JP2011256330A - Fluorine-containing curable resin and active energy ray-curable composition using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluorine-containing curable resin which can give excellent stainproof on a cured coating film surface, and to provide an active energy ray-curable composition which is added with the resin in which the cured product maintains excellent stainproof also even after saponification treatment.SOLUTION: The fluorine-containing curable resin comprises as follows. The polymerization of a compound (A) expressed by General formula (A), and a monomer component which makes indispensable a polymerizable unsaturated monomer (B) having a reactive group (b) is carried out to obtain a polymer (P), then a polymerization nature unsaturated group is introduced into the reactive group (b) which the polymer (P) has and a hydroxy group which the compound (A) has had. In addition, the fluorine-containing curable resin is used for the active energy ray-curable composition. In the formula, R, R, R, Rand Reach independently denote a hydrogen atom or a methyl group, Xand Xeach independently denote a divalent organic group, PFPE denotes a poly (perfluoro alkylene ether) chain, and n denotes the range of 0-10 in average.

Description

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

  Fluorine-containing surfactants or fluorine-containing surface modifiers are excellent in leveling, wettability, permeability, anti-blocking properties, slipperiness, water / oil repellency, antifouling properties, etc. Widely used in quality materials.

  Cured coating obtained by applying and curing an active energy ray-curable coating containing a fluorine-containing surfactant or fluorine-containing surface modifier (hereinafter simply referred to as “fluorine-containing surfactant”). While the film exhibits excellent antifouling properties, it has fluorine-containing surface activity by heating, humidification, exposure to chemicals such as acid and alkali, cleaning and wiping to remove stains in the manufacturing process of cured coatings. There was a problem that a part of the agent was detached or volatilized from the surface of the cured coating film and the antifouling property of the surface of the cured coating film was lowered.

  Specifically, for example, in the field of surface treatment agents for protective films such as triacetyl cellulose (hereinafter abbreviated as “TAC”) films in polarizing plates for liquid crystal displays, antifouling properties against fingerprints and dirt are imparted to the film surface. In order to achieve this, the surface of the protective film is coated with an ultraviolet curable hard coat material to which a fluorine-containing surfactant or the like is added. However, the protective film is subjected to saponification treatment (alkali treatment) for the purpose of imparting adhesiveness to the opposite surface of the hard coat surface to which the hard coat material is applied. Contact with the alkaline solution is unavoidable, and the fluorine-containing surfactant, etc. present on the hard coat surface is washed away with the strong alkaline solution or decomposed. There was a problem to do.

  Thus, as a fluorine-containing surfactant that can withstand saponification treatment, it has been proposed to polymerize with other materials having a polymerizable functional group and fix it in a cured coating film. For example, a copolymer obtained by copolymerizing a monoacrylate having a fluorinated alkyl group and an acrylic monomer having active hydrogen, and then reacting the resulting polymer with an acrylic monomer having an isocyanate group. A polymerizable fluorine-containing surfactant having a saturated group has been proposed (see, for example, Patent Document 1). This polymerization type fluorine-containing surfactant has a polymerizable group, and when used as an additive to the active energy ray-curable composition, it is bonded to the polymerization component in the composition by a covalent bond. However, there is a problem that the antifouling property after the saponification treatment is greatly reduced.

  Further, poly (perfluoroalkylene ether) produced from a compound having a (perfluoroalkylene ether) chain and having a di (meth) acryloyl group at both ends in the same manner as the above-described polymerization type fluorine-containing surfactant. A polymerization type fluorine-containing surfactant having a chain and an unsaturated group has been proposed (for example, see Patent Document 2). The fluorine-containing surfactant having a poly (perfluoroalkylene ether) chain is improved in antifouling property after saponification treatment than the one described in Patent Document 1, but requires a higher level of antifouling property. I was not satisfied.

  Therefore, there is a demand for a material that maintains a very excellent antifouling property even after saponification treatment.

JP 2007-246696 A International Publication WO2009 / 133770

  The problem to be solved by the present invention is to provide a fluorinated curable resin used as a fluorinated surfactant capable of imparting excellent antifouling properties to the surface of a cured coating film. Moreover, the active energy which can suppress the detachment | desorption of the said fluorine-containing surfactant from the cured coating film surface even if it saponifies after apply | coating and hardening, and can provide the outstanding antifouling property. It is to provide an article having a linear curable composition, a cured product thereof, and a cured coating film thereof.

  As a result of intensive studies to solve the above problems, the present inventors have obtained a reaction between a poly (perfluoroalkylene ether) chain, a compound having an epoxy group introduced at both ends thereof, and (meth) acrylic acid. A compound obtained by copolymerizing a compound obtained with a polymerizable unsaturated monomer having a reactive group, and a compound having a functional group reactive with the reactive group and a polymerizable unsaturated group The active energy ray-curable composition containing the fluorine-containing curable resin obtained by reacting with the resin imparts an excellent antifouling property to the cured coating film surface, and the antifouling property is reduced even after saponification treatment. The present invention has been completed by finding that it can be suppressed.

That is, the present invention comprises a poly (perfluoroalkylene ether) chain represented by the following general formula (A), a compound (A) having (meth) acryloyl groups at both ends thereof, a hydroxyl group, an epoxy group, and a carboxyl group. A polymer component (P) is obtained by polymerizing a monomer component essentially containing a polymerizable unsaturated monomer (B) having at least one reactive group (b) selected from the group consisting of The compound (C1) having a functional group (c1) and a polymerizable unsaturated group reactive to the reactive group (b) of the polymer (P), and the polymer (P) present in the polymer (P) A fluorine-containing curable resin obtained by reacting a functional group (c2) having a reactivity with a hydroxyl group which the compound (A) had and a compound (C2) having a polymerizable unsaturated group, ,
(1) When the reactive group (b) is a hydroxyl group, the functional group (c1) and the functional group (c2) are an isocyanate group, a carboxylic acid halide or an acid anhydride,
(2) When the reactive group (b) is an epoxy group, the functional group (c1) is a carboxyl group, and the functional group (c2) is an isocyanate group,
(3) When the reactive group (b) is a carboxyl group, the functional group (c1) is an epoxy group, and the functional group (c2) is an isocyanate group or an acid anhydride. The present invention relates to a fluorine-containing curable resin and an active energy ray-curable composition containing the fluorine-containing curable resin.

（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、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）鎖を表し、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, X ¹ and X ² each independently represent a divalent organic group, and PFPE Represents a poly (perfluoroalkylene ether) chain, and n represents an average range of 0 to 10.

