Fluorine-containing curable composition and article

Abstract

The following fluorinated curable composition can form a cured film having excellent antifouling properties and water repellency and a low dynamic friction coefficient, and the fluorinated curable composition contains the following components as essential components: component (A) composed of a compound having a fluoropolyether as a linear polymer in the main chain, a trifluoromethyl group at one end of one molecule, and two or more (meth)acryloyl groups at the other end; component (B) composed of a compound having a fluoropolyether as a linear polymer in the main chain, two or more (meth)acryloyl groups at each end of one molecule (meth)acryloyl group, a compound having an average of 4 to 10 (meth)acryloyl groups in one molecule; and component (C), which is composed of a non-fluorinated acrylic compound that does not contain a fluoropolyether structure and has an average of 2 or more (meth)acryloyl groups in one molecule, wherein the total amount of component (A) and component (B) is 0.05 to 50 parts by mass relative to 100 parts by mass of component (C), and the amount of component (A) relative to 100 parts by mass of component (B) is 1 to 100 parts by mass.

Description

Technical Field

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

[0002] So far, as a means of protecting the surface of a resin molded body, hard coating treatment is generally widely used. It is to form a hard cured resin layer (hard coating) on ​​the surface of the molded body to make it difficult to damage. 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 demand for high functionality of the cured resin layer (hard coating) is rising. As one of the requirements, it is necessary 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 coating layer, a method of applying and / or fixing a fluorine-containing antifouling agent on the surface of a temporarily formed hard coating layer is widely used, but a method of simultaneously forming a hard coating layer and imparting antifouling properties by adding a fluorine-containing curable component to a curable resin composition before curing and applying and curing the composition has also been studied. For example, Japanese Patent Publication No. 6-211945 (Patent Document 1) shows the manufacture of a hard coating 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 blended with such fluorinated acrylic compounds has been greatly expanded, and new functions have been increasingly required.

[0006] By greatly expanding the scope of application in this way, 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 the components with higher 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 hard coating agent that have not been fluorinated is reduced, and uneven parts such as defects on the coating surface cause partial coating defects and grapefruit-peel-like whole-surface coating defects.

[0007] In addition, as prior arts related to the present invention, the following documents can be cited 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 conducted various studies on fluorine compounds that can impart antifouling properties to such curable resin compositions, and for example, have proposed photocurable 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). 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 is 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 becomes difficult to concentrate the fluorine component on the coating surface, and as a result, it sometimes becomes difficult to show antifouling properties.

[0018] Therefore, the present inventors have conducted further studies and found that the following fluorinated curable composition can form a cured film having excellent antifouling properties and water repellency and a low dynamic friction coefficient, thereby completing the present invention. The fluorinated curable composition comprises the following components as essential components: component (A) composed of a compound having a fluoropolyether as a linear polymer in the main chain, a trifluoromethyl group at one end of one molecule, and two or more (meth)acryloyl groups at the other end; and component (B) composed of a compound having a fluoropolyether as a linear polymer in the main chain, a trifluoromethyl group at one end of one molecule, and two or more (meth)acryloyl groups at the other end. The invention further comprises a compound having two or more (meth)acryloyl groups at each end thereof and having an average of 4 to 10 (meth)acryloyl groups in one molecule; and a component (C) consisting of a non-fluorinated acrylic compound having no fluoropolyether structure and having an average of two or more (meth)acryloyl groups in one molecule, wherein the total amount of the components (A) and (B) is 0.05 to 50 parts by mass relative to 100 parts by mass of the component (C), and the amount of the component (A) relative to 100 parts by mass of the component (B) is 1 to 100 parts by mass.

[0019] Therefore, the present invention provides the following fluorine-containing curable composition and an article having a cured film of the composition on the surface.

[0020] [1] A fluorinated curable composition comprising the following essential components: a component (A) consisting of a compound which is a linear polymer having a fluoropolyether in the main chain, has a trifluoromethyl group at one terminal in one molecule, and has two or more (meth)acryloyl groups at the other terminal; a component (B) consisting of a compound which is a linear polymer having a fluoropolyether in the main chain, has two or more (meth)acryloyl groups at each terminal in one molecule, and has an average of 4 to 10 (meth)acryloyl groups in one molecule; and a component (C) consisting of a non-fluorinated acrylic compound which does not contain a fluoropolyether structure and has an average of two or more (meth)acryloyl groups in one molecule, wherein the total amount of the components (A) and (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).

[0021] [2] The fluorinated curable composition according to [1], further comprising a photopolymerization initiator (D).

[0022] [3] The fluorinated curable composition according to [1] or [2], wherein the component (A) is a fluorinated acrylic compound represented by the following general formula (1).

[0023] R A -Z 1 -Q 1 [X 1 ]a (1)

[0024] (Where Rf A Because it is not related to Z 1 The terminal on one side of the bonding is a trifluoromethyl monovalent perfluoropolyether group. 1 It is a linking group 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. 1 is a (a+1)-valent linking group containing at least (a+1) silicon atoms, which may form a ring structure. a is an integer of 2 to 5. 1 They are independently monovalent organic groups having a (meth)acryloyl group which may contain at least one hetero atom selected from an oxygen atom, a nitrogen atom and a silicon atom.

[0025] [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 (2).

[0026] [Chemistry 1]

[0027]

[0028] (Where Rf B Z is a divalent perfluoropolyether group. 1 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 oxygen atoms, nitrogen atoms and silicon atoms, may contain a cyclic structure, and a part of hydrogen atoms bonded to carbon atoms may be substituted with fluorine atoms. 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. 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 2 Each terminal in one molecule has two or more monovalent organic groups and an average of 4 to 10 monovalent organic groups are present in one molecule.

[0029] [5] The fluorinated curable composition according to [3] or [4], wherein in component (A), X of the general formula (1) 1 It is represented by any of the following.

[0030] -CH2CH2CH2OC(=O)NHCH2CH2OC(=O)CH=CH2

[0031] -CH2CH2CH2OCH2CH2OC(=O)NHCH2CH2OC(=O)CH=CH2

[0032] -CH2CH2CH2OC(=O)NHCH2CH2OC(=O)C(CH3)=CH2

[0033] -CH2CH2CH2OCH2CH2OC(=O)NHCH2CH2OC(=O)C(CH3)=CH2

[0034] -CH2CH2CH2OC(=O)NHC(CH3)[CH2OC(=O)CH=CH2]2

[0035] -CH2CH2CH2OCH2CH2OC(=O)NHC(CH3)[CH2OC(=O)CH=CH2]2

[0036] -CH2CH2CH2OC(=O)CH=CH2

[0037] -CH2CH2CH2OCH2CH2OC(=O)CH=CH2

[0038] -CH2CH2CH2OC(=O)C(CH3)=CH2

[0039] -CH2CH2CH2OCH2CH2OC(=O)C(CH3)=CH2

[0040] -CH2CH2Si[OSi(CH3)2CH2OC(=O)CH=CH2]3

[0041] -CH2CH2Si[OSi(CH3)2CH2OC(=O)C(CH3)=CH2]3

[0042] [Chemistry 2]

[0043]

[0044] [6] The fluorinated curable composition according to any one of [3] to [5], wherein in component (A), Q of the general formula (1) 1 It is represented by any of the following.

[0045] [Chemistry 3]

[0046]

[0047] (In the formula, a is an integer from 2 to 5, and b is an integer from 1 to 5.)

[0048] [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) is selected from compounds represented by the following formula.

[0049] [Chemistry 4]

[0050]

[0051] [Chemistry 5]

[0052]

[0053] [Chemistry 6]

[0054]

[0055] [Chemistry 7]

[0056]

[0057] [Chemistry 8]

[0058]

[0059] [Chemistry 9]

[0060]

[0061] [Chemistry 10]

[0062]

[0063] [Chemistry 11]

[0064]

[0065] [Chemistry 12]

[0066]

[0067] [Chemistry 13]

[0068]

[0069] (Where Rf A Same as above.)

[0070] [8] The fluorinated curable composition according to any one of [4] to [7], wherein in component (B), Z of the general formula (2) 1 It is represented by any of the following formulas.

[0071] -CH2CH2-

[0072] -CH2CH2CH2-

[0073] -CH2CH2CH2CH2-

[0074] -CH2OCH2CH2-

[0075] -CH2OCH2CH2CH2-

[0076] [9] The fluorinated curable composition according to any one of [4] to [8], wherein in component (B), Q of the general formula (2) 1 It is represented by the following formula.

[0077] [Chemistry 14]

[0078]

[0079] (In the formula, a1 is 2 or 3.)

[0080]

[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 (2) is a fluorinated acrylic compound represented by the following general formula (3) or (4).

[0081] [Chemistry 15]

[0082]

[0083] [Chemistry 16]

[0084]

[0085] (Where Z 1 , Q 1 , aAs mentioned above, Rf B ' 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, and d1 and e1 are integers of 0 to 10.)

[0086]

[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 (meth)acrylate having three or more (meth)acryloyl groups in one molecule obtained by reacting the polyfunctional acrylic compound, 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 polyfunctional urethane (meth)acrylate.

[0087]

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

[11] on its surface.

[0088] Effects of the Invention

[0089] The fluorine-containing curable composition of the present invention has stable solubility during coating and can form a cured surface having high antifouling property, dirt removability and sliding property. DETAILED DESCRIPTION

[0090] The fluorinated curable composition of the present invention comprises the following components: a component (A) composed of a compound having a fluoropolyether structure in a main chain, a trifluoromethyl group at one terminal in one molecule, and two or more (meth)acryloyl groups at the other terminal; a component (B) composed of a compound having a fluoropolyether structure in a main chain, two or more (meth)acryloyl groups at each terminal in one molecule, and an average of 4 to 10 (meth)acryloyl groups in one molecule; and a component (C) composed of a non-fluorinated acrylic compound having no fluoropolyether structure and an average of two or more (meth)acryloyl groups in one molecule, wherein the above components (A), (B) and (C) are essential components.

[0091] In the present invention, "acrylic compound" is a general term for compounds having an acryloyl group and a methacryloyl group. In addition, "(meth)acryloyl group" means one or both of acryloyl group and 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.

[0092] It should be noted that in the present invention, each component of components (A), (B), and (C) is not necessarily a single compound. For example, when the mass during blending is taken into consideration, the total blending amount of a mixture of multiple compounds of components (A), (B), and (C) that are consistent with their respective conditions can be regarded as the amount of each component.

[0093] [Ingredients (A)]

[0094] Component (A) as the first essential component in the fluorinated curable composition of the present invention is composed of a compound which is a linear polymer having a fluoropolyether in the main chain, has a trifluoromethyl group at one end of one molecule, and has two or more, preferably 2 to 15, more preferably 2 to 9 (meth)acryloyl groups at the other end (i.e., one end of the molecular chain).

[0095] As such a compound, for example, a fluorine-containing acrylic compound represented by the following general formula (1) can be mentioned.

