Fluorine-containing curable composition and article

Abstract

A fluorinated curable composition comprising the following components (A), (B) and (C), each in a predetermined blending ratio, can form a cured film having excellent antifouling properties and water repellency and a low dynamic friction coefficient: the component (A) is a linear polymer having a fluoropolyether in the main chain, composed of a compound having one or two (meth)acryloyl groups at one or both ends of the molecular chain, the average number of (meth)acryloyl groups contained in one molecule is 2 or less, and the fluorine content is 48 mass % or more and less than 62 mass %, the component (B) is composed of a compound having two or more (meth)acryloyl groups at each molecular chain end in one molecule of the linear polymer having a fluoropolyether in the main chain, the average number of (meth)acryloyl groups in one molecule is 4 to 10, and the fluorine content is 25 mass % or more and less than 45 mass %, and the component (C) is composed of a non-fluorinated acrylic compound having no fluoropolyether structure and having an average of two or more (meth)acryloyl groups in one molecule.

Description

Technical Field

[0001] The present invention relates to a fluorine-containing curable composition having excellent antifouling properties and sliding properties, and an article having a cured film of the composition on the surface. Background Art

[0002] Until now, hard coating treatment has been widely used as a means of protecting the surface of a resin molded body, etc. It is to form a hard cured resin layer (hard coating) on ​​the surface of the molded body to make it difficult to scratch. As a material constituting the hard coating, a large number of curable compositions using active energy rays such as thermosetting resins, ultraviolet or electron beam curing resins are used.

[0003] On the other hand, with the expansion of the application field of resin molded products and the trend of high added value, the urgent expectation for the high functionality of the cured resin layer (hard coating) is rising, and as one of them, it is required to give the hard coating antifouling properties. This is to give the surface of the hard coating water repellency, oil repellency and other properties, so that it is not easy to be contaminated or even if it is contaminated, it can be easily removed.

[0004] As a method for imparting antifouling properties to a hard coat layer, a method of applying and / or fixing a fluorine-containing antifouling agent on the surface of a temporarily formed hard coat layer is widely used, and a method of adding a fluorine-containing curable component to a curable resin composition before curing and applying and curing the composition to simultaneously form a hard coat layer and impart antifouling properties has also been studied. For example, Japanese Patent Publication No. 6-211945 (Patent Document 1) shows the manufacture of a hard coat layer imparted with antifouling properties by adding a fluoroalkyl acrylate to an acrylic curable resin composition and curing the composition.

[0005] In recent years, the use of active energy ray-curable compositions having excellent antifouling properties and containing such fluorinated acrylic compounds has been greatly expanded, and new functions have been required.

[0006] Due to the large expansion of the scope of application, in the hard coating, especially the antifouling treatment of the surface of large displays, the surface treatment of the displays and shells of portable information devices such as smart phones and tablets, higher performance is required for antifouling performance represented by water repellency and wear resistance represented by sliding. One means to meet these requirements is to arrange components with a high degree of fluorine modification on the surface. However, if the fluorine content is increased by using a single-structure fluorine-containing acrylic compound, the solubility of other components of the non-fluorinated hard coating agent is reduced, and uneven parts such as defects occur on the coating surface, resulting in poor coating.

[0007] In addition, as prior arts related to the present invention, the following documents are listed together with the above-mentioned documents.

[0008] Prior art literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent Application Laid-Open No. 6-211945

[0011] Patent Document 2: Japanese Patent Application Publication No. 2010-53114

[0012] Patent Document 3: Japanese Patent Application Publication No. 2010-138112

[0013] Patent Document 4: Japanese Patent Application Publication No. 2010-285501 Summary of the invention

[0014] Problems to be solved by the invention

[0015] The present invention has been made in view of the above-mentioned actual situation, and an object of the present invention is to provide a fluorine-containing curable composition having stable solubility and high antifouling property and high sliding property after curing, and an article having a cured film of the composition on the surface.

[0016] Means for solving problems

[0017] The inventors have developed various fluorine compounds that can impart antifouling properties to such curable resin compositions, for example, light-curable fluorine compounds shown in Japanese Patent Publication No. 2010-53114 (Patent Document 2), Japanese Patent Publication No. 2010-138112 (Patent Document 3), and Japanese Patent Publication No. 2010-285501 (Patent Document 4) have been proposed. When it is necessary to improve their antifouling properties and sliding properties, a method of increasing the content of the fluorine component in the compound has been considered. However, when the solubility in non-fluorinated components is improved by using a fluorine-containing acrylic compound of a single structure as described above, it is difficult to concentrate the fluorine component on the coating surface, and as a result, it is sometimes difficult to show antifouling properties.

[0018] Therefore, the present inventors have repeatedly conducted further studies and, as a result, have found that a fluorine-containing curable composition containing the following components (A), (B) and (C) at a predetermined blending ratio can form a cured film having excellent antifouling properties and water repellency and a low dynamic friction coefficient, thereby completing the present invention.

[0019] Component (A) is a linear polymer having a fluoropolyether in the main chain, and is composed of a compound having one or two (meth)acryloyl groups at the terminal, the average number of (meth)acryloyl groups contained in one molecule is 2 or less, and the fluorine content is 48% by mass or more and less than 62% by mass;

[0020] Component (B) is a compound having a fluorinated polyether linear polymer in the main chain, wherein each terminal of one molecule has two or more (meth)acryloyl groups, one molecule has an average of 4 to 10 (meth)acryloyl groups, and the fluorine content is 25% by mass or more and less than 45% by mass;

[0021] The component (C) is composed of a non-fluorinated acrylic compound having no fluoropolyether structure and having an average of two or more (meth)acryloyl groups in one molecule.

[0022] Therefore, the present invention provides the following fluorine-containing curable composition and an article having a cured film of the composition on the surface.

[0023] [1] A fluorinated curable composition comprising a component (A), a component (B) and a component (C) as essential components, wherein the total amount of the component (A) and the component (B) is 0.05 to 50 parts by mass per 100 parts by mass of the component (C), and the amount of the component (A) is 1 to 100 parts by mass per 100 parts by mass of the component (B), wherein the component (A) comprises a linear polymer having a fluoropolyether in the main chain, having one or two (meth)acryloyl groups at one or both ends of the molecular chain, and having a (meth)acryloyl group contained in one molecule The component (B) is composed of a compound having an average number of or less than 2 and a fluorine content of 48 mass % or more and less than 62 mass %, the component (B) is composed of a compound having two or more (meth)acryloyl groups at each molecular chain end in one molecule of a linear polymer having a fluoropolyether in the main chain, having an average of 4 to 10 (meth)acryloyl groups in one molecule, and a fluorine content of 25 mass % or more and less than 45 mass %, and the component (C) is composed of a non-fluorinated acrylic compound having no fluoropolyether structure and having an average of two or more (meth)acryloyl groups in one molecule.

[0024] [2] The fluorinated curable composition according to [1], further comprising a photopolymerization initiator (D).

[0025] [3] The fluorinated curable composition according to [1] or [2], wherein the component (A) is a fluorinated acrylic compound represented by any one of the following general formulas (1) or (2).

[0026] R 1 -O-Rf 2 -CF2-Z 1 -X 1 (1)

[0027] X 2 -Z 1 -CF2O-Rf 2 -CF2-Z 1 -X 1 (2)

[0028] (Where Rf 1 is a fluorine atom or a monovalent fluorinated alkyl group having 1 to 8 carbon atoms which may contain an oxygen atom, Rf 2 The following two repeating units

[0029] -CF2O-

[0030] -CF2CF2O-

[0031] Randomly arranged divalent perfluoropolyether groups with a molecular weight of 600 to 20,000. 1 is independently a linking group selected from a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain at least one hetero atom selected from an oxygen atom, a nitrogen atom and a silicon atom, -C(=O)- and -C(=O)O-, wherein the divalent hydrocarbon group may contain a cyclic structure in the middle, and a part of the hydrogen atoms bonded to the carbon atoms may be substituted by fluorine atoms. 1 are independently a monovalent organic group having a (meth)acryloyl group which may contain an oxygen atom and / or a nitrogen atom, and X 2 is hydroxyl or X 1 . )

[0032] [4] The fluorinated curable composition according to any one of [1] to [3], wherein the component (B) is a fluorinated acrylic compound represented by the following general formula (3).

[0033] [Chemistry 1]

[0034]

[0035] (Where Rf 2 The following two repeating units

[0036] -CF2O-

[0037] -CF2CF2O-

[0038] Randomly arranged divalent perfluoropolyether groups with a molecular weight of 600 to 20,000. 1 Each of the following is independently a (a+1)-valent linking group containing at least (a+1) silicon atoms, and may form a cyclic structure. a is an integer of 2 to 5. 2 Each is independently a divalent hydrocarbon group having 1 to 100 carbon atoms which may contain an oxygen atom and / or a nitrogen atom, and may contain a cyclic structure in the middle. 1 R is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms. 2 are independently a hydrogen atom, or a monovalent organic group having a (meth)acryloyl group which may contain an oxygen atom and / or a nitrogen atom, but R 2The monovalent organic group Z has two or more at each terminal in one molecule and has an average of 4 to 10 in one molecule. 3 A linking group independently composed of a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain at least one hetero atom selected from oxygen atoms, nitrogen atoms and silicon atoms, may contain a cyclic structure in the middle, and a part of the hydrogen atoms bonded to the carbon atoms may be substituted by fluorine atoms.

[0039] [5] The fluorinated curable composition according to [3] or [4], wherein in component (A), Z in the general formula (1) or (2) is 1 Any of the following structures.

[0040] -C(=O)-

[0041] -C(=O)O-

[0042] -C(=O)OCH2-

[0043] -C(=O)OCH2CH2-

[0044] -CH2-

[0045] -CH2O-

[0046] -CH2OCH2-

[0047] -CH2CH2-

[0048] -CH2CH2CH2-

[0049] -CH2CH2CH2CH2-

[0050] -CH2OC(=O)NH-

[0051] -CH2OC(=O)NHCH2CH2-

[0052] [6] The fluorinated curable composition according to any one of [3] to [5], wherein in component (A), X in the general formula (1) or (2) is 1 It is represented by any of the following.

[0053] -OC(=O)CH=CH2

[0054] -OC(=O)C(CH3)=CH2

[0055] -C[OC(=O)CH=CH2]2

[0056] -C[OC(=O)C(CH3)=CH2]2

[0057] -CH[CH2OC(=O)CH=CH2][CH2OC(=O)C(CH3)=CH2]

[0058] -C(CH3)[CH2OC(=O)CH=CH2]2

[0059] -CH2[CH2OC(=O)C(CH3)=CH2]2

[0060] -C[CH2OC(=O)CH=CH2]

[0061] -C(CH2CH3)[CH2OC(=O)CH=CH2]2

[0062] -C(CH2CH3)[CH2OC(=O)C(CH3)=CH2]2.

[0063] [7] The fluorinated curable composition according to any one of [3] to [6], wherein in component (A), the fluorinated acrylic compound represented by the general formula (1) or (2) is represented by any one of the following.

[0064] R 1 O 2 CF2CH2OC(=O)CH=CH2

[0065] R 1 O 2 CF2CH2OC(=O)C(CH3)=CH2

[0066] HOCH2CF2ORf 2 CF2CH2OC(=O)CH=CH2

[0067] HOCH2CF2ORf 2 CF2CH2OC(=O)C(CH3)=CH2

[0068] R 1 O 2 CF2C(=O)OCH2CH2OC(=O)CH=CH2

[0069] R 1 O 2 CF2C(=O)OCH2CH2OC(=O)C(CH3)=CH2

[0070] HOCH2CF2ORf 2 CF2C(=O)OCH2CH2OC(=O)CH=CH2

[0071] HOCH2CF2ORf 2CF2C(=O)OCH2CH2OC(=O)C(CH3)=CH2

[0072] Rf 1 ORf 2 CF2C(=O)OCH[CH2OC(=O)CH=CH2][CH2OC(=O)C(CH3)=CH2]

[0073] Rf 1 ORf 2 CF2CH2OC(=O)NHCH2CH2OC(=O)CH=CH2

[0074] Rf 1 ORf 2 CF2CH2OC(=O)NHCH2CH2OC(=O)C(CH3)=CH2

[0075] HOCH2CF2ORf 2 CF2CH2OC(=O)NHCH2CH2OC(=O)CH=CH2

[0076] HOCH2CF2ORf 2 CF2CH2OC(=O)NHCH2CH2OC(=O)C(CH3)=CH2

[0077] HOCH2CF2ORf 2 CF2CH2OC(=O)NHC(CH3)[CH2OC(=O)CH=CH2]2

[0078] CH2=C(CH3)C(=O)OCH2CF2ORf 2 CF2CH2OC(=O)C(CH3)=CH2

[0079] CH2=CHC(=O)OCH2CF2ORf 2 CF2CH2OC(=O)C(CH3)=CH2

[0080] CH2=CHC(=O)OCH2CF2ORf 2 CF2CH2OC(=O)CH=CH2

[0081] CH2=CHC(=O)OCH2CH2NHC(=O)OCH2CF2ORf 2 CF2CH2OCH2OC(=O)CH=CH2

[0082] CH2=C(CH3)C(=O)OCH2CH2NHC(=O)OCH2CF2ORf 2CF2CH2OCH2OC(=O)C(CH3)=CH2

[0083] CH2=CHC(=O)OCH2CH2NHC(=O)OCH2CF2ORf 2 CF2CH2OC(=O)NHCH2CH2OC(=O)CH=CH2

[0084] (Where Rf 1 , Rf 2 Same as above.)

