（ｍｌ）
Ｖｂ：空試験に要する０．１ｍｏｌ／ｌ ＨＣｌＯ_４の適定量（ｍｌ）
Ｆ_２０：０．１ｍｏｌ／ｌ ＨＣｌＯ_４の２０℃における力価
ｔ ：滴定時の０．１ｍｏｌ／ｌ ＨＣｌＯ_４の液温（℃）

W: Sample amount (g)
Vs: Appropriate amount of 0.1 mol / l HClO ₄ required for this test (ml)
Vb: Appropriate amount of 0.1 mol / l HClO ₄ required for the blank test (ml)
F ₂₀ : titer of 0.1 mol / l HClO ₄ at 20 ° C. t: liquid temperature of 0.1 mol / l HClO ₄ at titration (° C.)

  Examples of the method for producing the compound (A) include a compound (a2) having a hydroxyl group at both ends of a poly (perfluoroalkylene ether) chain and an epihalohydrin such as epichlorohydrin or β-methylepichlorohydrin. By reacting, a compound (a3) having an epoxy group at both ends of the poly (perfluoroalkylene ether) chain is obtained. Next, (meth) acrylic acid is reacted with the epoxy group of the compound (a3) to obtain a compound (a4) having (meth) acryloyl groups at both ends of the (perfluoroalkylene ether) chain. A method of reacting the hydroxyl group of the compound (a4) with a compound (a5) having a functional group reactive with a hydroxyl group and a (meth) acryloyl group can be mentioned.

  In the present invention, “(meth) acrylic acid” refers to one or both of methacrylic acid and acrylic acid, and “(meth) acryloyl” refers to one or both of methacryloyl and acryloyl. “Meth) acrylate” refers to one or both of methacrylate and acrylate.

  Examples of the compound (a2) include the following general formulas (a2-1) and (a2-2). In addition, “—PFPE—” in the following formula represents the poly (perfluoroalkylene ether) chain.

  Moreover, as said compound (a3), the following general formula (a3-1), (a3-2) etc. are mentioned, for example. In addition, when the said compound (a2) and epihalohydrin are made to react, in the process in which an epoxy group is introduce | transduced into the said compound (a2), an unreacted hydroxyl group in the said compound (a2) reacts, and a repeating unit is made. It becomes the epoxy compound which has. The range of the number of repeating units n is as described above.

  Examples of the reaction method of the compound (a2) and epihalohydrin include the compound (a2) and epihalohydrin such as epichlorohydrin, epibromohydrin, epiiodohydrin, β-methylepichlorohydrin, and the like. After mixing to form a dissolved mixture, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to the dissolved mixture as it is, or an aqueous solution of an alkali metal hydroxide is added dropwise at 20 to 120 ° C. The method of making it react for 10 hours is mentioned. Among the epihalohydrins, epichlorohydrin is preferable because of its good reactivity with the compound (a2).

  Here, the amount of the epihalohydrin added is preferably in the range of usually 0.3 to 30 molar equivalents relative to 1 molar equivalent of the hydroxyl group in the compound (a2), but the molecular weight can be easily adjusted. And since the process of removing excess epihalohydrin can be shortened and productivity can be improved, it is more preferable that it is the range of 1-15 equivalent, suppresses the oligomerization of an epoxy compound (a3), and described above average repeating unit number n Is more preferably in the range of 1.5 to 12 equivalents.

  In this reaction, when an alkali metal hydroxide is used as an aqueous solution, the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system, and water and epihalohydrin are continuously added under reduced pressure or normal pressure. A method of continuously distilling the epihalohydrin back into the reaction system while distilling off the distillate and removing water is preferable.

  The above reaction may be carried out at 50 to 150 ° C. when a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride is added as a catalyst to the dissolved mixture of the compound (a2) and epihalohydrin After reacting for 1 to 5 hours to obtain a halohydrin etherified product of the compound (a2), an alkali metal hydroxide is added as it is or in an aqueous solution, and the mixture is reacted again at 20 to 120 ° C. for 1 to 10 hours to remove. A method of hydrogen halide (ring closure) is preferred.

  In any of the above reactions, it is preferable to use an organic solvent in order to allow the reaction to proceed smoothly. Examples of organic solvents that can be used here include alcohol solvents such as methanol, ethanol, isopropyl alcohol, and butanol; ketones such as acetone and methyl ethyl ketone; ether solvents such as dioxane; and aprotic such as dimethyl sulfone and dimethyl sulfoxide. Examples include polar solvents. The amount of these organic solvents used is preferably 0.05 to 0.5 times, more preferably 0.10 to 0.30 times, based on mass with respect to the amount of epihalohydrin. . In particular, when an aprotic polar solvent is used, the amount is preferably 0.05 to 1 times, more preferably 0.10 to 0.6 times the amount of epihalohydrin.

  After performing the epoxidation reaction in this way, the crude product of the compound (a3), which is the obtained epoxy compound, is 110 to 250 ° C. and a pressure of 1.3 kPa or less under heating and reduced pressure without washing or washing with water. To remove the epihalohydrin and the organic solvent used. In order to reduce hydrolyzable halides, the crude product obtained after recovering epihalohydrin and the like is further dissolved in an organic solvent such as toluene and methyl isobutyl ketone, and sodium hydroxide, potassium hydroxide, etc. The concentration of the epoxy group can be further increased by adding an aqueous solution of an alkali metal hydroxide to cause a reaction to carry out a ring-closing reaction. The amount of alkali metal hydroxide used in this case is preferably in the range of 0.5 to 10 mol, and in the range of 1.2 to 5 mol, per 1 mol of hydrolyzable chlorine atoms remaining in the crude product. Is more preferable.

  It is preferable that the reaction temperature at the time of the ring-closing reaction is in the range of 50 to 120 ° C., and the reaction time is in the range of 0.5 to 3 hours. For the purpose of improving the reaction rate, a phase transfer catalyst such as a quaternary ammonium salt or crown ether may be present in the reaction system. When the phase transfer catalyst is used, the amount used is preferably in the range of 0.1 to 3% by mass relative to the crude product. After completion of the reaction, the produced salt is removed by filtration, washing with water, etc., and the solvent (e.g. toluene, methyl isobutyl ketone) is distilled off under heating and reduced pressure to obtain the compound (a3) which is the target epoxy compound. .

  The compound (A) can be obtained by reacting the epoxy group of the compound (a3) produced as described above with (meth) acrylic acid to form a ring-opening ester. This reaction can confirm the progress of the reaction by measuring the acid value, and 90 mol% or more, preferably 95 mol% or more of the epoxy group in the compound (a3) is (meth) acrylated. Do until. The acid value can be measured by the following method.

[Measurement method of acid value]
1.0 g of a sample is precisely weighed, and a toluene-methanol mixed solvent (70 parts by mass of toluene and 30 parts by mass of methanol are mixed and neutralized with a 0.1 mol / l potassium hydroxide alcohol solution using phenolphthalein as an indicator. ) Dissolve in 30 ml. Add 2-3 drops of phenolphthalein indicator and titrate with 0.1 mol / l potassium hydroxide alcohol solution (7 g of potassium hydroxide dissolved in 100 ml of pure water, then 1000 ml with ethanol and filtered after 2 days). . A drop of 0.1 mol / l potassium hydroxide alcohol solution is added to change from colorless to slightly crimson, and the titration is obtained with the end of the point where the crimson color is maintained for 30 seconds. Next, the acid value is determined according to the following formula (3) using the obtained titer.