[0096] R A -Z 1 -Q 1 [X 1 ] a (1)

[0097] In the above formula (1), Rf A Because it is not related to Z 1 The terminal of the bonding side is a monovalent perfluoropolyether group having a trifluoromethyl group, which can be used as Rf 1 -O-Rf 2 -CF2- indicates.

[0098] Among them, Rf 1 The end of the side not bonded to the oxygen atom is a trifluoromethyl group, a perfluoroalkyl group having 1 to 10 carbon atoms and containing an oxygen atom, preferably CF3-Z f -(Z f Rf is a group represented by a perfluoroalkylene group having 1 to 10 carbon atoms which is a single bond or may contain an oxygen atom. 1 Specifically, we can list

[0099] CF3-

[0100] CF3CF2-

[0101] CF3CF2-

[0102] CF3CF2CF2-

[0103] CF3CF2CF2CF2-

[0104] CF3CF2CF2CF2CF2-

[0105] CF3CF2CF2CF2CF2CF2-

[0106] CF3OCF2CF2CF2-

[0107] CF3CF2OCF2CF2CF2-

[0108] CF3OCF2CF2CF2-

[0109] CF3OCF2CF2CF2CF2-

[0110] CF3OCF(CF3)CF2-

[0111] CF3CF2CF2OCF(CF3)CF2-

[0112] (CF3)2CFOCF2CF2-

[0113] CF3CF2OCF2CF2CF2-

[0114] CF3CF2CF2OCF2CF2CF2-

[0115] CF3CF2CF2OCF2CF2CF2CF2-

[0116] (CF3)2CFCF2OCF2CF2-

[0117] CF3CF2CF2CF2OCF2CF2CF2-,

[0118] Among them, CF3- is particularly preferred.

[0119] In addition, Rf 2 The following 4 repeating units

[0120] -CF2O-

[0121] -CF2CF2O-

[0122] -CF2CF2CF2O-

[0123] -CF2CF2CF2CF2O-

[0124] One or more randomly arranged divalent perfluoropolyether groups with a molecular weight of 600 to 20,000, preferably 1,200 to 10,000, the molecular weight being based on 1 H-NMR and 19 The number average molecular weight is calculated from the ratio of the terminal structure to the main chain structure by F-NMR. 2 Preferred groups include, for example, the following groups. In the following structure, the left bonding end is bonded to O, and the right bonding end is bonded to CF2.

[0125] -(CF2O) m (CF2CF2O) n -

[0126] The arrangement of each repeating unit is random, 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 smaller than the above ranges, the effect of imparting antifouling properties to the cured film is reduced. If they are larger than the above ranges, the compatibility with non-fluorinated components deteriorates, causing turbidity of the coating solution and poor coating. These values ​​of m and n may have a distribution. In the case of a distribution, it is preferably 19 The value of m+n determined by F-NMR etc. satisfies the above range as a number average.

[0127] In the above formula (1), Z 1 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, and a part of hydrogen atoms bonded to carbon atoms may be substituted with fluorine atoms. 1 As a preferred structure, the following structure group can be listed. In the following structure, the left bonding end and Rf A Bonding, the right side of the bond end and Q 1 Bonding.

[0128] -CH2CH2-

[0129] -CH2CH2CH2-

[0130] -CH2CH2CH2CH2-

[0131] -CH2OCH2CH2-

[0132] -CH2OCH2CH2CH2-

[0133] [Chemistry 17]

[0134]

[0135] Among them, it is particularly preferred

[0136] -CH2CH2-

[0137] -CH2CH2CH2-

[0138] -CH2CH2CH2CH2-

[0139] -CH2OCH2CH2-

[0140] -CH2OCH2CH2CH2-

[0141] [Chemistry 18]

[0142]

[0143] In the above formula (1), 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) is reduced, which may cause unevenness of the coating liquid or defects in the coating film. If a is greater than 5, the compatibility with component (B) is excessively increased, and superior surface properties may not be obtained compared to the case where component (B) is blended alone without blending component (A).

[0144] In the above formula (1), Q 1 is a linking group having a valence of (a+1) and containing at least (a+1) silicon atoms, and may form a ring structure. 1 Preferred groups include (a+1)-valent linking groups composed of siloxane structures, unsubstituted or halogen-substituted silylene structures, silylene structures, or combinations of two or more thereof, each having at least (a+1) Si atoms. In this case, it is preferred that the (a+1) bonding ends each have (a+1) Si atoms. Specifically, the following structure is shown as a particularly preferred structure.

[0145] However, in the following structure, a is the same as a in the above formula (1). 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 (a+1) unit is connected to Z. 1 and a X enclosed in brackets [] 1 Any group in the bond.

[0146] [Chemistry 19]

[0147]

[0148] Here, T is a (a+1)-valent linking group, and examples thereof include the following groups.

[0149] [Chemistry 20]

[0150]

[0151] Among these, the following groups are particularly preferred.

[0152] [Chemistry 21]

[0153]

[0154] (In the formula, a2 is an integer from 2 to 4.)

[0155] In the above formula (1), X 1 They are independently monovalent organic groups having preferably 1 to 3 (meth)acryloyl groups, which may contain at least one hetero atom selected from the group consisting of an oxygen atom, a nitrogen atom and a silicon atom.

[0156] As X 1 There are no particular limitations on the group as long as it is a group having a (meth)acryloyl group and may contain at least one hetero atom selected from an oxygen atom, a nitrogen atom, and a silicon atom, but it is particularly preferably represented by the following formula.

[0157] [Chemistry 22]

[0158]

[0159] (Where R 4 is a hydrogen atom or a methyl group, Z 3 It is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain an oxygen atom and / or a nitrogen atom, and may contain a cyclic structure. 5 It is a monovalent organic group having a (meth)acryloyl group which may contain an oxygen atom and / or a nitrogen atom. 4 is a divalent hydrocarbon group having 1 to 6 carbon atoms, and d is 0 or 1. 6 are each independently a monovalent organic group having a diorganosilylene group and a (meth)acryloyl group, and R 7 is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and c is 0 or 1. )

[0160] Among them, R 4 It is a hydrogen atom or a methyl group, and is preferably a hydrogen atom.

[0161] Z 3 It is a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, which may contain an oxygen atom and / or a nitrogen atom, and may contain a cyclic structure. 3 The preferred structure of can be listed as follows. It should be noted that in the following structure, the left bonding end and CHR 4 Bonding, the right side of the bond end and OR 5 Bonding.

[0162] -CH2-

[0163] -CH2OCH2CH2-

[0164] [Chemistry 23]

[0165]

[0166] R 5 It is a monovalent organic group having a (meth)acryloyl group which may contain an oxygen atom and / or a nitrogen atom. As a monovalent organic group, it is preferred to have at least one, preferably one or two (meth)acryloyl groups at the end. In addition, it may have an amide bond, an ether bond, an ester bond, etc. in the middle of the structure. As such a structure, for example, the following structure can be cited.

[0167] -C(=O)CH=CH2

[0168] -C(=O)C(CH3)=CH2

[0169] -C(=O)NHCH2CH2OC(=O)CH=CH2

[0170] -C(=O)NHCH2CH2OC(=O)C(CH3)=CH2

[0171] -C(=O)NHCH2CH2OCH2CH2OC(=O)C(CH3)=CH2

[0172] -C(=O)NHC(CH3)[CH2OC(=O)CH=CH2]2

[0173] -C(=O)NHC(CH3)[CH2CH2OC(=O)CH=CH2]2

[0174] Among these, particularly preferred structures are the following structures.

[0175] -C(=O)NHCH2CH2OC(=O)CH=CH2

[0176] -C(=O)NHCH2CH2OC(=O)C(CH3)=CH2

[0177] Z 4 The divalent hydrocarbon group has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and examples thereof include alkylene groups such as methylene, ethylene, propylene (trimethylene, methylethylene), butylene (tetramethylene, methylpropylene), and hexamethylene, and phenylene.

[0178] d is 0 or 1, preferably 0.

[0179] R 6 Each of R is independently a monovalent organic group having a diorganosilylene group such as a dimethylsilylene group and a (meth)acryloyl group. 6 , the groups shown below can be exemplified.

[0180] -Si(CH3)2CH2OC(=O)CH=CH2

[0181] -Si(CH3)2CH2OC(=O)C(CH3)=CH2

[0182] -Si(CH3)2CH2CH2OC(=O)CH=CH2

[0183] -Si(CH3)2CH2CH2OC(=O)C(CH3)=CH2

[0184] -Si(CH3)2CH2CH2CH2OC(=O)CH=CH2

[0185] -Si(CH3)2CH2CH2CH2OC(=O)C(CH3)=CH2

[0186] Among them, it is particularly preferred

[0187] -Si(CH3)2CH2OC(=O)CH=CH2

[0188] -Si(CH3)2CH2OC(=O)C(CH3)=CH2.

[0189] R 7 It is a monovalent hydrocarbon group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and specifically includes alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, and hexyl, cycloalkyl groups such as cyclohexyl, alkenyl groups such as vinyl, allyl, and propenyl, and phenyl. 7 , preferably methyl.

[0190] c is 0 or 1, preferably 0.

[0191] As X 1 Specifically, the following structures can be exemplified as preferred structures.

[0192] -CH2CH2CH2OC(=O)NHCH2CH2OC(=O)CH=CH2

[0193] -CH2CH2CH2OCH2CH2OC(=O)NHCH2CH2OC(=O)CH=CH2

[0194] -CH2CH2CH2OC(=O)NHCH2CH2OC(=O)C(CH3)=CH2

[0195] -CH2CH2CH2OCH2CH2OC(=O)NHCH2CH2OC(=O)C(CH3)=CH2

[0196] -CH2CH2CH2OC(=O)NHC(CH3)[CH2OC(=O)CH=CH2]2

[0197] -CH2CH2CH2OCH2CH2OC(=O)NHC(CH3)[CH2OC(=O)CH=CH2]2

[0198] -CH2CH2CH2OC(=O)CH=CH2

[0199] -CH2CH2CH2OCH2CH2OC(=O)CH=CH2

[0200] -CH2CH2CH2OC(=O)C(CH3)=CH2

[0201] -CH2CH2CH2OCH2CH2OC(=O)C(CH3)=CH2

[0202] -CH2CH2Si[OSi(CH3)2CH2OC(=O)CH=CH2]3

[0203] -CH2CH2Si[OSi(CH3)2CH2OC(=O)C(CH3)=CH2]3

[0204] [Chemistry 24]

[0205]

[0206] Particularly preferred

[0207] -CH2CH2CH2OCH2CH2OC(=O)NHCH2CH2OC(=O)CH=CH2

[0208] -CH2CH2CH2OCH2CH2OC(=O)NHC(CH3)[CH2OC(=O)CH=CH2]2

[0209] -CH2CH2Si[OSi(CH3)2CH2OC(=O)CH=CH2]3

[0210] [Chemistry 25]

[0211]

[0212] More specifically, as such a component (A), compounds represented by the following structural groups can be cited.