[0085] [8] The fluorinated curable composition according to any one of [4] to [7], wherein in the component (B), Z in the general formula (3) is 3 It is represented by any of the following formulae.

[0086] -CH2CH2-

[0087] -CH2CH2CH2-

[0088] -CH2CH2CH2CH2-

[0089] -CH2OCH2CH2-

[0090] -CH2OCH2CH2CH2-

[0091] [9] The fluorinated curable composition according to any one of [4] to [8], wherein in the component (B), Q in the general formula (3) 1 It is represented by the following formula.

[0092] [Chemistry 2]

[0093]

[0094] (In the formula, a1 is 2 or 3.)

[0095]

[10] The fluorinated curable composition according to any one of [4] to [9], wherein in component (B), the fluorinated acrylic compound represented by the general formula (3) is a fluorinated acrylic compound represented by the following general formula (4) or (5).

[0096] [Chemistry 3]

[0097]

[0098] [Chemistry 4]

[0099]

[0100] (Where Z 3 , Q 1, a As mentioned above, Rf' is -CF2O(CF2O) m (CF2CF2O) n CF2-, m is an integer of 1 to 200, n is an integer of 1 to 170, m+n is an integer of 6 to 201, the arrangement of -(CF2O)- and -(CF2CF2O)- is random, R 3 is a hydrogen atom or a methyl group, d1 and e1 are integers of 0 to 10, and in the compounds represented by the formulae (4) and (5), the fluorine content is 25% by mass or more and less than 45% by mass.)

[0101]

[11] The fluorinated curable composition according to any one of [1] to

[10] , wherein the non-fluorinated acrylic compound of component (C) is a polyfunctional acrylic compound having two or more (meth)acryloyl groups in one molecule and having no urethane bond, or a polyfunctional urethane acrylate having three or more (meth)acryloyl groups in one molecule obtained by reacting the polyfunctional acrylic compound with an aliphatic polyisocyanate and an acrylic compound having a hydroxyl group, or a mixture of two or more acrylic compounds comprising the polyfunctional acrylic compound and the urethane acrylate.

[0102]

[12] An article having a cured film of the fluorinated curable composition according to any one of [1] to

[11] on its surface.

[0103] Effects of the Invention

[0104] The fluorine-containing curable composition of the present invention has stable solubility and can form a cured film having high antifouling property, dirt removability and sliding property. DETAILED DESCRIPTION

[0105] The fluorine-containing curable composition of the present invention comprises a component (A), a component (B) and a component (C), wherein the component (A) is a linear polymer having a fluoropolyether in the main chain, and is composed of a compound having one or two (meth)acryloyl groups at one or both ends of the molecular chain, the average number of (meth)acryloyl groups contained in one molecule is 2 or less, and the fluorine content is 48 mass % or more and less than 62 mass %, the component (B) is composed of a compound having two or more (meth)acryloyl groups at each molecular chain end (that is, both ends of the molecular chain) in one molecule of the linear polymer having a fluoropolyether in the main chain, the average number of (meth)acryloyl groups in one molecule is 4 to 10, and the fluorine content is 25 mass % or more and less than 45 mass %, and the component (C) is composed of a non-fluorinated acrylic compound having no fluoropolyether structure and having two or more (meth)acryloyl groups in one molecule on average, wherein the fluorine-containing curable composition comprises the above components (A), (B) and (C) as essential components.

[0106] In the present invention, "acrylic compound" is a general term for compounds having an acryloyl group and a methacryloyl group, and "(meth)acryloyl" means one or both of an acryloyl group and a methacryloyl group, "(meth)acrylic acid" means one or both of acrylic acid and methacrylic acid, and "(meth)acrylate" means one or both of acrylate and methacrylate. Furthermore, "acrylates" is a general term for compounds having an acrylate and a methacrylate.

[0107] Furthermore, in the present invention, each component of components (A), (B), and (C) does not necessarily have to be a single compound. For example, when the mass during blending is taken into consideration, the total blending amount of a mixture of multiple compounds that are consistent with the respective conditions of components (A), (B), and (C) can be regarded as the amount of each component.

[0108] [Ingredients (A)]

[0109] The component (A) as the first essential component in the fluorinated curable composition of the present invention is a linear polymer having a fluoropolyether in the main chain, and is composed of a compound having one or two (meth)acryloyl groups at one or both ends of the molecular chain, the average number of (meth)acryloyl groups contained in one molecule is 2 or less (1 to 2) (that is, the linear polymer has one (meth)acryloyl group at each of the two ends of the molecular chain, or has one or two (meth)acryloyl groups at one end of the molecular chain), and a fluorine content of 48 mass% or more and less than 62 mass%.

[0110] Among them, the fluorine content of the compound of component (A) is 48% by mass or more and less than 62% by mass, preferably 55% by mass or more and 61.5% by mass or less, and more preferably 57% by mass or more and 61% by mass or less. If the fluorine content is less than 48% by mass, the improvement of antifouling performance is insufficient compared with the case where component (A) is not used. If it is 62% by mass or more, the solubility of component (C) is insufficient, and it is difficult to obtain a smooth coating surface of the cured film. It should be noted that in the present invention, the fluorine content is the fluorine atoms in the molecule relative to the amount of fluorine atoms in the molecule according to the formula 19 F-NMR and 1 The mass % value of the number average molecular weight calculated from the molecular formula of the compound determined by H-NMR (the same applies hereinafter).

[0111] As such a compound, for example, a fluorine-containing acrylic compound represented by the following general formula (1) or (2) can be shown.

[0112] R 1 -O-Rf 2 -CF2-Z 1 -X 1 (1)

[0113] X 2 -Z 1 -CF2O-Rf 2 -CF2-Z 1 -X 1 (2)

[0114] In the above formula (1), Rf 1 is a fluorine atom or a monovalent fluorinated alkyl group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, which may contain an oxygen atom. Specifically, in addition to the fluorine atom, there can be mentioned trifluoromethyl, pentafluoroethyl, perfluoroisopropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, and

[0115] CF3OCF2CF2-

[0116] CF3OCF2CF2CF2-

[0117] CF3CF2OCF2CF2-

[0118] (CF3)2CFOCF2CF2-

[0119] CF3OCF2CF2CF2CF2-

[0120] CF3CF2OCF2CF2CF2-

[0121] CF3CF2CF2OCF2CF2-

[0122] (CF3)2CFCF2OCF2CF2-

[0123] CF3CF2CF2CF2OCF2CF2-

[0124] CF3CF2CF2OCF2CF2CF2-

[0125] Among these, CF3- and CF3CF2- are particularly preferred.

[0126] In the above formulas (1) and (2), Rf 2 The following two repeating units

[0127] -CF2O-

[0128] -CF2CF2O-

[0129] The randomly arranged divalent perfluoropolyether groups having a molecular weight of 600 to 20,000, preferably 1,200 to 10,000 can be represented, for example, as follows.

[0130] -(CF2O) m (CF2CF2O) n -

[0131] m is an integer of 1 to 200, preferably an integer of 6 to 50, n is an integer of 1 to 170, preferably an integer of 6 to 50, and m+n is an integer of 6 to 201, preferably an integer of 12 to 100. If the values ​​of m, n, and m+n are too small compared to these values, the effect of imparting antifouling properties to the cured composition becomes small. If they are too large compared to these values, the compatibility with the non-fluorinated component becomes poor, which becomes a cause of turbidity of the coating liquid and poor coating. These values ​​of m and n may have a distribution. In the case of having a distribution, it is preferably 19 The value of m+n determined by F-NMR or the like is expressed as a number average and satisfies the above range.

[0132] In the above formulas (1) and (2), Z 1 is independently a linking group selected from a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain at least one hetero atom selected from an oxygen atom, a nitrogen atom and a silicon atom, -C(=O)- and -C(=O)O-, wherein the divalent hydrocarbon group may contain a cyclic structure in the middle, and a part of the hydrogen atoms bonded to the carbon atoms may be substituted with fluorine atoms. 1 As a preferred structure, the following structural groups can be listed.

[0133] -C(=O)-

[0134] -C(=O)O-

[0135] -C(=O)OCH2-

[0136] -C(=O)OCH2CH2-

[0137] -CH2-

[0138] -CH2O-

[0139] -CH2OCH2-

[0140] -CH2CH2-

[0141] -CH2CH2CH2-

[0142] -CH2CH2CH2CH2-

[0143] -CH2OC(=O)NH-

[0144] -CH2OC(=O)NHCH2CH2-

[0145] Among these, particularly preferred

[0146] -CH2-

[0147] -CH2OC(=O)NH-

[0148] -CH2OC(=O)NHCH2CH2.

[0149] In the above formulas (1) and (2), X 1 is independently a monovalent organic group which may contain an oxygen atom and / or a nitrogen atom and preferably has one or two (meth)acryloyl groups, but one or two of the above monovalent organic groups are contained in one molecule. 2 is hydroxyl or X 1 .

[0150] As X 1 Specifically, the following structures can be exemplified as preferred structures.

[0151] -OC(=O)CH=CH2

[0152] -OC(=O)C(CH3)=CH2

[0153] -C[OC(=O)CH=CH2]2

[0154] -C[OC(=O)C(CH3)=CH2]2

[0155] -CH[CH2OC(=O)CH=CH2][CH2OC(=O)C(CH3)=CH2]

[0156] -C(CH3)[CH2OC(=O)CH=CH2]2

[0157] -CH2[CH2OC(=O)C(CH3)=CH2]2

[0158] -C[CH2OC(=O)CH=CH2]

[0159] -C(CH2CH3)[CH2OC(=O)CH=CH2]2

[0160] -C(CH2CH3)[CH2OC(=O)C(CH3)=CH2]2

[0161] Particularly preferred

[0162] -OC(=O)CH=CH2

[0163] -OC(=O)C(CH3)=CH2.

[0164] As X 2 Specifically, the following structures can be exemplified as preferred structures.

[0165] HO-

[0166] CH2=C(CH3)C(=O)O-

[0167] CH2=CHC(=O)O-

[0168] More specifically, as such a component (A), compounds represented by the following structural groups can be cited.

[0169] R 1 O 2 CF2CH2OC(=O)CH=CH2

[0170] R 1 O 2 CF2CH2OC(=O)C(CH3)=CH2

[0171] HOCH2CF2ORf 2 CF2CH2OC(=O)CH=CH2

[0172] HOCH2CF2ORf 2 CF2CH2OC(=O)C(CH3)=CH2

[0173] R 1 O 2 CF2C(=O)OCH2CH2OC(=O)CH=CH2

[0174] R 1 O 2 CF2C(=O)OCH2CH2OC(=O)C(CH3)=CH2

[0175] HOCH2CF2ORf 2 CF2C(=O)OCH2CH2OC(=O)CH=CH2

[0176] HOCH2CF2ORf 2 CF2C(=O)OCH2CH2OC(=O)C(CH3)=CH2

[0177] R 1 O 2 CF2C(=O)OCH[CH2OC(=O)CH=CH2][CH2OC(=O)C(CH3)=CH2]

[0178] R 1 O 2 CF2CH2OC(=O)NHCH2CH2OC(=O)CH=CH2

[0179] R 1 O 2CF2CH2OC(=O)NHCH2CH2OC(=O)C(CH3)=CH2

[0180] HOCH2CF2ORf 2 CF2CH2OC(=O)NHCH2CH2OC(=O)CH=CH2

[0181] HOCH2CF2ORf 2 CF2CH2OC(=O)NHCH2CH2OC(=O)C(CH3)=CH2

[0182] HOCH2CF2ORf 2 CF2CH2OC(=O)NHC(CH3)[CH2OC(=O)CH=CH2]2

[0183] CH2=C(CH3)C(=O)OCH2CF2ORf2CF2CH2OC(=O)C(CH3)=CH2

[0184] CH2=CHC(=O)OCH2CF2ORf 2 CF2CH2OC(=O)C(CH3)=CH2

[0185] CH2=CHC(=O)OCH2CF2ORf 2 CF2CH2OC(=O)CH=CH2

[0186] CH2=CHC(=O)OCH2CH2NHC(=O)OCH2CF2ORf 2 CF2CH2OCH2OC(=O)CH=CH2

[0187] CH2=C(CH3)C(=O)OCH2CH2NHC(=O)OCH2CF2ORf 2 CF2CH2OCH2OC(=O)C(CH3)=CH2

[0188] CH2=CHC(=O)OCH2CH2NHC(=O)OCH2CF2ORf 2 CF2CH2OC(=O)NHCH2CH2OC(=O)CH=CH2

[0189] (Where Rf 1 , Rf 2 As described above, it is particularly preferred that the average fluorine content of the compound corresponding to component (A) is 55% by mass or more and less than 62% by mass.)