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

  The fluorine-containing curable resin of the present invention can impart antifouling property to the substrate surface by coating the substrate alone to form a cured coating film. In addition, the active energy ray-curable composition containing the fluorine-containing curable resin 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 fluorine-containing curable resin 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 fluorine-containing curable resin can be polymerized with other curable components in the active energy ray-curable composition, the fluorine-containing curable resin of the present invention is stronger in the cured coating film. Therefore, volatilization and detachment of the fluorine-containing curable resin or a decomposition product thereof can be suppressed from the surface of the cured coating film even if heat treatment or the like is performed.

  On the other hand, the cured coating film using the fluorine-containing curable resin of the present invention has high resistance to saponification treatment, and can suppress a decrease in antifouling property even when saponification treatment is performed. Therefore, the active energy ray-curable composition using the fluorine-containing curable resin of the present invention is used for a polarizing plate for liquid crystal displays that needs to be imparted with antifouling properties and is subjected to saponification treatment with alkali. It is extremely useful as a hard coat material for a TAC film.

FIG. 1 is an IR spectrum chart of the compound obtained in Synthesis Example 1 and a compound having methacryloyl groups at both ends thereof. FIG. 2 is a chart of the ¹ H-NMR spectrum of the compound having a methacryloyl group at both ends thereof and the poly (perfluoroalkylene ether) chain obtained in Synthesis Example 1. FIG. 3 is a chart of ¹³ C-NMR spectrum of the compound having a methacryloyl group at both ends thereof and the poly (perfluoroalkylene ether) chain obtained in Synthesis Example 1. FIG. 4 is a GPC chart of the fluorinated curable resin (1) obtained in Example 1. FIG. 5 is a GPC chart of the fluorinated curable resin (5) obtained in Example 5.

  The fluorine-containing curable resin of the present invention includes a poly (perfluoroalkylene ether) chain represented by the following general formula (A), a compound (A) having (meth) acryloyl groups at both ends thereof, a hydroxyl group, and an epoxy group. And a monomer component essentially comprising a polymerizable unsaturated monomer (B) having at least one reactive group (b) selected from the group consisting of carboxyl groups, to obtain a polymer (P) Thereafter, a compound (C1) having a functional group (c1) and a polymerizable unsaturated group reactive to the reactive group (b) of the polymer (P), and the polymer (P) It is obtained by reacting the functional group (c2) having a reactivity with the hydroxyl group contained in the compound (A) present in the compound and the compound (C2) having a polymerizable unsaturated group.

（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、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）鎖を表し、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, X ¹ and X ² each independently represent a divalent organic group, and PFPE Represents a poly (perfluoroalkylene ether) chain, and n represents an average range of 0 to 10.

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

  The compound (A) will be described below. This compound (A) is a compound represented by the following general formula (A). In addition, the return part of the bond in the following general formula (A) represents a single bond not involving a carbon atom. Moreover, the folding | returning part of the coupling | bonding in another formula is also synonymous.

（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、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）鎖を表し、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, X ¹ and X ² each independently represent a divalent organic group, and PFPE Represents a poly (perfluoroalkylene ether) chain, and n represents an average range of 0 to 10.

R ¹ and R ² in the general formula (A) are each independently a hydrogen atom or a methyl group, but since the polymerizability with the monomer (B) is good, R ¹ and R ² are Both are preferably methyl groups.

X ¹ and X ² in the general formula (A) 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.

  The poly (perfluoroalkylene ether) chain represented by “PFPE” in the general formula (A) has a structure in which divalent fluorocarbon groups 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（ａ）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、ｍは繰り返し単位数を表す１以上の整数である。）

(In the structural formula (a), 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 m 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 m 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 (A) is in the range of 0 to 10 on average, but when the fluorine-containing curable resin 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 of repeating units n in the general formula (A) can be calculated using the hydroxyl equivalent value of the compound (a2) and the epoxy equivalent value 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 (A) is obtained by the following formula (1). Can do. The hydroxyl equivalent of the compound (a2) is, for example, ¹⁹ F-NMR measured with the compound (a2) represented by the general formula (a2-1) described later, and is adjacent to the hydroxyl group via 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., And the number of other perfluoromethylene groups, perfluoroethylene groups, etc. is determined from the respective integral ratios, with the integral ratio of the chemical shift of the adjacent CF ₂ moiety being ₂ , and the resulting compound (a2) It can be determined by dividing the molecular weight by 2. Moreover, the epoxy equivalent of a compound (a3) can be measured with the following method.

[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 poly (perfluoroalkylene ether) chain and hydroxyl groups at both ends thereof, and an epihalohydrin such as epichlorohydrin and β-methylepichlorohydrin. After obtaining a compound (a3) having an epoxy group at both ends thereof with a poly (perfluoroalkylene ether) chain, (meth) acrylic acid is reacted with the epoxy group of this compound (a3) A method is mentioned.

  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. The amount of the phase transfer catalyst 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 (A) obtained by the above reaction include compounds represented by the following general formulas (A-1) and (A-2). In addition, the present invention is characterized in that the hydroxyl group of the compound (A) is used as a site for introducing a polymerizable unsaturated group.

  Next, the polymerizable unsaturated monomer (B) having a reactive group (b) will be described. The monomer (B) can be easily converted into a high molecular weight polymer by an ordinary radical polymerization method. In this case, the reaction is performed by bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, or the like. A known method can be used. The radical polymerization reaction can be performed by simple heating or irradiation with ultraviolet rays, but can be quickly started by adding a radical initiator.

  The reactive group (b) of the monomer (B) is at least one selected from the group consisting of a hydroxyl group, an epoxy group, and a carboxyl group. Further, the polymerizable unsaturated group possessed by the monomer (B) is preferably a carbon-carbon unsaturated double bond having radical polymerizability, and more specifically, a vinyl group, a (meth) acryloyl group, a maleimide. A (meth) acryloyl group is more preferable from the viewpoint of easy polymerization.

  Specific examples of the polymerizable unsaturated monomer (B) include those in which the reactive group (b) is a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3- Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, N- (2-hydroxyethyl) (meth) acrylamide , Glycerol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl F Examples of the reactive group (b) include glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether, and the like. Examples of b) having a carboxyl group include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, maleic acid, itaconic acid and the like.

  When producing the polymer (P), in addition to the compound (A) and the monomer (B), other polymerizable unsaturated monomers that can be copolymerized therewith may be used. Examples of such other radical polymerizable unsaturated monomers include methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylate-n-propyl, (meth) acrylate-n-butyl, (Meth) acrylic acid isobutyl, (meth) acrylic acid-n-pentyl, (meth) acrylic acid-n-hexyl, (meth) acrylic acid-n-heptyl, (meth) acrylic acid-n-octyl, (meth) (Meth) acrylates such as 2-ethylhexyl acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate Aromatic vinyls such as styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene; maleimide, methylmer Imides, ethylmaleimide, propyl maleimide, butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, stearyl maleimide, phenyl maleimide, and the like maleimides such as cyclohexyl maleimide.