[0213] [Chemistry 26]

[0214]

[0215] [Chemistry 27]

[0216]

[0217] [Chemistry 28]

[0218]

[0219] [Chemistry 29]

[0220]

[0221] [Chemistry 30]

[0222]

[0223] [Chemistry 31]

[0224]

[0225] [Chemistry 32]

[0226]

[0227] [Chemistry 33]

[0228]

[0229] [Chemistry 34]

[0230]

[0231] [Chemistry 35]

[0232]

[0233] (Where Rf A Same as above, preferably CF3O-(CF2O) m (CF2CF2O) n -CF2-, m, n and m+n are as described above.)

[0234] As the above-mentioned component (A), it is represented by the following general formula (1):

[0235] R A -Z 1 -Q 1 [X 1 ] a (1)

[0236] (Where Rf A , Z 1 , Q 1 , X 1 , a is the same as above. )

[0237] A preferred method for synthesizing the fluorine-containing acrylic compound represented by, for example, is to make a fluorine-containing acrylic compound represented by the following general formula (5):

[0238] R A -Z 1 -Q 1 [H] a (5)

[0239] (Where Rf A , Z 1 , Q 1 , a is the same as above, all the a Hs enclosed in [] are the same as Q 1The silicon atoms in the structure are bonded.)

[0240] The fluorine-containing compound having a Si-H group at the terminal represented by the following general formula (6):

[0241] CH2=CR 4 -Z 3 -OH (6)

[0242] (Where R 4 , Z 3 Same as above.)

[0243] The terminal unsaturated group-containing alcohol represented by is subjected to a hydrosilylation reaction to obtain a fluorine-containing alcohol compound as an intermediate.

[0244] Examples of the fluorine-containing compound represented by the above formula (5) and having a number of Si—H groups at the terminal include the following compounds.

[0245] [Chemistry 36]

[0246]

[0247] (Where Rf A Same as above.)

[0248] Examples of the terminal unsaturated group-containing alcohol represented by the above formula (6) include the following alcohols.

[0249] CH2=CH-CH2-OH

[0250] CH2=CH-CH2OCH2CH2-OH

[0251] [Chemistry 37]

[0252]

[0253] In the hydrosilylation (addition) reaction, it is preferred to mix the fluorine-containing compound having a Si-H group at the terminal represented by formula (5) and the alcohol containing a terminal unsaturated group represented by formula (6), and react them 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 stop without the reaction proceeding sufficiently, while if it is too high, the reaction may no longer be controlled due to the temperature rise caused by the reaction heat of the hydrosilylation, and sudden boiling or decomposition of the raw materials may occur.

[0254] In this case, in terms of the reaction ratio of the fluorine-containing compound having a Si-H groups at the terminal represented by formula (5) and the alcohol having a terminal unsaturated group represented by formula (6), it is preferred to use 0.5 to 5 times, particularly 0.9 to 2 times, the moles of the terminal unsaturated group of the alcohol having a terminal unsaturated group represented by formula (6) relative to the total moles of H enclosed in brackets [] of the fluorine-containing compound having a Si-H groups at the terminal represented by formula (5). If the alcohol having a terminal unsaturated group represented by formula (6) is too small compared to the total moles, 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 (6) is removed after the reaction, the amount of unreacted alcohol remaining increases, and accordingly, the conditions of heating, decompression, extraction, etc. must be strictly controlled.

[0255] The addition reaction catalyst can use a compound containing a platinum group metal such as platinum, rhodium or palladium. 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.

[0256] 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 fluorine-containing compound having a Si-H groups at the terminal represented by formula (5).

[0257] Even if solvent does not exist in the above-mentioned addition reaction, it can be implemented, and as required, can be diluted with solvent. The diluting solvent at this moment can utilize the generally widely used organic solvents such as toluene, dimethylbenzene, isooctane, and the preferred boiling point is the target reaction temperature or more and does not hinder the reaction, 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 particularly preferably hexafluoro-meta-xylene.

[0258] 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 fluorine-containing compound having a Si-H group at the end represented by formula (5). If it is less than this, the dilution effect of the solvent becomes weak, and if it is more, the dilution degree is excessively increased, sometimes resulting in a decrease in the reaction rate.

[0259] After the reaction is completed, the unreacted terminal unsaturated group-containing alcohol represented by formula (6) and the diluent solvent are preferably removed by a known method such as vacuum distillation, extraction, adsorption, etc., but the reaction mixture containing them can be used in the next reaction.

[0260] By subjecting the fluorine-containing compound represented by the general formula (5) having a Si-H groups at the terminal to a hydrosilylation reaction with the alcohol having a terminal unsaturated group represented by the general formula (6), a fluorine-containing alcohol compound represented by the following general formula (7) can be obtained.

[0261] R A -Z 1 -Q 1 [CH2-CHR 4 -Z 3 -OH] a (7)

[0262] (Where Rf A , Z 1 , Q 1 , R 4 , Z 3 , a is the same as above. In addition, all a CH2 enclosed in brackets [] are connected to Q 1 The silicon atoms in the structure are bonded.)

[0263] Examples of the fluorine-containing alcohol compound represented by the formula (7) include the following compounds.

[0264] [Chemistry 38]

[0265]

[0266] [Chemistry 39]

[0267]

[0268] [Chemistry 40]

[0269]

[0270] (Where Rf A Same as above.)

[0271] Next, by introducing a (meth)acryloyl group into the fluorine-containing alcohol compound represented by the formula (7) obtained above, the target fluorine-containing acrylic compound can be obtained.

[0272] As a method for introducing a (meth)acryloyl group into such a fluorinated alcohol compound represented by formula (7), one method can be listed as a method of reacting with a (meth)acryloyl halide represented by the following formula (8) to form an ester, and another method can be listed as a method of reacting with an isocyanate compound containing a (meth)acryloyl group represented by the following formula (9a) or (9b). By using these methods, the fluorinated acrylic compound represented by the above formula (1) can be obtained.

[0273] XC(=O)CR 3 =CH2 (8)

[0274] O=C=N-CH2CH2OC(=O)CR 3 =CH2 (9a)

[0275] O=C=NC(CH3)[CH2OC(=O)CR 3 =CH2]2 (9b)

[0276] (where X is a halogen atom, R 3 is a hydrogen atom or a methyl group.)

[0277] Among them, examples of the (meth)acrylic acid halide represented by the formula (8) include the following compounds.

[0278] XC(=O)CH=CH2

[0279] XC(=O)C(CH3)=CH2

[0280] (Wherein, X is the same as above.)

[0281] Acryloyl chloride and methacryloyl chloride are particularly preferred.

[0282] Examples of the (meth)acryloyl group-containing isocyanate compound represented by the formula (9a) or (9b) include the following compounds.

[0283] O=C=N-CH2CH2OC(=O)CH=CH2

[0284] O=C=N-CH2CH2OC(=O)C(CH3)=CH2

[0285] O=C=NC(CH3)[CH2OC(=O)CH=CH2]2

[0286] With regard to these (meth) acryloyl halides or isocyanate compounds containing (meth) acryloyl, relative to the total amount of hydroxyl groups of fluorinated alcohol compounds, equimolar or more feeds can be reacted to react, so that all hydroxyl groups react, relative to 1 mole of fluorinated alcohol compounds, an average of more than 1 mole of (meth) acryloyl groups can be introduced, by making the hydroxyl group excessive, so that unreacted (meth) acryloyl halides or isocyanate compounds containing (meth) acryloyl groups do not remain. Specifically, when the amount of fluorinated alcohol compounds in the reaction system is set to x moles, and the total amount of hydroxyl groups of fluorinated alcohol compounds is set to y moles, preferably (meth) acryloyl halides or isocyanate compounds containing (meth) acryloyl groups are more than x moles and less than 2y moles, and particularly preferably more than 0.6y moles and less than 1.4y moles. In the case of too little, the possibility of the fluorinated alcohol compounds that are not completely introduced into (meth) acryloyl groups remaining increases, and the solubility of the product is likely to decrease. In the case of too much, it becomes difficult to remove the remaining unreacted (meth) acryloyl halides or isocyanate compounds containing (meth) acryloyl groups.

[0287] 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 containing (methyl) acryloyl, then can use without particular restriction, specifically, can list the ketone solvents such as hexafluoro-m-xylene (another name: hexafluoro-m-xylene), fluorine-modified aromatic hydrocarbon solvents such as benzyl trifluoro, fluorine-modified ether solvents such as methyl perfluorobutyl ether etc. such as hydrocarbon solvents such as toluene, xylene, isooctane, tetrahydrofuran (THF), diisopropyl ether, dibutyl ether, acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclohexanone.This solvent can adopt known methods such as decompression distillation to remove after reaction, according to the purposes of target, also can directly be used as dilute solution and use.

[0288] 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.

[0289] In addition, during the reaction, a polymerization inhibitor may be added as needed. There is no particular limitation on the polymerization inhibitor, 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. The amount of the polymerization inhibitor used can be determined by the reaction conditions, the refining conditions after the reaction, and the final use conditions, and is not particularly limited. Generally, it is 0.01 to 5000 ppm relative to the total mass of the reaction components, and is particularly preferably 0.1 to 500 ppm.

[0290] 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 molar number of the feed (meth)acryloyl halide. If it is too little, a large amount of acid that is not captured will remain, and if it is too much, it becomes difficult to remove the remaining acid acceptor.

[0291] The (meth)acrylic acid halide is added dropwise, the temperature of the reaction mixture is maintained at 0 to 35° C., and the mixture is stirred for 20 to 60 minutes. The mixture is stirred for 30 minutes to 10 hours. After the reaction is completed, the unreacted (meth)acrylic acid halide, the salt produced by the reaction, the reaction solvent, etc. are removed by distillation, adsorption, filtration, washing, etc., thereby obtaining the fluorine-containing acrylic compound represented by the above formula (1).

[0292] In addition, when the reaction is stopped, an alcohol compound such as methanol or ethanol may be added to the system to esterify the unreacted (meth)acrylic acid halide. The generated (meth)acrylic acid esters may be removed by the same method as the unreacted (meth)acrylic acid halide, or may be used in a residual state.

[0293] 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.

[0294] 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 [another name: orthotitanic acid tetra(2-ethylhexyl) ester], 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-butoxy bis(ethyl acetoacetate) zirconium, tetraacetylacetonate zirconium, zirconium chelate compounds, etc. can be illustrated. These are not limited to one kind, and can be used as a mixture of two kinds or more, and particularly from the aspect of reactivity, the use of titanium compounds and tin compounds is preferred. 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.

[0295] 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.

[0296] 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).

[0297] When the reaction is stopped, an alcohol compound such as methanol or ethanol may be added to the system to form a urethane bond with the unreacted isocyanate compound. The generated urethane (meth)acrylate may be removed in the same manner as the unreacted isocyanate compound, or may be used in a residual state.