[0190] As the above-mentioned component (A), it is represented by the following general formula (1) or (2):

[0191] R 1 -O-Rf 2 -CF2-Z 1 -X 1 (1)

[0192] X 2 -Z 1 -CF2O-Rf 2 -CF2-Z 1 -X 1 (2)

[0193] (Where Rf 1 , Rf 2 , Z 1 , X 1 , X 2 Same as above.)

[0194] A preferred method for synthesizing the fluorine-containing acrylic compound represented by the general formula (6) or (7) is as follows:

[0195] R 1 -O-Rf 2 -CF2-CH2-OH (6)

[0196] HO-CH2-CF2O-Rf 2 -CF2-CH2-OH (7)

[0197] (Where Rf 1 , Rf 2 Same as above.)

[0198] A fluorine-containing alcohol compound represented by:

[0199] CH2=CR 3 C(=O)X (8)

[0200] (Where R 3 As in the above, X is a halogen atom such as a fluorine atom, a chlorine atom, or a bromine atom. A method of reacting a (meth)acrylic acid halide represented by the following general formula (9) to form an ester, and another method of reacting a (meth)acrylic acid halide represented by the following general formula (9) to form an ester

[0201] CH2=CR 3 C(=O)OCH2CH2-N=C=O (9)

[0202] (Where R 3 Same as above.)

[0203] A method for reacting an isocyanate compound containing an (meth)acryloyl group is provided. By using these methods, a fluorine-containing acrylic compound represented by the above formula (1) or (2) can be obtained.

[0204] Among them, as the (meth)acryloyl halide represented by the formula (8), the following compounds can be cited.

[0205] CH2=CHC(=O)X

[0206] CH2=C(CH3)C(=O)X

[0207] (In the formula, X is the same as above.)

[0208] Acryloyl chloride and methacryloyl chloride are particularly preferred.

[0209] In addition, as the isocyanate compound containing an (meth)acryloyl group represented by the formula (9), the following compounds can be cited.

[0210] CH2=CHC(=O)OCH2CH2-N=C=O

[0211] CH2=C(CH3)C(=O)OCH2CH2-N=C=O

[0212] Relative to the total amount of hydroxyl groups of the fluorine-containing alcohol compound, by reacting with an equimolar amount or more of these (meth)acryloyl halides or isocyanate compounds containing an (meth)acryloyl group, all hydroxyl groups can react. In the compound of formula (7), relative to 1 mole of the fluorine-containing alcohol compound, an average of more than 1 mole of (meth)acryloyl groups can be introduced. By making the hydroxyl groups in excess, unreacted (meth)acryloyl halides or isocyanate compounds containing an (meth)acryloyl group can be prevented from remaining. Specifically, when the amount of the fluorine-containing alcohol compound in the reaction system is set as x moles and the total amount of hydroxyl groups of the fluorine-containing alcohol compound is set as y moles, it is preferred that the (meth)acryloyl halide or isocyanate compound containing an (meth)acryloyl group is x moles or more and 2y moles or less, and particularly preferably 0.6y moles or more and 1.4y moles or less. If the amount is too small, the possibility of residual fluorine-containing alcohol compounds with incomplete introduction of (meth)acryloyl groups increases, and the solubility of the product may decrease. If the amount is too large, it becomes difficult to remove the remaining unreacted (meth)acryloyl halides or isocyanate compounds containing an (meth)acryloyl group.

[0213] With regard to these reactions, the reaction can be carried out by diluting with a suitable solvent as required. As such solvent, as long as it is not the solvent of the isocyanate group reaction of the isocyanate compound containing (meth) acryloyl with the hydroxyl group of fluorinated alcohol compound, the halogen atom of (meth) acryloyl halide, then can be used without particular restriction, specifically, can list the ketone solvents such as toluene, xylene, hydrocarbon solvents such as isooctane, tetrahydrofuran (THF), diisopropyl ether, dibutyl ether, acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclohexanone, hexafluoro-m-xylene (another name: meta-bistrifluorotoluene), fluorine-modified aromatic hydrocarbon solvents such as benzyl trifluoro, fluorine-modified ether solvents such as methyl perfluorobutyl ether etc. This solvent can adopt known methods such as decompression distillation to remove after the reaction, according to the purposes of target, can directly be used as diluted solution and use.

[0214] The amount of the solvent used is not particularly limited, but is preferably 10 times or less of the total mass of the reaction components. If the amount of the solvent used is too large, the reaction rate may be significantly reduced.

[0215] In addition, during the reaction, a polymerization inhibitor may be added as needed. The polymerization inhibitor is not particularly limited, and generally, a polymerization inhibitor used as a polymerization inhibitor for acrylic compounds can be used. Specifically, hydroquinone, hydroquinone monomethyl ether, 4-tert-butylcatechol, dibutylhydroxytoluene, etc. can be cited.

[0216] The amount of the polymerization inhibitor used is determined by the reaction conditions, purification conditions after the reaction, and final use conditions and is not particularly limited. It is usually 0.01 to 5000 ppm, particularly preferably 0.1 to 500 ppm, based on the total mass of the reaction components.

[0217] When reacting (meth)acryloyl halide with a fluorine-containing alcohol compound, it is particularly preferred to react acryloyl chloride and methacryloyl chloride to form an ester. The ester formation reaction is carried out by dropping (meth)acryloyl halide while mixing and stirring the above-mentioned reaction intermediate (fluorine-containing alcohol compound) and an acid acceptor. The acid acceptor can be triethylamine, pyridine, urea, etc. The amount of the acid acceptor used is preferably about 0.9 to 3 times the number of moles of the feed (meth)acryloyl halide. If it is too little, a large amount of uncaptured acid remains, and if it is too much, it becomes difficult to remove the remaining acid acceptor.

[0218] The (meth)acrylic acid halide is dripped for 20 to 60 minutes by maintaining the temperature of the reaction mixture at 0 to 35°C. Then, stirring is continued for 30 minutes to 10 hours. After the reaction is completed, the unreacted (meth)acrylic acid halide, salts produced by the reaction, and the reaction solvent are removed by distillation, adsorption, filtration, washing, etc., thereby obtaining the fluorine-containing acrylic compound represented by the above formula (1) or (2).

[0219] When the reaction is stopped, an alcohol compound such as methanol or ethanol can be added to the system to esterify the unreacted (meth)acrylic acid halide. The generated acrylic acid esters can be removed by the same method as the unreacted (meth)acrylic acid halide, or can be used in the remaining state.

[0220] In the case of the reaction between the fluorine-containing alcohol compound and the (meth)acryloyl group-containing isocyanate compound, the fluorine-containing alcohol compound and the (meth)acryloyl group-containing isocyanate compound are stirred with a solvent as necessary to allow the reaction to proceed.

[0221] In this reaction, in order to increase the speed of the reaction, a suitable catalyst can be added. As a catalyst, for example, alkyl tin ester compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin dioctoate, dioctanoate, stannous dioctoate, tetraisopropoxy titanium, tetra-n-butoxy titanium, tetra(2-ethylhexyl) titanium, dipropoxybis(acetylacetone) titanium, isopropoxy octanediol titanium, and other titanates or titanium chelate compounds, tetraacetylacetonate zirconium, tri-butoxy monoacetylacetonate zirconium, mono-butoxy acetylacetonate bis(ethyl acetoacetate) zirconium, di-butoxybis(ethyl acetoacetate) zirconium, tetraacetylacetonate zirconium, zirconium chelate compounds, etc. can be exemplified. These catalysts are not limited to one kind thereof, and can be used as a mixture of two or more kinds. By adding 0.01 to 2 mass %, preferably 0.05 to 1 mass % of these catalysts relative to the total mass of the reactants, the reaction rate can be increased.

[0222] The above reaction is carried out at a temperature of 0 to 120° C., preferably 10 to 70° C., for 1 minute to 500 hours, preferably 10 minutes to 48 hours. If the reaction temperature is too low, the reaction rate may be excessively slow, and if the reaction temperature is too high, polymerization of (meth)acryloyl groups may occur as a side reaction.

[0223] After completion of the reaction, the unreacted isocyanate compound and the reaction solvent are removed by distillation, adsorption, filtration, washing or the like, thereby obtaining the fluorine-containing acrylic compound represented by the above formula (1) or (2).

[0224] When the reaction is stopped, an alcohol compound such as methanol or ethanol is added to the system to form a urethane bond with the unreacted isocyanate compound. The generated urethane acrylate can be removed in the same manner as the unreacted isocyanate compound, or can be left to be used.

[0225] [Ingredient (B)]

[0226] The component (B) as the second essential component in the fluorinated curable composition of the present invention is composed of a compound having 2 or more, preferably 2 to 4 (meth)acryloyl groups at each molecular chain end (i.e., both molecular chain ends) in one molecule of a linear polymer having a fluoropolyether in the main chain, and having an average of 4 to 10, preferably 4 to 8 (meth)acryloyl groups in one molecule, and a fluorine content of 25 mass % or more and less than 45 mass %.

[0227] Wherein, the fluorine content of the compound of component (B) is 25 mass % or more and less than 45 mass %, preferably 28 mass % or more and 43 mass % or less, more preferably 33 mass % or more and 42 mass % or less. If the fluorine content is less than 25 mass %, the solubility of component (A) is reduced, and if it is 45 mass % or more, the solubility of component (C) is reduced, so it becomes difficult to apply the composition smoothly as a whole.

[0228] As such a compound, specifically, a fluorine-containing acrylic compound represented by the following general formula (3) can be shown.

[0229] [Chemistry 5]

[0230]

[0231] In the above formula (3), Rf 2 Rf of the above formula (1) and (2) 2 same.

[0232] In the above formula (3), R 1 R is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms. Specific examples of the monovalent hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, and octyl, cycloalkyl groups such as cyclohexyl, alkenyl groups such as vinyl, allyl, and propenyl, aryl groups such as phenyl, tolyl, and xylyl, and aralkyl groups such as benzyl and phenylethyl. 1 , preferably a hydrogen atom and a methyl group.

[0233] In the above formula (3), R 2 It is independently a hydrogen atom, or a monovalent organic group having a (meth)acryloyl group which may contain an oxygen atom and / or a nitrogen atom. As the monovalent organic group, it is preferred to have at least one, preferably one or two (meth)acryloyl groups at the terminal. In addition, it may have an amide bond, an ether bond, an ester bond, etc. in the middle of the structure.

[0234] As such a structure, for example, the following structures can be cited.

[0235] CH2=CHC(=O)-

[0236] CH2=C(CH3)C(=O)-

[0237] CH2=CHC(=O)OCH2CH2-NHC(=O)-

[0238] CH2=C(CH3)C(=O)OCH2CH2-NHC(=O)-

[0239] CH2=C(CH3)C(=O)OCH2CH2OCH2CH2-NHC(=O)-(CH2=CHC(=O)OCH2CH2)2C(CH3)-NHC(=O)-

[0240] Among these, the following structures are particularly preferred.

[0241] CH2=CHC(=O)OCH2CH2-NHC(=O)-

[0242] CH2=C(CH3)C(=O)OCH2CH2-NHC(=O)-

[0243] In the above formula (3), a is independently an integer of 2 to 5, preferably an integer of 2 to 4, and more preferably 2 or 3. If a is less than 2, the solubility in component (C) may decrease, and if a is greater than 5, the solubility in component (A) may decrease.

[0244] In the above formula (3), Q 1 Each of the following is independently a (a+1)-valent linking group containing at least (a+1) silicon atoms, and may form a ring structure. 1 The preferred structure includes a siloxane structure, an unsubstituted or halogen-substituted silylene structure, a silylene structure, or a combination of two or more thereof, each having at least (a+1) silicon atoms and a linking group having an (a+1) valence. In this case, it is preferred that the (a+1) bonding ends each have (a+1) silicon atoms. Specifically, the following structure is shown as a particularly preferred structure.

