Fluoropolyether-based curable composition, cured product, and article

Abstract

This fluoropolyether-based curable composition, which comprises (A) a fluorine-containing compound having at least two thiol groups in one molecule and a divalent perfluoropolyether group in the main chain, (B) a compound having at least two epoxy groups in one molecule, and (C) a curing accelerator, has good storage stability and curability under relatively low temperature conditions, and furthermore, provides a cured product having excellent mechanical properties, electrical properties (insulating properties), chemical resistance, and low moisture permeability.

Description

Fluoropolyether-based curable composition, cured product, and article

[0001] The present invention relates to a fluoropolyether-based curable composition that cures through the reaction of a thiol with an epoxide, has good storage stability, and cures at relatively low temperatures (for example, 100°C or less), and gives a cured product that has excellent mechanical properties, electrical properties (insulating properties), chemical resistance, and low moisture permeability; a cured product of the composition; and an article comprising the cured product.

[0002] Fluoropolyether-based curable compositions utilizing the addition reaction between alkenyl groups and hydrosilyl groups (SiH groups) are known. For example, as curable compositions, compositions containing a linear fluoropolyether compound having two or more alkenyl groups per molecule and a perfluoropolyether structure in the main chain, a fluorine-containing organohydrogensiloxane having two or more hydrogen atoms directly bonded to silicon atoms per molecule, and a platinum group metal compound have been proposed (Patent Document 1, Patent Document 2 (JP-A-8-199070, JP-A-2011-201940)). Furthermore, compositions have been proposed in which self-adhesiveness is imparted by adding an organopolysiloxane having hydrosilyl groups and epoxy groups and / or trialkoxysilyl groups as a third component (adhesion improver) to the composition (Patent Document 3, Patent Document 4 (JP-A-9-95615, JP-A-2011-219692)). The composition can be cured by heating for a short time, and the resulting cured product (fluoropolyether-based cured product) has excellent solvent resistance, chemical resistance, heat resistance, low-temperature properties, low moisture permeability, electrical properties, etc., and is therefore used in various industrial fields where these properties are required.

[0003] A drawback of fluoropolyether-based curable compositions is that they undergo poor curing in the presence of substances containing atoms such as phosphorus, sulfur, and nitrogen. This drawback makes them difficult to apply to many applications, and a fluoropolyether-based curable composition that can be cured even in the presence of these atoms is needed. Patent Document 5 (JP 2008-19398 A) describes a fluoropolyether-based curable composition in which a curing reaction proceeds by mixing a fluorine-containing amide compound having a divalent perfluoropolyether group and a secondary amino group with an aniline derivative having three epoxy groups. However, the aniline derivative does not contain fluorine atoms, and immediately after mixing, it is incompatible with the fluorine-containing amide compound, while its shelf life is short, at approximately 3 to 8 hours. Furthermore, it has been found that achieving good storage stability significantly deteriorates curability, and that there is a trade-off between storage stability and curability. Therefore, there is a need for a fluoropolyether-based curable composition that has high storage stability and good curability under relatively low temperature conditions (e.g., below 100°C).

[0004] Japanese Patent Laid-Open No. 8-199070 Japanese Patent Laid-Open No. 2011-201940 Japanese Patent Laid-Open No. 9-95615 Japanese Patent Laid-Open No. 2011-219692 Japanese Patent Laid-Open No. 2008-19398

[0005] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a fluoropolyether-based curable composition that has good storage stability and curability under relatively low temperature conditions, and that gives a cured product that has good mechanical properties and electrical properties (insulating properties), chemical resistance, and low moisture permeability; a cured product obtained by curing the composition; and an article containing the cured product.

[0006] The present inventors have conducted extensive research to achieve the above object, and have found that a fluoropolyether-based curable composition containing (A) a fluorine-containing compound having at least two thiol groups per molecule and a divalent perfluoropolyether group in the main chain, (B) a compound having at least two epoxy groups per molecule, and (C) a curing accelerator, can be cured even in the presence of a substance containing atoms such as phosphorus, sulfur, or nitrogen, and has good storage stability.Furthermore, the present inventors have found that the composition also has good curability under relatively low temperature conditions, and that the cured product obtained by curing the composition has good mechanical properties, electrical properties (insulating properties), chemical resistance, and low moisture permeability, thereby completing the present invention.