[0298] Another preferred method for synthesizing the fluorine-containing acrylic compound represented by the general formula (1) is to react a fluorine-containing compound represented by the general formula (5) having a Si-H group at the terminal with a fluorine-containing compound represented by the general formula (10)

[0299] CH2=CR 4 -(Z 4 ) d -SiR 7 c M 3-c (10)

[0300] (Where R 4 , Z 4 , R 7 , d, c are as described above. M is each independently alkoxy or alkoxyalkoxy.)

[0301] The reactive silane compound having a terminal unsaturated group represented by the formula (A) is subjected to a hydrosilylation reaction to obtain a fluorine-containing reactive silane compound as an intermediate.

[0302] In the above formula (10), M is an alkoxy group or an alkoxyalkoxy group, and specific examples thereof include alkoxy groups having 1 to 9 carbon atoms such as methoxy, ethoxy, and propoxy groups, and alkoxyalkoxy groups having 2 to 10 carbon atoms such as methoxymethoxy, methoxyethoxy, ethoxymethoxy, and ethoxyethoxy groups.

[0303] Examples of the reactive silane compound having a terminal unsaturated group represented by the above formula (10) include the following compounds.

[0304] CH2=CHSi(OCH3)3

[0305] CH2=CHCH2Si(OCH3)3

[0306] CH2=CHCH2CH2Si(OCH3)3

[0307] CH2=CHCH2CH2CH2Si(OCH3)3

[0308] CH2=CHCH2CH2CH2CH2Si(OCH3)3

[0309] CH2=CHSi(OC2H5)3

[0310] CH2=CHCH2Si(OC2H5)3

[0311] CH2=CHCH2CH2Si(OC2H5)3

[0312] CH2=CHCH2CH2CH2Si(OC2H5)3

[0313] CH2=CHCH2CH2CH2CH2Si(OC2H5)3

[0314] CH2=CHSi(OC3H7)3

[0315] CH2=CHCH2Si(OC3H7)3

[0316] CH2=CHCH2CH2Si(OC3H7)3

[0317] CH2=CHCH2CH2CH2CH2Si(OC3H7)3

[0318] CH2=CHSiCH3(OCH3)2

[0319] CH2=CHCH2SiCH3(OCH3)2

[0320] CH2=CHCH2CH2CH2CH2SiCH3(OCH3)2

[0321] CH2=CHSiCH3(OC2H5)2

[0322] CH2=CHCH2SiCH3(OC2H5)2

[0323] CH2=CHCH2CH2SiCH3(OC2H5)2

[0324] CH2=CHCH2CH2CH2CH2SiCH3(OC2H5)2

[0325] Among them, the following compounds are particularly preferred.

[0326] CH2=CHSi(OCH3)3

[0327] CH2=CHCH2Si(OCH3)3

[0328] CH2=CHCH2CH2Si(OCH3)3

[0329] CH2=CHCH2CH2CH2Si(OCH3)3

[0330] CH2=CHCH2CH2CH2CH2Si(OCH3)3

[0331] CH2=CHSi(OC2H5)3

[0332] CH2=CHCH2Si(OC2H5)3

[0333] The fluorine-containing compound having a Si-H group at the terminal represented by the above formula (5) and the reactive silane compound containing a terminal unsaturated group represented by the formula (10) are preferably mixed and stirred, 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 72 hours, particularly 5 minutes to 12 hours. If the reaction temperature is too low, the reaction may stop without fully proceeding, while if it is too high, the reaction may no longer be controlled due to the temperature rise caused by the reaction heat of hydrosilylation, and sudden boiling or decomposition of the raw materials may occur.

[0334] In this case, with respect to the feed ratio of the fluorine-containing compound having a Si-H groups at the terminal represented by formula (5) and the reactive silane compound having a terminal unsaturated group represented by formula (10), it is preferred to use 0.1 to 5 times, particularly 0.8 to 2 times, the moles of the unsaturated groups of the reactive silane compound having a terminal unsaturated group represented by formula (10) for the reaction relative to the total moles of H enclosed by [] of the fluorine-containing compound having a Si-H groups at the terminal represented by formula (5). If the amount of the reactive silane compound having a terminal unsaturated group represented by formula (10) is too small compared to the amount of the reactive silane compound having a terminal unsaturated group represented by formula (10), a large amount of Si-H groups remain in the fluoropolyether compound having a multifunctional Si-H group represented by formula (5), and the target effect may not be obtained. If it is too much, the uniformity of the reaction solution decreases and the reaction rate becomes unstable. In addition, when the reactive silane compound containing a terminal unsaturated group represented by formula (10) is removed after the reaction, the remaining unreacted components increase, and accordingly, the conditions of heating, decompression, extraction, etc. must be strictly controlled.

[0335] The addition reaction catalyst can use a compound containing a platinum group metal such as platinum, rhodium or palladium. 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, complexes of chloroplatinic acid and olefins, aldehydes, vinylsiloxanes or acetylenic alcohols, or platinum supported on activated carbon can be used.

[0336] The amount of the addition reaction catalyst to be added is preferably 0.1 to 5000 ppm by mass, more preferably 0.2 to 1000 ppm by mass, of the metal contained in the fluoropolyether compound having a polyfunctional Si-H group represented by the formula (10).

[0337] Even if the solvent does not exist, the above-mentioned addition reaction can be implemented, and as needed, it can be diluted with a solvent. The diluting solvent at this time can utilize generally widely used organic solvents such as toluene, xylene, isooctane, etc. As such an organic solvent, it is preferred that the boiling point is above the target reaction temperature and does not hinder the reaction, and that the fluorine-containing reactive silane compound generated after the reaction is soluble at the above-mentioned reaction temperature. For example, preferably hexafluoro-meta-xylene, fluorine-modified aromatic hydrocarbon solvents such as benzyl trifluoro, fluorine-modified ether solvents such as methyl perfluorobutyl ether, and the like are partially fluorine-modified solvents, and hexafluoro-meta-xylene is particularly preferred.

[0338] 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 fluorine-containing compound having a Si-H group at the terminal represented by formula (5). If it 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.

[0339] After the reaction is completed, the unreacted reactive silane compound having a terminal unsaturated group represented by formula (10) and the diluent solvent are preferably removed by a known method such as vacuum distillation, extraction, adsorption, etc., but the reaction mixture containing them can also be used in the next reaction.

[0340] By reacting the fluorine-containing compound having a Si-H groups at the terminal represented by the general formula (5) with the reactive silane compound having a terminal unsaturated group represented by the general formula (10), a fluorine-containing reactive silane compound represented by the following general formula (11) can be obtained.

[0341] R A -Z 1 -Q 1 [CH2CHR 4 -(Z 4 ) d -SiR7 c M 3-c ] a (11)

[0342] (Where Rf A , Z 1 , Q 1 , R 4 , Z 4 ,d,R 7 , c, M, and a are the same as above. )

[0343] Examples of the fluorine-containing reactive silane compound represented by the formula (11) include the following compounds.

[0344] [Chemistry 41]

[0345]

[0346] [Chemistry 42]

[0347]

[0348] (Where Rf A Same as above.)

[0349] Next, the fluorine-containing reactive silane compound represented by the formula (11) obtained above is reacted with a silanol compound containing a diorganosilylene group and a (meth)acryloyl group, thereby obtaining the target fluorine-containing acrylic compound.

[0350] Specific examples of the silanol compound containing a diorganosilylene group and a (meth)acryloyl group include the following compounds.

[0351] HOSi(CH3)2CH2OC(=O)CH=CH2

[0352] HOSi(CH3)2CH2OC(=O)C(CH3)=CH2

[0353] HOSi(CH3)2CH2CH2OC(=O)CH=CH2

[0354] HOSi(CH3)2CH2CH2OC(=O)C(CH3)=CH2

[0355] HOSi(CH3)2CH2CH2CH2OC(=O)CH=CH2

[0356] HOSi(CH3)2CH2CH2CH2OC(=O)C(CH3)=CH2

[0357] Among them, it is particularly preferred

[0358] HOSi(CH3)2CH2OC(=O)CH=CH2

[0359] HOSi(CH3)2CH2OC(=O)C(CH3)=CH2.

[0360] The reaction of the fluorine-containing reactive silane compound represented by formula (11) with the above-mentioned silanol compound containing a diorganosilylene group and a (meth)acryloyl group can be carried out by stirring them together with a catalyst and a solvent as needed. The reaction can be carried out at a temperature of 0 to 120° C., preferably 10 to 70° C., for 1 minute to 300 hours, preferably 30 minutes to 72 hours. If the reaction temperature is too low, the reaction rate may be excessively slowed down. If the reaction temperature is too high, polymerization of the (meth)acryloyl group as a side reaction and dehydration condensation between the silanol compound containing a diorganosilylene group and a (meth)acryloyl group may occur.

[0361] In the reaction of the fluorine-containing reactive silane compound represented by the formula (11) and the silanol compound containing a diorganosilylene group and a (meth)acryloyl group, the amount of the silanol compound containing a diorganosilylene group and a (meth)acryloyl group can be 0.9 to 2 times the total molar amount of M contained in the fluorine-containing reactive silane compound represented by the formula (11) present in the reaction system, preferably 0.95 to 1.1 times the total molar amount of M. Alternatively, the following method can be adopted: the silanol compound containing a diorganosilylene group and a (meth)acryloyl group is used in an excess amount relative to the total molar amount of M in the fluorine-containing reactive silane compound represented by the formula (11), the reaction is stopped at an appropriate reaction rate in the middle of the reaction, and the remaining silanol compound is removed.

[0362] In this reaction, in order to increase the speed of the reaction, a suitable catalyst may be added. For example, when M in the fluorine-containing reactive silane compound represented by formula (11) is an alkoxy group, as the catalyst, alkyl tin ester compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin dioctoate, dioctyl stannous dioctoate, tetraisopropoxytitanium, tetra-n-butoxytitanium, tetra-2-ethylhexyl titanium, dipropoxybis(acetylacetonate)titanium, isopropoxyoctanediol titanium and other titanates or titanium chelate compounds, tetraacetylacetonate zirconium, tributoxymonoacetylacetonate zirconium, monobutoxyacetylacetonate bis(ethyl acetoacetate) zirconium, dibutoxybis(ethyl acetoacetate) zirconium, tetraacetylacetonate zirconium, zirconium chelate compounds, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide and the like may be exemplified. These are not limited to one kind, and can be used as a mixture of two or more kinds. In particular, the use of titanium compounds, zirconium compounds, and alkaline earth hydroxides, which have a low impact on the environment, is preferred.

[0363] The reaction rate can be increased by adding 0.01 to 10% by mass, preferably 0.01 to 5% by mass of these catalysts based on the total mass of the reactants.