[0245] However, in the following structure, a is the same as a in the above formula (3). In addition, b is an integer of 1 to 5, preferably an integer of 1 to 3. The arrangement of each unit is random, and the bonding end of each unit (a+1) is connected to Z. 3 Combined with any one of the a CH2 groups enclosed by [].

[0246] [Chemistry 6]

[0247]

[0248] Here, T' is a (a+1)-valent linking group, and examples thereof include the following linking groups.

[0249] [Chemistry 7]

[0250]

[0251] Among these, the following linking groups are particularly preferred.

[0252] [Chemistry 8]

[0253]

[0254] (In the formula, a1 is 2 or 3.)

[0255] In the above formula (3), Z 2 Each independently represents a divalent hydrocarbon group having 1 to 100 carbon atoms, preferably 1 to 40 carbon atoms, which may contain an oxygen atom and / or a nitrogen atom, and may contain a cyclic structure in the middle.

[0256] As Z 2 The preferred structure can include the following structures.

[0257] -CH2[OC2H4] d [OC3H6] e [OC4H8] f OC c H 2c -

[0258] (In the formula, d is an integer of 0 to 29, preferably an integer of 0 to 10, e is an integer of 0 to 29, preferably an integer of 0 to 10, f is an integer of 0 to 14, preferably an integer of 0 to 7, and c is an integer of 2 to 4. The total of the above structures can satisfy the carbon number of 3 to 100, preferably 3 to 30. The arrangement of the repeating units is random regardless of the type. In addition, each repeating unit may not be a single structure, but a mixture of structural isomers.)

[0259] As Z 2 As particularly preferred structures, the following two structures can be listed, among which the structure in which d is an integer of 0 to 10 and e is an integer of 0 to 10 is preferred.

[0260] -CH2[OC2H4] d OC2H4-

[0261] -CH2[OC3H6] e OCH2CH(CH3)-

[0262] In addition, as Z 2 , the following structures can also be listed.

[0263] [Chemistry 9]

[0264]

[0265] In the above formula (3), Z 3 is independently a linking group consisting of a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain at least one hetero atom selected from oxygen atoms, nitrogen atoms and silicon atoms, may contain a cyclic structure in the middle, and a part of the hydrogen atoms bonded to the carbon atoms may be substituted by fluorine atoms. 3 As a preferred structure, the following structural groups can be listed.

[0266] -CH2CH2-

[0267] -CH2CH2CH2-

[0268] -CH2CH2CH2CH2-

[0269] -CH2OCH2CH2-

[0270] -CH2OCH2CH2CH2-

[0271] [Chemistry 10]

[0272]

[0273] Among these, particularly preferred

[0274] -CH2CH2-

[0275] -CH2CH2CH2-

[0276] -CH2CH2CH2CH2-

[0277] -CH2OCH2CH2-

[0278] -CH2OCH2CH2CH2-.

[0279] As the fluorine-containing acrylic compound represented by the above formula (3), compounds represented by the following general formulae (4) and (5) can be exemplified as more preferable structures.

[0280] [Chemistry 11]

[0281]

[0282] [Chemistry 12]

[0283]

[0284] (Where Z 3 , Q 1 , a As mentioned above, Rf' is -CF2O(CF2O) m (CF2CF2O)n CF2-, m, n, m+n are the same as above, the arrangement of -(CF2O)- and -(CF2CF2O)- is random, R 3 is a hydrogen atom or a methyl group, d1 and e1 are integers of 0 to 10, and in the compounds represented by the formulae (4) and (5), the fluorine content is 25% by mass or more and less than 45% by mass.)

[0285] Specific examples of the component (B) include the following compounds.

[0286] [Chemistry 13]

[0287]

[0288] [Chemistry 14]

[0289]

[0290] [Chemistry 15]

[0291]

[0292] [Chemistry 16]

[0293]

[0294] [Chemistry 17]

[0295]

[0296] (In the formula, Rf' is the same as above, for example, n / m = 0.9, m + n ≈ 45. e2 is an integer from 1 to 10, for example, 4.)

[0297] The fluorine-containing acrylic compound represented by the formula (3) as the component (B) can be synthesized by the method described in, for example, JP-A-2010-285501 and JP-A-2015-199910.

[0298] For example, the fluorine-containing acrylic compound represented by the above formula (3) is firstly prepared by mixing the fluorine-containing acrylic compound represented by the following general formula (10):

[0299] [Chemistry 18]

[0300]

[0301] (Where Rf 2 , Z 3 , Q 1 , a is the same as above, all the a Hs enclosed in [] are the same as Q 1 The silicon atoms in the structure are bonded.)

[0302] The fluoropolyether compound having a multifunctional Si-H group represented by the following general formula (11):

[0303] CH2=CR 1 -Z 2 -OH (11)

[0304] (Where R 1 , Z 2 Same as above.)

[0305] By subjecting an alcohol having a terminal unsaturated group (a compound having an alkenyl group and a hydroxyl group at a molecular terminal) represented by the hydrosilylation reaction, a fluorine-containing alcohol compound can be obtained as an intermediate.

[0306] Among them, examples of the fluoropolyether compound having a polyfunctional Si—H group represented by the above formula (10) include the following compounds.

[0307] [Chemistry 19]

[0308]

[0309] (Wherein, Rf' is the same as above.)

[0310] Examples of the terminal unsaturated group-containing alcohol represented by the above formula (11) include the following alcohols.

[0311] CH2=CH-CH2-OCH2CH2-OH

[0312] CH2=CH-CH2-OCH2CH(CH3)-OH

[0313] CH2=CH-CH2-(OC3H6)2-OCH2CH(CH3)-OH

[0314] CH2=CH-CH2-(OC3H6)4-OCH2CH(CH3)-OH

[0315] CH2=CH-CH2-(OC3H6)9-OCH2CH(CH3)-OH

[0316] [Chemistry 20]

[0317]

[0318] In the hydrosilylation (addition) reaction, it is preferred that the fluoropolyether compound having a multifunctional Si-H group represented by formula (10) and the alcohol having a terminal unsaturated group represented by formula (11) are mixed and reacted in the presence of a platinum group metal addition reaction catalyst at a reaction temperature of 50 to 150° C., preferably 60 to 120° C., for 1 minute to 48 hours, particularly 10 minutes to 12 hours. If the reaction temperature is too low, the reaction may not proceed sufficiently and the reaction may stop. If it is too high, the temperature rise caused by the reaction heat of the hydrosilylation reaction may make it impossible to control the reaction and sudden boiling or decomposition of the raw materials may occur.

[0319] In this case, the reaction ratio of the fluoropolyether compound having a multifunctional Si-H group represented by formula (10) and the alcohol having a terminal unsaturated group represented by formula (11) is preferably 0.5 to 5 times, particularly 0.9 to 2 times, the total molar number of H enclosed in brackets [] of the fluoropolyether compound having a multifunctional Si-H group represented by formula (10). If the alcohol having a terminal unsaturated group represented by formula (11) is too small, it may be difficult to obtain a fluorine-containing alcohol compound having high solubility. If it is too large, the uniformity of the reaction solution decreases and the reaction rate becomes unstable. In addition, when the alcohol having a terminal unsaturated group represented by formula (11) is removed after the reaction, the amount of unreacted alcohol remaining must be strictly controlled according to the increase in the heating, pressure reduction, extraction and other conditions.

[0320] As the addition reaction catalyst, for example, a compound containing a platinum group metal such as platinum, rhodium or palladium can be used. Among them, a compound containing platinum is preferred, and hexachloroplatinic acid (IV) hexahydrate, platinum carbonyl vinylmethyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, platinum-octanal / octanol complex, or platinum supported on activated carbon can be used.

[0321] The amount of the addition reaction catalyst to be added is preferably an amount such that the metal content is 0.1 to 5000 ppm by mass, more preferably 0.2 to 1000 ppm by mass, relative to the fluoropolyether compound having a polyfunctional Si-H group represented by formula (10).

[0322] Even if the above-mentioned addition reaction does not exist solvent, it can be implemented, and can be diluted with solvent as required. At this time, the diluting solvent can utilize the generally widely used organic solvents such as toluene, dimethylbenzene, isooctane, etc., and the preferred boiling point is above the reaction temperature of the target and does not hinder the reaction, and the fluorine-containing alcohol compound generated after the reaction is soluble under the above-mentioned reaction temperature. As such solvent, for example, the solvents of part fluorine-modified ether-based solvents such as fluorine-modified aromatic hydrocarbon-based solvents such as preferred hexafluoro-meta-xylene, benzyltrifluoro, methyl perfluorobutyl ether, etc. are preferred hexafluoro-meta-xylene.

[0323] When a solvent is used, the amount used is preferably 5 to 2000 parts by mass, more preferably 50 to 500 parts by mass, relative to 100 parts by mass of the fluoropolyether compound having a multifunctional Si-H group represented by formula (10). If the amount is less than this, the dilution effect of the solvent becomes weak, and if it is more, the dilution degree increases excessively, sometimes resulting in a decrease in the reaction rate.

[0324] After the reaction is completed, the unreacted alcohol having a terminal unsaturated group represented by formula (11) and the diluent solvent are preferably removed by a known method such as vacuum distillation, extraction, adsorption, etc., or the reaction mixture containing them can be used directly in the next reaction.

[0325] Examples of the fluorine-containing alcohol compound obtained in this manner include the following compounds.

[0326] [Chemistry 21]

[0327]

[0328] [Chemistry 22]

[0329]

[0330] [Chemistry 23]

[0331]

[0332] (Wherein, Rf' and e are the same as above.)

[0333] Next, a fluorinated acrylic compound can be obtained by introducing a (meth)acryloyl group into the fluorinated alcohol compound obtained above. As a method for introducing a (meth)acryloyl group into a fluorinated alcohol compound, one method that can be cited is a method of reacting with a (meth)acryloyl halide represented by the following formula (12) to form an ester, and another method that can be cited is a method of reacting with an isocyanate compound having a (meth)acryloyl group represented by the following formula (13). By using these methods, the fluorinated acrylic compound of the present invention can be obtained.

[0334] CH2=CR 3C(=O)X (12)

[0335] CH2=CR 3 C(=O)OCH2CH2-N=C=O (13)

[0336] (Where R 3 , X is the same as above. )

[0337] Among them, examples of the (meth)acrylic acid halide represented by the formula (12) include the following compounds.

[0338] CH2=CHC(=O)X

[0339] CH2=C(CH3)C(=O)X

[0340] (Wherein, X is the same as above.)

[0341] Acryloyl chloride and methacryloyl chloride are particularly preferred.

[0342] Examples of the (meth)acryloyl group-containing isocyanate compound represented by the formula (13) include the following compounds.

[0343] CH2=CHC(=O)OCH2CH2-N=C=O

[0344] CH2=C(CH3)C(=O)OCH2CH2-N=C=O

[0345] Relative to the total of the hydroxyl amount of fluorinated alcohol compound, these (meth) acryloyl halides or isocyanate compounds containing (meth) acryloyl groups can be loaded with equimolar or more than them to react, make all hydroxyl reactions, relative to 1 mole of fluorinated alcohol compound, can import (meth) acryloyl groups more than an average of 1 mole, by making hydroxyl groups excessive, thus can not make unreacted (meth) acryloyl halides or isocyanate compounds containing (meth) acryloyl groups remain. Specifically, in the case where the fluorinated alcohol compound amount in the reaction system is set to x moles, the total of the hydroxyl amount of fluorinated alcohol compound is set to y moles, (meth) acryloyl halides or isocyanate compounds containing (meth) acryloyl groups are preferably more than x moles and less than 2y moles, particularly preferably more than 0.6y moles and less than 1.4y moles. In the case of too few, the possibility of the fluorinated alcohol compound that does not import (meth) acryloyl groups remaining at all increases, and the solubility of the product is likely to reduce. When the amount is too large, it becomes difficult to remove the remaining unreacted (meth)acryloyl halide or (meth)acryloyl group-containing isocyanate compound.

[0346] With regard to these reactions, react with suitable solvent dilution as required.As such solvent, as long as it is not with the hydroxyl of fluorinated alcohol compound, the halogen atom of (methyl) acryloyl halide, the solvent of the isocyanate group reaction of the isocyanate compound that contains (methyl) acryloyl, then can use without particular restriction, specifically, can list out the ketone solvents such as toluene, xylene, hydrocarbon solvents such as isooctane, THF, diisopropyl ether, ether solvents such as dibutyl ether, acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclohexanone, hexafluoro-m-xylene, fluorine-modified aromatic hydrocarbon solvents such as benzyl trifluoro, fluorine-modified ether solvents such as methyl perfluorobutyl ether etc.This solvent can adopt known methods such as underpressure distillation to remove after reaction, according to the purposes of target, can directly be used as diluted solution and use.