Ｓ ：試料量（ｇ）
Ｖ ：０．１ｍｏｌ／ｌ水酸化カリウムアルコール溶液の適定量（ｍｌ）
Ｆ ：０．１ｍｏｌ／ｌ水酸化カリウムアルコール溶液の力価

S: Sample amount (g)
V: Appropriate amount of 0.1 mol / l potassium hydroxide alcohol solution (ml)
F: Potency of 0.1 mol / l potassium hydroxide alcohol solution

  The ratio of the compound (a3) and (meth) acrylic acid used is such that (meth) acrylic acid is 0.90 to 1.10 molar equivalents relative to 1 molar equivalent of the epoxy group in the compound (a3). Is preferred.

  The reaction of the compound (a3) and (meth) acrylic acid may be performed in such a manner that the whole amount is batch-reacted at the above-mentioned use ratio or sequentially reacted so as to finally reach the above-mentioned use ratio. The reaction is preferably performed in the presence of an esterification catalyst. Examples of the esterification catalyst include triethylamine, N, N-benzyldimethylamine, N, N-dimethylphenylamine, N, N-dimethylaniline. , Tertiary amine compounds such as diazabicyclooctane; quaternary ammonium salts such as trimethylbenzylammonium chloride, triethylbenzylammonium chloride, methyltriethylammonium chloride; phosphine compounds such as triphenylphosphine and tributylphosphine; 2-methylimidazole, 1 , Imidazole compounds such as 2-dimethylimidazole and 2-ethyl-4-methylimidazole; and anion exchange resins. The amount of the catalyst used is preferably in the range of 0.01 to 1% by mass and more preferably in the range of 0.05 to 0.5% by mass with respect to the total amount of the reaction mixture.

  In the reaction between the compound (a3) and (meth) acrylic acid, it is possible to prevent polymerization and gelation during the reaction, and therefore the total amount of the compound (a3) and (meth) acrylic acid. It is preferable to use a polymerization inhibitor in the range of 100 to 2,000 ppm. Examples of the polymerization inhibitor include quinone compounds such as p-benzoquinone, anthraquinone, 1,4-naphthoquinone, p-toluquinone, and methoquinone; hydroquinone compounds such as hydroquinone, monomethylhydroquinone, and mono-t-butylhydroquinone; copper naphthenate Sulfur compounds such as phenothiazine and the like are preferred, and among these polymerization inhibitors, methoquinone and hydroquinone are more preferred because of their remarkable effects.

  The reaction is usually preferably carried out without solvent, but can also be carried out in the presence of an organic solvent. Examples of the organic solvent that can be used here include ketone compounds such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbon compounds such as toluene, xylene and tetramethylbenzene; glycol ether compounds such as dipropylene glycol dimethyl ether and dipropylene glycol diethyl ether; Ester compounds such as ethyl, butyl acetate, butyl cellosolve acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate; aliphatic hydrocarbon compounds such as octane and decane, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha, etc. Examples include petroleum solvents. Among these, it is preferable to use propylene glycol monomethyl ether acetate or diethylene glycol monoethyl ether acetate alone or in combination with an aromatic hydrocarbon compound in view of the possibility of reaction under high temperature conditions.

  The reaction temperature in the reaction is preferably in the range of 60 to 150 ° C. from the viewpoint of allowing the reaction to proceed suitably. However, since the reaction time is short and economically advantageous, 80 to 130 ° C. is particularly preferable. It is more preferable that Further, the reaction is preferably performed in an air atmosphere so that (meth) acrylic acid is not polymerized, and the reaction may be performed by appropriately adjusting with an inert gas so as not to polymerize.

  The esterification catalyst can be added all at once when the compound (a3) and (meth) acrylic acid are reacted, but a part of the esterification catalyst is first added (primary addition) and the reaction proceeds. Then, the remaining esterification catalyst may be further continuously or intermittently added (secondary addition). As for the amount of the esterification catalyst used in the primary addition and the secondary addition, it is preferable that 50 to 90% by mass of the total amount is added by the primary addition and the remainder is added by the secondary addition.

  Specific examples of the compound (a4) obtained by the above reaction include compounds represented by the following general formulas (a4-1) and (a4-2). In the present invention, the hydroxyl group of the compound (a4) is used as a site for introducing a polymerizable unsaturated group. In addition, about the range of the repeating unit number n in the following general formula (a4-1) and (a4-2), it is as above-mentioned.

（式中、Ｒ^１及びＲ^２はそれぞれ独立に水素原子又はメチル基を表す。）

(In the formula, R ¹ and R ² each independently represents a hydrogen atom or a methyl group.)

  By reacting the compound (a4) obtained as described above with the compound (a5) having a reactive functional group and a (meth) acryloyl group with the hydroxyl group of the compound (a4), A polymerizable fluorine-based compound is obtained.

  Examples of the functional group reactive with the hydroxyl group of the compound (a5) include an isocyanate group, a carboxylic acid halide, and an acid anhydride. Specific examples of the compound (a5) include 2- (meth) acryloyloxyethyl isocyanate, 2- (2- (meth) acryloyloxyethoxy) ethyl isocyanate, and 1,1-bis as a compound having an isocyanate group. ((Meth) acryloyloxymethyl) ethyl isocyanate and the like, and as a compound having a carboxylic acid halide, (meth) acrylic acid chloride, (meth) acrylic acid bromide and the like are mentioned, and as a compound having an acid anhydride, Examples thereof include maleic anhydride and itaconic anhydride.

  Among these, 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and 1,1-bis (acryloyloxymethyl) ethyl isocyanate are preferable from the viewpoint of preferable polymerization curability under ultraviolet irradiation.

  The method of reacting the compound (a4) with the compound (a5) having a functional group reactive with the hydroxyl group of the compound (a4) and the (meth) acryloyl group is a polymerizable unsaturated group in the compound (C). What is necessary is just to carry out on the conditions which a group does not superpose | polymerize, for example, it is preferable to make it react by adjusting temperature conditions in the range of 30-120 degreeC. This reaction is preferably carried out in the presence of a catalyst or a polymerization inhibitor, and if necessary in the presence of an organic solvent.

  For example, when the functional group having reactivity with the hydroxyl group of the compound (a5) is an isocyanate group, p-methoxyphenol, hydroquinone, 2,6-di-t-butyl-4-methylphenol and the like as a polymerization inhibitor And dibutyltin dilaurate, dibutyltin diacetate, tin octylate, zinc octylate, etc. are used as the urethanization reaction catalyst, and the reaction temperature is in the range of 20 to 150 ° C., particularly in the range of 40 to 120 ° C. The method of making it preferable is.

  The organic solvent used in the above reaction is preferably ketones, esters, amides, sulfoxides, ethers, hydrocarbons, specifically, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, Examples include propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, xylene and the like. These may be appropriately selected in consideration of the boiling point and compatibility.

  Since the polymerizable fluorine-based compound of the present invention obtained as described above can impart excellent antifouling properties to the cured coating film, its number average molecular weight (Mn) is in the range of 1,000 to 5,000. It is preferable that the range is 1,500 to 3,000. The weight average molecular weight (Mw) is preferably in the range of 1,000 to 10,000, and more preferably in the range of 1,500 to 4,000. In addition, a number average molecular weight (Mn) and a weight average molecular weight (Mw) are the values converted into polystyrene based on said GPC measurement.