  The method for producing the polymer (P) is a radical polymerization initiator in the organic solvent with the compound (A) and the monomer (B) and, if necessary, other polymerizable unsaturated monomers. And a method of copolymerization in the presence of. As the organic solvent used here, ketones, esters, amides, sulfoxides, ethers, hydrocarbons are preferable. 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 organic solvents are appropriately selected in consideration of the boiling point, compatibility with the raw material or polymer, and polymerizability.

  Examples of the radical polymerization initiator include acetyl peroxide, cumyl peroxide, t-butyl peroxide, propionyl peroxide, benzoyl peroxide, 2-chlorobenzoyl peroxide, 3-chlorobenzoyl peroxide, 4-hydroxy peroxide. Chlorobenzoyl, 2,4-dichlorobenzoyl peroxide, 4-bromomethylbenzoyl peroxide, lauroyl peroxide, diisopropyl peroxycarbonate, tetralin hydroperoxide, 1-phenyl-2-methylpropyl-1-hydroperoxide, pertriphenylacetic acid t-butyl, t-butyl hydroperoxide, t-butyl formate, t-butyl peracetate, t-butyl perbenzoate, t-butyl perethylhexanoate, t-butyl perphenylacetate, 4-methoxy Peroxides such as t-butyl acetate; 2,2′-dichloro-2,2′-a Bispropane, 1,1′-azo (methylethyl) diacetate, 2,2′-azobis (2-amidinopropane) nitrate, 2,2′-azobisisobutane, 2,2′-azobisisobutyramide, 2 2,2′-azobisisobutyronitrile, methyl 2,2′-azobis-2-methylpropionate, 2,2′-dichloro-2,2′-azobisbutane, 2,2′-azobis-2-methylbutyrate Ronitrile, dimethyl 2,2′-azobisisobutyrate, dimethyl 2,2′-azobisisobutyrate, 2- (4-methylphenylazo) -2-methylmalonodinitrile, 4,4′-azobis-4-cyanovaleric acid 3,5-dihydroxymethylphenylazo-2-methylmalonodinitrile, 1,1′-azobis-1-cyclohexanecarbonitrile, 1,1′-azobis 1-phenylethane, 1,1′-azobiscumene, ethyl 4-nitrophenylazobenzylcyanoacetate, phenylazodiphenylmethane, phenylazotriphenylmethane, 4-nitrotriphenylazotriphenylmethane, 1,1′-azobis- An azo compound such as 1,2-diphenylethane may be mentioned. Furthermore, a chain transfer agent such as lauryl mercaptan, 2-mercaptoethanol, thioglycerol, ethylthioglycolic acid, octylthioglycolic acid or the like can be used as necessary.

  The molecular weight of the resulting polymer (P) needs to be in a range in which insolubilization in the solvent does not occur due to intermolecular crosslinking during the polymerization, and the insolubilization occurs when the molecular weight becomes very high. Therefore, the molecular weight of the obtained polymer (P) may be in a range in which insolubilization does not occur, and the number average molecular weight (Mn) of the obtained polymer (P) is preferably in the range of 800 to 10,000, More preferably, it is in the range of 5,000 to 5,000, and the weight average molecular weight (Mw) of the resulting polymer (P) is preferably in the range of 2,000 to 100,000. More preferably, it is in the range of ˜50,000.

  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

  The polymer (P) obtained as described above, the functional group (c1) having reactivity with the reactive group (b) and the compound (C1) having a polymerizable unsaturated group, and the polymer By reacting the compound (C2) having a polymerizable unsaturated group with the functional group (c2) having a reactivity with respect to the hydroxyl group of the compound (A) present in (P), The fluorine-containing curable resin of the invention is obtained.

  The functional group (c1) of the compound (C1) is a hydroxyl group, an isocyanate group, an epoxy group, a carboxyl group, a carboxylic acid halide or an acid anhydride, and the functional group (c2) of the compound (C2) is: Isocyanate group, epoxy group, carboxylic acid halide or acid anhydride. These functional group (c1) and functional group (c2) are selected according to the type of reactive group (b) of the monomer (B) used as the raw material of the polymer (P), and the combination is It is as follows.

(1) When the reactive group (b) is a hydroxyl group, the functional group (c1) and the functional group (c2) are an isocyanate group, a carboxylic acid halide, or an acid anhydride.
(2) When the reactive group (b) is an epoxy group, the functional group (c1) is a carboxyl group, and the functional group (c2) is an isocyanate group.
(3) When the reactive group (b) is a carboxyl group, the functional group (c1) is an epoxy group, and the functional group (c2) is an isocyanate group or an acid anhydride.

  Among the above combinations, since the types of raw materials can be reduced, the reactivity is good, and the productivity is high, the reactive group (b) of the monomer (B) is a hydroxyl group, and the compound A combination in which the functional group (c1) of (C1) and the functional group (c2) of the compound (C2) are isocyanate groups is preferable.

  Specific examples of the compound (C1) or (C2) include those in which the functional group (c1) or (c2) is an isocyanate group, 2- (meth) acryloyloxyethyl isocyanate, 2- (2- (meth) Examples include acryloyloxyethoxy) ethyl isocyanate, 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate, and the functional group (c1) or (c2) is an epoxy group, such as glycidyl methacrylate, 4-hydroxy Butyl acrylate glycidyl ether and the like, wherein the functional group (c1) or (c2) is a carboxyl group, (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxy And ethyl phthalic acid, maleic acid, itaconic acid, etc. Examples of the functional group (c1) or (c2) having a carboxylic acid halide include (meth) acrylic acid chloride, (meth) acrylic acid bromide, and the functional group (c1) or (c2) is acid anhydride. Examples of the product include maleic anhydride, itaconic anhydride and the like.

  Among these, 2-acryloyloxyethyl isocyanate, 4-hydroxybutyl acrylate glycidyl ether, and acrylic acid are particularly preferable from the viewpoint of preferable polymerization curability under ultraviolet irradiation.