[0364] The above-mentioned reaction can be carried out with appropriate solvent dilution as required. As such solvent, as long as it is a solvent that does not directly react with each reactive group in the reaction system, it can be used without particular restriction, specifically, ketone solvents such as hydrocarbon solvents such as toluene, xylene, isooctane, ether solvents such as tetrahydrofuran, diisopropyl ether, 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. can be listed. The solvent can be removed by known methods such as vacuum distillation after the reaction, and according to the purposes of the target, it can also be directly used as a dilute solution.

[0365] When a solvent is used, the amount used is preferably 0.1 to 1000 parts by mass, more preferably 20 to 500 parts by mass, relative to 100 parts by mass of the total of the fluorine-containing reactive silane compound represented by formula (11) and the silanol compound containing a diorganosilylene group and a (meth)acryloyl group. If the amount is more than this, the concentration of the reaction system is excessively reduced, and the reaction rate is sometimes greatly reduced.

[0366] In addition, during the reaction, a polymerization inhibitor may be added as needed. There is no particular limitation on the polymerization inhibitor, and polymerization inhibitors commonly used as polymerization inhibitors for acrylic compounds can be used. Specifically, hydroquinone, hydroquinone monomethyl ether, 4-tert-butylcatechol, dibutylhydroxytoluene, etc. can be cited. The amount of the polymerization inhibitor used can be determined by the reaction conditions, the refining conditions after the reaction, and the final use conditions, and is not particularly limited. Generally, it is 0.01 to 5000 ppm relative to the total mass of the reaction components, and is particularly preferably 0.1 to 500 ppm.

[0367] After the reaction is completed, unreacted diorganosilylene group-containing silanol compound and (meth)acryloyl group-containing silanol compound and reaction solvent are removed by distillation, adsorption, reprecipitation, filtration, washing or the like as necessary to obtain the fluorine-containing acrylic compound represented by the above formula (1).

[0368] [Ingredient (B)]

[0369] The component (B) as the second essential component in the fluorinated curable composition of the present invention is composed of a compound which is a linear polymer having a fluoropolyether in the main chain, has 2 or more, preferably 2 to 5, more preferably 2 to 4 (meth)acryloyl groups at each end in one molecule (i.e., at each of the two ends of the molecular chain), and has an average of 4 to 10, preferably 4 to 8 (meth)acryloyl groups in one molecule.

[0370] As such a compound, specifically, a fluorine-containing acrylic compound represented by the following general formula (2) can be shown.

[0371] [Chemistry 43]

[0372]

[0373] In the above formula (2), Rf B It is a divalent perfluoropolyether group, which can be -CF2O-Rf 2 -CF2- indicates.

[0374] Among them, Rf 2 Rf of the above formula (1) A Rf 2 Similarly, the above Rf can be exemplified 2 Same group.

[0375] In the above formula (2), Z 1 Independently of Z in the above formula (1) 1 Similarly, the above Z can be exemplified 1 The same groups, among which the following groups are particularly preferred. In the following structure, the left bonding end and Rf B Bonding, the right side of the bond end and Q 1 Bonding.

[0376] -CH2CH2-

[0377] -CH2CH2CH2-

[0378] -CH2CH2CH2CH2-

[0379] -CH2OCH2CH2-

[0380] -CH2OCH2CH2CH2-

[0381] In the above formula (2), Q 1 Independently with Q of the above formula (1) 1 Similarly, the above Q 1 The same groups, among which the following groups are particularly preferred. However, in the following structure, the bonding end of each unit (a1+1) is connected to Z 1Bonded to any one of the a CH2 groups enclosed by [].

[0382] [Chemistry 44]

[0383]

[0384] (In the formula, a1 is 2 or 3.)

[0385] In the above formula (2), 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.

[0386] In the above formula (2), R 2 A monovalent organic group having a (meth)acryloyl group which is independently a hydrogen atom or may contain an oxygen atom and / or a nitrogen atom. As the monovalent organic group, a group having at least one, preferably one or two (meth)acryloyl groups at the terminal is preferred. In addition, an amide bond, an ether bond, an ester bond, etc. may be present in the middle of the structure.

[0387] As such a structure, for example, the following structures can be cited.

[0388] -C(=O)CH=CH2

[0389] -C(=O)C(CH3)=CH2

[0390] -C(=O)NHCH2CH2OC(=O)CH=CH2

[0391] -C(=O)NHCH2CH2OC(=O)C(CH3)=CH2

[0392] -C(=O)NHCH2CH2OCH2CH2OC(=O)C(CH3)=CH2

[0393] -C(=O)NHC(CH3)(CH2CH2OC(=O)CH=CH2)2

[0394] Among these, the following groups are particularly preferred.

[0395] -C(=O)NHCH2CH2OC(=O)CH=CH2

[0396] -C(=O)NHCH2CH2OC(=O)C(CH3)=CH2

[0397] In the above formula (2), 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.

[0398] In the above formula (2), Z 2 Each independently is 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.

[0399] As Z 2 The preferred structure can include the following structures.

[0400] -CH2[OC2H4] d [OC3H6] e [OC4H8] f OC c H 2c -

[0401] (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 may be 3 to 100 carbon atoms, preferably 3 to 30 carbon atoms. The arrangement of the repeating units is random regardless of the type. In addition, each repeating unit may not be a single structure, but may be a mixture of structural isomers.)

[0402] [Chemistry 45]

[0403]

[0404] As Z 2 As particularly preferred structures, the following two 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. In the following structure, the left bonding end is bonded to CHR 1 Bonding, the right side of the bond end and OR 2 Bonding.

[0405] -CH2[OC2H4] d OC2H4-

[0406] -CH2[OC3H6] e OCH2CH(CH3)-

[0407] As the fluorine-containing acrylic compound represented by the above formula (2), structures represented by the following general formulae (3) and (4) can be exemplified as more preferable structures.

[0408] [Chemistry 46]

[0409]

[0410] [Chemistry 47]

[0411]

[0412] (Where Z 1 , Q 1 , a as shown above, Rf B ' 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, and d1 and e1 are integers of 0 to 10.)

[0413] Specific examples of the component (B) include the following compounds.

[0414] [Chemistry 48]

[0415]

[0416] [Chemistry 49]

[0417]

[0418] [Chemistry 50]

[0419]

[0420] [Chemistry 51]

[0421]

[0422] [Chemistry 52]

[0423]

[0424] (Where Rf B 'Same as above, e2 is an integer from 1 to 10, for example, 4. )

[0425] The fluorine-containing acrylic compound represented by the formula (2) as the component (B) can be synthesized by the method described in, for example, JP-A-2010-285501 and JP-A-2015-199910.

[0426] For example, the fluorine-containing acrylic compound represented by the above formula (2) is first prepared by making the following general formula (12):

[0427] [Chemistry 53]

[0428]

[0429] (Where Rf B , Z 1 , 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.)

[0430] The fluoropolyether compound having a multifunctional Si-H group represented by the following general formula (13):

[0431] CH2=CR 1 -Z 2 -OH (13)

[0432] (Where R 1 , Z 2 Same as above.)

[0433] By subjecting an alcohol having a terminal unsaturated group represented by the formula (a compound having an alkenyl group and a hydroxyl group at a molecular terminal) to a hydrosilylation reaction, a fluorine-containing alcohol compound can be obtained as an intermediate.

[0434] Among them, examples of the fluoropolyether compound having a polyfunctional Si—H group represented by the above formula (12) include the following compounds.

[0435] [Chemistry 54]

[0436]

[0437] (Where Rf B 'Same as above. )

[0438] Examples of the terminal unsaturated group-containing alcohol represented by the above formula (13) include the following alcohols.

[0439] CH2=CH-CH2-OCH2CH2-OH

[0440] CH2=CH-CH2-OCH2CH(CH3)-OH

[0441] CH2=CH-CH2-(OC3H6)2-OCH2CH(CH3)-OH

[0442] CH2=CH-CH2-(OC3H6)4-OCH2CH(CH3)-OH

[0443] CH2=CH-CH2-(OC3H6)9-OCH2CH(CH3)-OH

[0444] [Chemistry 55]

[0445]

[0446] In the hydrosilylation (addition) reaction, it is preferred that the fluoropolyether compound having a multifunctional Si-H group represented by formula (12) and the alcohol having a terminal unsaturated group represented by formula (13) 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 reaction may no longer be controlled due to the temperature rise caused by the reaction heat of the hydrosilylation, and sudden boiling or decomposition of the raw materials may occur.

[0447] In this case, the reaction ratio of the fluoropolyether compound having a multifunctional Si-H group represented by formula (12) and the alcohol having a terminal unsaturated group represented by formula (13) 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 (13) 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 (13) is removed after the reaction, the amount of unreacted alcohol remaining increases, and accordingly, the conditions of heating, pressure reduction, extraction, etc. must be strictly controlled.

[0448] The addition reaction catalyst can use a compound containing a platinum group metal such as platinum, rhodium or palladium. 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.

[0449] The amount of the addition reaction catalyst to be added is preferably an amount such that the amount of metal contained is 0.1 to 5000 ppm by mass, more preferably 0.2 to 1000 ppm by mass, based on the fluoropolyether compound having a polyfunctional Si-H group represented by formula (12).

[0450] Even if solvent does not exist in the above-mentioned addition reaction, it can be implemented, and as required, can be diluted with solvent. The diluting solvent at this moment can utilize the generally widely used organic solvents such as toluene, dimethylbenzene, isooctane, preferably the organic solvent that the fluorine-containing alcohol compound generated after boiling point is above the target reaction temperature and does not hinder reaction, reaction, is soluble under the above-mentioned reaction temperature. As such solvent, for example, the solvent of part fluorine modification such as fluorine modification ether solvents such as fluorine modification aromatic hydrocarbon solvents such as preferred hexafluoro-meta-xylene, benzyltrifluoro, methyl perfluorobutyl ether, particularly preferred hexafluoro-meta-xylene.

[0451] 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 (12). 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.

[0452] After the reaction is completed, the unreacted terminal unsaturated group-containing alcohol represented by formula (13) and the diluent solvent are preferably removed by a known method such as vacuum distillation, extraction, adsorption, etc., but the reaction mixture containing them can be used in the next reaction.

[0453] By subjecting the fluoropolyether compound having a multifunctional Si-H group represented by the general formula (12) and the alcohol having a terminal unsaturated group represented by the general formula (13) to a hydrosilylation reaction, a fluorine-containing alcohol compound represented by the following general formula (14) can be obtained.

[0454] [Chemistry 56]

[0455]

[0456] (Where Rf B , Q 1 , R 1 , Z 1 , Z 2 , a is the same as above. In addition, all a CH2 enclosed in brackets [] are connected to Q 1 The silicon atoms in the structure are bonded.)

[0457] Examples of the fluorine-containing alcohol compound represented by the formula (14) thus obtained include the following fluorine-containing alcohol compounds.

[0458] [Chemistry 57]

[0459]

[0460] [Chemistry 58]

[0461]

[0462] [Chemistry 59]

[0463]

[0464] (Where Rf B ', e are the same as above.)