[0347] The amount of the solvent used is not particularly limited, but is preferably 10 times or less of the total mass of the reaction components. If the amount of the solvent used is too large, the reaction rate may be greatly reduced.

[0348] In addition, during the reaction, a polymerization inhibitor may be added as needed. The polymerization inhibitor is not particularly limited, and generally, a polymerization inhibitor used as a polymerization inhibitor for acrylic compounds can be used. Specifically, hydroquinone, hydroquinone monomethyl ether, 4-tert-butylcatechol, dibutylhydroxytoluene, etc. can be cited.

[0349] The amount of the polymerization inhibitor used is determined by the reaction conditions, purification conditions after the reaction, and final use conditions and is not particularly limited. It is usually 0.01 to 5000 ppm, particularly preferably 0.1 to 500 ppm, based on the total mass of the reaction components.

[0350] When reacting (meth)acryloyl halide with a fluorine-containing alcohol compound, it is particularly preferred to react acryloyl chloride and methacryloyl chloride to form an ester. The ester formation reaction is carried out by dropping (meth)acryloyl halide while mixing and stirring the above-mentioned reaction intermediate (fluorine-containing alcohol compound) and an acid acceptor. The acid acceptor can be triethylamine, pyridine, urea, etc. The amount of the acid acceptor used is preferably about 0.9 to 3 times the number of moles of the feed (meth)acryloyl halide. If it is too little, a large amount of uncaptured acid remains, and if it is too much, it becomes difficult to remove the remaining acid acceptor.

[0351] The (meth)acrylic acid halide is added dropwise for 20 to 60 minutes by maintaining the temperature of the reaction mixture at 0 to 35°C. Then, stirring is continued for 30 minutes to 10 hours. After the reaction is completed, unreacted (meth)acrylic acid halide, salts produced by the reaction, and reaction solvent are removed by distillation, adsorption, filtration, washing, etc., thereby obtaining the fluorine-containing acrylic compound represented by the above formula (3).

[0352] In addition, when the reaction is stopped, an alcohol compound such as methanol or ethanol can be added to the system to esterify the unreacted (meth)acrylic acid halide. The generated (meth)acrylic acid esters can be removed by the same method as the unreacted (meth)acrylic acid halide, or can be used in the remaining state.

[0353] In the case of the reaction between the fluorine-containing alcohol compound and the (meth)acryloyl group-containing isocyanate compound, the fluorine-containing alcohol compound and the (meth)acryloyl group-containing isocyanate compound are stirred with a solvent as necessary to allow the reaction to proceed.

[0354] In this reaction, in order to increase the speed of reaction, suitable catalyst can be added.As catalyst, for example, alkyl tin ester compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin dioctoate, dioctanoate, stannous octoate, tetraisopropoxy titanium, tetra-n-butoxy titanium, four (2-ethylhexyl) titanium, dipropoxybis (acetylacetone) titanium, isopropoxy octanediol titanium and other titanic acid esters or titanium chelate compounds, tetraacetylacetonate zirconium, tri-butoxy monoacetylacetonate zirconium, mono-butoxy acetylacetonate bis (ethyl acetoacetate) zirconium, di-butoxybis (ethyl acetoacetate) zirconium, tetraacetylacetonate zirconium, zirconium chelate compounds etc. can be illustrated.These catalysts are not limited to one thereof, can be used as 2 kinds or their above mixtures, and particularly preferably use titanium compounds and tin compounds low in environmental impact. The reaction rate can be increased by adding 0.01 to 2% by mass, preferably 0.05 to 1% by mass of these catalysts based on the total mass of the reactants.

[0355] The above reaction is carried out at a temperature of 0 to 120° C., preferably 10 to 70° C., for 1 minute to 500 hours, preferably 10 minutes to 48 hours. If the reaction temperature is too low, the reaction rate may be excessively slow, and if the reaction temperature is too high, polymerization of (meth)acryloyl groups may occur as a side reaction.

[0356] After completion of the reaction, the unreacted isocyanate compound and the reaction solvent are removed by distillation, adsorption, filtration, washing or the like, thereby obtaining the fluorine-containing acrylic compound represented by the above formula (3).

[0357] When the reaction is stopped, an alcohol compound such as methanol or ethanol is added to the system to form a urethane bond with the unreacted isocyanate compound. The generated urethane acrylate can be removed in the same manner as the unreacted isocyanate compound, or can be left to be used.

[0358] [Ingredient (C)]

[0359] The third essential component (C) in the fluorinated curable composition of the present invention is a non-fluorinated acrylic compound having no fluoropolyether structure and having an average of two or more (meth)acryloyl groups in one molecule. Component (C) also includes urethane acrylates having a urethane bond in the molecule, or compounds in which two or more (meth)acryloyl groups are introduced into the side chains or terminals of various polymers by any method.

[0360] Such a non-fluorinated acrylic compound (C) may have two or more (meth)acryloyl groups in one molecule, and examples thereof include 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, isocyanuric acid ethylene oxide-modified di(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerol tri(meth)acrylate, tri(meth)acryloyloxyethyl phosphate, hydrogen-(2,2,2-tri-(meth)acryloyl)phthalate. The invention also includes difunctional to hexafunctional (meth)acrylic compounds such as ethyl methacrylate, glycerol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, di(trimethylolpropane) tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and sorbitol hexa(meth)acrylate; epoxy acrylates obtained by adding (meth)acrylic acid to epoxy resins and modifying these (meth)acrylic compounds with ethylene oxide, propylene oxide, epichlorohydrin, fatty acids, and alkyl groups; and copolymers obtained by introducing (meth)acryloyl groups into side linkages of (meth)acrylate copolymers.

[0361] In addition, urethane acrylates, products obtained by reacting a (meth)acrylate having a hydroxyl group with a polyisocyanate, products obtained by reacting a (meth)acrylate having a hydroxyl group with a polyisocyanate and a polyester having a terminal diol, and products obtained by reacting a (meth)acrylate having a hydroxyl group with a polyisocyanate obtained by reacting an excess of a diisocyanate with a polyol can also be used. Among them, preferred are urethane acrylates obtained by reacting a (meth)acrylate having a hydroxyl group selected from 2-hydroxyethyl (meth)acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, and pentaerythritol tri(meth)acrylate with a polyisocyanate selected from hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, lysine diisocyanate, norbornane diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, methylenebis(4-cyclohexyl isocyanate), 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5-diisocyanatocyclohexane, and diphenylmethane diisocyanate.

[0362] The component (C) may be used alone or in combination of two or more to improve coating properties and the properties of the film after curing.

[0363] It is particularly preferred to use a polyfunctional acrylic compound having two or more (meth)acryloyl groups in one molecule and having no urethane bond, or a mixture of at least two acrylic compounds comprising the polyfunctional acrylic compound and a polyfunctional urethane acrylate having three or more (meth)acryloyl groups in one molecule obtained by reacting an aliphatic polyisocyanate with an acrylic compound having a hydroxyl group.

[0364] Among them, examples of the polyfunctional acrylic compound having two or more (meth)acryloyl groups in one molecule and having no urethane bond include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, di(trimethylolpropane) tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, and compounds obtained by modifying these with ethylene oxide or propylene oxide.

[0365] Examples of the polyfunctional urethane acrylates having three or more (meth)acryloyl groups in one molecule obtained by reacting an aliphatic polyisocyanate with an acrylic compound having a hydroxyl group include hexamethylene diisocyanate, norbornane diisocyanate, isophorone diisocyanate and trimers thereof, and bifunctional or higher polyisocyanates obtained by reacting these bifunctional or trifunctional isocyanates with an aliphatic diol, an aliphatic polyol and polyacrylates having a hydroxyl group in a side chain, trimethylolpropane di(meth)acrylate, glycerol diisocyanate, and polyisocyanates having hydroxyl groups in a side chain. Products obtained by reacting (meth)acrylate, bis(2-(meth)acryloyloxyethyl)hydroxyethyl isocyanurate, pentaerythritol tri(meth)acrylate, di(trimethylolpropane) tri(meth)acrylate, dipentaerythritol penta(meth)acrylate and ethylene oxide or propylene oxide modified products thereof; products obtained by reacting aliphatic polyols and polyacrylates having hydroxyl groups in side chains with acrylic compounds having isocyanate groups such as 2-isocyanatoethyl(meth)acrylate and 1,1-(bisacryloyloxymethyl)ethyl isocyanate.

[0366] In addition, the component (C) includes not only liquid components but also products obtained by modifying the surface of fine-particle high molecular weight products or the surface of fine inorganic filler particles with a (meth)acryloyl group.

[0367] In the fluorine-containing curable composition of the present invention, with respect to the composition ratio of each component, relative to 100 parts by mass of component (C), the total amount of component (A) and component (B) is preferably 0.05 to 50 parts by mass, particularly preferably 0.1 to 10 parts by mass, and the amount of component (A) relative to 100 parts by mass of component (B) is 1 to 100 parts by mass, particularly preferably in the range of 3 to 50 parts by mass. Relative to component (C), if the total amount of components (A) and (B) is too much compared with it, the performance as a hard coat film is reduced, and if it is too little, it is not possible to exert sufficient antifouling performance. Relative to component (B), if the amount of component (A) is too much compared with it, it is possible that the solubility of component (C) is excessively deteriorated, resulting in poor coating, and if it is too little, no difference is observed relative to the use of component (B) alone.

[0368] The fluorine-containing curable composition of the present invention contains the above-mentioned three components (A), (B) and (C) as essential components, but a product containing only these components can be cured by heat, electron beam or the like, and may contain components other than these three components as necessary depending on workability.

[0369] In particular, by containing a photopolymerization initiator as the component (D), a curable composition can be prepared in which curability is improved when ultraviolet rays are used as active energy rays.

[0370] [Ingredient (D)]

[0371] The photopolymerization initiator of component (D) is not particularly limited as long as it is a photopolymerization initiator that can cure the acrylic compound by ultraviolet irradiation. Preferred examples include acetophenone, benzophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-(dimethylthiophenyl)-1-methyl-2-thiophene-1-one, and 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one. 1-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyloxime)], ethylone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetoxime), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propane-1-one, and the like may be used alone or in combination of two or more.

[0372] The content of component (D) can be appropriately determined according to the curing conditions and the desired physical properties of the composition. For example, it is preferably 0.1 to 15 parts by mass, and particularly preferably 1 to 10 parts by mass, relative to 100 parts by mass of component (C). If the added amount is less than this, the curability may be reduced, and if it is more than this, the effect on the physical properties after curing may increase.

[0373] These components (A), (B), (C), and (D) can be used as a single compound or a mixture of multiple compounds with the same structure under the definition of each compound. In the case of a mixture of multiple compounds, the total mass of each compound group can be considered as the mass of each compound group when considering the blending amount.

[0374] The fluorine-containing curable composition of the present invention may further contain, depending on the purpose, a monofunctional acrylic compound, a thiol compound, a maleimide compound, etc. as a reactive diluent, an active energy ray-reactive compound other than a (meth)acryloyl group, an organic solvent, an inhibitor, an antistatic agent, a defoaming agent, a viscosity modifier, a light stabilizer, a heat stabilizer, an antioxidant, a surfactant, a colorant, and a polymer or inorganic filler.

[0375] Examples of the organic solvent include alcohols such as 1-propanol, 2-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, and diacetone alcohol; ketones such as methyl propyl ketone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethers such as dipropyl ether, dibutyl ether, anisole, dioxane, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate; esters such as propyl acetate, butyl acetate, and cyclohexyl acetate; toluene, xylene, triethylbenzene, alkylbenzene aromatics, etc. The above solvents may be used alone or in combination of two or more.

[0376] The amount of the solvent used is not particularly limited, but is preferably 20 to 10,000 parts by mass, particularly preferably 100 to 1,000 parts by mass, based on 100 parts by mass of the total of components (A) to (C).

[0377] The polymerization inhibitor, antistatic agent, defoaming agent, viscosity modifier, light stabilizer, heat stabilizer, antioxidant, surfactant, colorant, and filler are not particularly limited, and known components can be used within a range not impairing the purpose of the present invention.

[0378] Furthermore, within the scope of not impairing the purpose and effect of the present invention, by-products generated when manufacturing components (A) and (B) in the present invention, residual unreacted components, etc. may be included. As such components, for example, the above-mentioned fluorine-containing alcohol compounds represented by formula (6) and (7) are considered to remain as unreacted components.