  The method of reacting the polymer (P) with the compound (C) containing a functional group (c1) reactive with the functional group (b) and a polymerizable unsaturated group is the compound (C). The reaction may be performed under conditions in which the polymerizable unsaturated group therein does not polymerize. For example, the reaction is preferably carried out by adjusting the temperature condition in the range of 30 to 120 ° C. 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 (b) is a hydroxyl group and the functional group (c1) is an isocyanate group, p-methoxyphenol, hydroquinone, 2,6-di-t-butyl-4-methyl is used as a polymerization inhibitor. Using phenol or the like, dibutyltin dilaurate, dibutyltin diacetate, tin octylate, zinc octylate or the like 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 react with is preferable. When the functional group (b) is an epoxy group and the functional group (c1) is a carboxyl group, or the functional group (b) is a carboxyl group and the functional group (c) is an epoxy group. In this case, p-methoxyphenol, hydroquinone, 2,6-di-t-butyl-4-methylphenol or the like is used as a polymerization inhibitor, and tertiary amines such as triethylamine are used as an esterification reaction catalyst. Using a quaternary ammonium such as tetramethylammonium, a tertiary phosphine such as triphenylphosphine, a quaternary phosphonium such as tetrabutylphosphonium chloride, etc., and a reaction temperature of 80 to 130 ° C., particularly 100 to 120 ° C. It is preferable to make it react with.

  Moreover, when making the said compound (C2) whose said functional group (c2) is an isocyanate group react with the hydroxyl group in the said polymer (P), said functional group (b) is a hydroxyl group, and the said functional group ( The same reaction method as that when c1) is an isocyanate group can be used, and the compound (C1) and the compound (C2) can be made the same compound, which is preferable.

  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.

  The fluorine-containing curable resin of the present invention obtained as described above can prevent gelation during production and can impart excellent antifouling properties to the cured coating film, so that its number average molecular weight (Mn) is 1, The range is preferably from 000 to 20,000, and more preferably from 1,500 to 10,000. Moreover, it is preferable that a weight average molecular weight (Mw) is the range of 3,000-80,000, and it is preferable that it is the range of 5,000-50,000. 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.

  In addition, the fluorine content in the fluorine-containing curable resin of the present invention is preferably in the range of 2 to 50% by mass because both antifouling properties and compatibility with other components can be achieved. The range of 40% by mass is more preferable, and the range of 10 to 35% by mass is more preferable. The fluorine content in the fluorine-containing radical polymerizable copolymer of the present invention is a value calculated from the mass ratio of fluorine atoms with respect to the total amount of raw materials used.

  Although the fluorine-containing curable resin of the present invention can be used as a main component of the active energy ray-curable composition itself, it is extremely 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 a blend of the fluorine-containing curable resin of the present invention. The main component thereof is an active energy ray-curable resin (D) or active energy ray-curable. Contains monomer (E). In the active energy ray-curable composition of the present invention, the active energy ray-curable resin (D) and the active energy ray-curable monomer (E) may be used alone or in combination. It doesn't matter. The fluorine-containing curable resin 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 (D) 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 (meth) acrylate, propoxylated trimethylolpropane di (meth) acrylate, glycerin di (meth) Mono- or di (meth) acrylates of trivalent alcohols such as acrylate and bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, or hydroxyl groups obtained by modifying some 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 further modified with ε-caprolactone; dipropylene glycol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, polypropylene (Meth) acrylate compounds having an oxyalkylene chain such as polyethylene glycol 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 (F) can be used alone or in combination of two or more.

  Examples of the active energy ray-curable monomer (E) 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 (E) can be used alone or in combination of two or more.

  In the active energy ray-curable composition of the present invention, when the fluorine-containing curable resin of the present invention is used as a fluorine-containing surfactant, the amount used thereof is the active energy ray-curable resin (D) and the active energy ray. 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 (E). If the amount of the fluorine-containing curable resin of the present invention is in 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 fluorine-containing curable resin or 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 (F) is added to the fluorine-containing curable resin 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. F) or a photosensitizer need not be added.

  Examples of the photopolymerization initiator (F) 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 (F), the compatibility with the active energy ray curable resin (D) and the active energy ray curable monomer (E) 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 (F) 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 fluorine-containing curable resin of the present invention has excellent antifouling properties (ink repellency, fingerprint resistance, etc.), scratch resistance, etc. It is possible to impart antifouling property, scratch resistance, etc. The fluorine-containing curable resin of the present invention can also 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 fluorine-containing curable resin 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; Scan; woodworking materials such as furniture, 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 fluorine-containing curable resin 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. Further, the fluorine-containing curable resin of the present invention can be added to various paints suitable for each article, applied, and dried to impart antifouling properties to the article surface.

  Further, as a coating material that can improve the leveling property by adding the fluorine-containing curable resin 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, printing ink, inkjet ink or paint for forming each pixel of RGB used for a color filter for liquid crystal display (hereinafter referred to as “CF”); Black resist for black matrix of CF, Printing ink, inkjet ink or paint; plasma display (PDP) Resin composition for pixel partition walls of organic EL displays, etc .; paint or hard coat material for mobile phone casings; hard coat material for mobile phone screens; hard coat material for optical recording media such as CD, DVD, Blu-ray disc; insert mold Hard coating material for transfer film for (IMD, IMF); Coating material for rubber roller for OA equipment such as copying machines and printers; Coating material for glass for reading parts of OA equipment such as copying machines and scanners; Cameras, video cameras, Coating materials for optical lenses such as glasses; windshields for watches such as watches; coating materials for glasses; coating materials for windows of various vehicles such as automobiles and railway vehicles; printing inks or paints for various building materials such as decorative panels; Coating materials for glass; wood coatings for furniture, etc .; coating materials for artificial and synthetic leather; various plastic moldings such as housings for home appliances Use paint or coating material; such as 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 fluorine-containing curable resin or active energy ray-curable composition of the present invention, a prism sheet that is an LCD backlight member or Examples thereof include a diffusion sheet. Further, by adding the fluorine-containing curable resin 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 fluorinated curable resin 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 fluorine-containing curable resin 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 fluorine-containing curable resin or the 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 fluorine-containing curable resin or 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.

  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 fluorine-containing curable resin of the present invention and the epoxy equivalent of a compound having an epoxy group at both ends thereof, the poly (perfluoroalkylene ether) chain and both ends thereof The measurement method of the acid value of the compound having a (meth) acryloyl group, the IR spectrum and the NMR spectrum, and the measurement conditions of GPC of the fluorine-containing curable resin are as follows.

[IR spectrum measurement method]
Using a measuring device of “IR Prestige-21” manufactured by Shimadzu Corporation, a very small amount of the sample solution was dropped on a KBr plate and the solvent was dried, and then the measurement was performed.

[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

(Synthesis 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) 50.0 parts by mass, epichlorohydrin 62.5 parts by mass, and ethanol 18.0 parts by mass. 8.3 parts by mass of a 49% by mass aqueous sodium hydroxide solution was added dropwise over 2 hours while maintaining the temperature in the flask at 50 ° C. After completion of the addition, the temperature was raised to 60 ° C. and stirred for 3 hours. It returned to room temperature.