[0465] Next, by introducing a (meth)acryloyl group into the fluorine-containing alcohol compound represented by the formula (14) obtained above, the target fluorine-containing acrylic compound can be obtained.

[0466] As a method for introducing a (meth)acryloyl group into such a fluorinated alcohol compound represented by formula (14), one method can be listed as a method of reacting with a (meth)acryloyl halide represented by the following formula (15) to form an ester, and another method can be listed as a method of reacting with an isocyanate compound containing a (meth)acryloyl group represented by the following formula (16). By using these methods, the fluorinated acrylic compound represented by the above formula (2) can be obtained.

[0467] XC(=O)CR 3 =CH2 (15)

[0468] O=C=N-CH2CH2OC(=O)CR 3 =CH2 (16)

[0469] (Where R 3 , X is the same as above. )

[0470] Among them, examples of the (meth)acrylic acid halide represented by the formula (15) include the following compounds.

[0471] XC(=O)CH=CH2

[0472] XC(=O)C(CH3)=CH2

[0473] (Wherein, X is the same as above.)

[0474] Acryloyl chloride and methacryloyl chloride are particularly preferred.

[0475] Examples of the (meth)acryloyl group-containing isocyanate compound represented by the formula (16) include the following compounds.

[0476] O=C=N-CH2CH2OC(=O)CH=CH2

[0477] O=C=N-CH2CH2OC(=O)C(CH3)=CH2

[0478] With regard to these (meth) acryloyl halides or isocyanate compounds containing (meth) acryloyl, relative to the total amount of hydroxyl groups of fluorinated alcohol compounds, it is possible to feed and react at equimolar or above, so that all hydroxyl groups react, relative to 1 mole of fluorinated alcohol compounds, an average of more than 1 mole of (meth) acryloyl groups can be introduced, by making the hydroxyl group excessive, so that unreacted (meth) acryloyl halides or isocyanate compounds containing (meth) acryloyl groups do not remain. Specifically, when the amount of fluorinated alcohol compounds in the reaction system is set to x moles, and the total amount of hydroxyl groups of fluorinated alcohol compounds is set to y moles, it is preferred that (meth) acryloyl halides or isocyanate compounds containing (meth) acryloyl groups are more than x moles and less than 2y moles, and particularly preferably more than 0.6y moles and less than 1.4y moles. In the case of too little, the possibility of the fluorinated alcohol compounds that are not completely introduced into (meth) acryloyl groups remaining increases, and the solubility of the product is likely to decrease. In the case of too much, it becomes difficult to remove the remaining unreacted (meth) acryloyl halides or isocyanate compounds containing (meth) acryloyl groups.

[0479] 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 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, 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, also can directly be used as diluted solution and use.

[0480] 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.

[0481] 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.

[0482] 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.

[0483] 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 molar number of the feed (meth)acryloyl halide. If it is too little, a large amount of acid that is not captured will remain, and if it is too much, it becomes difficult to remove the remaining acid acceptor.

[0484] The (meth)acrylic acid halide is dripped in a reaction mixture at a temperature of 0 to 35° C. for 20 to 60 minutes. The mixture is stirred for 30 minutes to 10 hours. After the reaction is completed, the unreacted (meth)acrylic acid halide, the salt produced by the reaction, the reaction solvent, etc. are removed by distillation, adsorption, filtration, washing, etc., thereby obtaining the fluorine-containing acrylic compound represented by the above formula (2).

[0485] In addition, when the reaction is stopped, an alcohol compound such as methanol or ethanol may be added to the system to esterify the unreacted (meth)acrylic acid halide. The generated (meth)acrylic acid esters may be removed by the same method as the unreacted (meth)acrylic acid halide, or may be used in a residual state.

[0486] 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.

[0487] 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 [another name: orthotitanic acid tetra(2-ethylhexyl) ester], dipropoxybis(acetylacetonate) 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-butoxy bis(ethyl acetoacetate) zirconium, tetraacetylacetonate zirconium, zirconium chelate compounds, etc. can be exemplified. These are not limited to one kind, and can be used as a mixture of two kinds or more, and the use of titanium compounds and tin compounds with low environmental impact is particularly preferred. 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.

[0488] 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.

[0489] 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 (2).

[0490] When the reaction is stopped, an alcohol compound such as methanol or ethanol may be added to the system to form a urethane bond with the unreacted isocyanate compound. The generated urethane (meth)acrylate may be removed in the same manner as the unreacted isocyanate compound, or may be used in a residual state.

[0491] [Ingredient (C)]

[0492] The third essential component, 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 (meth)acrylates having a urethane bond in the molecule and compounds in which two or more (meth)acryloyl groups are introduced by any method into the side chains or terminals of various polymers.

[0493] Such a non-fluorinated acrylic compound (C) may be any compound having 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, di- 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; ethylene oxide, propylene oxide, epichlorohydrin, fatty acid, and alkyl-modified products of these (meth)acrylic compounds; epoxy (meth)acrylates obtained by adding (meth)acrylic acid to an epoxy resin; and copolymers in which a (meth)acryloyl group is introduced into the side chain of a (meth)acrylate copolymer.

[0494] In addition, urethane (meth)acrylates, products obtained by reacting a polyisocyanate with a (meth)acrylate having a hydroxyl group, products obtained by reacting a polyester of a polyisocyanate and a terminal diol with a (meth)acrylate having a hydroxyl group, products obtained by reacting a polyisocyanate obtained by reacting a polyol with an excess of a diisocyanate with a (meth)acrylate having a hydroxyl group, and the like can also be used. Among them, preferably, there can be mentioned urethane (meth)acrylates obtained by reacting a (meth)acrylate having a hydroxyl group selected from 2-hydroxyethyl (meth)acrylate, 2-hydroxy-3-acryloxypropyl 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.

[0495] The component (C) may be used alone or in combination of a plurality of compounds suitable for improving coating properties and properties of a film after curing.

[0496] 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 types of acrylic compounds comprising the polyfunctional acrylic compound and a polyfunctional urethane (meth)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.

[0497] 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.

[0498] Examples of the polyfunctional urethane (meth)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 any of these bifunctional or trifunctional isocyanates with an aliphatic diol or an aliphatic polyol, and poly(meth)acrylates having a hydroxyl group in a side chain, trimethylolpropane di(meth)acrylates, Products obtained by reacting poly(meth)acrylates having hydroxyl groups in side chains with acrylic compounds having isocyanate groups such as 2-isocyanatoethyl (meth)acrylate or 1,1-(bisacryloxymethyl)ethyl isocyanate.

[0499] In addition, the component (C) may include not only a liquid component but also a component obtained by modifying the surface of a fine-particle high molecular weight body or the surface of an inorganic filler fine particle with a (meth)acryloyl group.

[0500] In the fluorine-containing curable composition of the present invention, with respect to the composition ratio of each component, the total amount of the compounding amount of the preferred component (A) and the component (B) is 0.05 to 50 parts by mass, particularly preferably 0.1 to 10 parts by mass, relative to 100 parts by mass of the component (C), and the compounding amount of the component (A) relative to 100 parts by mass of the component (B) is 1 to 100 parts by mass, particularly preferably in the range of 3 to 50 parts by mass. If the total amount of the components (A) and (B) is too much relative to the component (C), the performance as a hard coating film is reduced, and if it is too little, the full antifouling performance cannot be exerted. Relative to the component (B), if the amount of the component (A) is too much relative to the component (B), the solubility of the component (C) is excessively deteriorated, and poor coating may occur. If it is too little, the difference relative to the use of the component (B) alone cannot be seen.

[0501] The fluorine-containing curable composition of the present invention contains the above-mentioned three components (A), (B) and (C) as essential components. A product obtained by simply mixing these components can be cured by heat, electron beam or the like. Depending on workability and necessity, components other than these three components may be contained.

[0502] In particular, by containing a photopolymerization initiator as the component (D), a curable composition can be prepared with improved curability when ultraviolet rays are used as active energy rays.

[0503] [Ingredient (D)]

[0504] The photopolymerization initiator of component (D) is not particularly limited as long as it can cure the acrylic compound by ultraviolet irradiation, and preferably includes, for example, acetophenone, benzophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-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)-butane-1-one, 2-(dimethylamino)-2-methyl-1-(4-morpholinophenyl)-butane-1-one, and 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one. )-2-[(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)], ethyl ketone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropane-1-one, etc., can be used alone or in combination of two or more.

[0505] The content of component (D) can be appropriately determined according to the curing conditions and the desired physical properties of the composition, and is preferably 0.1 to 15 parts by mass, particularly 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 be increased.

[0506] These components (A), (B), (C), and (D) can be used as a single compound or a mixture of multiple compounds having the same structure as defined in 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 when considering the blending amount.

[0507] The fluorine-containing curable composition of the present invention may further contain, depending on the purpose, active energy line-reactive compounds other than (meth)acryloyl groups such as monofunctional acrylic compounds, thiol compounds, maleimide compounds, etc. as reactive diluents, organic solvents, polymerization inhibitors, antistatic agents, defoaming agents, viscosity modifiers, light stabilizers, heat stabilizers, antioxidants, surfactants, colorants, and polymer or inorganic fillers.

[0508] 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; aromatics such as toluene, xylene, triethylbenzene, and alkylbenzenes, etc. The above solvents may be used alone or in combination of two or more.

[0509] 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).

[0510] 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.

[0511] Furthermore, within the scope of not hindering 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 situation where the fluorine-containing alcohol compound represented by the above-mentioned formula (7) or formula (14) remains as an unreacted component, etc.

[0512] Furthermore, various products of hard coating agents mixed with component (C) and various additives have been sold by various companies. The fluorine-containing curable composition of the present invention can be a product in which component (A) and component (B) are added to such a commercially available hard coating agent. As commercially available hard coating agents, for example, "Beamset" of Arakawa Chemical Industries, Ltd., "Yubic" of Ohashi Chemical Industries, Ltd., "UV coat" of Origin Electric Co., Ltd., "Cashew UV" of Cashew Co., Ltd., "Desolite" of JSR Co., Ltd., "Seikabeam" of Dainichi Seika Industries, Co., Ltd., "Purple Light" of Nippon Synthetic Chemical Co., Ltd., "Fujihard" of Fujikura Chemical Co., Ltd., "Diabeam" of Mitsubishi Rayon Co., Ltd., and "Diabeam" of Musashi Paint Co., Ltd. can be cited.

[0513] Even when a commercially available hard coating agent is used as described above, an organic solvent, polymerization inhibitor, antistatic agent, defoaming agent, viscosity modifier, light stabilizer, heat stabilizer, antioxidant, surfactant, colorant, filler, etc. can be additionally compounded according to the purpose.