  Here, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are values converted to polystyrene based on gel permeation chromatography (hereinafter abbreviated as “GPC”) measurement. The measurement conditions for GPC are as follows.

[GPC measurement conditions]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HHR-H” manufactured by Tosoh Corporation (6.0 mm ID × 4 cm)
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
Detector: ELSD ("ELSD2000" manufactured by Oltec)
Data processing: “GPC-8020 Model II data analysis version 4.30” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran (THF)
Flow rate 1.0 ml / min Sample: A 1.0% by mass tetrahydrofuran solution filtered in terms of resin solids through a microfilter (100 μl).
Standard sample: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II Data Analysis Version 4.30”.

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

  In addition, the fluorine content in the polymerizable fluorine-based compound of the present invention can satisfy both the antifouling property and its durability, and compatibility with other components. Preferably, the range of 10-55 mass% is more preferable, and the range of 15-50 mass% is further more preferable. The fluorine content in the polymerizable fluorine compound of the present invention is a value calculated from the mass ratio of fluorine atoms to the total amount of raw materials used.

  The polymerizable fluorine-based compound of the present invention can itself be used as the main component of the active energy ray-curable composition, but is very easy to segregate on the surface and has excellent surface modification performance even in a small amount. By using it as a fluorine-containing surfactant added to the active energy ray-curable composition, excellent antifouling properties can be imparted to the cured coating film.

  The active energy ray-curable composition of the present invention is obtained by blending the polymerizable fluorine-based compound of the present invention, and the main component thereof is an active energy ray-curable resin (B) or active energy ray curable. Contains monomer (C). In the active energy ray curable composition of the present invention, the active energy ray curable resin (B) and the active energy ray curable monomer (C) may be used alone or in combination. It doesn't matter. The polymerizable fluorine-based compound of the present invention is preferably used as a fluorine-containing surfactant in the active energy ray-curable composition.

  The active energy ray-curable resin (B) is a urethane (meth) acrylate resin, unsaturated polyester resin, epoxy (meth) acrylate resin, polyester (meth) acrylate resin, acrylic (meth) acrylate resin, maleimide group-containing resin, etc. In the present invention, a urethane (meth) acrylate resin is particularly preferable from the viewpoint of transparency and low shrinkage.

  The urethane (meth) acrylate resin used here is a resin having a urethane bond and a (meth) acryloyl group obtained by reacting an aliphatic polyisocyanate compound or an aromatic polyisocyanate compound with a hydroxy group-containing (meth) acrylate compound. Is mentioned.

  Examples of the aliphatic polyisocyanate compound include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, 2-methyl-1,5-pentane diisocyanate, 3-methyl- 1,5-pentane diisocyanate, dodecamethylene diisocyanate, 2-methylpentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate, hydrogenated diphenylmethane diisocyanate , Hydrogenated tolylene diisocyanate, hydrogenated xylile Examples include diisocyanate, hydrogenated tetramethylxylylene diisocyanate, cyclohexyl diisocyanate, and the aromatic polyisocyanate compound includes tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, Examples include toridine diisocyanate and p-phenylene diisocyanate.

  On the other hand, examples of the hydroxy group-containing acrylate compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1, Monovalent dihydric alcohols such as 5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, and hydroxypivalate neopentyl glycol mono (meth) acrylate ( (Meth) acrylate; trimethylolpropane di (meth) acrylate, ethoxylated trimethylolpropane di (meth) acrylate, propoxylated trimethylolpropane di (meth) acrylate, glycerin di (meth) Mono- or di (meth) acrylate of trivalent alcohol such as acrylate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, or a hydroxyl group obtained by modifying a part of these alcoholic hydroxyl groups with ε-caprolactone Containing mono- and di (meth) acrylates; monofunctional hydroxyl groups such as pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and more than trifunctional (meth) acryloyl groups Or a hydroxyl group-containing polyfunctional (meth) acrylate modified with ε-caprolactone; dipropylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, polypro (Meth) acrylate compounds having an oxyalkylene chain such as lenglycol mono (meth) acrylate and polyethylene glycol mono (meth) acrylate; polyethylene glycol-polypropylene glycol mono (meth) acrylate, polyoxybutylene-polyoxypropylene mono (meth) (Meth) acrylate compounds having a block structure oxyalkylene chain such as acrylate; random structures such as poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate and poly (propylene glycol-tetramethylene glycol) mono (meth) acrylate And (meth) acrylate compounds having an oxyalkylene chain.

  The reaction of the above-mentioned aliphatic polyisocyanate compound or aromatic polyisocyanate compound and the hydroxy group-containing acrylate compound can be carried out by a conventional method in the presence of a urethanization catalyst. Specific examples of urethanization catalysts that can be used here include amines such as pyridine, pyrrole, triethylamine, diethylamine, and dibutylamine, phosphines such as triphenylphosphine and triethylphosphine, dibutyltin dilaurate, octyltin trilaurate, and octyl. Examples thereof include organotin compounds such as tin diacetate, dibutyltin diacetate, and tin octylate, and organometallic compounds such as zinc octylate.

  Among these urethane acrylate resins, those obtained by reacting an aliphatic polyisocyanate compound with a hydroxy group-containing (meth) acrylate compound are excellent in transparency of the cured coating film and have good sensitivity to active energy rays. It is preferable from the viewpoint of excellent curability.

  Next, the unsaturated polyester resin is a curable resin obtained by polycondensation of α, β-unsaturated dibasic acid or acid anhydride thereof, aromatic saturated dibasic acid or acid anhydride thereof, and glycols. The α, β-unsaturated dibasic acid or its acid anhydride includes maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chloromaleic acid, and esters thereof. As aromatic saturated dibasic acid or acid anhydride thereof, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, halogenated phthalic anhydride and these Examples include esters. Examples of the aliphatic or alicyclic saturated dibasic acid include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, hexahydrophthalic anhydride, and esters thereof. As glycols, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methylpropane-1,3-diol, neopentyl glycol, triethylene glycol, Examples include tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene glycol carbonate, 2,2-di- (4-hydroxypropoxydiphenyl) propane, and others. In addition, oxides such as ethylene oxide and propylene oxide can be used in the same manner.

  Next, as an epoxy vinyl ester resin, (meth) acrylic acid is reacted with an epoxy group of an epoxy resin such as a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolac type epoxy resin, or a cresol novolak type epoxy resin. What is obtained is mentioned.

  As the maleimide group-containing resin, a bifunctional maleimide urethane compound obtained by urethanizing N-hydroxyethylmaleimide and isophorone diisocyanate, a bifunctional maleimide ester compound obtained by esterifying maleimide acetic acid and polytetramethylene glycol, Examples thereof include a tetrafunctional maleimide ester compound obtained by esterification of maleimidocaproic acid and a tetraethylene oxide adduct of pentaerythritol, a polyfunctional maleimide ester compound obtained by esterification of maleimide acetic acid and a polyhydric alcohol compound, and the like. These active energy ray-curable resins (B) can be used alone or in combination of two or more.