[0379] Furthermore, hard coating agents mixed with component (C) and various additives are commercially available in various products from various companies. The fluorine-containing curable composition of the present invention may be a product in which component (A) and component (B) are added to such commercially available hard coating agents. Examples of commercially available hard coating agents include "BEAMSET" from Arakawa Chemical Industries, Ltd., "Ubic" from Ohashi Chemical Industries, Ltd., "UV coat" from Origin Electric, "Cashew UV" from Cashew, "DeSolite" from JSR, "SEIKABEAM" from Dainichi Seika Industries, "Ziguang" from Nippon Synthetic Chemical, Ltd., "FUJIHARD" from Fujikura Chemical, Ltd., "Diabeam" from Mitsubishi Rayon, and "ULTRA VIN" from Musashi Paint Co., Ltd.

[0380] Even when a commercially available hard coating agent is used as described above, an organic solvent, a polymerization inhibitor, an antistatic agent, a defoaming agent, a viscosity modifier, a light stabilizer, a heat stabilizer, an antioxidant, a surfactant, a colorant, a filler, etc. may be added according to the purpose.

[0381] Regarding the above components (C), (D) and other additives that can be arbitrarily compounded, a large number of well-known additives are shown in, for example, "Photocuring Technology Data Book Materials Edition" edited by TECHNINET Co., Ltd. (2000, TECHNINET Co., Ltd.), "Photopolymer Handbook" edited by Photopolymer Symposium (1989, Industrial Research Council), "UV·EB Curing Technology" edited by Comprehensive Technology Center (1982, Comprehensive Technology Center), "UV·EB Curing Materials" edited by RadTech Research Institute (1992, CMC), "Poor Curing·Causes of Obstruction and Countermeasures in UV Curing" edited by Technical Information Association (2003, Technical Information Association), "Blending Design, Property Evaluation and New Applications of UV Curing Resins" edited by Technical Information Association (2017, Technical Information Association), "Market Reality and Prospects of UV·EB Curing Materials·Products" edited by CMC Publishing (2007, CMC Publishing), "Optimization of UV Curing Process" edited by Science & Technology (2008, Science & Technology), etc., and they can be used in any combination.

[0382] The method for compounding the fluorinated curable composition of the present invention may be carried out by any method depending on the application without particular limitation. It is preferred that the component (A) and the component (B) are sufficiently mixed before mixing with other components. For example, it is preferred that the component (A) and the component (B) are mixed at a desired ratio, the product diluted with a solvent as required is mixed with the component (C) and other components, or the component (A) diluted with a solvent and the component (B) diluted with a solvent are mixed and mixed with the component (C) and other components.

[0383] There is no particular limitation on the curing method of the fluorine-containing curable composition of the present invention. The composition containing components (A), (B), and (C) can be cured by appropriately diluting the composition with a solvent and applying the composition using active energy lines such as heat and electron beams. When a photopolymerization initiator as component (D) is also contained, ultraviolet rays can be used to cure the composition. When ultraviolet rays are used for curing, ultraviolet rays can be irradiated in the air. In order to prevent curing hindrance caused by oxygen, the oxygen concentration is preferably suppressed to below 5000 ppm. It is particularly preferred to cure the composition in an atmosphere of an inert gas such as nitrogen, carbon dioxide, or argon.

[0384] In addition, as a general use form of the fluorine-containing curable composition of the present invention, as long as the fluorine-containing curable composition layer of the present invention is closely attached or bonded after curing, it can be coated on any substrate, and in particular, resin substrates can be listed, such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, cellophane, diacetyl cellulose, triacetyl cellulose, acetyl cellulose butyrate, cellulose acetate propionate, cycloolefin polymer, cycloolefin copolymer, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl acetate copolymer, polystyrene, polycarbonate, polymethylpentene, polysulfone, polyetheretherketone, polyethersulfone, polyetherimide, polyimide, fluororesin, nylon, acrylic resin and other resins. These can be in any form such as film, plate and molded member, and can be used on its surface.

[0385] When applied to a film substrate, a pressure-sensitive adhesive may be applied to the surface opposite to the surface on which the fluorine-containing curable composition layer is applied, and a release film may be further provided to protect the pressure-sensitive adhesive.

[0386] In addition, the film substrate may be a substrate consisting only of the above-mentioned resin film, or may be a film substrate having a primer layer provided on the resin film in order to improve the adhesion with the fluorine-containing curable composition of the present invention. Examples of the primer layer include primer layers consisting of polyester resins, polyurethane resins, acrylic resins, and the like.

[0387] In addition, the fluorine-containing curable composition of the present invention can be coated and cured on a cured or uncured layer that does not correspond to the curable composition of the present invention. For example, the fluorine-containing curable composition of the present invention can be overlapped on a cured layer having higher hardness, durability, antistatic properties, curling and other deformation prevention properties.

[0388] In order to improve the adhesion with the fluorine-containing curable composition of the present invention, the surface of the resin substrate may be treated by surface roughening treatment using a sandblasting method, a solvent treatment method, etc., corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, oxidation treatment, etc.

[0389] The method for applying the fluorinated curable composition of the present invention to the substrate or article is not particularly limited, and known coating methods such as roll coating, gravure coating, flow coating, curtain coating, dip coating, spray coating, spin coating, bar coating, and screen printing can be used.

[0390] After coating, the coating film is irradiated with active energy rays to cure it. Among them, as active energy rays, any active energy rays such as electron beams and ultraviolet rays can be used, and ultraviolet rays are particularly preferred. As ultraviolet light sources, mercury lamps, metal halide lamps, and LED lamps are preferred. As for the ultraviolet light irradiation amount, if it is too little, uncured components will remain, and if it is too much, the coating film and the substrate may deteriorate, so it is preferably 10 to 10000 mJ / cm 2 , especially 100~4000mJ / cm 2 range.

[0391] In addition, in order to prevent the curing hindrance caused by oxygen, the irradiation atmosphere can be replaced with an inert gas containing no oxygen molecules such as nitrogen, carbon dioxide, argon, etc. during ultraviolet irradiation, or the coating surface can be covered with a protective layer having release properties and ultraviolet permeability, and ultraviolet rays can be irradiated from there. In the case of ultraviolet permeability of the substrate, the coating surface can be covered with a protective layer having release properties and ultraviolet rays can be irradiated from the opposite side of the coating surface of the substrate. In addition, in order to effectively level the coating film or polymerize the (meth)acryloyl group in the coating film, the coating film and the substrate can be heated by any method such as infrared rays, hot air drying furnace, etc. before and during ultraviolet irradiation.

[0392] The thickness of the cured product layer of the fluorinated curable composition thus obtained is not particularly limited, but is preferably from 0.01 to 5000 μm, particularly preferably from 0.05 to 200 μm.

[0393] In addition, the cured material layer of the fluorine-containing curable composition of the present invention thus obtained is preferably a water-repellent and oil-repellent surface having a static water contact angle of 114° or more, especially 115° or more, and a static oleic acid contact angle of 73° or more, especially 74° or more, measured according to the angle formed by the liquid surface and the solid surface after 1 second of a 2 μL droplet of ion exchange water from the contact droplet. In addition, the cured material layer of the fluorine-containing curable composition of the present invention is preferably a water-repellent and oil-repellent surface having a low dynamic friction coefficient of 0.10 or less, especially 0.09 or less, which can be a cured film. In addition, in order to become the above-mentioned contact angle and / or dynamic friction coefficient, it is preferred that the cured material layer of the fluorine-containing curable composition of the present invention forms a layer having a thickness of 10 nm or more on average relative to the total surface area of ​​the cured material layer. Furthermore, it is more preferable that no unreacted (meth)acryloyl groups remain on the surface of the cured layer. Therefore, the cured layer is preferably cured in an inert gas atmosphere such as nitrogen or carbon dioxide.

[0394] As described above, the fluorine-containing curable composition of the present invention can be cured by active energy rays such as ultraviolet rays, and can form a cured resin layer excellent in water and oil repellency, antifouling property, sliding property and abrasion resistance on the surface of an article.

[0395] Furthermore, in the present invention, there is provided an article having a cured film of the above-mentioned fluorine-containing curable composition of the present invention applied to a surface and cured. As mentioned above, if the fluorine-containing curable composition of the present invention is used, a cured film (cured resin layer) with excellent surface properties can be formed on the surface of a substrate (article). In particular, it can be used to impart water repellency, oil repellency, and antifouling properties to the surface of an acrylic hard coat. Thus, it is possible to impart to the substrate a hard coat surface that is not easy to adhere to and is also excellent in erasability due to dirt, machine oil, etc., produced by human fat, cosmetics, etc., such as fingerprints, sebum, sweat, etc. Therefore, the fluorine-containing curable composition of the present invention can provide an antifouling coating film or a protective film on the surface of a process material film, etc., which may be contaminated by human fat, cosmetics, etc., and may be contaminated by human fat, machine oil, etc., of an operator, etc., for a substrate.

[0396] The cured film (cured resin layer) formed using the fluorine-containing curable composition of the present invention can be used as a display operation device such as a screen of various flat panel displays such as tablet computers, notebook PCs, portable (communication) information terminals such as mobile phones and smart phones, digital media players, and electronic book readers, clock-type and glasses-type wearable computers, head-mounted displays, liquid crystal displays, plasma displays, organic EL (electroluminescence) displays, rear projection displays, fluorescent display tubes (VFDs), field emission projection displays, CRTs, toner-based displays, quantum dot (QD) displays, and TV screens. Various optical films used on surfaces and inside them, automobile exteriors, pianos, and furniture glossy surfaces, marble and other architectural stone surfaces, decorative building materials around water in toilets, bathrooms, and washrooms, protective glass for art displays, display windows, showcases, photo frame covers, watches, cosmetic container exteriors, decorative container exteriors, automobile window glass, window glass for trains, aircraft, etc., transparent glass or transparent plastic (acrylic, polycarbonate, etc.) components for automobile headlights, taillights, etc., cover components for automotive sensors such as millimeter wave lasers, and various reflector components, etc., coating films and surface protective films.

[0397] Among them, it can be used as a surface protective film for various devices having a touch panel display or other display input device that uses human fingers or palms to operate on the screen, such as tablet computers, notebook PCs, smart phones, mobile phones, other portable (communication) information terminals, smart watches, digital media players, e-book readers, digital photo frames, game consoles, digital cameras, digital video cameras, GPS display and recording devices, navigation devices for cars, control panels for cars, etc., automatic cash withdrawal and deposit devices, cash automatic payment machines, vending machines, digital signage (electronic signs), security system terminals, POS terminals, various controllers such as remote controls, display input devices such as panel switches for vehicle-mounted devices, etc.

[0398] Furthermore, the cured film formed by the fluorine-containing curable composition of the present invention can also be used as an optical recording medium such as a magneto-optical disk and an optical disk; and as a surface protective film for optical parts and optical devices such as eyeglass lenses, prisms, lens sheets, surface films, polarizing plates, optical filters, biconvex lenses, Fresnel lenses, antireflection films, various camera lenses, various lens protection filters, optical fibers, optical couplers, etc.

[0399] As described above, the fluorinated curable composition of the present invention is essentially characterized in that the fluorinated polyether structure in the compounds of components (A) and (B) of the present invention is arranged on the surface of the target article, thereby imparting excellent properties such as water repellency, oil repellency, slip, antifouling, fingerprint inconspicuousness, fingerprint erasability, abrasion resistance, low refractive index characteristics, solvent resistance, and chemical resistance.

[0400] When using such a fluorine-containing curable composition of the present invention, an appropriate method of use can be selected based on the known techniques that are consistent with each application, depending on the combination of the compounding materials, the composition ratio, and which properties are emphasized. Such known techniques include not only methods used for fluorine-containing compositions but also methods used for existing active energy ray-curable compositions, and can be included in the scope of research.

[0401] For example, when preparing the fluorine-containing curable composition of the present invention by compounding, in addition to the components (A) and (B) of the present invention, when combining the various ingredients in the above-mentioned fluorine-containing curable composition, when emphasizing the low refractive index property and utilizing its low reflective property, reactive hollow silica or hollow silica having no reactive group is used, or as component (C), a non-fluorine-based polyfunctional acrylic compound having a functionality of more than 3 or more is used; further, in order to improve the film strength and scratch resistance, two or more non-fluorine-based polyfunctional acrylic compounds are compounded in appropriate amounts as component (C); or in order to obtain a balance between hardness and bendability, a non-fluorine-based polyfunctional acrylic compound having a functionality of more than 6 or more and an acrylic compound having a functionality of less than 3 or more are combined as component (C), etc., and the above-mentioned can be easily deduced from the knowledge of compounding of known acrylic curable compositions.

[0402] In addition, in the case of obtaining an article by coating the fluorine-containing curable composition of the present invention, for example, when coating on a film substrate, in order to prevent interference fringes, the coating film thickness is adjusted in a manner to be appropriate, or the thickness of the film substrate is adjusted so that curling is easily suppressed, or the elastic modulus of the substrate film is adjusted to suppress deformation of the coating film of the fluorine-containing curable composition after curing, cracking of the coating film, etc., and selection is performed based on a combination of existing conditions that match each characteristic, which can be easily achieved by combining the present invention with the prior art.