（式中、Ｘはパーフルオロメチレン基及びパーフルオロエチレン基であり、１分子あたり、パーフルオロメチレン基が平均７個、パーフルオロエチレン基が平均８個存在するものであり、フッ素原子の数が平均４６である。また、ＧＰＣ測定による数平均分子量は１，５００である。）

(In the formula, X is a perfluoromethylene group and a perfluoroethylene group, and an average of 7 perfluoromethylene groups and an average of 8 perfluoroethylene groups are present per molecule, and the number of fluorine atoms is (The average is 46. The number average molecular weight by GPC measurement is 1,500.)

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 0.3. 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 -) chemical shifts, perfluoro ethylene group (-CF 2 CF _{2 -)} after obtaining the integral ratio of the chemical shift, etc., the integral ratio of the chemical shifts of the CF ₂ moiety which is adjacent via a hydroxyl group and methylene as 2 The number of other perfluoromethylene groups, perfluoroethylene groups, etc. was determined from the respective integral ratios, and the molecular weight of the compound (a2) obtained from the results was determined by dividing by 2. Moreover, the epoxy equivalent of the compound (a3) was measured by the above method. For the following Synthesis Examples 2 to 4, the average value of the number of repeating units n 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, stirring is started under an air stream, and reaction is performed at 90 ° C. for 20 hours, thereby being represented by the following formula (A-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 (A-1-1)”) were obtained. This compound (A-1-1) was a transparent liquid, its acid value was 2, and the average value of the number of repeating units n in the formula was 0.3. Further, ¹ H-NMR and ¹³ C-NMR spectra of the obtained compound (A-1-1) were measured and identified. FIG. 1 shows a chart of the IR spectrum, FIG. 2 shows a chart of the ¹ H-NMR spectrum, and FIG. 3 shows a chart of the ¹³ C-NMR spectrum.

(Synthesis Example 2)
In a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, 52.2 parts by mass of compound (a3-1-1) obtained by the same method as in Synthesis Example 1, 3.7 parts by mass of acrylic acid, By adding 0.03 part by weight of methoquinone as a polymerization inhibitor and 0.17 part by weight of triphenylphosphine as a catalyst, stirring was started under an air stream, and the reaction was carried out at 90 ° C. for 20 hours to obtain the following formula (A-1- 25.9 parts of a poly (perfluoroalkylene ether) chain represented by 2) and a compound having an acryloyl group at both ends thereof (hereinafter abbreviated as “compound (A-1-2)”) were obtained. . This compound (A-1-2) was a transparent liquid, its acid value was 2.4, and the average value of the number of repeating units n in the formula was 0.3.

(Synthesis Example 3)
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 50 parts by mass of the compound (a2-1-1), 12.5 parts by mass of epichlorohydrin, and 5 parts by mass of ethanol. Next, stirring was started under a nitrogen stream, and 8.3 parts by mass of a 49% by mass aqueous sodium hydroxide solution was added dropwise over 2 hours while maintaining the temperature in the flask at 50 ° C. After completion of dropping, the temperature was raised to 60 ° C. and stirred for 3 hours, and then returned to room temperature.

  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, and the poly (perfluoroalkylene ether) chain represented by the following formula (a3-1-2) and both ends thereof are removed. 51.1 parts by mass of an epoxy group-containing compound (hereinafter abbreviated as “compound (a3-1-2)”) was obtained. This compound (a3-1-1) is a slightly cloudy liquid and has an epoxy equivalent of 1,445 g / eq. The average value of the number of repeating units n in the formula was 0.8.

  Subsequently, 51.1 parts by mass of the compound (a3-1-2) obtained above, 3.2 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. 0.03 part by mass and 0.16 part by mass of triphenylphosphine as a catalyst, starting stirring under an air stream, and reacting at 90 ° C. for 20 hours are represented by the following formula (A-1-3). A compound having a poly (perfluoroalkylene ether) chain and a methacryloyl group at both ends thereof (hereinafter abbreviated as “compound (A-1-3)”) 54.2 parts by mass was obtained. This compound (A-1-3) was a slightly cloudy liquid, its acid value was 1, and the average value of the number of repeating units n in the formula was 0.8.

(Synthesis Example 4)
A glass flask equipped with a stirrer, a thermometer, a condenser tube and a dropping device was charged with 50 parts by mass of the compound (a2-1-1), 72 parts by mass of β-methylepichlorohydrin and 21.6 parts by mass of ethanol. . Next, stirring was started under a nitrogen stream, and 8.3 parts by mass of a 49% by mass aqueous sodium hydroxide solution was added dropwise over 2 hours while maintaining the temperature in the flask at 50 ° C. After completion of dropping, the temperature was raised to 60 ° C. and stirred for 3 hours, and then returned to room temperature.

  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. Unreacted β-methylepichlorohydrin is distilled off from the washed reaction solution by distillation under reduced pressure, and the poly (perfluoroalkylene ether) chain represented by the following formula (a3-1-3) and its 53.1 parts by mass of a compound having an epoxy group at both ends (hereinafter abbreviated as “compound (a3-1-3)”) was obtained. This compound (a3-1-3) is a yellow transparent liquid having an epoxy equivalent of 1,168 g / eq. The average value of the number of repeating units n in the formula was 0.5.

  Subsequently, 53.1 parts by mass of the compound (a3-1-3) obtained above, 4.1 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 part by mass of triphenylphosphine as a catalyst, stirring is started under an air stream, and reaction is performed at 90 ° C. for 20 hours, thereby being represented by the following formula (A-1-4) 57.2 parts by mass of a poly (perfluoroalkylene ether) chain and a compound having a methacryloyl group at both ends thereof (hereinafter abbreviated as “compound (A-1-4)”) were obtained. This compound (A-1-4) was a transparent liquid, its acid value was 2.3, and the average value of the number of repeating units n in the formula was 0.5.

(Synthesis Example 5)
In a glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device, 20 parts by mass of compound (a2-1-1), 20 parts by mass of diisopropyl ether as a solvent, and 0.02 mass of p-methoxyphenol as a polymerization inhibitor. In addition, 3.1 parts by mass of triethylamine as a part 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. Subsequently, 0.02 parts by mass of p-methoxyphenol was added as a polymerization inhibitor, 8 parts by mass 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. .

  Next, by distilling off the solvent under reduced pressure, a compound (hereinafter referred to as “compound (A ′)”) having a poly (perfluoroalkylene ether) chain represented by the following formula (A ′) and an acryloyl group at both ends thereof. For short).