  Examples of the active energy ray-curable monomer (C) include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and a number average molecular weight in the range of 150 to 1,000. Polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di having a number average molecular weight in the range of 150 to 1000 (Meth) acrylate, neopentyl glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol (Meth) acrylate, hydroxypivalate ester neopentyl glycol di (meth) acrylate, bisphenol A di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol Hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane di (meth) acrylate, dipentaerythritol penta (meth) acrylate, dicyclopentenyl (meth) acrylate, methyl (meth) acrylate, Propyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meta Aliphatic alkyl (meth) acrylates such as acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, glycerol (meth) acrylate, 2-hydroxyethyl (meth) acrylate , 3-chloro-2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, allyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, 2- (diethylamino) ethyl (meth) acrylate, 2- (dimethyl Amino) ethyl (meth) acrylate, γ- (meth) acryloxypropyltrimethoxysilane, 2-methoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxydi Lopylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydipropylene glycolicol (meth) acrylate, phenoxypolypropylene glycol (meth) acrylate, Polybutadiene (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polyethylene glycol-polybutylene glycol (meth) acrylate, polystyrylethyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopenta Nyl (meth) acrylate, dicyclopentenyl (meth) acryl , Isobornyl (meth) acrylate, methoxylated cyclodecatriene (meth) acrylate, phenyl (meth) acrylate; maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-hexyl Maleimide, N-octylmaleimide, N-dodecylmaleimide, N-stearylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, 2-maleimidoethyl-ethylcarbonate, 2-maleimidoethyl-propylcarbonate, N-ethyl- (2- Maleimidoethyl) carbamate, N, N-hexamethylene bismaleimide, polypropylene glycol-bis (3-maleimidopropyl) ether, bis (2-maleimidoethyl) carbonate, 1,4-di And maleimides such as maleimide cyclohexane.

  Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra ( A trifunctional or higher polyfunctional (meth) acrylate such as (meth) acrylate is preferred. These active energy ray-curable monomers (C) can be used alone or in combination of two or more.

  In the active energy ray-curable composition of the present invention, when the polymerizable fluorine-based compound of the present invention is used as a fluorine-containing surfactant, the amount used thereof is the active energy ray-curable resin (B) and the active energy beam. The range is preferably from 0.01 to 10 parts by mass, more preferably from 0.1 to 5% by mass, based on 100 parts by mass of the total amount of the curable monomer (C). If the amount of the polymerizable fluorine-based compound of the present invention is within this range, the leveling property, water / oil repellency and antifouling property can be made sufficient, and the hardness and transparency after curing of the composition can be achieved. Can also be sufficient.

  The polymerizable fluorine-based compound or the active energy ray-curable composition of the present invention can be formed into a cured coating film by irradiating active energy rays after being applied to a substrate. The active energy rays refer to ionizing radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. When a cured coating film is formed by irradiating ultraviolet rays as active energy rays, a photopolymerization initiator (D) is added to the polymerizable fluorine compound or active energy ray curable composition to improve curability. It is preferable. Further, if necessary, a photosensitizer can be further added to improve curability. On the other hand, when ionizing radiation such as electron beam, α-ray, β-ray, and γ-ray is used, it cures quickly without using a photopolymerization initiator or photosensitizer. It is not necessary to add D) or a photosensitizer.

  Examples of the photopolymerization initiator (D) include intramolecular cleavage type photopolymerization initiators and hydrogen abstraction type photopolymerization initiators. Examples of the intramolecular cleavage type photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy. 2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4-thio) Acetophenone-based compounds such as methylphenyl) propan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone; benzoins such as benzoin, benzoin methyl ether and benzoin isopropyl ether; 4,6-trimethylbenzoindiphenylphos In'okishido, bis (2,4,6-trimethylbenzoyl) - acyl phosphine oxide-based compounds such as triphenylphosphine oxide; benzyl, and methyl phenylglyoxylate ester.

  On the other hand, examples of the hydrogen abstraction type photopolymerization initiator include benzophenone, methyl 4-phenylbenzophenone, o-benzoylbenzoate, 4,4′-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide. Benzophenone compounds such as acrylated benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3′-dimethyl-4-methoxybenzophenone; 2-isopropylthioxanthone, 2,4 A thioxanthone compound such as dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone; an aminobenzophenone compound such as Michler's ketone and 4,4′-diethylaminobenzophenone; 2-chloro acridone, 2-ethyl anthraquinone, 9,10-phenanthrenequinone, camphorquinone, and the like.

  Among the photopolymerization initiators (D), the compatibility with the active energy ray curable resin (B) and the active energy ray curable monomer (C) in the active energy ray curable composition is excellent. Therefore, 1-hydroxycyclohexyl phenyl ketone and benzophenone are preferable, and 1-hydroxycyclohexyl phenyl ketone is particularly preferable. These photopolymerization initiators (D) can 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-toluenesulfonate, and the like. And sulfur compounds.

  These photopolymerization initiators and photosensitizers are preferably used in an amount of 0.01 to 20 parts by weight, preferably 0.1 to 15 parts by weight, based on 100 parts by weight of the nonvolatile component in the active energy ray-curable composition. % Is more preferable, and 0.3 to 7 parts by mass is more preferable.

  Furthermore, the active energy ray-curable composition of the present invention is not limited to the effects of the present invention, depending on the purpose of use, characteristics, etc. Various compounding materials for the purpose of adjusting coating properties and coating film properties, such as various organic solvents, acrylic resins, phenol resins, polyester resins, polystyrene resins, urethane resins, urea resins, melamine resins, alkyd resins, epoxy resins, Various resins such as polyamide resin, polycarbonate resin, petroleum resin, fluororesin, various organic or inorganic particles such as PTFE (polytetrafluoroethylene), polyethylene, polypropylene, carbon, titanium oxide, alumina, copper, silica fine particles, polymerization initiation Agent, polymerization inhibitor, antistatic agent, antifoaming agent, viscosity modifier, light resistance stabilizer, weather resistance stabilizer, heat resistance Fixing agent, antioxidant, rust inhibitor, slip agent, wax, gloss adjuster, mold release agent, compatibilizer, conductivity modifier, pigment, dye, dispersant, dispersion stabilizer, silicone-based, hydrocarbon-based interface An activator or the like can be used in combination.

  Among the above ingredients, the organic solvent is useful for appropriately adjusting the solution viscosity of the active energy ray-curable composition of the present invention. In particular, in order to perform thin film coating, the film thickness can be adjusted. It becomes easy. Examples of the organic solvent that can be used here include aromatic hydrocarbons such as toluene and xylene; alcohols such as methanol, ethanol, isopropanol, and t-butanol; esters such as ethyl acetate and propylene glycol monomethyl ether acetate; Examples thereof include ketones such as methyl isobutyl ketone and cyclohexanone. These solvents can be used alone or in combination of two or more.

  Here, the amount of the organic solvent used varies depending on the intended use and the target film thickness and viscosity, but is preferably in the range of 0.5 to 4 times the mass of the total mass of the curing component.

  As described above, the active energy rays for curing the active energy ray-curable composition of the present invention are ionizing radiations such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. Or as a curing device, for example, a germicidal lamp, an ultraviolet fluorescent lamp, a carbon arc, a xenon lamp, a high-pressure mercury lamp for copying, a medium or high-pressure mercury lamp, an ultra-high pressure mercury lamp, an electrodeless lamp, a metal halide lamp, natural light, etc. Examples of the electron beam include ultraviolet rays, a scanning type, and a curtain type electron beam accelerator.

  Among these, ultraviolet rays are particularly preferable, and ultraviolet rays are preferably irradiated in an inert gas atmosphere such as nitrogen gas in order to avoid curing inhibition due to oxygen or the like. Further, if necessary, heat may be used as an energy source and heat treatment may be performed after curing with ultraviolet rays.