[0007] Accordingly, the present invention provides the following fluoropolyether-based curable composition, a cured product of the composition, and an article comprising the cured product. [1] A fluoropolyether-based curable composition comprising: (A) a fluorine-containing compound having at least two thiol groups per molecule and having a divalent perfluoropolyether group in the main chain, (B) a compound having at least two epoxy groups per molecule, and (C) a curing accelerator. [2] The fluoropolyether-based curable composition according to [1], wherein component (A) is a fluorine-containing thiol compound represented by the following average formula (1): (wherein Rf is independently a divalent perfluoropolyether group, A is independently a divalent organic group having 1 to 20 carbon atoms which may have at least one bond selected from a carbonyl bond, an amide bond, an ether bond, an ester bond, and a thioester bond, X is independently a carbonyl bond, or a divalent to tetravalent organic group having 1 to 20 carbon atoms which may have at least one bond selected from an amide bond, an ester bond, an ether bond, and an amino bond, a is 0 or a positive number, and b is independently an integer of 1 to 3.) [3] The fluoropolyether-based curable composition according to [2], wherein A in the above average formula (1) is independently any group selected from groups represented by the following general formulas (2) to (5): (In the formula, R 1 are independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms; R 2are independently unsubstituted or substituted divalent hydrocarbon groups having 1 to 20 carbon atoms.) [4] X in the above average formula (1) is -(CH2) f -*, -(CH2) f OCH2-*,-(CH2) f -NR 5 -CH2-*, -CH(CH3)-(CH2) f -NR 5 -CH2-*, -CO-*, -(CH2) f -NR 5 -CO-*, -CH(CH3)-(CH2) f -NR 5 -CO-*, -(CH2) f The fluoropolyether-based curable composition according to [2] or [3], wherein the fluoropolyether-based curable composition is any group selected from the group consisting of —O—CO—* and groups represented by the following general formulas (6) to (8): (In the formula, R 4 are independently a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, or a trifluoromethyl group, and R 5 represents a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, or a phenyl group, e' is 0 or 1, and f is an integer of 1 to 12. The bond marked with an asterisk (*) indicates bonding to Rf. [5] The fluoropolyether-based curable composition according to any one of [1] to [4], wherein the thiol group in component (A) is either a primary thiol group or a secondary thiol group. [6] The fluoropolyether-based curable composition according to any one of [1] to [5], wherein the amount of component (B) blended is such that the epoxy group in component (B) is 0.5 to 5 mol per 1 mol of thiol group in component (A). [7] The fluoropolyether-based curable composition according to [1], wherein component (B) is a fluorine-containing epoxy compound represented by the following general formula (9): [wherein, Rf 1 Rf are independently monovalent or divalent groups having a fluoropolyether structure and a number average molecular weight of 400 to 40,000. 1 When Rf is monovalent, d' is 1, d is an integer of 1 to 6, and e is an integer of 2 to 20. 1is divalent, then d' is 2, d is 1, and e is an integer from 1 to 20. Q is independently a (d+e)-valent group having at least (d+e) Si atoms, and has a siloxane structure, a silalkylene structure, a silarylene structure, or a combination thereof, and may have a cyclic structure. Z is independently a divalent hydrocarbon group having 1 to 20 carbon atoms, and may contain an ether bond or an ester bond, and may have a cyclic structure. E is independently a group represented by the following formula (I) or (II): (In the formula, R 6 are independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, which may contain an ether bond or an ester bond and may have a cyclic structure. (In the formula, R 7 are independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, v is independently 1 or 2, and the sum of v's is 7.) [8] The fluoropolyether-based curable composition according to [7], wherein, in the general formula (9), Z is independently selected from groups represented by the following formulas: -CH2CH2-*, -CH2CH2CH2-*, -CH2CH2CH2CH2-*, -CH2CH2CH2CH2CH2-*, -CH2CH2CH2CH2CH2CH2-*, -CH2CH2CH2CH2CH2CH2-*, -CH2CH2CH2CH2CH2CH2CH2-*, -CH2CH2CH2CH2CH2CH2CH2-*, -CH2CH2CH2CH2CH2CH2CH2-*, -CH2CH2CH2OCH2-*, -CH2CH2CH2OCH2CH2OCH2CH2-*, -CH2CH2CH2OCH2CH2OCH2CH2-* (wherein the bond marked with * is bonded to E, and the bond without a mark is bonded to Q.) [9] The fluoropolyether-based curable composition according to [7] or [8], wherein the structure represented by -ZE in the general formula (9) is selected from groups represented by the following formulas (a) to (d): (In the formula, g is an integer of 1 to 20, h is an integer of 1 to 10, i is an integer of 1 to 5, l is an integer of 0 to 9, and h+2l+i is 2 to 20. R 7is a hydrogen atom, or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms.)

[10] The fluoropolyether-based curable composition according to any one of [7] to [9], wherein the structure represented by -ZE in the general formula (9) is selected from groups represented by the following formulas:

[11] The fluoropolyether-based curable composition according to any one of [7] to

[10] , wherein in the general formula (9), Q is selected from groups represented by the following formulas: (wherein d1 is Rf 1 is an integer of 1 to 4 when Rf is monovalent; 1 is divalent, e1 is an integer of 2 to 4, and d1' is an integer that satisfies d1+e1=3 to 6. 1 is 1 or 2 when Rf is monovalent; 1 is divalent, e1' is 1, e1' is 2 or 3, f1 is 0 or 1, and d1' + e1' + f1 = 4. D is a monovalent hydrocarbon group having 1 to 6 carbon atoms. Each silicon atom of the unit shown in parentheses having d1 and d1' repeats is Rf 1 and each silicon atom of the unit shown in parentheses having e1 and e1' repeats is bonded to Z, and the arrangement of the units shown in parentheses may be random.)

[12] The fluoropolyether-based curable composition according to any one of [1] to

[11] , wherein component (C) is at least one selected from the group consisting of phosphorus compounds, tertiary amine compounds, imidazole compounds, urea compounds, amine adduct compounds, and urea adduct compounds.

[13] A cured product obtained by curing the fluoropolyether-based curable composition according to any one of [1] to

[12] .

[14] An article having the cured product according to

[13] .

[15] The article according to

[14] , which is for use in automobiles, ships, aircraft, space-related equipment, generators, sports equipment, lighting equipment, organic electroluminescence (OLED), LED, civil engineering / construction, chemical plants, analytical / physical / chemical equipment, living environments, communication equipment, communication facilities, or railway vehicles.

[0008] According to the present invention, a fluoropolyether-based curable composition can be obtained that exhibits both good storage stability and curability at relatively low temperatures. Furthermore, by curing the composition, a cured product having excellent mechanical properties, electrical properties (insulating properties), chemical resistance, and low moisture permeability can be obtained.

[0009] In the present invention, the "main chain" refers to the "trunk" portion of a polymer that is made up of the longest chain of atoms.

[0010] In the present invention, "storage stability" refers to the ability of a fluoropolyether-based curable composition to maintain its fluidity for a certain period of time (16 hours or more, preferably 24 hours or more, and more preferably 48 hours or more) at room temperature (23°C ± 15°C) after preparation, and "storage time" refers to the time during which the fluidity of the composition is maintained by visual observation at room temperature after preparation. Specifically, after mixing the main component (component (A)), the crosslinking agent (component (B)), and other components including the curing accelerator (component (C)), the time until the fluidity is significantly lost by visual observation at room temperature is determined, and the time during which the fluidity is maintained is measured.

[0011] Furthermore, in the present invention, the degree of polymerization (or molecular weight) of the fluorine-containing compound, which reflects the number of repetitions of perfluorooxyalkylene units constituting the perfluoropolyether group of the main chain, can be determined, for example, as the number-average degree of polymerization (or number-average molecular weight) converted into polystyrene in gel permeation chromatography (GPC) analysis using a fluorine-based solvent as a developing solvent. Furthermore, the perfluoropolyether group (Rf, Rf', Rf", and Rf, which are described later) is composed of repetitions of perfluorooxyalkylene units constituting the main chain. 2 , Rf 3 , Rf 0 ) is the number average degree of polymerization (or number average molecular weight) 19 It can also be calculated from F-NMR.