（式中、Ｘはパーフルオロメチレン基及びパーフルオロエチレン基であり、１分子あたり、パーフルオロメチレン基が平均７個、パーフルオロエチレン基が平均８個存在するものであり、フッ素原子の数が平均４６である。）

(In the formula, X is a perfluoromethylene group and a perfluoroethylene group, and an average of 7 perfluoromethylene groups and an average of 8 perfluoroethylene groups are present per molecule, and the number of fluorine atoms is (The average is 46.)

Example 1
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 61.1 parts by mass of methyl isobutyl ketone as a solvent and heated to 105 ° C. while stirring under a nitrogen stream. Subsequently, 29.1 parts by mass of the compound (A-1-1) obtained in Synthesis Example 1, 32 parts by mass of 2-hydroxyethyl methacrylate, and t-butylperoxy-2-ethylhexanoate as a radical polymerization initiator 9.2 parts by weight of the polymerization initiator solution dissolved in 122.2 parts by weight of methyl isobutyl ketone was set in separate dropping devices, and the flask was kept at 105 ° C for 2 hours at the same time. And dripped. After completion of the dropwise addition, the mixture was stirred at 105 ° C. for 10 hours and then distilled off under reduced pressure to obtain a polymer (P-1).

Next, after adding 67.3 parts by mass of methyl ethyl ketone to the polymer (P-1) obtained above and dissolving, 0.09 parts by mass of p-methoxyphenol as a polymerization inhibitor and dibutyltin dilaurate 0 as a urethanization catalyst. .05 parts by weight were charged, stirring was started under an air stream, and 38.9 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour while maintaining 60 ° C. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour, then heated to 80 ° C. and stirred for 10 hours, whereby the disappearance of the absorption peak near 2360 cm ⁻¹ derived from isocyanate groups was confirmed by IR spectrum measurement. Subsequently, it returned to room temperature and 33.6 mass parts of methyl ethyl ketone was added, and the methyl ethyl ketone solution containing 50 mass% of fluorine-containing curable resin (1) was obtained. As a result of measuring the molecular weight of the obtained fluorinated curable resin (1) by GPC (polystyrene equivalent molecular weight), it was a number average molecular weight of 2,200 and a weight average molecular weight of 7,700. The fluorine content was 15% by mass.

(Example 2)
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 61.1 parts by mass of methyl isobutyl ketone as a solvent and heated to 105 ° C. while stirring under a nitrogen stream. Subsequently, 29.1 parts by mass of the compound (A-1-1) obtained in Synthesis Example 1, 32 parts by mass of 2-hydroxyethyl methacrylate, and t-butylperoxy-2-ethylhexanoate as a radical polymerization initiator 6.1 parts by weight of the polymerization initiator solution in which 12 parts by weight of methyl isobutyl ketone was dissolved in 122.2 parts by weight of the polymerization initiator were set in separate dropping devices, and the flask was kept at 105 ° C for 2 hours at the same time. And dripped. After completion of the dropwise addition, the mixture was stirred at 105 ° C. for 10 hours and then distilled under reduced pressure to obtain a polymer (P-2).

Subsequently, after adding 66.7 mass parts of methyl ethyl ketone to the polymer (P-2) obtained above and dissolving, 0.09 mass parts of p-methoxyphenol as a polymerization inhibitor and dibutyltin dilaurate 0 as a urethanization catalyst. .05 parts by weight were charged, stirring was started under an air stream, and 38.9 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour while maintaining 60 ° C. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour, then heated to 80 ° C. and stirred for 10 hours, whereby the disappearance of the absorption peak near 2360 cm ⁻¹ derived from isocyanate groups was confirmed by IR spectrum measurement. Subsequently, it returned to room temperature and 33.4 mass parts of methyl ethyl ketone was added, and the methyl ethyl ketone solution containing 50 mass% of fluorine-containing curable resin (2) was obtained. As a result of measuring the molecular weight of the obtained fluorine-containing curable resin (2) by GPC (polystyrene equivalent molecular weight), it was a number average molecular weight 2,600 and a weight average molecular weight 13,000. The fluorine content was 15% by mass.

(Example 3)
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 67.6 parts by mass of methyl isobutyl ketone as a solvent and heated to 105 ° C. while stirring under a nitrogen stream. Subsequently, 43.7 parts by mass of the compound (A-1-1) obtained in Synthesis Example 1, 24 parts by mass of 2-hydroxyethyl methacrylate, and t-butylperoxy-2-ethylhexanoate as a radical polymerization initiator Three types of dripping liquid with a polymerization initiator solution in which 10.1 parts by mass are dissolved in 202.9 parts by mass of methyl isobutyl ketone are set in separate dripping apparatuses, and the flask is kept at 105 ° C. for 2 hours at the same time. And dripped. After completion of the dropwise addition, the mixture was stirred at 105 ° C. for 10 hours and then distilled under reduced pressure to obtain a polymer (P-3).

Next, 67.3 parts by mass of methyl ethyl ketone was added to the polymer (P-3) obtained above and dissolved, then 0.09 parts by mass of p-methoxyphenol as a polymerization inhibitor, and dibutyltin dilaurate 0 as a urethanization catalyst. .05 parts by weight were charged, stirring was started under an air stream, and 32.4 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour while maintaining 60 ° C. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour, then heated to 80 ° C. and stirred for 10 hours, whereby the disappearance of the absorption peak near 2360 cm ⁻¹ derived from isocyanate groups was confirmed by IR spectrum measurement. Subsequently, it returned to room temperature and 33.7 mass parts of methyl ethyl ketone was added, and the methyl ethyl ketone solution containing 50 mass% of fluorine-containing curable resin (3) was obtained. As a result of measuring the molecular weight of the obtained fluorine-containing curable resin (3) by GPC (polystyrene equivalent molecular weight), it was a number average molecular weight 2,200 and a weight average molecular weight 7,300. The fluorine content was 23% by mass.

Example 4
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 57.3 parts by mass of methyl isobutyl ketone as a solvent and heated to 105 ° C. while stirring under a nitrogen stream. Subsequently, 20.2 parts by mass of the compound (A-1-2) obtained in Synthesis Example 2, 32.7 parts by mass of 2-hydroxyethyl methacrylate, and t-butylperoxy-2-ethylhexa as a radical polymerization initiator Three types of dripping liquids with a polymerization initiator solution in which 8.6 parts by mass of noate was dissolved in 114.6 parts by mass of methyl isobutyl ketone were set in separate dripping apparatuses, respectively. It was added dropwise over time. After completion of the dropwise addition, the mixture was stirred at 105 ° C. for 10 hours, and then distilled under reduced pressure to obtain a polymer (P-4).