[0514] Regarding the above components (C), (D) and other additives that can be arbitrarily compounded, a large number of well-known components are shown in, for example, "Photocuring Technology Data Book Materials Edition" edited by Technonet Ed. Co., Ltd. (2000, Technonet 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 Rad-Tech Research Institute (1992, CMC), "Poor Curing, Causes of Obstacles 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), "Actual Market Status 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.

[0515] The compounding method of the fluorine-containing curable composition of the present invention may be carried out by any method depending on the application without particular limitation. It is preferred that component (A) and component (B) are fully mixed before mixing with other components. For example, the following method is preferred: component (A) and component (B) are mixed in a desired ratio and the product diluted with a solvent as required is mixed with component (C) and other components; or component (A) diluted with a solvent and component (B) diluted with a solvent are mixed, and then mixed with component (C) and other components.

[0516] 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 diluted with a solvent as appropriate, applied and cured by active energy rays such as heat or electron beams. When a photopolymerization initiator containing component (D) is further 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 controlled to be below 5000 ppm, and it is particularly preferred to cure the composition in an atmosphere of an inert gas such as nitrogen, carbon dioxide or argon.

[0517] 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. For these substrates in any form such as film, plate and molded member, it can be used on the surface thereof.

[0518] When the film substrate is coated, the pressure sensitive adhesive may be coated on the surface opposite to the surface on which the fluorine-containing curable composition layer is coated and formed, and a release film may be further provided to protect the pressure sensitive adhesive.

[0519] 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.

[0520] In addition, the fluorine-containing curable composition of the present invention can be coated and cured on a cured or uncured curable composition layer that does not conform to the present invention. For example, the fluorine-containing curable composition of the present invention can be overlapped on a cured material layer having higher hardness, durability, antistatic properties, curling and other deformation prevention properties.

[0521] In order to improve the adhesion with the fluorine-containing curable composition of the present invention, the surface of the resin film 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.

[0522] 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.

[0523] 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 , particularly preferably 100 to 4000 mJ / cm 2 range.

[0524] In addition, in order to prevent the curing hindrance caused by oxygen, the irradiation atmosphere may be replaced with an inert gas containing no oxygen molecules such as nitrogen, carbon dioxide, argon, etc. during ultraviolet irradiation, or the coating surface may be covered with a protective layer having release properties and ultraviolet permeability, and ultraviolet rays may be irradiated from there, or in the case of a substrate having ultraviolet permeability, the coating surface may be covered with a protective layer having release properties and then ultraviolet rays may 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 may be heated by any method such as infrared rays, a hot air drying furnace, etc. before and during ultraviolet irradiation.

[0525] 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.

[0526] In addition, for the cured product layer of the fluorine-containing curable composition of the present invention obtained in this way, it is preferred that the static water contact angle measured by the angle formed by the liquid surface and the solid surface after 1 second of the droplet of 2 μL of ion exchange water from the contact droplet is more than 100 °, particularly more than 105 °, and the static oleic acid contact angle measured by the angle formed by the liquid surface and the solid surface after 1 second of the droplet of 4 μL of oleic acid from the contact droplet is more than 60 °, particularly more than 65 ° of water-repellent and oil-repellent surface. In addition, in order to become the above-mentioned contact angle, the cured product layer of the fluorine-containing curable composition of the present invention is preferably the amount of the layer with a thickness of more than 10nm on average relative to the total surface area of ​​the cured product layer. In addition, it is preferred that there is no residual unreacted (methyl) acryloyl group on the cured product layer surface, therefore, it is preferably a cured product layer cured under an inert gas atmosphere such as nitrogen and carbon dioxide.

[0527] 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.

[0528] Furthermore, in the present invention, it is possible to provide an article having a cured film cured by coating the above-mentioned fluorine-containing curable composition of the present invention on the surface. As described 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 give a substrate a hard coat surface that is difficult 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., which may be contaminated by human fat, cosmetics, etc., and the surface of an engineering material film used inside a machine that may be contaminated by human fat, machine oil, etc., which may be contacted by a person. Therefore, the fluorine-containing curable composition of the present invention can provide an antifouling coating film or a protective film.

[0529] The cured film (cured resin layer) formed by 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 and TVs, 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 the like. Various optical films used on the surface of equipment and in their interiors, automobile exteriors, pianos, and glossy surfaces of furniture, marble and other building stone surfaces, decorative building materials around water such as toilets, bathtubs, and washrooms, protective glass for displaying artworks, display windows, display cabinets, photo frame covers, watches, exteriors of cosmetic containers, exteriors of decorative containers, automobile window glass, window glass for trains, aircraft, etc., transparent glass or transparent plastic (acrylic resin, polycarbonate, etc.) components such as automobile headlights and taillights, cover components of automotive sensors such as millimeter-wave radars, and various reflector components, etc., as well as coating films and surface protective films.

[0530] Among them, in particular, it can be used as a surface protective film for various devices such as touch panel displays that have display input devices for performing operations on the screen with human fingers or palms, 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, etc., control panels for cars, etc., automatic cash deposit and withdrawal 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.

[0531] 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 magnetic disk and an optical disk; a surface protective film for optical components and optical devices such as eyeglass lenses, prisms, lens sheets, protective films, polarizing plates, optical filters, biconvex lenses, Fresnel lenses, antireflection films, various camera lenses, various lens protection filters, optical fibers, optical couplers, etc.

[0532] The essence of the fluorinated curable composition of the present invention is that the fluorinated polyether structure of 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 resistance, fingerprint erasability, abrasion resistance, low refractive index characteristics, solvent resistance, and chemical resistance.

[0533] When using such a fluorine-containing curable composition of the present invention, depending on which characteristics of the combination and composition ratio of the compounding materials are emphasized, an appropriate method of use can be selected based on known techniques that are consistent with each application. 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.

[0534] For example, when preparing the fluorine-containing curable composition of the present invention, in addition to the components (A) and (B) of the present invention, when combining 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, hollow silica having no reactive group, or a non-fluorine-containing polyfunctional acrylic compound having a functional group of more than 3 or more is used as the component (C); further, when improving the film strength and scratch resistance, two or more non-fluorine-containing polyfunctional acrylic compounds are mixed as the component (C) in a preferred amount, or in order to obtain a balance between hardness and bendability, a non-fluorine-containing polyfunctional acrylic compound having a functional group of more than 6 or more and an acrylic compound having a functional group of less than 3 or more are combined as the component (C), etc., which can be easily inferred from the knowledge of the mixing of known acrylic curable compositions.

[0535] In addition, in the case of obtaining an article by coating the fluorine-containing curable composition of the present invention, for example, when coating a film substrate, adjustment is made to an appropriate coating film thickness in order to prevent interference fringes; by adjusting the thickness of the film substrate to easily suppress curling, or adjusting the elastic modulus of the substrate film to suppress deformation of the coating film of the fluorine-containing curable composition after curing, cracking of the coating film, etc., a screening operation is performed based on a combination of existing conditions that match each characteristic, and selection can be easily achieved by combining the present invention with the prior art.

[0536] Example

[0537] 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.

[0538] [Synthesis Example 1] Synthesis of fluorinated acrylic compound (A-1)

[0539] A 300L four-necked flask equipped with a reflux device and a stirring device was charged with the following formula (I):

[0540] [Chemistry 60]

[0541]

[0542] 100 g (0.0737 mol of Si-H group) of the compound represented by (wherein the arrangement of the repeating units of -CF2CF2O- and -CF2O- is random), the compound of the following formula (II)

[0543] CH2=CH2Si(OCH3)3(II)

[0544] 12.0 g (0.0811 mol) and 200 g of hexafluoro-m-xylene were heated to 90° C. under a dry air atmosphere while stirring. 0.0884 g of a toluene solution of a platinum / 1,3-divinyl-tetramethyldisiloxane complex (containing 2.2×10 -7 mole), and continued heating and stirring for 4 hours before stopping. 1 H-NMR and IR confirmed the disappearance of the peak derived from the Si-H group. The obtained reaction liquid was distilled off under reduced pressure to obtain 101.1 g of a compound (III) represented by the following structure.

[0545] [Chemistry 61]

[0546]

[0547] In a 100 mL three-necked flask equipped with a reflux device and a stirring device, 20 g of the compound (III) obtained above (0.0398 mol in terms of -Si-OCH3 groups) and the following formula (IV) were placed.

[0548] CH2=CHC(=O)OCH2Si(CH3)2OH (IV)

[0549] 6.74 g (0.0421 mol) of the compound (IV) represented by the invention and 40 g of hexafluoro-meta-xylene were stirred at 40°C under a nitrogen atmosphere. 0.2 g of a 10% by mass solution of tetra-2-ethylhexyl titanium in hexafluoro-meta-xylene was added thereto, and stirring was continued for 4 hours. The reaction solution was cooled and returned to room temperature (25°C, the same below), and was added to 500 mL of isopropanol. After stirring for 1 hour, the precipitate obtained by standing for 24 hours was dissolved in 50 g of acetone, and distilled off at 50°C / 267 Pa for 1 hour using an evaporator to obtain 23.4 g of a white ointment-like substance. By 1 As a result of H-NMR and IR, it was confirmed to be the fluorinated acrylic compound (A-1) shown below.

[0550] [Chemistry 62]

[0551]

[0552] [Synthesis Example 2] Synthesis of fluorinated acrylic compound (A-2)

[0553] In a dry air atmosphere, 100.0 g of the compound (I) used in the above-mentioned Synthesis Example 1 (0.0737 mol of Si-H group) was mixed with 8.06 g (0.0789 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. 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 53.6 g of a pale colorless transparent liquid fluorinated alcohol compound (V) represented by the following formula.

[0554] [Chemistry 63]

[0555]

[0556] In a dry air atmosphere, 50.0 g of the obtained liquid fluorine-containing alcohol compound (V) (hydroxyl content 0.0343 mol) was mixed with 50.0 g of THF and 4.93 g of acryloyloxyethyl isocyanate (0.0349 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 52.0 g of a slightly turbid liquid with high viscosity. 1 As a result of H-NMR and IR, it was confirmed to be a fluorine-containing acrylic compound (A-2) shown below.

[0557] [Chemistry 64]

[0558]

[0559] [Synthesis Example 3] Synthesis of fluorinated acrylic compound (B-1)

[0560] 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:

[0561] CH2=CH-CH2-O-CH2-Rf B1 -CH2-O-CH2-CH=CH2

[0562] R B1 :-CF2O(CF2CF2O) 20.9 (CF2O) 21.2 CF2-

[0563] 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 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 (VI) represented by the following formula.

[0564] [Chemistry 65]

[0565]

[0566] R B1 :-CF2O(CF2CF2O) 20.9 (CF2O) 21.2 CF2-

[0567] In a dry air atmosphere, 50.0 g of the compound (VI) 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 (VII) represented by the following formula.

[0568] [Chemistry 66]

[0569]

[0570] R B1 :-CF2O(CF2CF2O) 20.9 (CF2O) 21.2 CF2-

[0571] In a dry air atmosphere, 50.0 g of the obtained fluorinated alcohol compound (VII) (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 pale yellow paste. 1 As a result of H-NMR and IR, it was confirmed to be the fluorinated acrylic compound (B-1) shown below.