[0012] The fluoropolyether-based curable composition of the present invention uses, as component (A), a fluorine-containing compound having at least two thiol groups per molecule and a divalent perfluoropolyether group in the main chain, and as component (B), a compound having at least two epoxy groups per molecule that is reactive with the thiol groups in the compound, together with a curing accelerator (component (C)), thereby achieving both good storage stability and curability at relatively low temperatures (for example, 100°C or less). Furthermore, by curing the composition, a cured product having excellent mechanical properties, electrical properties (insulating properties), chemical resistance, and low moisture permeability can be obtained.

[0013] The present invention will be described in further detail below. [Component (A)] The fluorine-containing compound of component (A) used in the fluoropolyether-based curable composition of the present invention has at least two thiol groups in one molecule and a divalent perfluoropolyether group in the main chain, and acts as a base agent in the fluoropolyether-based curable composition of the present invention.

[0014] The component (A) is preferably a fluorine-containing thiol compound represented by the following average formula (1): (In the formula, Rf independently represents a divalent perfluoropolyether group; A independently represents a divalent organic group having 1 to 20 carbon atoms which may have at least one bond selected from a carbonyl bond, an amide bond, an ether bond, an ester bond, and a thioester bond; X independently represents a carbonyl bond, or a divalent to tetravalent organic group having 1 to 20 carbon atoms which may have at least one bond selected from an amide bond, an ester bond, an ether bond, and an amino bond; a is 0 or a positive number; and b independently represents an integer of 1 to 3.)

[0015] In the average formula (1), A is independently a divalent organic group having 1 to 20 carbon atoms which may have at least one bond selected from the group consisting of a carbonyl bond, an amino bond, an amide bond, an ether bond, an ester bond, and a thioester bond. Specifically, A is -CH2O-(CH2) f -OCH2-, -COO-(CH2) f -COO-, -COS-(CH2) fExamples of suitable groups include -SCO- and groups represented by the following general formulas (2) to (5). The groups represented by the following general formulas (2) to (5) are preferred in terms of ease of production of component (A) and ability to enhance the durability of the cured product.

[0016] In the above general formulas (2) and (5), R 1 is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms. As the unsubstituted or substituted monovalent hydrocarbon group, one having 1 to 10 carbon atoms is particularly preferred. Examples include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, and decyl; cycloalkyl groups such as cyclopentyl, cyclohexyl, and cycloheptyl; aryl groups such as phenyl, tolyl, and naphthyl; aralkyl groups such as benzyl and phenylethyl; and groups in which some of the hydrogen atoms of these groups have been substituted with halogen atoms such as fluorine, chlorine, or bromine, such as a chloromethyl group, bromoethyl group, chloropropyl group, trifluoropropyl group, or 3,3,4,4,5,5,6,6,6-nonafluorohexyl group.

[0017] In the above general formulas (2) to (5), R 2 is an unsubstituted or substituted divalent hydrocarbon group having 1 to 20 carbon atoms, and particularly preferably one having 1 to 10 carbon atoms. Examples include alkylene groups such as methylene, ethylene, n-propylene, i-propylene, butylene, hexylene, octylene, and dodecamethylene; cycloalkylene groups such as cyclohexylene; arylene groups such as phenylene, tolylene, xylylene, naphthylene, and biphenylylene; and groups in which some of the hydrogen atoms of these groups have been substituted with halogen atoms such as fluorine.

[0018] In the above average formula (1), A may consist of one of these alone or a combination of two or more of them.

[0019] Examples of A include the following groups: In the following formulae, Me represents a methyl group, and Ph represents a phenyl group.

[0020] In the average formula (1), X is independently a carbonyl bond or a divalent to tetravalent, preferably divalent, organic group (particularly a hydrocarbon group) having 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, which may have at least one bond selected from an amide bond, an ester bond, an ether bond, and an amino bond. X is -(CH2) f -*, -(CH2) f OCH2-*, -CO-*, -(CH2) f -NR 5 -CH2-*, -CH(CH3)-(CH2) f -NR 5 -CH2-*, -(CH2) f -NR 5 -CO-*, -CH(CH3)-(CH2) f -NR 5 -CO-*, -(CH2) f It is preferably any group selected from —O—CO—* and groups represented by the following general formulas (6) to (8). Note that the bond marked with * indicates that it is bonded to Rf, and the bond without a mark indicates that it is bonded to SH (thiol group). (In the formula, R 4 are independently a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, or a trifluoromethyl group, and R 5 is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, or a phenyl group, e' is 0 or 1, and f is an integer from 1 to 12.

[0021] Examples of X include: -CH2-*, -CH2CH2CH2-*, -OCH2-*, -CH2OCH2-*, -(CH2)2OCH2-*, -(CH2)3OCH2-*, -(CH2)6OCH2-*, -(CH2)2-NH-CH2-*, -(CH2)3NHCH2-*, -CH2-NH-CH2-*, -CH2-N(CH3)-CH2-*, -CH2-N(CH2CH3)-CH2-*, -CH2CH2-N(CH3)-CH2-*, -CH2CH2-N(CH2CH3)-CH2-*, -(CH2)3-N(CH3)-CH2-*, -(CH2)3-N(CH2CH3)-CH2-*, -(CH2)3-N(CH(CH3)2)-CH2-*, -(CH2)6-NH-CH2-*, -(CH2)6-N(CH3)-CH2-*, -(CH2)6-N(CH2CH3)-CH2-*, -(CH2)8-NH-CH2-*, -(CH2) 11 -NH-CH2-*, -CH(CH3)CH2-NH-CH2-*, -CH(CH3)(CH2)3-NH-CH2-*, -CH(CH3)(CH2)4-NH-CH2-*, -CO-*, -CH2-NH-CO-*, -CH2-N(CH3)-CO-*, -CH2-N(CH2CH3)-CO-*, -CH2CH2-NH-CO-*, -CH2CH2-N(CH3)-CO-*, -CH2CH2-N(CH2CH3)-CO-*, -(CH2)3-NH-CO-*, -(CH2)3-N(CH3)-CO-*, -(CH2)3-N(CH2CH3)-CO-*, -(CH2)3-N(CH(CH3)2)-CO-*, -(CH2)6-NH-CO-*, -(CH2)6-N(CH3)-CO-*, -(CH2)6-N(CH2CH3)-CO-*, -(CH2)8-NH-CO-*, -(CH2) 11-NH-CO-*, -CH(CH3)-CH2-NH-CO-*, -CH(CH3)-(CH2)3-NH-CO-*, -CH(CH3)-(CH2)4-NH-CO-*, -CH(CH3)-(CH2 )3-N(C6H5)-CO-*, -(CH2)2-O-CO-*, -(CH2)3-O-CO-*, 2(-(CH2)3-)N-CO-*, 2(-CH(CH3)-CH(C2H5)-)N-CO-* Examples of such groups include groups represented by the following general formulae (6A), (6B), (6C), (6D), (6E), (7A), (7B), (7C), (8A), (8B), and (8C). Among these, -CHCH-NH-CO-*, -(CH)-NH-CO-*, -CH(CH)-(CH)-NH-CO-*, -CH(CH)-(CH)-NH-CO-*, and groups represented by general formula (7B) or (8A) are preferred. Note that the bond marked with an * indicates a bond to Rf, and the unmarked bond indicates a bond to SH (thiol group). Furthermore, in the formulae, Me is a methyl group, and Et is an ethyl group.