Subsequently, after adding 67.3 parts by mass of methyl ethyl ketone to the polymer (P-4) obtained above and dissolving, 0.09 parts by mass of p-methoxyphenol as a polymerization inhibitor and dibutyltin dilaurate 0 as a urethanization catalyst. .05 parts by weight were charged, stirring was started under an air stream, and 42.7 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour while maintaining 60 ° C. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour, then heated to 80 ° C. and stirred for 10 hours, whereby the disappearance of the absorption peak near 2360 cm ⁻¹ derived from isocyanate groups was confirmed by IR spectrum measurement. Subsequently, it returned to room temperature and 33.6 mass parts of methyl ethyl ketone was added, and the methyl ethyl ketone solution containing 50 mass% of fluorine-containing curable resin (4) was obtained. As a result of measuring the molecular weight of the obtained fluorine-containing curable resin (4) by GPC (polystyrene equivalent molecular weight), it was a number average molecular weight 2,600 and a weight average molecular weight 45,500. The fluorine content was 11% by mass.

(Example 5)
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 57.2 parts by mass of methyl isobutyl ketone as a solvent and heated to 105 ° C. while stirring under a nitrogen stream. Subsequently, 20.2 parts by mass of the compound (A-1-3) obtained in Synthesis Example 3, 37 parts by mass of 2-hydroxyethyl methacrylate, and t-butylperoxy-2-ethylhexanoate as a radical polymerization initiator Three kinds of dropping solutions with a polymerization initiator solution in which 8.6 parts by weight of methyl isobutyl ketone was dissolved in 114.3 parts by weight were set in separate dropping devices, and the flask was kept at 105 ° C. for 2 hours at the same time. And dripped. After completion of the dropwise addition, the mixture was stirred at 105 ° C. for 10 hours and then distilled under reduced pressure to obtain a polymer (P-5).

Subsequently, after adding 67.2 mass parts of methyl ethyl ketone to the polymer (P-5) obtained above and dissolving, 0.09 mass parts of p-methoxyphenol as a polymerization inhibitor and dibutyltin dilaurate 0 as a urethanization catalyst. .05 parts by weight were charged, stirring was started under an air stream, and 42.8 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour while maintaining 60 ° C. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour, then heated to 80 ° C. and stirred for 10 hours, whereby the disappearance of the absorption peak near 2360 cm ⁻¹ derived from isocyanate groups was confirmed by IR spectrum measurement. Subsequently, it returned to room temperature and 33.7 mass parts of methyl ethyl ketone was added, and the methyl ethyl ketone solution containing 50 mass% of fluorine-containing curable resin (5) was obtained. As a result of measuring the molecular weight of the obtained fluorine-containing curable resin (5) by GPC (polystyrene equivalent molecular weight), it was a number average molecular weight 2,400 and a weight average molecular weight 6,600. The fluorine content was 11% by mass.

(Example 6)
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 57.1 parts by mass of methyl isobutyl ketone as a solvent and heated to 105 ° C. while stirring under a nitrogen stream. Next, 20.2 parts by mass of the compound (A-1-4) obtained in Synthesis Example 4, 36.9 parts by mass of 2-hydroxyethyl methacrylate, and t-butylperoxy-2-ethylhexa as a radical polymerization initiator Three types of dripping liquids with a polymerization initiator solution in which 8.6 parts by mass of noate was dissolved in 114.2 parts by mass of methyl isobutyl ketone were set in separate dripping apparatuses, respectively. It was added dropwise over time. After completion of the dropwise addition, the mixture was stirred at 105 ° C. for 10 hours and then distilled off under reduced pressure to obtain a polymer (P-6).

Subsequently, after adding 67.2 mass parts of methyl ethyl ketone to the polymer (P-6) obtained above and dissolving, 0.09 mass parts of p-methoxyphenol as a polymerization inhibitor and dibutyltin dilaurate 0 as a urethanization catalyst. .05 parts by weight were charged, stirring was started under an air stream, and 42.9 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour while maintaining 60 ° C. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour, then heated to 80 ° C. and stirred for 10 hours, whereby the disappearance of the absorption peak near 2360 cm ⁻¹ derived from isocyanate groups was confirmed by IR spectrum measurement. Subsequently, it returned to room temperature and 33.7 mass parts of methyl ethyl ketone was added, and the methyl ethyl ketone solution containing 50 mass% of fluorine-containing curable resin (6) was obtained. As a result of measuring the molecular weight of the obtained fluorine-containing curable resin (6) by GPC (polystyrene equivalent molecular weight), it was a number average molecular weight 2,500 and a weight average molecular weight 6,000. The fluorine content was 11% by mass.

(Comparative Example 1)
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 69 parts by mass of methyl isobutyl ketone as a solvent and heated to 105 ° C. while stirring under a nitrogen stream. Subsequently, 137.8 parts by mass of a monomer solution obtained by dissolving 40 parts by mass of a fluorinated alkyl group-containing acrylate represented by the following formula (Y-1) and 28.8 parts by mass of 2-hydroxyethyl methacrylate in 69 parts by mass of methyl isobutyl ketone. And 25.9 parts by mass of a polymerization initiator solution obtained by dissolving 3.4 parts by mass of t-butylperoxy-2-ethylhexanoate in 22.5 parts by mass of methyl isobutyl ketone as a radical polymerization initiator The liquids were set in separate dropping devices, and dropped simultaneously over 3 hours while keeping the inside of the flask at 105 ° C. After completion of dropping, the mixture was stirred at 105 ° C. for 10 hours to obtain a polymer.

Next, 0.1 parts by mass of p-methoxyphenol as a polymerization inhibitor and 0.05 parts by mass of dibutyltin dilaurate as a urethanization catalyst were charged, and 31.2 masses of 2-acryloyloxyethyl isocyanate while maintaining 60 ° C. in an air stream. The part was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour, then heated to 80 ° C. and stirred for 10 hours, whereby the disappearance of the absorption peak near 2360 cm ⁻¹ derived from isocyanate groups was confirmed by IR spectrum measurement. Subsequently, a part of the solvent was distilled off under reduced pressure to obtain a methyl isobutyl ketone solution containing 50% by mass of the fluorine-containing curable resin (7). As a result of measuring the molecular weight of the fluorine-containing curable resin (7) by GPC (polystyrene equivalent molecular weight), the number average molecular weight was 3,000 and the weight average molecular weight was 7,000. The fluorine content was 20% by mass.