  The application method of the active energy ray-curable composition of the present invention varies depending on the application. For example, a gravure coater, roll coater, comma coater, knife coater, air knife coater, curtain coater, kiss coater, shower coater, wheeler coater, spin coater , Coating methods using dipping, screen printing, spraying, applicators, bar coaters, etc., or molding methods using various molds.

  The cured coating film of the polymerizable fluorine-based compound of the present invention has excellent antifouling properties (ink repellency, fingerprint resistance, etc.), scratch resistance, and the like. It is possible to impart antifouling property, scratch resistance, etc. Further, the polymerizable fluorine-based compound of the present invention can impart leveling properties to the coating material by adding it as a fluorine-containing surfactant to the coating material. Therefore, the active energy ray-curable composition of the present invention. Has high leveling properties.

  Examples of articles that can be imparted with antifouling properties (ink repellency, fingerprint resistance, etc.) using the polymerizable fluorine-based compound or active energy ray-curable composition of the present invention include polarization of liquid crystal displays (LCD) such as TAC films. Films for plates; Various display screens such as plasma display (PDP) and organic EL display; Touch panel; Mobile phone casing or mobile phone screen; Optical recording media such as CD, DVD, Blu-ray disc; Insert mold (IMD, IMF) Transfer film for use; Rubber rollers for OA equipment such as copiers and printers; Glass surfaces of reading parts of OA equipment such as copiers and scanners; Optical lenses such as cameras, video cameras and glasses; Windshields for watches such as watches; Glass Surface: windows of various vehicles such as automobiles and railway vehicles; various building materials such as decorative panels; windows of houses Las; furniture such woodworking materials, artificial-synthetic leather, home appliances of the housing or the like of various plastic molded products, such as FRP bathtubs and the like. By applying the polymerizable fluorine-based compound or active energy ray-curable composition of the present invention to the surface of these articles and irradiating active energy rays such as ultraviolet rays to form a cured coating film, antifouling properties are formed on the article surfaces. Can be granted. Moreover, it is also possible to add antifouling property to the article surface by adding the polymerizable fluorine-based compound of the present invention to various paints suitable for each article, coating and drying.

  In addition, as a coating material that can improve the leveling property by adding the polymerizable fluorine-based compound of the present invention and impart antifouling properties (ink repellency, fingerprint resistance, etc.) to the coating film, an LCD such as a TAC film can be used. Hard coating material for polarizing film, anti-glare (AG: anti-glare) coating material or anti-reflection (LR) coating material; hard coating material for various display screens such as plasma display and organic EL display (PDP); Coating material: Color resist and printing ink for forming each pixel of RGB used for a color filter (hereinafter referred to as “CF”) used for an image sensor such as a liquid crystal display, an organic EL display, a CCD, a CMOS, etc. , Inkjet ink or paint; black resist for CF black matrix, printing Ink, inkjet ink or paint; Resin composition for pixel partition walls such as plasma display (PDP), organic EL display; Mobile phone casing paint or hard coat material; Mobile phone screen hard coat material; CD, DVD, Blu-ray Hard coating materials for optical recording media such as discs; Hard coating materials for transfer films for insert molds (IMD, IMF); Coating materials for rubber rollers for OA equipment such as copying machines and printers; OA equipment such as copying machines and scanners Glass coating material for reading unit; Coating material for optical lenses such as cameras, video cameras and glasses; Windshield for watches such as watches; Coating material for glass; Window coating materials for various vehicles such as automobiles and railway vehicles; Printing ink or paint for various building materials such as coating materials for window glass in houses; Paints; artificial & synthetic leather for coating material; consumer electronics enclosure such as various plastic article for paint or coating material; and FRP tub paint or coating material and the like.

  Further, as an article that can be provided with scratch resistance (scratch resistance) and antifouling property using the polymerizable fluorine-based compound or active energy ray-curable composition of the present invention, a prism sheet that is a backlight member of an LCD or Examples thereof include a diffusion sheet. Further, by adding the polymerizable fluorine-based compound of the present invention to the prism sheet or the diffusion sheet coating material, the leveling property of the coating material is improved and the coating film of the coating material is scratch resistant (scratch resistance). And antifouling property can be provided.

  Further, since the cured coating film of the polymerizable fluorine-based compound of the present invention has a low refractive index, the coating for the low refractive index layer in the antireflection layer for preventing the reflection of a fluorescent lamp or the like on the surface of various displays such as LCDs. It can also be used as a material. Further, by adding the polymerizable fluorine-based compound of the present invention to the coating material for the antireflection layer, particularly the coating material for the low refractive index layer in the antireflection layer, the coating material can be applied while maintaining the low refractive index of the coating film. Antifouling properties can also be imparted to the membrane surface.

  Furthermore, as other applications in which the polymerizable fluorine-based compound or active energy ray-curable composition of the present invention can be used, optical fiber cladding materials, waveguides, liquid crystal panel sealing materials, various optical sealing materials, optical Adhesives and the like.

  In particular, when the active energy ray-curable composition of the present invention is used as an antiglare coating material among coating materials for protective films for polarizing plates for LCDs, among the above-mentioned compositions, silica fine particles, acrylic resin fine particles, polystyrene resin Excellent anti-glare properties by blending inorganic or organic fine particles such as 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. Since it becomes a thing, it is preferable.

  In addition, when the polymerizable fluorine-based compound or the active energy ray-curable composition of the present invention is used for an antiglare coating material for a protective film of a polarizing plate for LCD, it is applied to a mold having an uneven surface shape before the coating material is cured. After the contact, the active energy ray is irradiated from the side opposite to the mold and cured, and the surface of the coating layer can be embossed to apply an antiglare property. In addition, a transfer method in which the surface of the coating film is mirrored by irradiating with an active energy ray from the opposite side of the mold or film after contacting the mold or film having a mirror surface before curing the coating material. It can also be applied to.

  Hereinafter, the present invention will be described in more detail with reference to specific examples. The poly (perfluoroalkylene ether) chain, which is an intermediate of the polymerizable fluorine-based compound of the present invention, and the epoxy equivalent of the compound having an epoxy group at both ends thereof, the poly (perfluoroalkylene ether) chain and both ends thereof. The acid value of the compound having a (meth) acryloyl group, the measurement method of the IR spectrum and the NMR spectrum, and the measurement conditions of GPC of the polymerizable fluorine-based compound are as follows.

[IR spectrum measurement method]
Using a measuring device of “IR Prestige-21” manufactured by Shimadzu Corporation, the sample was applied to a KBr plate and measured.

[Measurement method of epoxy equivalent]
Dissolve the sample (1 ± 0.3 mmol equivalent) in 20 ml of methyl ethyl ketone, add 5 ml of 20% by mass acetic acid solution (CTMAB) of cetyltrimethylammonium bromide, add 4-6 drops of crystal violet indicator (acetic acid solution), and stir with a stirrer. The solution was titrated with a 0.1 mol / l perchloric acid acetic acid solution (0.1 mol / l HClO ₄ ). One drop of 0.1 mol / l perchloric acid acetic acid solution was added to change the color from blue-violet to blue, and the titration was obtained with the end point being blue for 1 minute. Moreover, since the volume expansion coefficient of the solvent needs to be corrected by temperature, the temperature of the perchloric acid acetic acid solution was recorded. At the same time, a blank test without using a sample was performed to measure the titration amount in the same manner, and the epoxy equivalent was determined according to the following formula (2) using the obtained titration amount.