[0572] [Chemistry 67]

[0573]

[0574] R B1 :-CF2O(CF2CF2O) 20.9 (CF2O) 21.2 CF2-

[0575] [Synthesis Example 4] Synthesis of fluorinated acrylic compound (B-2)

[0576] 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:

[0577] CH2=CH-CH2-O-CH2-Rf B2 -CH2-O-CH2-CH=CH2

[0578] R B2 :-CF2O(CF2CF2O) 9.8 (CF2O) 9.1 CF2-

[0579] 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 (VIII) represented by the following formula.

[0580] [Chemistry 68]

[0581]

[0582] R B2 :-CF2O(CF2CF2O) 9.8 (CF2O) 9.1 CF2-

[0583] In a dry air atmosphere, 50.0 g of the compound (VIII) 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 (IX) represented by the following formula.

[0584] [Chemistry 69]

[0585]

[0586] R B2 :-CF2O(CF2CF2O) 9.8 (CF2O) 9.1 CF2-

[0587] In a dry air atmosphere, 50.0 g of the obtained fluorinated alcohol compound (IX) (hydroxyl content 0.097 mol) was mixed with 50.0 g of THF and 17.7 g of acryloyloxyethyl isocyanate (0.125 mol), 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, highly viscous liquid. 1 As a result of H-NMR and IR, it was confirmed to be the fluorine-containing acrylic compound (B-2) shown below.

[0588] [Chemistry 70]

[0589]

[0590] R B2 :-CF2O(CF2CF2O) 9.8 (CF2O) 9.1 CF2-

[0591] [Examples 1 to 9, Comparative Examples 1 to 6]

[0592] The raw material components of the fluorine-containing curable composition of the present invention are shown below.

[0593] (A) Fluorinated acrylic compounds

[0594] (A-1) Fluorine-containing acrylic compound obtained in Synthesis Example 1

[0595] (A-2) Fluorine-containing acrylic compound obtained in Synthesis Example 2

[0596] (B) Fluorinated acrylic compounds

[0597] (B-1) Fluorine-containing acrylic compound obtained in Synthesis Example 3

[0598] (B-2) Fluorine-containing acrylic compound obtained in Synthesis Example 4

[0599] (C) Non-fluorinated acrylic compounds

[0600] (C-1) Pentaerythritol ethoxylate tetraacrylate

[0601] [EBECRYL 40 manufactured by Daicel Allnex Ltd.]

[0602] (C-2) Pentaerythritol triacrylate

[0603] (C-3) Multifunctional acrylate composed of a reaction product of pentaerythritol triacrylate and hexamethylene diisocyanate [UA-306H manufactured by Kyoeisha Chemical Co., Ltd.]

[0604] (D) Photopolymerization initiator

[0605] (D-1) 1-Hydroxycyclohexylphenylketone (trade name: IRGACURE 184, manufactured by BASF Japan Ltd.)

[0606] (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.)

[0607] [Preparation of fluorine-containing curable composition]

[0608] Components (A) and (B) were all diluted with methyl ethyl ketone to 20% by mass, and component (C) was diluted with butyl acetate to 40% by mass. In addition, (C-1) was diluted to 40% by mass by replacing the diluting solvent with 2-propanol from butyl acetate, and was blended as (C-4).

[0609] The components (A) to (D) were mixed in a mixing ratio excluding the solvent component as shown in Table 1 below, thereby obtaining a fluorinated curable composition.

[0610] Compounding ratio of components (A) to (D) in Examples and Comparative Examples (excluding solvent components)

[0611] [Table 1]

[0612]

[0613] Preparation of coating and cured products

[0614] The compositions of the examples and comparative examples were coated on a polycarbonate substrate using a wire rod No. 7 (wet film thickness 16.0 μm). After coating, the coating was dried at 100° C. for 1 minute, and then a conveyor-type metal halide UV irradiation device (manufactured by Matsushita Electric Works Co., Ltd.) was used to irradiate the substrate in a nitrogen atmosphere at a cumulative irradiation dose of 400 mJ / cm 2 The coated surface was irradiated with ultraviolet rays to cure the composition, thereby obtaining a cured film having a thickness of 5 μm.

[0615] [Applied state of composition]

[0616] The coating of each composition (appearance of the coating surface) was visually observed. In addition, for the composition that could not be coated smoothly, no subsequent evaluation was performed. The results are shown in Table 2.

[0617] [Evaluation of water and oil repellency]

[0618] 1) Water contact angle measurement

[0619] Using a contact angle meter (Drop Master manufactured by Kyowa Interface Science Co., Ltd.), 2 μL 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.

[0620] 2) Oleic acid contact angle measurement

[0621] Using a contact angle meter (Drop Master 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.

[0622] [Determination of dynamic friction coefficient]

[0623] The dynamic friction coefficient of the cured film of BEMCOT (manufactured by Asahi Kasei Corporation) was measured under the following conditions using a surface tester 14FW (manufactured by Shinto Scientific Co., Ltd.).

[0624] Contact area: 10mm×35mm

[0625] Load: 100g

[0626] [Evaluation of the repellency of the marker]

[0627] A straight line was drawn on the surface of the cured film using a marker (Zebra Co., Ltd., High Marking Bold), and the repellency was evaluated by visual observation.

[0628] [Evaluation of erasability of a marker]

[0629] A straight line was drawn on the surface of the cured film using a marker (Zebra Co., Ltd. High Marking Bold), and after 1 minute, it was gently wiped three times with toilet paper. The case where no trace of the marker remained was evaluated as "erased", and the case where a trace remained was evaluated as "not erased". The results are shown in Table 2.

[0630] [Table 2]

[0631]

[0632] From the above results, it can be seen that the compositions of Comparative Examples 1 and 2, in which component (B) is not added but only components (A) and (C) are added, have poor coating properties and no smooth surface is obtained, but the compositions of Examples 1 to 9 of the present invention, in which components (A), (B) and (C) are added, can produce a smooth coating surface. In addition, the compositions of Examples 1 to 9 of the present invention can form a surface with high liquid repellency and slip properties compared with the compositions of Comparative Examples 3, 4 and 6 in which component (B) and (C) are not added and only components (A) and (C) are added, and Comparative Example 5 in which component (C) is not added and only components (A) and (B) are added.

Claims

1. A fluorine-containing curable composition comprising component (A), component (B) and component (C) as essential components: Component (A) is a linear polymer having a fluoropolyether in the main chain, and is composed of a fluorinated acrylic compound represented by the following general formula (1) having a trifluoromethyl group at one end of one molecule and two or more (meth)acryloyl groups at the other end. Rf A -Z 1 -Q 1 [X 1 ] a (1) In formula (1), Rf A Because it is not related to Z 1 The terminal of the bonding side is a trifluoromethyl monovalent perfluoropolyether group, and Rf 1 -O-Rf 2 -CF2- means, where R 1 The end of the side not bonded to the oxygen atom is a trifluoromethyl group and may contain an oxygen atom and has 1 to 10 carbon atoms, Rf 2 For -(CF2O) m (CF2CF2O) n -represented by a divalent perfluoropolyether group, m is an integer of 1 to 200, n is an integer of 1 to 170, and m+n is an integer of 6 to 201; Z 1 Q is 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; 1 is a (a+1)-valent linking group containing at least (a+1) silicon atoms, which can form a ring structure; a is an integer of 2 to 5; X 1 are independently a monovalent organic group having a (meth)acryloyl group which may contain at least one hetero atom selected from an oxygen atom, a nitrogen atom and a silicon atom; Component (B) is composed of a fluorine-containing acrylic compound represented by the following general formula (2): [Chemistry 1] In the formula, Rf B is a divalent perfluoropolyether group; Z 1 Q 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; 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 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; 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 Each terminal in one molecule has two or more monovalent organic groups and an average of 4 to 10 monovalent organic groups in one molecule; Component (C) is composed of a non-fluorinated acrylic compound having no fluoropolyether structure and having an average of 2 or more (meth)acryloyl groups in one molecule, 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). 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), X of the general formula (1) 1 Represented by any of the following: -CH2CH2CH2OC(=O)NHCH2CH2OC(=O)CH=CH2 -CH2CH2CH2OCH2CH2OC(=O)NHCH2CH2OC(=O)CH=CH2 -CH2CH2CH2OC(=O)NHCH2CH2OC(=O)C(CH3)=CH2 -CH2CH2CH2OCH2CH2OC(=O)NHCH2CH2OC(=O)C(CH3)=CH2 -CH2CH2CH2OC(=O)NHC(CH3)[CH2OC(=O)CH=CH2]2 -CH2CH2CH2OCH2CH2OC(=O)NHC(CH3)[CH2OC(=O)CH=CH2]2 -CH2CH2CH2OC(=O)CH=CH2 -CH2CH2CH2OCH2CH2OC(=O)CH=CH2 -CH2CH2CH2OC(=O)C(CH3)=CH2 -CH2CH2CH2OCH2CH2OC(=O)C(CH3)=CH2 -CH2CH2Si[OSi(CH3)2CH2OC(=O)CH=CH2]3 -CH2CH2Si[OSi(CH3)2CH2OC(=O)C(CH3)=CH2]3 [Chemistry 2] 4. The fluorine-containing curable composition according to claim 1 or 2, wherein In component (A), Q of the general formula (1) 1 is represented by any of the following, [Chemistry 3] In the formula, a is an integer of 2 to 5, and b is an integer of 1 to 5.

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) is selected from compounds represented by the following formulas, [Chemistry 4] [Chemistry 5] [Chemistry 6] [Chemistry 7] [Chemistry 8] [Chemistry 9] [Chemistry 10] [Chemistry 11] [Chemistry 12] [Chemistry 13] In the formula, Rf A Because it is not related to Z 1 The terminal of the bonding side is a trifluoromethyl monovalent perfluoropolyether group, and Rf 1 -O-Rf 2 -CF2- means, where Rf 1 The terminal of the side not bonded to the oxygen atom is a trifluoromethyl group and the perfluoroalkyl group has 1 to 10 carbon atoms and may contain an oxygen atom.

6. The fluorine-containing curable composition according to claim 1 or 2, wherein In component (B), Z of general formula (2) 1 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 of general formula (2) 1 It is expressed by the following formula: [Chemistry 14] 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 (2) is a fluorine-containing acrylic compound represented by the following general formula (3) or (4), [Chemistry 15] [Chemistry 16] In the formula, Z 1 Q is 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; 1 is a (a+1)-valent linking group containing at least (a+1) silicon atoms, which can form a ring structure; a is an integer from 2 to 5, Rf B’ -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, and d1 and e1 are integers of 0 to 10.

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 (meth)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, or a mixture of two or more acrylic compounds containing the polyfunctional acrylic compound and the polyfunctional urethane (meth)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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