[0022] In the above average formula (1), X may consist of one of these alone or a combination of two or more of them.

[0023] In the above average formula (1), Rf is independently a divalent perfluoropolyether group, -C x F 2x O- (wherein x is an integer of 1 to 6) repeating units, and examples thereof include those represented by the following formula (10): -(C x F 2x O) y - (10) (wherein x is an integer of 1 to 6, and y is an integer of 5 to 600, preferably an integer of 10 to 400, and more preferably an integer of 30 to 200.)

[0024] The above formula -C x F 2xExamples of the repeating unit represented by O- include units represented by the following formulae: -CF2O-, -CF2CF2O-, -CF2CF2CF2O-, -CF(CF3)CF2O-, -CF2CF2CF2CF2CF2O-, -CF2CF2CF2CF2CF2CF2O-

[0025] Among these, units represented by the following formulae are particularly preferred: -CF2O-, -CF2CF2O-, -CF2CF2CF2O-, -CF(CF3)CF2O-

[0026] The repeating unit in the divalent perfluoropolyether group may be composed of one of these alone or a combination of two or more of them.

[0027] The divalent perfluoropolyether group preferably has the following structure: (wherein G is a fluorine atom or a trifluoromethyl group; p1, q1, and r1 are integers satisfying p1≧0, q1≧0, 0≦p1+q1≦200, particularly 2≦p1+q1≦150, and 0≦r1≦6 (when p1+q1=0, 1≦r1≦6); k1, a1, s1, t1, and u1 are integers satisfying 1≦k1≦3, 2≦a1≦6, 0≦s1≦100, 0≦t1≦100, 2≦s1+t1≦200, 0≦u1≦6, particularly 2≦s1+t1≦15 are integers satisfying 0, 0≦u1≦4, 2≦s1+t1+u1≦150, v1 and w1 are integers satisfying 1≦v1≦100, 1≦w1≦100, 2≦v1+w1≦200, z1 is an integer satisfying 1≦z1≦200, k1', a1' and a1" are integers satisfying 1≦k1'≦3, 1≦a1'≦6, 1≦a1"≦6, a1'≠a1" respectively, and z1' is an integer satisfying 1≦z1'≦200. The repeating units shown in parentheses followed by v1 and w1 may be bonded randomly.

[0028] In the above average formula (1), specific examples of Rf include those represented by the following formulas. (In the formula, p1, q1, p1+q1, r1, v1, w1, v1+w1, z1, and z1' are the same as above. s1' and t1' each represent an integer of 1 to 100, and s1'+t1'=an integer of 2 to 200. t1" is an integer of 2 to 100. The repeating units shown in parentheses followed by v1 and w1 may be bonded randomly.)

[0029] In the above average formula (1), a is 0 or a positive number, preferably 0 or a positive number of 3 or less, and more preferably 0 or a positive number of 1 or less. For each molecule of the fluorine-containing thiol compound represented by the above average formula (1), a is an integer of 0 or more, preferably an integer of 0 to 3, and more preferably 0 or 1. However, in the average formula of the entire component (A) containing two or more compounds having different values ​​of a, which is the number of repetitions of the main chain structure -[Rf-A]-, a may be 0 or a positive number.

[0030] In the average formula (1), b is independently an integer of 1 to 3, preferably 1 or 2, and particularly preferably 1. By making b an integer of 1 to 3, the fluoropolyether-based curable composition of the present invention will exhibit good curability, and the cured product will also be more easily obtained as an elastic body.

[0031] In the above average formula (1), —SH (thiol group) may be any of a primary thiol group, a secondary thiol group, a tertiary thiol group, and an aromatic thiol group. From the viewpoint of achieving both good curability and excellent storage stability in the fluoropolyether-based curable composition, however, it is preferably any of a primary thiol group and a secondary thiol group.

[0032] As the fluorine-containing thiol compound represented by the above average formula (1), the compound represented by the following formula is particularly preferred: In the formula, Me is a methyl group, and Et is an ethyl group.

[0033] (In the formula, s1' and t1' are each an integer of 1 to 100, and s1' + t1' = an integer of 2 to 200.)

[0034] (In the formula, s1' and t1' are each an integer of 1 to 100, and s1' + t1' = an integer of 2 to 200.)

[0035] (In the formula, s1' and t1' are each an integer of 1 to 100, and s1' + t1' = an integer of 2 to 200.)

[0036] (In the formula, s1' and t1' are each an integer of 1 to 100, and s1' + t1' = an integer of 2 to 200.)

[0037] (In the formula, v1 and w1 are each an integer of 1 to 100, and v1+w1=an integer of 2 to 200. The repeating units shown in parentheses with v1 and w1 may be bonded randomly.)

[0038] (In the formula, s1' and t1' are each an integer of 1 to 100, s1'+t1'=an integer of 2 to 200 for each Rf in the above formula (1), and a' is a positive number of 3 or less.)