Ｗ ：試料量（ｇ）
Ｖｓ：本試験に要する０．１ｍｏｌ／ｌ ＨＣｌＯ_４の適定量（ｍｌ）
Ｖｂ：空試験に要する０．１ｍｏｌ／ｌ ＨＣｌＯ_４の適定量（ｍｌ）
Ｆ_２０：０．１ｍｏｌ／ｌ ＨＣｌＯ_４の２０℃における力価
ｔ ：滴定時の０．１ｍｏｌ／ｌ ＨＣｌＯ_４の液温（℃）

W: Sample amount (g)
Vs: Appropriate amount of 0.1 mol / l HClO ₄ required for this test (ml)
Vb: Appropriate amount of 0.1 mol / l HClO ₄ required for the blank test (ml)
F ₂₀ : titer of 0.1 mol / l HClO ₄ at 20 ° C. t: liquid temperature of 0.1 mol / l HClO ₄ at titration (° C.)

[Measurement method of acid value]
1.0 g of a sample is precisely weighed, and a toluene-methanol mixed solvent (70 parts by mass of toluene and 30 parts by mass of methanol are mixed and neutralized with a 0.1 mol / l potassium hydroxide alcohol solution using phenolphthalein as an indicator. ) Dissolved in 30 ml. 2 to 3 drops of phenolphthalein indicator were added and titrated with a 0.1 mol / l potassium hydroxide alcohol solution (7 g of potassium hydroxide dissolved in 100 ml of pure water, then 1000 ml with ethanol and filtered after 2 days). . A drop of 0.1 mol / l potassium hydroxide alcohol solution was added to change the color from colorless to slightly red, and a titration was obtained with the end point being a slight red color lasting 30 seconds. Subsequently, the acid value was calculated | required according to the following Formula (3) using the obtained titer.

Ｓ ：試料量（ｇ）
Ｖ ：０．１ｍｏｌ／ｌ水酸化カリウムアルコール溶液の適定量（ｍｌ）
Ｆ ：０．１ｍｏｌ／ｌ水酸化カリウムアルコール溶液の力価

S: Sample amount (g)
V: Appropriate amount of 0.1 mol / l potassium hydroxide alcohol solution (ml)
F: Potency of 0.1 mol / l potassium hydroxide alcohol solution

[Method for Measuring ¹ H-NMR and ¹³ C-NMR Spectra]
Using “AL-400” manufactured by JEOL Ltd., the sample acetone-d ₆ solution was analyzed to analyze the structure of the compound.

[GPC measurement conditions]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HHR-H” manufactured by Tosoh Corporation (6.0 mm ID × 4 cm)
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
+ "TSK-GEL GMHHR-N" (7.8 mm ID x 30 cm) manufactured by Tosoh Corporation
Detector: ELSD ("ELSD2000" manufactured by Oltec)
Data processing: “GPC-8020 Model II data analysis version 4.30” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran (THF)
Flow rate 1.0 ml / min Sample: A 1.0% by mass tetrahydrofuran solution filtered in terms of resin solids through a microfilter (100 μl).
Standard sample: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II Data Analysis Version 4.30”.

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

Example 1
In a glass flask equipped with a stirrer, a thermometer, a condenser and a dropping device, a perfluoropolyether compound having a hydroxyl group at both ends represented by the following formula (a2-1-1) (hereinafter referred to as “compound (a2- 1-1) The hydroxyl group equivalent was 740 g / eq), 50 parts by mass, epichlorohydrin 62.5 parts by mass and ethanol 20 parts by mass. While maintaining the internal temperature at 50 ° C., 8.3 parts by mass of a 49% by mass aqueous sodium hydroxide solution was added dropwise over 2 hours, and after completion of the addition, the temperature was raised to 60 ° C. and stirred for 3 hours, and then returned to room temperature. .

（式中、ａは平均５、ｂは平均８であり、フッ素原子数が平均４６である。また、ＧＰＣ測定による数平均分子量は１，５００である。なお、オキシパーフルオロメチレン単位とオキシパーフルオロエチレン単位とはランダム結合である。以下同じ。）

(In the formula, a is 5 on average, b is 8 on average, and the number of fluorine atoms is 46 on average. The number average molecular weight by GPC measurement is 1,500. In addition, oxyperfluoromethylene units and oxyper (The fluoroethylene unit is a random bond. The same shall apply hereinafter.)

Next, the reaction solution returned to room temperature was washed with ion-exchanged water. Washing was performed by repeating the operation of adding 50 parts by mass of ion-exchanged water to the reaction solution and stirring and then allowing to stand and separating the aqueous layer by liquid separation twice. From the washed reaction solution, unreacted epichlorohydrin is distilled off by distillation under reduced pressure, filtered and taken out to obtain a poly (perfluoroalkylene ether) represented by the following formula (a3-1-1) ) 52.2 parts by mass of a chain and a compound having an epoxy group at both ends thereof (hereinafter abbreviated as “compound (a3-1-1)”) were obtained. This compound (a3-1-1) is a transparent liquid and has an epoxy equivalent of 1,060 g / eq. The average value of the number of repeating units n in the following formula (a3-1-1) was 0.4. In addition, the average value of the repeating unit number n was computed by the following Formula (1) using the value of the hydroxyl equivalent of the said compound (a2-1-1), and the epoxy equivalent of a compound (a3-1-1). The hydroxyl equivalent of the compound (a2-1-1) ^measures 19 F-NMR, the chemical shift of the CF ₂ moiety adjacent is through a hydroxyl group and methylene, perfluoro methylene group _(-CF 2 -) And the integral ratio of the chemical shift of the CF ₂ moiety adjacent to each other through the hydroxyl group and methylene is determined as 4 and the integral ratio of the chemical shift of the perfluoroethylene group (—CF ₂ CF ₂ —) is obtained. The number of other perfluoromethylene groups, perfluoroethylene groups, etc. was determined from the respective integration ratios, and the molecular weight of the compound (a2-1-1) obtained from the results was determined by dividing by 2. Moreover, the epoxy equivalent of the compound (a3-1-1) was measured by the above method. For Examples 2 and 3 below, the average value of the number n of repeating units was calculated in the same manner.

  Subsequently, 52.2 parts by mass of the compound (a3-1-1) obtained above, 4.4 parts by mass of methacrylic acid, and methoquinone 0 as a polymerization inhibitor were placed in a glass flask equipped with a stirrer, a thermometer and a condenser. .03 parts by mass and 0.17 parts by mass of triphenylphosphine as a catalyst, start stirring under an air stream, and react at 90 ° C. for 20 hours to be represented by the following formula (a4-1-1) 56.5 parts by mass of a poly (perfluoroalkylene ether) chain and a compound having a methacryloyl group at both ends thereof (hereinafter abbreviated as “compound (a4-1-1)”) were obtained. This compound (a4-1-1) is a transparent liquid, and its epoxy equivalent is 16,000 g / eq. The acid value was 2, and the average value of the number of repeating units n in the formula was 0.4.