[0403] Example

[0404] The present invention will be specifically described below with reference to synthesis examples, examples and comparative examples, but the present invention is not limited to the following examples.

[0405] [Synthesis Example 1] Synthesis of fluorinated acrylic compound (A-1)

[0406] A 300L four-necked flask equipped with a reflux device and a stirring device was charged with the following formula (I):

[0407] HOCH2CF2O(CF2CF2O) 20.1 (CF2O) 21.6 CF2CH2OH (I)

[0408] 100 g (0.0508 mol of OH group) of a compound represented by the following formula (II) (wherein the arrangement of the repeating units of -CF2CF2O- and -CF2O- is random)

[0409] CH2=CHC(=O)OCH2CH2-N=C=O (II)

[0410] 7.17 g of the compound represented by the invention and 200 g of hexafluoro-m-xylene were heated to 40°C under a dry air atmosphere while stirring. Then, 0.01 g of dioctyltin dilaurate was added, and heating and stirring were continued for 6 hours, after which heating was stopped. 19 F-NMR confirmed that the peaks of CF2 from -OCF2CH2OH (-81.1ppm, -83.15ppm) all changed to those from -OCF2CH2OC(=O)- (-78.4ppm, -80.4ppm). 2g of activated carbon was added to the obtained reaction solution, stirred at room temperature for 3 hours, and then filtered with a filter plate. The obtained filtrate was distilled under reduced pressure at 50°C to obtain 97.8g of the compound with the average structure of the following (A-1) with a target fluorine content of 57.5% by mass.

[0411] CH2=CHC(=O)OCH2CH2NHC(=O)OCH2CF2O(CF2CF2O) 20.1 (CF2O) 21.6 CF2CH2OC(=O)NHCH2CH2OC(=O)CH=CH2 (A-1)

[0412] [Synthesis Example 2] Synthesis of fluorinated acrylic compound (A-2)

[0413] In Synthesis Example 1, instead of the above formula (I), the following formula (III) was used as the average structure:

[0414] HOCH2CF2O(CF2CF2O) 31.1 (CF2O) 30.5 CF2CH2OH(III)

[0415] 100 g (0.0345 mol of OH group) of the compound represented by the formula (wherein the arrangement of the repeating units of -CF2CF2O- and -CF2O- is random) was added, and the same procedures as in Synthesis Example 1 were adopted to obtain 96.2 g of the following compound (A-2) having a fluorine content of 59.2% by mass as an average structure.

[0416] CH2=CHC(=O)OCH2CH2NHC(=O)OCH2CF2O(CF2CF2O)31.1 (CF2O) 30.5 CF2CH2OC(=O)NHCH2CH2OC(=O)CH=CH2 (A-2)

[0417] [Synthesis Example 3] Synthesis of fluorinated acrylic compound (A-3)

[0418] In a 300L four-necked flask equipped with a reflux device and a stirring device, 100g of the compound of formula (I) (0.0508mol of OH group), 7.20g of triethylamine, and 150g of hexafluoro-m-xylene were stirred at room temperature under a dry air atmosphere, and a mixed solution of 6.38g (0.0704mol) of acryloyl chloride and 50g of hexafluoro-m-xylene was dropped over 30 minutes. Stirring was continued for 6 hours and then stopped, and filtered using filter paper. The obtained filtrate was put into 1000g of hexane, the produced precipitate was recovered, dissolved with 100g of hexafluoro-m-xylene, and the solvent was removed by reduced pressure distillation at 50°C. 19 F-NMR confirmed that 90.5 g of the target compound (A-3) having the following average structure and a fluorine content of 60.0 mass% was obtained.

[0419] CH2=CHC(=O)OCH2CF2O(CF2CF2O) 20.1 (CF2O) 21.6 CF2CH2OC(=O)CH=CH2 (A-3)

[0420] [Synthesis Example 4] Synthesis of fluorinated acrylic compound (A-4)

[0421] In Synthesis Example 1, instead of the above formula (I), the following formula (IV) was used as the average structure:

[0422] CF3O(CF2CF2O) 20.1 (CF2O) 19.2 CF2CH2OH (IV)

[0423] The compound represented by (wherein the arrangement of the repeating units of -CF2CF2O- and -CF2O- is random) 100 g (0.0264 mol of OH group), the mixing amount of the compound of the above formula (II) was changed to 4.11 g, and 0.2 g of tetra(2-ethylhexyl)orthotitanate was used instead of dioctyltin dilaurate. The same procedures as in Synthesis Example 1 were adopted to obtain 97.5 g of the following compound (A-4) with a fluorine content of 60.2% by mass as an average structure.

[0424] CF3O(CF2CF2O) 20.1 (CF2O) 19.2CF2CH2OC(=O)NHCH2CH2OC(=O)CH=CH2(A-4)

[0425] [Synthesis Example 5] Synthesis of fluorinated acrylic compound (B-1)

[0426] In a dry nitrogen atmosphere, a 5000 mL three-necked flask equipped with a reflux device and a stirring device was charged with the following formula:

[0427] CH2=CH-CH2-O-CH2-Rf'-CH2-O-CH2-CH=CH2

[0428] Rf': -CF2O(CF2CF2O) 20.9 (CF2O) 21.2 CF2-

[0429] 1000 g (0.245 mol) of perfluoropolyether represented by the invention, 1400 g of hexafluoro-m-xylene and 722 g (3.00 mol) of tetramethylcyclotetrasiloxane were heated to 90° C. while stirring. 0.884 g of a toluene solution of a platinum / 1,3-divinyl-tetramethyldisiloxane complex (containing 2.2×10 -6 mol), and the stirring was continued for 4 hours while maintaining the internal temperature at 90°C or above. 1 After H-NMR confirmed the disappearance of the allyl group in the raw material, the solvent and excess tetramethylcyclotetrasiloxane were distilled off under reduced pressure and then treated with activated carbon to obtain 993 g of a colorless, transparent liquid compound (V) represented by the following formula.

[0430] [Chemistry 24]

[0431]

[0432] Rf': -CF2O(CF2CF2O) 20.9 (CF2O) 21.2 CF2-

[0433] In a dry air atmosphere, 50.0 g of the compound (V) obtained above (0.0657 mol of Si-H group) were mixed with 7.05 g (0.0690 mol) of 2-allyloxyethanol, 50.0 g of hexafluoro-m-xylene, and 0.0442 g of a toluene solution of a chloroplatinic acid / vinylsiloxane complex (containing 1.1×10 -7 mol), and stirred at 100°C for 4 hours. 1After H-NMR and IR confirmed the disappearance of the Si-H group, the solvent and excess 2-allyloxyethanol were distilled off under reduced pressure and treated with activated carbon to obtain 54.9 g of a pale yellow transparent liquid fluorinated alcohol compound (VI) represented by the following formula.

[0434] [Chemistry 25]

[0435]

[0436] Rf': -CF2O(CF2CF2O) 20.9 (CF2O) 21.2 CF2-

[0437] In a dry air atmosphere, 50.0 g of the obtained fluorine-containing alcohol compound (VI) (hydroxyl content 0.058 mol) was mixed with 50.0 g of THF and 9.00 g of acryloyloxyethyl isocyanate (0.0638 mol), and heated to 50°C. 0.15 g of tetra(2-ethylhexyl) orthotitanate was added thereto, and stirred at 50°C for 24 hours. After heating, the mixture was distilled off under reduced pressure at 80°C / 0.266 kPa to obtain 58.5 g of a light yellow paste. 1 As a result of H-NMR and IR, it was confirmed to be a fluorine-containing acrylic compound having a fluorine content of 41.0 mass % as shown below.

[0438] [Chemistry 26]

[0439]

[0440] Rf': -CF2O(CF2CF2O) 20.9 (CF2O) 21.2 CF2-

[0441] [Synthesis Example 6] Synthesis of fluorinated acrylic compound (B-2)

[0442] In a dry nitrogen atmosphere, a 500 mL three-necked flask equipped with a reflux device and a stirring device was charged with the following formula:

[0443] CH2=CH-CH2-O-CH2-Rf”-CH2-O-CH2-CH=CH2

[0444] Rf”: -CF2O(CF2CF2O) 9.8 (CF2O) 9.1 CF2-

[0445] 100 g (0.0501 mol) of perfluoropolyether represented by the invention, 100 g of hexafluoro-m-xylene, and 121 g (0.502 mol) of tetramethylcyclotetrasiloxane were heated to 90° C. while stirring. 0.442 g of a toluene solution of a platinum / 1,3-divinyl-tetramethyldisiloxane complex (containing 1.1×10 -6 mol), and stirring was continued for 4 hours while maintaining the internal temperature at 90°C or above. 1 After H-NMR confirmed the disappearance of the allyl group in the raw material, the solvent and excess tetramethylcyclotetrasiloxane were distilled off under reduced pressure and then treated with activated carbon to obtain 112 g of a colorless, transparent liquid compound (VII) represented by the following formula.

[0446] [Chemistry 27]

[0447]

[0448] Rf”: -CF2O(CF2CF2O) 9.8 (CF2O) 9.1 CF2-

[0449] In a dry air atmosphere, 50.0 g of the compound (VII) obtained above (0.121 mol of Si-H group) were mixed with 15.1 g (0.149 mol) of 2-allyloxyethanol, 100.0 g of hexafluoro-m-xylene, and 0.0884 g of a toluene solution of a chloroplatinic acid / vinylsiloxane complex (containing 2.2 × 10 -7 mol), and stirred at 100°C for 4 hours. 1 After H-NMR and IR confirmed the disappearance of the Si-H group, the solvent and excess 2-allyloxyethanol were distilled off under reduced pressure and treated with activated carbon to obtain 60.2 g of a pale yellow transparent liquid fluorinated alcohol compound (VIII) represented by the following formula.

[0450] [Chemistry 28]

[0451]

[0452] Rf”: -CF2O(CF2CF2O) 9.8 (CF2O) 9.1 CF2-

[0453] In a dry air atmosphere, 50.0 g of the obtained fluorinated alcohol compound (VIII) (hydroxyl content 0.097 mol) was mixed with 50.0 g of THF and 17.7 g (0.125 mol) of acryloyloxyethyl isocyanate and heated to 50°C. 0.05 g of dioctyltin dilaurate was added thereto and stirred at 50°C for 24 hours. After heating, the mixture was distilled off under reduced pressure at 80°C / 0.266 kPa to obtain 63.5 g of a light yellow high-viscosity liquid. 1 As a result of H-NMR and IR, it was confirmed that the compound was a fluorine-containing acrylic compound having a fluorine content of 29.7% by mass as shown below.

[0454] [Chemistry 29]

[0455]

[0456] Rf”: -CF2O(CF2CF2O) 9.8 (CF2O) 9.1 CF2-

[0457] [Examples 1 to 11, Comparative Examples 1 to 7]

[0458] The raw material components of the fluorine-containing curable composition of the present invention are shown below.

[0459] (A) Fluorinated acrylic compounds

[0460] (A-1) Fluorine-containing acrylic compound obtained in Synthesis Example 1

[0461] (A-2) Fluorine-containing acrylic compound obtained in Synthesis Example 2

[0462] (A-3) Fluorine-containing acrylic compound obtained in Synthesis Example 3

[0463] (A-4) Fluorine-containing acrylic compound obtained in Synthesis Example 4

[0464] (B) Fluorinated acrylic compounds

[0465] (B-1) Fluorine-containing acrylic compound obtained in Synthesis Example 5

[0466] (B-2) Fluorine-containing acrylic compound obtained in Synthesis Example 6

[0467] (C) Non-fluorinated acrylic compounds

[0468] (C-1) Pentaerythritol ethoxylate tetraacrylate

[0469] [EBECRYL 40 manufactured by Daicel-Allnex Ltd.]

[0470] (C-2) Pentaerythritol triacrylate

[0471] (C-3) Multifunctional acrylate composed of a reaction product of pentaerythritol triacrylate and hexamethylene diisocyanate [UA-306H manufactured by Kyoeisha Chemical Co., Ltd.]

[0472] (D) Photopolymerization initiator

[0473] (D-1) 1-Hydroxycyclohexylphenylketone (trade name: IRGACURE 184, manufactured by BASF Japan Ltd.)

[0474] (D-2) 2-Hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one (trade name: IRGACURE 127, manufactured by BASF Japan Ltd.)

[0475] [Preparation of fluorine-containing curable composition]

[0476] Components (A) and (B) were diluted to 20% by mass with methyl ethyl ketone, and component (C) was diluted to 40% by mass with butyl acetate. In addition, the dilution solvent of (C-1) was replaced with 2-propanol from butyl acetate, and the product diluted to 40% by mass was blended as (C-4).