[0039] [Production Method 1 of Component (A)] The production method of the fluorine-containing thiol compound represented by the above average formula (1) is not particularly limited, but for example, when a is 0 or more and less than 1, the compound can be prepared by mixing and reacting a fluorine-containing compound represented by the following general formula (1A) with a compound having an amino group and a thiol group represented by the following general formula (1B): (wherein E is at least one selected from a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a tosyl group (including a group in which a hydrogen atom on a phenyl group is replaced with a carbon atom, a halogen atom, or a heteroatom), an alkoxy group having 1 to 6 carbon atoms, and a hydroxy group; A L is a carbonyl group.) (wherein b is the same as above, and X L is a divalent organic group having 1 to 20 carbon atoms, and R 3 is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms.

[0040] Below is shown an example of a preferred production process (reaction formula) for the compound represented by the above average formula (1) (when a is 0 or more and less than 1). However, the production method for the fluorine-containing compound represented by the above average formula (1) (when a is 0 or more and less than 1) is not limited to the following.

[0041] Rf, A, X, E, and A in the reaction formula shown in the above process L , X L , R 3 , a, b are Rf, A, X, a, b in the average formula (1), E, ​​A in the general formula (1A), L , R in the above general formula (1B) 3 , X L is the same as

[0042] In the above step, a fluorine-containing compound represented by the general formula (1A) is reacted with a compound represented by the general formula (1B) to produce a fluorine-containing thiol compound represented by the average formula (1) (when a is 0 or more and less than 1). In the above step, E in formula (1A) mainly reacts with the NH group in formula (1B), but also reacts to some extent with the SH group in formula (1B). Therefore, the finally obtained formula (1) has a fluorine-containing compound in which a is 0 or more and less than 1 on average.

[0043] In the above general formula (1A), E is at least one selected from a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a tosyl group (including groups in which a hydrogen atom on a phenyl group is replaced with a carbon atom, a halogen atom, or a heteroatom), an alkoxy group having 1 to 6 carbon atoms such as a methoxy group or an ethoxy group, and a hydroxy group. Among these, from the viewpoint of availability of the compound represented by the above general formula (1A), a fluorine atom is preferred. In the above general formula (1A), A L is a carbonyl group.

[0044] In the above general formula (1B), X L is a divalent organic group having 1 to 20 carbon atoms. LExamples of the structure include -CH2-*, -CH2CH2-*, -CH2CH2CH2-*, -OCH2-*, -CH2OCH2-*, -(CH2)2OCH2-*, -(CH2)3OCH2-*, -(CH2)6OCH2-*, -(CH2)3NHCH2-*, -(CH2)6-*, -(CH2)8-*, -(CH2) 11 -*, -(CH2) 12 -*, -CH(CH3)-CH2-*, -CH(CH3)-(CH2)2-*, -CH(CH3)-(CH2)3-*, -CH(CH3)-(CH2)4-*, -CH(CH3)-(CH2)5-*, -CH(CH3)CH(CH2CH3)-*, cycloalkylene groups such as cyclopentylene, arylene groups such as phenylene and naphthylene. Note that the bond marked with * indicates that it is bonded to the nitrogen atom in general formula (1B), and the unmarked bond indicates that it is bonded to the sulfur atom.

[0045] In the above general formula (1B), R 3 is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R 1 It is the same as R 3 Examples of the structure include a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, or a decyl group; a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, or a cycloheptyl group; an aryl group such as a phenyl group, a tolyl group, or a naphthyl group; an aralkyl group such as a benzyl group or a phenylethyl group; or a chloromethyl group, bromoethyl group, chloropropyl group, trifluoropropyl group, or 3,3,4,4,5,5,6,6,6-nonafluorohexyl group in which some of the hydrogen atoms of these groups have been substituted with halogen atoms such as fluorine, chlorine, or bromine.

[0046] In the above reaction, the following compounds can be used as the fluorine-containing compound represented by the general formula (1A). (In the formula, s1' and t1' each represent an integer of 1 to 100, and s1'+t1'=an integer of 2 to 200. v1 and w1 each represent an integer of 1 to 100, and v1+w1=an integer of 2 to 200. The repeating units shown in parentheses followed by v1 and w1 may be bonded randomly.)

[0047] Examples of the compound having an amino group and a thiol group represented by the above general formula (1B) include the following compounds.

[0048] The compound represented by the general formula (1B) may be used alone or in combination of two or more.

[0049] The amount of the compound having an amino group and a thiol group represented by the general formula (1B) used is 1 to 10 mol, preferably 1 to 5 mol, per mol of functional group E in the fluorine-containing compound represented by the general formula (1A). When the amount of the compound represented by the general formula (1B) used falls within the above range, the functional group E is completely consumed in the reaction, and the fluorine-containing thiol compound represented by the average formula (1) (when a is 0 or more and less than 1) can be efficiently obtained.

[0050] In the above production method, particularly when E in the average formula (1A) is a fluorine atom, chlorine atom, bromine atom, or iodine atom, an amine compound may be used for the purpose of trapping hydrogen halide generated as a by-product. However, it is preferable that the amine compound does not have reactivity with the fluorine-containing compound represented by the general formula (1A). The amine compound is preferably a tertiary amine, an aniline-based compound having no hydrogen atom on the nitrogen, or a pyridine-based compound. Examples of the amine compound include tertiary amine compounds such as trimethylamine, triethylamine, diisopropylethylamine, dimethylisopropylamine, diethylmethylamine, dimethylallylamine, dimethylethylamine, dimethylpropan-1-amine, and triisopropylamine, and aniline-based compounds and pyridine-based compounds such as pyridine, chloropyridine, fluoropyridine, 2-chloro-6-methoxypyridine, 4,4'-dibromo-2,2'-bipyridyl, 2-methoxypyridine, and N,N-dimethylaniline.

[0051] The amount of the amine compound used is preferably 5 mol or less, more preferably 3 mol or less, and even more preferably 0 to 1.2 mol, relative to 1 mol of functional group E in the fluorine-containing compound represented by general formula (1A). By using the amine compound within the above range, a side reaction between the fluorine-containing thiol compound represented by average formula (1) to be purified and the fluorine-containing compound represented by general formula (1A) can be suppressed, and a in average formula (1) can be set to 0.