Next, 22.9 parts by mass of compound (a4-1-1), 0.01 parts by mass of p-methoxyphenol as a polymerization inhibitor, and urethanization were added to a glass flask equipped with a stirrer, thermometer, condenser, and dropping device. As a catalyst, 0.01 part by mass of dibutyltin dilaurate was charged, stirring was started under an air stream, and the temperature was raised to 80 ° C. Thereafter, 4.8 parts by mass of 1,1-bis (acryloyloxymethyl) ethyl isocyanate (hereinafter abbreviated as “BEI”) were added in portions while paying attention to heat generation. After completion of the addition of BEI, the reaction was carried out by stirring at 80 ° C. for 10 hours. After confirming the disappearance of the absorption peak near 2360 cm ⁻¹ derived from the isocyanate group by IR spectrum measurement, the polymerizable fluorine-based compound (1) 27 .6 parts by mass were obtained. This polymerizable fluorine-based compound (1) was a viscous liquid. As a result of measuring the molecular weight of the obtained polymerizable fluorine-based compound (1) by GPC (polystyrene equivalent molecular weight), it was a number average molecular weight 1,900 and a weight average molecular weight 2,300. The fluorine content was 40% by mass.

In addition, ¹ H-NMR and ¹³ C-NMR spectra of the obtained polymerizable fluorine-based compound (1) were measured, and the structure of the following formula (A-1-1) was identified. FIG. 1 shows a chart of IR spectrum, FIG. 2 shows a chart of ¹ H-NMR spectrum, and FIG. 3 shows a chart of ¹³ C-NMR spectrum.

(Example 2)
In a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, 22.9 parts by mass of the compound (a4-1-1) obtained in Example 1, and p-methoxyphenol 0.01 as a polymerization inhibitor. 0.01 parts by mass of dibutyltin dilaurate as a part by mass and a urethanization catalyst were charged, stirring was started under an air stream, and the temperature was raised to 80 ° C. Thereafter, 3.4 parts by mass of 2-acryloyloxyethyl isocyanate (hereinafter abbreviated as “AOI”) were added in portions while paying attention to heat generation. After completion of the addition of AOI, the reaction was carried out by stirring at 80 ° C. for 6 hours. After confirming the disappearance of the absorption peak near 2360 cm ⁻¹ derived from the isocyanate group by IR spectrum measurement, polymerizable fluorine-based compound (2) 26 A mass part was obtained. This polymerizable fluorine-based compound (2) was a viscous liquid. As a result of measuring the molecular weight of the obtained polymerizable fluorine-based compound (2) by GPC (polystyrene equivalent molecular weight), it was a number average molecular weight 1,700 and a weight average molecular weight 1,900. The fluorine content was 44% by mass.

In addition, ¹ H-NMR and ¹³ C-NMR spectra of the resulting polymerizable fluorine-based compound (2) were measured, and the structure of the following formula (A-1-2) was identified.

(Example 3)
In a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, 22.9 parts by mass of the compound (a4-1-1) obtained in Example 1, and p-methoxyphenol 0.01 as a polymerization inhibitor. 0.01 parts by mass of dibutyltin dilaurate as a part by mass and a urethanization catalyst were charged, stirring was started under an air stream, and the temperature was raised to 80 ° C. Thereafter, 3.4 parts by mass of 2-methacryloyloxyethyl isocyanate (hereinafter abbreviated as “MOI”) was added in portions while paying attention to heat generation. After completion of the addition of MOI, the reaction was carried out by stirring at 80 ° C. for 6 hours. After confirming the disappearance of the absorption peak in the vicinity of 2360 cm ⁻¹ derived from the isocyanate group by IR spectrum measurement, polymerizable fluorine-based compound (3) 26 Obtained 3 parts by weight. This polymerizable fluorine-based compound (3) was a viscous liquid. As a result of measuring the molecular weight of the obtained polymerizable fluorine-based compound (3) by GPC (polystyrene equivalent molecular weight), it was a number average molecular weight 1,800 and a weight average molecular weight 2,000. The fluorine content was 43% by mass.

In addition, ¹ H-NMR and ¹³ C-NMR spectra of the resulting polymerizable fluorine-based compound (3) were measured, and the structure of the following formula (A-1-3) was identified.

(Comparative Example 1)
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 100 parts by mass of methyl isobutyl ketone as a solvent and heated to 105 ° C. while stirring under a nitrogen stream. Next, 50 parts by mass of an acrylate having a fluorinated alkyl group represented by the following formula (3) and 50 parts by mass of an acrylate having an ethylene oxide chain and a propylene oxide chain represented by the following formula (4) are 150 parts by mass of methyl isobutyl ketone. 250 parts by mass of a monomer solution dissolved in parts, 65 parts by mass of a polymerization initiator solution in which 5 parts by mass of t-butylperoxy-2-ethylhexanoate was dissolved in 50 parts by mass of methyl isobutyl ketone as a radical polymerization initiator, These two types of dropping liquids were set in separate dropping devices, and dropped simultaneously over 3 hours while maintaining the inside of the flask at 105 ° C. After completion of the dropping, the mixture was stirred at 105 ° C. for 10 hours to complete the polymerization, and then a part of the solvent was distilled off under reduced pressure to give 204 parts of a methyl isobutyl ketone solution containing 50% by mass of a fluorosurfactant (H1). Got. As a result of measuring the molecular weight of the obtained fluorosurfactant (H1) by GPC (polystyrene equivalent molecular weight), the number average molecular weight was 4,000 and the weight average molecular weight was 10,000. The fluorine content was 32% by mass.

（式中、ｍは平均３であり、ｎは平均４である。）

(Where m is an average of 3 and n is an average of 4)

(Comparative Example 2)
In a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, 20 parts by mass of the compound (a2-1-1), 20 parts by mass of diisopropyl ether as a solvent, and 0.02 of p-methoxyphenol as a polymerization inhibitor. 3.1 parts by mass of triethylamine as a part by mass and a neutralizing agent were added, stirring was started under an air stream, and 2.7 parts by mass of acrylic acid chloride was added dropwise over 1 hour while maintaining the inside of the flask at 10 ° C. After completion of dropping, the mixture is stirred at 10 ° C. for 1 hour, heated to 30 ° C. for 1 hour, then heated to 50 ° C. and stirred for 10 hours, and acrylic acid is measured by gas chromatography. The disappearance of chloride was confirmed. Next, after adding 40 parts by mass of diisopropyl ether as a solvent, 80 parts by mass of ion-exchanged water was mixed and stirred, and then left to stand to separate and remove the aqueous layer, and washing was repeated 3 times. Next, 0.02 parts by mass of p-methoxyphenol was added as a polymerization inhibitor, 8 parts of magnesium sulfate was added as a dehydrating agent, and the mixture was allowed to stand for 1 day for complete dehydration, and then the dehydrating agent was filtered off. Subsequently, the solvent was distilled off under reduced pressure to obtain 21.5 parts by mass of a compound having an acryloyl group at both ends of the perfluoropolyether chain represented by the following formula (5).

（式中、ａは平均５、ｂは平均８である。なお、オキシパーフルオロメチレン単位とオキシパーフルオロエチレン単位とはランダム結合である。）

(Wherein, a is an average of 5 and b is an average of 8. Note that the oxyperfluoromethylene unit and the oxyperfluoroethylene unit are random bonds.)

  Next, 63 parts by mass of methyl isobutyl ketone as a solvent was charged in a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, and the temperature was raised to 105 ° C. while stirring under a nitrogen stream. Then, 21.5 parts by mass of the compound represented by the formula (5) obtained above, 41.3 parts by mass of 2-hydroxyethyl methacrylate, and t-butylperoxy-2-ethylhexano as a radical polymerization initiator. Three types of dripping liquids with 135.4 parts by mass of a polymerization initiator solution in which 9.4 parts by mass of ate was dissolved in 126 parts by mass of methyl isobutyl ketone were set in separate dripping apparatuses, and the flask was kept at 105 ° C. It was dripped simultaneously over 2 hours. After completion of dropping, the mixture was stirred at 105 ° C. for 10 hours, and then the solvent was distilled off under reduced pressure to obtain 67.5 parts by mass of a polymer.