(Comparative Example 2)
A glass flask equipped with a stirrer, thermometer, condenser, and dropping device was charged with 63 parts by mass of methyl isobutyl ketone as a solvent and heated to 105 ° C. while stirring under a nitrogen stream. Next, 21.5 parts by mass of the poly (perfluoroalkylene ether) chain obtained in Synthesis Example 5 and the compound (A ′) having an acryloyl group at both ends thereof, 41.3 parts by mass of 2-hydroxyethyl methacrylate, As the radical polymerization initiator, three types of dripping liquids each having 135.4 parts by mass of a polymerization initiator solution obtained by dissolving 9.4 parts by mass of t-butylperoxy-2-ethylhexanoate in 126 parts by mass of methyl isobutyl ketone were separately provided. Were added dropwise over 2 hours while keeping the inside of the flask at 105 ° C. After completion of dropping, the mixture was stirred at 105 ° C. for 10 hours, and then a part of the solvent was distilled off under reduced pressure to obtain a polymer.

Next, 74.7 parts by mass of methyl ethyl ketone, 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 added, and stirring was started under an air stream. While maintaining, 44.8 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 1 hour, then heated to 80 ° C. and stirred for 10 hours to confirm the disappearance of the absorption peak near 2360 cm ⁻¹ derived from the isocyanate group by IR spectrum measurement. A methyl ethyl ketone solution containing 50% by mass of the fluorine curable resin (8) was obtained. As a result of measuring the molecular weight of the obtained fluorinated curable resin (8) by GPC (polystyrene equivalent molecular weight), it was a number average molecular weight 2,400 and a weight average molecular weight 7,100. The fluorine content was 11% by mass.

  About fluorine-containing curable resin (1)-(8) obtained in said Examples 1-6 and Comparative Examples 1-2, it summarized in Table 1 about the raw material, molecular weight, etc.

The abbreviations in Table 1 are as follows.
HEMA: 2-hydroxyethyl methacrylate AOI: 2-acryloyloxyethyl isocyanate

(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 (Ciba Specialty Chemicals Co., Ltd.) as a photopolymerization initiator “Irgacure 184”) 5 parts by weight, 54 parts by weight of toluene as a solvent, 28 parts by weight of 2-propanol, 28 parts by weight of ethyl acetate, 28 parts by weight of propylene glycol monomethyl ether are mixed and dissolved to obtain an active energy ray-curable composition A base resin composition was obtained.

(Examples 7-12, Comparative Examples 3-5)
Resin the fluorine-containing curable resin solutions (1) to (8) obtained in Examples 1 to 6 and Comparative Examples 1 and 2 as fluorine-containing surfactants to 268 parts by mass of the base resin composition obtained above. An amount of 1 part by mass was added and mixed uniformly to obtain an active energy ray-curable composition. 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 7 to 12 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, stain adhesion preventing property, and stain wiping ease.

[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 criteria for 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 criteria for ease of wiping off dirt]
After the above test for preventing soil adhesion, the number of times of wiping required to wipe all the adhered ink with a tissue paper under a load of 1 kg was measured. From the results, the ease of soil wiping was evaluated according to the following criteria.
A: The ink can be completely removed by wiping once.
B: The ink was completely removed by wiping 2 to 10 times.
C: The ink could not be completely removed by 10 wiping operations.

[Evaluation of antifouling property after alkali treatment]
The coated film obtained above was immersed in a strong alkaline aqueous solution (2 mol / l potassium hydroxide aqueous solution) at 70 ° C. for 1 minute, washed with pure water, dried at 100 ° C. for 3 minutes, and then room temperature. The coating film which was allowed to cool in the same manner as described above was evaluated for the contact angle of water and n-dodecane on the coated surface, the anti-smudge property and the ease of wiping off the soil in the same manner as described above.

  The evaluation results are shown in Table 2.

  Curing coating of active energy ray-curable compositions of Examples 7 to 12 to which the fluorine-containing curable resins (1) to (6) obtained in Examples 1 to 6 which are fluorine-containing curable resins of the present invention were added. It was found that the membrane has a high contact angle of water and n-dodecane, and the contact angle does not decrease greatly even after alkali treatment. Further, it was found that the antifouling property was high and the dirt wiping property was also high. Furthermore, it has been found that even after the alkali treatment, the deterioration of the antifouling property is suppressed.

  On the other hand, Comparative Example 3 using a fluorine-containing curable resin (7) into which a perfluoroalkyl group was introduced instead of the poly (perfluoroalkylene ether) chain produced in Comparative Example 1 is a contact angle between water and n-dodecane. However, it was found that the contact angle between water and n-dodecane after the alkali treatment was slightly decreased. It was also found that the ease of wiping off dirt was insufficient, and the ease of wiping off dirt after alkali treatment was greatly reduced.

  Comparative example using fluorine-containing curable resin (8) made from a compound having acryloyl groups at both ends of the poly (perfluoroalkylene ether) chain produced in Comparative Example 2 but not corresponding to general formula (A) No. 4 has a high contact angle between water and n-dodecane, but after alkali treatment, the contact angle was greatly reduced, and it was found that both dirt adhesion prevention and dirt wiping ease were reduced.

  In Comparative Example 5 in which no additive was added, it was found that the contact angles of water and n-dodecane were low, and the soil adhesion preventing property and the soil wiping ease were poor.

Claims (4)

At least selected from the group consisting of a poly (perfluoroalkylene ether) chain represented by the following general formula (A), a compound (A) having a (meth) acryloyl group at both ends thereof, a hydroxyl group, an epoxy group and a carboxyl group A polymer component (P) is obtained by polymerizing a monomer component essentially comprising a polymerizable unsaturated monomer (B) having one reactive group (b), and then the polymer (P) has The compound (C1) having a functional group (c1) and a polymerizable unsaturated group reactive to the reactive group (b) and the compound (A) present in the polymer (P) are present. A fluorine-containing curable resin obtained by reacting a functional group (c2) having a reactivity with a hydroxyl group and a compound (C2) having a polymerizable unsaturated group,
(1) When the reactive group (b) is a hydroxyl group, the functional group (c1) and the functional group (c2) are an isocyanate group, a carboxylic acid halide or an acid anhydride,
(2) When the reactive group (b) is an epoxy group, the functional group (c1) is a carboxyl group, and the functional group (c2) is an isocyanate group,
(3) When the reactive group (b) is a carboxyl group, the functional group (c1) is an epoxy group, and the functional group (c2) is an isocyanate group or an acid anhydride. Fluorine-containing curable resin.

(In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or a methyl group, X ¹ and X ² each independently represent a divalent organic group, and PFPE Represents a poly (perfluoroalkylene ether) chain, and n represents an average range of 0 to 10.   An active energy ray-curable composition comprising the fluorine-containing curable resin according to claim 1 and an active energy ray-curable resin (D) or an active energy ray-curable monomer (E).   A cured product obtained by applying the fluorine-containing curable resin according to claim 1 or the active energy ray-curable composition according to claim 2 to a substrate and irradiating the active energy ray to cure.   An article having a cured coating film of the fluorine-containing curable resin according to claim 1 or the active energy ray-curable composition according to claim 2.

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