[0052] In the above production method, a solvent may be used to enhance the reaction efficiency. The type of solvent is not particularly limited, and both non-fluorine-containing organic solvents and fluorine-containing solvents can be used as long as they enhance the reaction efficiency. Specific examples include acetonitrile, N,N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, acetone, methyl ethyl ketone, toluene, and 1,3-bis(trifluoromethyl)benzene. The amount of the solvent used may be determined appropriately taking into consideration the time required for the reaction with the fluorine-containing compound represented by general formula (1A) to be completed and the stirring efficiency.

[0053] In the above production method, the reaction temperature is 0 to 80°C, preferably 0 to 60°C, and the reaction time is 1 to 48 hours, preferably 2 to 24 hours. By setting the reaction temperature within the above range, it is possible to suppress a side reaction between the fluorine-containing thiol compound represented by the average formula (1) to be purified and the fluorine-containing compound represented by the general formula (1A), and to produce a fluorine-containing thiol compound in which a in the average formula (1) is 0 or more and less than 1.

[0054] [Production method 2 of component (A)] In the production method of the fluorine-containing thiol compound represented by the above average formula (1), for example, when a is 1 or more, in the following production step (reaction formula), in addition to the compound represented by the above general formula (1B), a diamine compound represented by the following general formula (1C-1), (1C-2) or (1C-3) can also be used in combination. (In the formula, R 1 , R 2 is the same as above.)

[0055] An example of a preferred production process (reaction formula) for the fluorine-containing compound represented by the above average formula (1) (when a is 1 or more) is shown below. However, the method for producing the fluorine-containing compound represented by the above average formula (1) is not limited to the following.

[0056]

[0057] Rf, A, X, E, and A in the reaction formula shown in the above process L , X L , R 1 , R 2 , R 3 , a, b are Rf, A, X, a, b in the average formula (1), R in the general formulas (2) to (5), 1 , R 2 , E and A in the above general formula (1A) L , R in the above general formula (1B) 3 , X L The fluorine-containing compound represented by the general formula (1A), the compound represented by (1B), and the fluorine-containing thiol compound represented by the average formula (1) are the same as those described above.

[0058] The production method in which a diamine compound represented by the general formula (1C-1), (1C-2) or (1C-3) is used in combination includes a step (first step) of reacting a fluorine-containing compound represented by the general formula (1A) with a compound represented by any one of the general formulas (1C-1), (1C-2) or (1C-3) to produce a fluorine-containing compound represented by the average formula (P1) (a is 1 or more), and a step (second step) of reacting the fluorine-containing compound with a compound represented by the general formula (1B) to obtain a fluorine-containing thiol compound represented by the average formula (1) (a is 1 or more).

[0059] Examples of the diamine compounds represented by the above general formula (1C-1), (1C-2) or (1C-3) include the following compounds.

[0060] In the first step, the compound represented by the general formula (1C-1), (1C-2) or (1C-3) may be used alone or in combination of two or more.

[0061] In the first step, the amount of the compound represented by the general formula (1C-1), (1C-2) or (1C-3) used may be appropriately determined according to the value of a in the average formula (1), within a range not exceeding 0.5 mol relative to 1 mol of functional group E in the fluorine-containing compound represented by the general formula (1A), and specifically, it is preferably an amount of 0.25 to 0.5 mol relative to 1 mol of functional group E in the fluorine-containing compound represented by the general formula (1A). This leaves unreacted functional groups E, and produces a fluorine-containing compound where a in the average formula (P1) is 1 or more, and in the second step, by reaction with the general formula (1B), the fluorine-containing thiol compound (a is 1 or more) represented by the average formula (1) can be efficiently obtained.

[0062] In the first step, an amine compound may be used for the purpose of trapping hydrogen halide generated as a by-product. However, it is preferable that the amine compound does not have reactivity with the fluorine-containing compounds represented by the general formulas (1A) and (P1). The amine compound is preferably a tertiary amine, an aniline-based compound having no hydrogen atom on the nitrogen, or a pyridine-based compound. Examples of the amine compound include tertiary amine compounds such as trimethylamine, triethylamine, diisopropylethylamine, dimethylisopropylamine, diethylmethylamine, dimethylallylamine, dimethylethylamine, dimethylpropan-1-amine, and triisopropylamine, and aniline-based compounds and pyridine-based compounds such as pyridine, chloropyridine, fluoropyridine, 2-chloro-6-methoxypyridine, 4,4'-dibromo-2,2'-bipyridyl, 2-methoxypyridine, and N,N-dimethylaniline.

[0063] The amount of the amine compound used is preferably 0.5 to 2.5 mol, more preferably 0.5 to 2 mol, relative to the amount of the compound represented by general formula (1C-1), (1C-2), or (1C-3) used. By using the amine compound within the above range, the unreacted rate of the compound represented by general formula (1C-1), (1C-2), or (1C-3) is reduced, and the fluorine-containing compound represented by average formula (P1) can be efficiently obtained.

[0064] The reaction temperature in the first step is 0 to 100°C, preferably 0 to 80°C, and the reaction time is 1 to 24 hours, preferably 1 to 6 hours. By setting the reaction temperature within the above range, the unreacted rate of the compound represented by general formula (1C-1), (1C-2) or (1C-3) is reduced, and the fluorine-containing compound represented by average formula (P1) can be efficiently obtained.

[0065] Examples of the fluorine-containing compound represented by the above average formula (P1) obtained in this manner include the compounds shown below. (In the formula, s1' and t1' are each an integer of 1 to 100, s1'+t1'=an integer of 2 to 200 for each Rf in the above formula (1), and a' is a positive number of 3 or less.)

[0066] In the second step, the compound represented by the general formula (1B) may be used alone or in combination of two or more.

[0067] In the second step, the amount of the compound represented by the general formula (1B) used is 1 to 10 mol, preferably 1 to 5 mol, per mol of the functional group E in the average formula (P1) obtained in the first step. When the amount of the compound represented by the general formula (1B) used falls within the above range, the functional group E in the average formula (P1) is completely consumed in the reaction, and the fluorine-containing thiol compound (a is 1 or more) represented by the average formula (1) can be efficiently obtained.