Subsequently, 74.7 parts by mass of methyl ethyl ketone as a solvent, 0.1 part by mass of p-methoxyphenol as a polymerization inhibitor, and 0.06 part by mass of dibutyltin dilaurate as a urethanization catalyst were charged into the polymer obtained above, Then, 44.8 parts by mass of AOI was added dropwise over 1 hour while maintaining 60 ° C. After completion of the dropwise addition, the mixture was stirred for 1 hour at 60 ° C., 80 ° C. heated to a result of performing the reaction by stirring for 10 hours, the disappearance of the absorption peak around 2360 cm ^-1 stemming from an isocyanate group in IR spectrum measurement confirmed. Next, 37.4 parts by mass of methyl ethyl ketone was added as a solvent to obtain 224.6 parts by mass of a methyl ethyl ketone solution containing 50% by mass of the polymerizable fluorine-based compound (H2). As a result of measuring the molecular weight of this polymerizable fluorine-based compound (H2) by GPC (polystyrene equivalent molecular weight), it was a number average molecular weight 2,200 and a weight average molecular weight 6,500. The fluorine content was 11% by mass.

  The polymerizable fluorine compounds (1) to (3) obtained in Examples 1 to 3, the fluorine surfactant (H1) and the polymerizable fluorine compound (H2) obtained in Comparative Examples 1 to 3 Table 1 summarizes characteristic values such as molecular weight.

(Preparation of base resin composition of active energy ray-curable composition)
125 parts by mass of UV curable urethane acrylate resin (“Unidic 17-806” manufactured by DIC Corporation; butyl acetate solution with a resin content of 80% by mass), 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF Japan Ltd.) as a photopolymerization initiator "Irgacure 184") 5 parts by mass, 54 parts by mass of toluene as a solvent, 28 parts by mass of 2-propanol, 28 parts by mass of ethyl acetate, and 28 parts by mass of propylene glycol monomethyl ether are mixed and dissolved to obtain an active energy ray-curable composition The base resin composition was obtained.

(Examples 4-6, Comparative Examples 4-5)
Obtained in 268 parts by mass of the base resin composition obtained above with the polymerizable fluorine-based compounds (1) to (3) obtained in Examples 1 to 3 and Comparative Examples 1 and 2 as a fluorine-containing surfactant. An active energy ray-curable composition was obtained by adding 1 part by mass of solid fluorine-containing surfactant (H1) and polymerizable fluorine-based compound (H2) and mixing them uniformly. Next, this active energy ray-curable composition was applied to a bar coater No. 13 was applied to a polyethylene terephthalate (PET) film having a thickness of 188 μm, and then placed in a dryer at 60 ° C. for 5 minutes to volatilize the solvent. Next, the dried coating film was cured by irradiating with ultraviolet rays (UV) with an ultraviolet curing device (in a nitrogen atmosphere, a high-pressure mercury lamp, an ultraviolet irradiation amount of ² kJ / m ² ), and Examples 4 to 6 and Comparative Examples 3 to 4 were cured. A coated film was prepared. Moreover, the coating film was similarly produced about only the base resin composition of the active energy ray hardening-type composition, without adding anything, and it was set as the comparative example 5.

[Evaluation of antifouling properties]
The antifouling property of the coated surface of the coated film obtained above was evaluated from the following contact angles of water and n-dodecane and antifouling property.

[Measurement of contact angle of water and n-dodecane]
About the coating surface of the coating film, the contact angle of water and n-dodecane was measured using the contact angle measuring apparatus (Kyowa Interface Science Co., Ltd. "MODEL CA-W150").

[Evaluation of dirt adhesion prevention]
On the coated surface of the coated film, draw a line with a felt pen ("Uni Mediax" black, manufactured by Mitsubishi Pencil Co., Ltd.), and visually evaluate the adhesion state of the black ink to evaluate the antifouling property. went. The evaluation criteria are as follows.
AA: The antifouling property is the best and the ink repels.
A: The ink does not repel and forms a linear repelling (the line width is less than 50% of the width of the tip of the felt pen).
B: Ink repelling occurred and the line width was 50% or more and less than 100% of the width of the tip of the felt pen.
C: The ink can be drawn cleanly on the surface without repelling at all.

[Evaluation of antifouling properties after wear treatment]
As the evaluation of antifouling durability, the coating film whose surface was subjected to abrasion treatment was subjected to measurement of the contact angle of water and n-dodecane and evaluation of antifouling property in the same manner as described above. The wear treatment was performed by attaching a non-woven fabric (“Bencot S” manufactured by Asahi Kasei Fibers Co., Ltd.) to a jig using a reciprocating wear tester (“HEIDON Tribogear TYPE: 30S” manufactured by Shinto Kagaku Co., Ltd.) of 1.72N. It was performed by carrying out 5000 round-trip wear with a load of / cm ² .

  The results of the above measurement and evaluation are shown in Table 2.

  In Examples 4 to 6 to which the polymerizable fluorine-based compounds (1) to (3) obtained in Examples 1 to 3 which are polymerizable fluorine-based compounds of the present invention were added, the contact angles of water and n-dodecane were It was found to be high and also highly resistant to dirt adhesion. It was also found that the contact angles of water and n-dodecane did not significantly decrease even after the abrasion treatment, the stain adhesion preventing property was sufficiently maintained, and the antifouling durability was also high.

  On the other hand, Comparative Example 3 using the fluorosurfactant (H1) having no polymerizable group produced in Comparative Example 1 has a high contact angle of water and n-dodecane, and has a relatively good antifouling property. However, the contact angle between water and n-dodecane after abrasion treatment was greatly reduced, the antifouling property was also greatly reduced, and it was found that the antifouling durability was not sufficient.

  Comparative Example 4 using the polymerizable fluorine-based compound (H2) produced in Comparative Example 2 had a high contact angle of water and n-dodecane and had a relatively good antifouling property. It turned out that the contact angle of water and n-dodecane afterwards is greatly reduced, the antifouling property is greatly reduced, and the antifouling durability is not sufficient.

  It was found that Comparative Example 5 in which no additive was added had a low contact angle of water and n-dodecane and was inferior in soil adhesion prevention.

Claims (4)

A polymerizable fluorine-based compound represented by the following general formula (1).

(In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or a methyl group, and R ⁶ , R ⁷ and R ⁸ each independently represent a hydroxyl group or the following general formula (2) X ¹ and X ² each independently represent a divalent organic group, and PFPE represents a poly (perfluoroalkylene ether) chain, provided that R ⁶ , R ⁷ and R ⁸ (At least one is a group represented by the following general formula (2), and n represents a range of 0 to 10 on average.)

(In the formula, each R ⁹ independently represents a hydrogen atom or a methyl group, each X ³ independently represents a single bond, a divalent or trivalent organic group, and m represents 1 or 2.)   An active energy ray-curable composition comprising the polymerizable fluorine-based compound according to claim 1 and an active energy ray-curable resin (B) or an active energy ray-curable monomer (C).   A cured product obtained by applying the polymerizable fluorine-based compound according to claim 1 or the active energy ray-curable composition according to claim 2 to a substrate, and irradiating and curing the active energy ray.   An article comprising a cured coating film of the polymerizable fluorine-based compound according to claim 1 or the active energy ray-curable composition according to claim 2.

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