[0477] The components (A) to (D) excluding the solvent component were mixed in a mixing ratio as shown in the following Table 1 to obtain a fluorinated curable composition.

[0478] [Table 1]

[0479] Compounding ratio of components (A) to (D) in Examples and Comparative Examples (excluding solvent components)

[0480]

[0481] [Dissolution state of composition]

[0482] The dissolution state (appearance of the coating solution) of each composition was visually observed. It should be noted that no further evaluation was performed for the composition that produced a precipitate. The results are shown in Table 2.

[0483] Preparation of coating and cured products

[0484] Each composition of the examples and comparative examples was coated on a polycarbonate substrate using a wire rod No. 7 (wet film thickness 16.0 μm). After coating, it was dried at 100° C. for 1 minute, and then a conveyor-type metal halide UV irradiation device (manufactured by Matsushita Electric Works) was used to irradiate the substrate in a nitrogen atmosphere at a cumulative irradiation dose of 400 mJ / cm 2The coated surface was irradiated with ultraviolet rays to cure the composition, thereby obtaining a cured film having a thickness of 5 μm.

[0485] [Evaluation of water and oil repellency]

[0486] 1) Water contact angle measurement

[0487] Using a contact angle meter (DropMaster manufactured by Kyowa Interface Science Co., Ltd.), a 2 μL drop of water was dropped onto the cured film, and the water contact angle was measured 1 second later. The average value of N=5 was taken as the measured value. The results are shown in Table 2.

[0488] 2) Oleic acid contact angle measurement

[0489] Using a contact angle meter (DropMaster manufactured by Kyowa Interface Science Co., Ltd.), 4 μL of oleic acid was dropped onto the cured film, and the contact angle of oleic acid was measured 1 second later. The average value of N=5 was taken as the measured value. The results are shown in Table 2.

[0490] [Determination of dynamic friction coefficient]

[0491] The dynamic friction coefficient of the cured film with respect to Bencot (manufactured by Asahi Kasei Corporation) was measured under the following conditions using a surface tester 14FW (manufactured by Shinto Scientific Co., Ltd.).

[0492] Contact area: 10mm×35mm

[0493] Load: 100g

[0494] [Evaluation of the repellency of the marker]

[0495] A straight line was drawn on the surface of the cured film with a marker (HI McKee boldface, manufactured by ZEBRA Corporation), and the repellency was evaluated by visual observation.

[0496] [Evaluation of erasability of a marker]

[0497] A straight line was drawn on the surface of the cured film with a marker (HI McKee Bold, manufactured by ZEBRA Co., Ltd.), and after 1 minute, the surface was gently rubbed 3 times with toilet paper. If no trace of the marker remained, it was evaluated as "erased", and if a trace remained, it was evaluated as "not erased". The results are shown in Table 2.

[0498] [Table 2]

[0499]

[0500] From the above results, it can be seen that for the compositions of Comparative Examples 1 to 3 in which component (B) was not added but only components (A) and (C) were added, the solubility of the compositions was poor and precipitates were generated, while for the compositions of Examples 1 to 11 of the present invention in which components (A), (B) and (C) were added, transparent and uniform coating liquids could be prepared. In addition, the compositions of Examples 1 to 11 of the present invention were able to form surfaces having high liquid repellency and slip properties compared to the compositions of Comparative Examples 4, 5 and 7 in which component (A) was not added but only components (B) and (C) were added.

Claims

1. A fluorinated curable composition comprising component (A), component (B) and component (C) as essential components, wherein the total amount of component (A) and component (B) is 0.05 to 50 parts by mass per 100 parts by mass of component (C), and the amount of component (A) is 1 to 100 parts by mass per 100 parts by mass of component (B), Component (A) is a linear polymer having a fluoropolyether in the main chain, and is composed of a compound having one or two (meth)acryloyl groups at one or both ends of the molecular chain, the average number of (meth)acryloyl groups contained in one molecule is 2 or less, and the fluorine content is 48% by mass or more and less than 62% by mass, and component (A) is represented by the following general formula (1) or (2): Rf 1 -O-Rf 2 -CF2-Z 1 -X 1 (1) X 2 -Z 1 -CF2O-Rf 2 -CF2-Z 1 -X 1 (2) In the formula, Rf 1 is a fluorine atom or a monovalent fluorinated alkyl group having 1 to 8 carbon atoms which may contain an oxygen atom, Rf 2 It is a divalent perfluoropolyether group having a molecular weight of 600 to 20,000 in which the following two repeating units are randomly arranged, -CF2O- -CF2CF2O- Z 1 X is independently a linking group selected from a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain at least one hetero atom selected from an oxygen atom, a nitrogen atom and a silicon atom, -C(=O)- and -C(=O)O-, wherein the divalent hydrocarbon group may contain a cyclic structure in the middle, and a part of the hydrogen atoms bonded to the carbon atoms may be substituted by fluorine atoms; 1 are independently a monovalent organic group having a (meth)acryloyl group which may contain an oxygen atom and / or a nitrogen atom, and X 2 is hydroxyl or X 1 ; Component (B) is composed of a compound having two or more (meth)acryloyl groups at each molecular chain terminal in one molecule of a linear polymer having a fluoropolyether in the main chain, having an average of 4 to 10 (meth)acryloyl groups in one molecule, and having a fluorine content of 25 mass % or more and less than 45 mass %, and is represented by the following general formula (3): [Chemistry 1] In the formula, Rf 2 Same as above; Q 1 are independently (a+1)-valent linking groups containing at least (a+1) silicon atoms, which may form a ring structure; a is an integer from 2 to 5; Z 2 Each independently represents a divalent hydrocarbon group having 1 to 100 carbon atoms which may contain an oxygen atom and / or a nitrogen atom; and may contain a cyclic structure; R 1 R is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms; 2 are independently a hydrogen atom, or a monovalent organic group having a (meth)acryloyl group which may contain an oxygen atom and / or a nitrogen atom, wherein: R 2 Z is a monovalent organic group having two or more at each end in one molecule and having an average of 4 to 10 in one molecule; 3 A linking group is independently composed of a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain at least one hetero atom selected from an oxygen atom, a nitrogen atom and a silicon atom, may contain a cyclic structure in the middle, and a part of the hydrogen atoms bonded to the carbon atoms may be substituted by fluorine atoms; The component (C) is composed of a non-fluorinated acrylic compound having no fluoropolyether structure and having an average of two or more (meth)acryloyl groups in one molecule. 2 . The fluorinated curable composition according to claim 1 , further comprising a photopolymerization initiator (D).

3. The fluorine-containing curable composition according to claim 1 or 2, wherein In component (A), Z in the general formula (1) or (2) 1 For any of the following structures, -C(=O)- -C(=O)O- -C(=O)OCH2- -C(=O)OCH2CH2- -CH2- -CH2O- -CH2OCH2- -CH2CH2- -CH2CH2CH2- -CH2CH2CH2CH2- -CH2OC(=O)NH- -CH2OC(=O)NHCH2CH2-.

4. The fluorine-containing curable composition according to claim 1 or 2, wherein In component (A), X in the general formula (1) or (2) 1 is represented by any of the following, -OC(=O)CH=CH2 -OC(=O)C(CH3)=CH2 -CH[CH2OC(=O)CH=CH2][CH2OC(=O)C(CH3)=CH2] -C(CH3)[CH2OC(=O)CH=CH2]2 -C(CH2CH3)[CH2OC(=O)CH=CH2]2 -C(CH2CH3)[CH2OC(=O)C(CH3)=CH2]2.

5. The fluorine-containing curable composition according to claim 1 or 2, wherein In the component (A), the fluorine-containing acrylic compound represented by the general formula (1) or (2) is represented by any of the following, Rf 1 ORf 2 CF2CH2OC(=O)CH=CH2 Rf 1 ORf 2 CF2CH2OC(=O)C(CH3)=CH2 HOCH2CF2ORf 2 CF2CH2OC(=O)CH=CH2 HOCH2CF2ORf 2 CF2CH2OC(=O)C(CH3)=CH2 Rf 1 ORf 2 CF2C(=O)OCH2CH2OC(=O)CH=CH2 Rf 1 ORf 2 CF2C(=O)OCH2CH2OC(=O)C(CH3)=CH2 HOCH2CF2ORf 2 CF2C(=O)OCH2CH2OC(=O)CH=CH2 HOCH2CF2ORf 2 CF2C(=O)OCH2CH2OC(=O)C(CH3)=CH2 Rf 1 ORF 2 CF2C(=O)OCH[CH2OC(=O)CH=CH2][CH2OC(=O)C(CH3)=CH2] <h2 style=";text-align:left;direction:ltr">Rf<h2 style=";text-align:left;direction:ltr"> 1 <h2 style=";text-align:left;direction:ltr"> ORf<h2 style=";text-align:left;direction:ltr"> 2 <h2 style=";text-align:left;direction:ltr"> CF2CH2OC(=O)NHCH2CH2OC(=O)CH=CH2 <h2 style=";text-align:left;direction:ltr">Rf<h2 style=";text-align:left;direction:ltr"> 1 <h2 style=";text-align:left;direction:ltr"> ORf<h2 style=";text-align:left;direction:ltr"> 2 <h2 style=";text-align:left;direction:ltr"> CF2CH2OC(=O)NHCH2CH2OC(=O)C(CH3)=CH2 <h2 style=";text-align:left;direction:ltr">HOCH2CF2ORf<h2 style=";text-align:left;direction:ltr"> 2 <h2 style=";text-align:left;direction:ltr"> CF2CH2OC(=O)NHCH2CH2OC(=O)CH=CH2 HOCH2CF2ORf 2 CF2CH2OC(=O)NHCH2CH2OC(=O)C(CH3)=CH2 HOCH2CF2ORf 2 CF2CH2OC(=O)NHC(CH3)[CH2OC(=O)CH=CH2]2 CH2=C(CH3)C(=O)OCH2CF2ORf 2 CF2CH2OC(=O)C(CH3)=CH2 CH2=CHC(=O)OCH2CF2ORf 2 CF2CH2OC(=O)C(CH3)=CH2 CH2=CHC(=O)OCH2CF2ORf 2 CF2CH2OC(=O)CH=CH2 CH2=CHC(=O)OCH2CH2NHC(=O)OCH2CF2ORf 2 CF2CH2OCH2OC(=O)CH=CH2 CH2=C(CH3)C(=O)OCH2CH2NHC(=O)OCH2CF2ORf 2 CF2CH2OCH2OC(=O)C(CH3)=CH2 CH2=CHC(=O)OCH2CH2NHC(=O)OCH2CF2ORf 2 CF2CH2OC(=O)NHCH2CH2OC(=O)CH=CH2 In the formula, Rf 1 , Rf 2 Same as above.

6. The fluorine-containing curable composition according to claim 1 or 2, wherein In component (B), Z in general formula (3) 3 It is represented by any of the following formulas: -CH2CH2- -CH2CH2CH2- -CH2CH2CH2CH2- -CH2OCH2CH2- -CH2OCH2CH2CH2-.

7. The fluorine-containing curable composition according to claim 1 or 2, wherein In component (B), Q in general formula (3) 1 It is expressed by the following formula: [Chemistry 2] Wherein, a1 is 2 or 3.

8. The fluorine-containing curable composition according to claim 1 or 2, wherein In the component (B), the fluorine-containing acrylic compound represented by the general formula (3) is a fluorine-containing acrylic compound represented by the following general formula (4) or (5), [Chemistry 3] [Chemistry 4] In the formula, Z 3 , Q 1 , a As mentioned above, Rf' is -CF2O(CF2O) m (CF2CF2O) n CF2-, m is an integer of 1 to 200, n is an integer of 1 to 170, m+n is an integer of 6 to 201, the arrangement of -(CF2O)- and -(CF2CF2O)- is random, R 3 is a hydrogen atom or a methyl group, d1 and e1 are integers of 0 to 10, and in the compounds represented by the formulae (4) and (5), the fluorine content is 25 mass % or more and less than 45 mass %.

9. The fluorine-containing curable composition according to claim 1 or 2, wherein The non-fluorinated acrylic compound of the component (C) is a polyfunctional acrylic compound having two or more (meth)acryloyl groups in one molecule and having no urethane bond, or a polyfunctional urethane acrylate having three or more (meth)acryloyl groups in one molecule obtained by reacting the polyfunctional acrylic compound with an aliphatic polyisocyanate and an acrylic compound having a hydroxyl group, or a mixture of two or more acrylic compounds containing the polyfunctional acrylic compound and the urethane acrylate.

10. An article having a cured film of the fluorinated curable composition according to any one of claims 1 to 9 on its surface.

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