[0068] In the second step, an amine compound may be used for the purpose of trapping hydrogen halide generated as a by-product. However, it is preferable that the amine compound does not have reactivity with the fluorine-containing compound represented by the average formula (P1) above. The amine compound is preferably a tertiary amine, an aniline-based compound having no hydrogen atom on the nitrogen, or a pyridine-based compound. Examples of the amine compound include tertiary amine compounds such as trimethylamine, triethylamine, diisopropylethylamine, dimethylisopropylamine, diethylmethylamine, dimethylallylamine, dimethylethylamine, dimethylpropan-1-amine, and triisopropylamine, and aniline-based compounds and pyridine-based compounds such as pyridine, chloropyridine, fluoropyridine, 2-chloro-6-methoxypyridine, 4,4'-dibromo-2,2'-bipyridyl, 2-methoxypyridine, and N,N-dimethylaniline.

[0069] In the second step, the amount of the amine compound used is preferably 1.2 mol or less, more preferably 0.5 mol or less, and even more preferably 0 mol, relative to 1 mol of functional group E in the average formula (P1).By using the amine compound within the above range, a side reaction between the produced fluorine-containing thiol compound represented by the average formula (1) and the fluorine-containing compound represented by the average formula (P1) can be suppressed, and the fluorine-containing thiol compound represented by the average formula (1) showing the value of a in the average formula (P1) produced in the first step can be obtained.However, when the amine compound remains in the first step, it is preferable that the amount of the amine compound used in the second step be limited to the amount obtained by subtracting the amount remaining in the first step from the amount used.

[0070] In the second step, the reaction temperature is 0 to 80° C., preferably 0 to 60° C., and the reaction time is 1 to 48 hours, preferably 2 to 24 hours. By setting the reaction temperature within the above range, a side reaction between the produced fluorine-containing thiol compound represented by the average formula (1) and the fluorine-containing compound represented by the average formula (P1) can be suppressed, and the fluorine-containing thiol compound represented by the average formula (1) which represents the value of a in the average formula (P1) produced in the first step can be obtained.

[0071] The amount of thiol groups contained in the fluorine-containing compound of component (A) is preferably 0.002 to 0.4 mol / 100g, and more preferably 0.008 to 0.3 mol / 100g. By making the amount of thiol groups contained in the fluorine-containing compound 0.002 mol / 100g or more, the degree of crosslinking is not insufficient, reducing the possibility of curing defects, and by making the amount of thiol groups 0.4 mol / 100g or less, the mechanical properties of the resulting cured product as a rubber elastomer are less likely to be impaired. In the present invention, the amount of thiol groups is 1 It can be measured by H-NMR.

[0072] The viscosity (23°C) of the fluorine-containing compound of component (A) is preferably in the range of 40 to 500,000 mPa·s, more preferably 50 to 300,000 mPa·s, and even more preferably 60 to 150,000 mPa·s, in order to ensure that the cured product obtained from the fluoropolyether-based curable composition of the present invention has appropriate physical properties. Within this viscosity range, the most appropriate viscosity can be selected depending on the application. In the present invention, the viscosity (23°C) can be measured using a rotational viscometer (e.g., BL type, BH type, BS type, cone-plate type, rheometer, etc.) (the same applies hereinafter).

[0073] As the component (A), these fluorine-containing compounds can be used alone or in combination of two or more.

[0074] [Component (B)] The compound of component (B) (hereinafter also referred to as epoxy compound) used in the fluoropolyether-based curable composition of the present invention is a compound having at least two epoxy groups in one molecule, and acts as a chain extender and crosslinking agent in the fluoropolyether-based curable composition of the present invention. The epoxy compound of component (B) is preferably a fluorine-containing epoxy compound represented by the following general formula (9): [wherein, Rf 1 Rf are independently monovalent or divalent groups having a fluoropolyether structure and a number average molecular weight of 400 to 40,000. 1 When Rf is monovalent, d' is 1, d is an integer of 1 to 6, and e is an integer of 2 to 20. 1 is divalent, then d' is 2, d is 1, and e is an integer from 1 to 20. Q is independently a (d+e)-valent group having at least (d+e) Si atoms, and has a siloxane structure, a silalkylene structure, a silarylene structure, or a combination thereof, and may have a cyclic structure. Z is independently a divalent hydrocarbon group having 1 to 20 carbon atoms, and may contain an ether bond or an ester bond, and may have a cyclic structure. E is independently a group represented by the following formula (I) or (II): (In the formula, R 6are independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, which may contain an ether bond or an ester bond and may have a cyclic structure. (In the formula, R 7 are independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, v is independently 1 or 2, and the total of v is 7.

[0075] In the above general formula (9), Rf 1 When Rf is monovalent, d' is 1, d is an integer of 1 to 6, preferably an integer of 1 to 4, more preferably an integer of 1, and e is an integer of 2 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 4. 1 is divalent, d' is 2, d is 1, and e is an integer of 1 to 20, preferably an integer of 1 to 6, and more preferably an integer of 2 to 4. Furthermore, in the above general formula (9), d+e is preferably an integer of 3 to 6.

[0076] In the above general formula (9), E is independently a group represented by the following formula (I) or (II). (In the formula, R 6 are independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, which may contain an ether bond or an ester bond and may have a cyclic structure. (In the formula, R 7 are independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, v is independently 1 or 2, and the total of v is 7.

[0077] In the above formula (I), R 6are independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 8 carbon atoms, which may contain an ether bond or an ester bond and may have a cyclic structure. Examples of the monovalent hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, octyl, and decyl; alkenyl groups such as vinyl, allyl, propenyl, butenyl, and hexenyl; and cycloalkyl groups such as cyclopentyl and cyclohexyl. Furthermore, halogen-substituted monovalent hydrocarbon groups, such as fluoromethyl, bromoethyl, and trifluoropropyl groups, may be used, in which some or all of the hydrogen atoms of these hydrocarbon groups have been substituted with halogen atoms such as chlorine, fluorine, or bromine. A hydrogen atom is preferred.

[0078] In the above formula (II), R 7 are independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 8 carbon atoms. Examples of the monovalent hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, octyl, and decyl; and alkenyl groups such as vinyl, allyl, propenyl, butenyl, and hexenyl. Furthermore, the monovalent hydrocarbon group may be a halogen-substituted monovalent hydrocarbon group, such as a fluoromethyl group, a bromoethyl group, or a trifluoropropyl group, in which some or all of the hydrogen atoms of these hydrocarbon groups have been substituted with halogen atoms such as chlorine, fluorine, or bromine. A hydrogen atom or a methyl group is preferred.

[0079] Examples of the structure represented by the above formula (I) or (II) include the following. (In the formula, R 7 is the same as above.)

[0080] The following are preferred:

[0081] In the above general formula (9), Z is a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably 2 to 15 carbon atoms, which may contain an ether bond (—O—) or an ester bond (—COO—) and may have a cyclic structure.

[0082] Examples of Z include the following structures. The bond marked with * indicates that it is bonded to E, and the bond without a mark indicates that it is bonded to Q. -CH2CH2-*, -CH2CH2CH2-*, -CH2CH2CH2CH2-*, -CH2CH2CH2CH2CH2CH2-*, -CH2CH2CH2CH2CH2CH2CH2-*, -CH2CH2CH2CH2CH2CH2CH2-*, -CH2CH2CH2CH2CH2CH2CH2-*, -CH2CH2CH2CH2CH2CH2CH2-*, -CH2CH2CH2OCH2-*, -CH2CH2CH2OCH2CH2OCH2CH2-*, -CH2CH2CH2OCH2CH2OCH2CH2-*

[0083] Examples of the structure represented by -ZE include structures represented by the following formulae (a) to (d).

[0084] In the above formula, g is an integer of 1 to 20, preferably an integer of 2 to 15. h is an integer of 1 to 10, i is an integer of 1 to 5, l is an integer of 0 to 9, and h+2l+i is 2 to 20, preferably h is an integer of 1 to 6, i is 1 or 2, l is an integer of 0 to 4, and h+2l+i is 2 to 15. R 7 is as defined above, and is preferably a hydrogen atom or a methyl group.

[0085] As the structure represented by -ZE, the following is particularly preferred.

[0086] In the general formula (9), Q is independently a (d+e)-valent group having at least (d+e) Si atoms, and has a siloxane structure, a silalkylene structure, a silarylene structure, or a combination thereof, and may have a cyclic structure.

[0087] Q may have the following structure, for example. (wherein d and e are as defined above; c is an integer of 0 or more, preferably an integer of 0 to 10, more preferably an integer of 0 to 6; each silicon atom of the unit shown in parentheses having d repeats is Rf 1 and each silicon atom of the unit shown in parentheses having e repeats is bonded to Z. The arrangement of the units shown in parentheses may be random.

[0088] Q can also be expressed by the following formula: In the above formula, d and e are as defined above. Each silicon atom of the unit shown in parentheses having d repeats is Rf 1 and each silicon atom of the unit shown in parentheses having e repeats is bonded to Z. W is a silicon atom or a (d+e)-valent group having a siloxane structure, a silalkylene structure, a silarylene structure or a combination thereof.

[0089] Examples of W include the following structures: (In the formula, D is a monovalent hydrocarbon group having 1 to 6 carbon atoms, such as an alkyl group such as a methyl group, an ethyl group, or a propyl group.)

[0090] Examples of the above Q include the following structures.

[0091] Among the above Q groups, the following structures are particularly preferred. (wherein d1 is Rf 1 When Rf is monovalent, it is an integer of 1 to 4, more preferably 1; 1 is divalent, e1 is an integer of 2 to 4, and d1' is an integer that satisfies d1+e1=3 to 6. 1 When Rf is monovalent, it is 1 or 2, more preferably 1; 1 is divalent, e1' is 1, e1' is 2 or 3, f1 is 0 or 1, and d1' + e1' + f1 = 4. D is a monovalent hydrocarbon group having 1 to 6 carbon atoms. Each silicon atom of the unit shown in parentheses having d1 and d1' repeats is Rf1 and each silicon atom of the unit shown in the parentheses having e1 and e1' repeats is bonded to Z, and the arrangement of the units shown in the parentheses may be random.

[0092] In the above general formula (9), Rf 1 Rf are independently monovalent or divalent groups having a fluoropolyether structure and a number average molecular weight of 400 to 40,000. 1 The number average molecular weight of Rf is preferably in the range of 500 to 20,000. 1 The number average molecular weight of, for example, 19 Rf calculated from F-NMR 1 The number average molecular weight and Rf of the repeating structure of perfluorooxyalkylene units in 1 The number average molecular weight of the entire compound of component (B) can be calculated as the sum of the molecular weight of the linking group in the component (B) and the molecular weight of the linking group in the component (B). 1 H-NMR and 19 Terminal structure and main chain structure based on F-NMR (Rf 1 ) can be calculated from the ratio.

[0093] In particular, Rf 1 is the following formula -C x F 2x Suitable examples include those containing 1 to 500, preferably 2 to 400, and more preferably 4 to 200 repeating units represented by the formula: O- (x is an integer of 1 to 6). The repeating units may be branched.

[0094] Repeating unit-C x F 2x Examples of O- include units represented by the following formulas: -CF2O-, -CF2CF2O-, -CF2CF2CF2O-, -CF(CF3)CF2O-, -CF2CF(CF3)O-, -CF2CF2CF2CF2CF2O-, -CF2CF2CF2CF2CF2CF2O-, -CF2CF2CF2CF2CF2CF2O-

[0095] Rf 1 may have one of these repeating units or a combination of two or more of them.

[0096] Rf is monovalent 1 A particularly preferred structure of the above can be represented by the following general formula (11): Rf"-V- (11) (wherein Rf" is a monovalent perfluoropolyether group having a number average molecular weight of 300 to 30,000, and V is a divalent organic group having 2 to 20 carbon atoms which may contain at least one atom selected from oxygen atoms, nitrogen atoms, fluorine atoms, and silicon atoms, and which may have a cyclic structure or an unsaturated bond.)

[0097] Divalent Rf 1 A particularly preferred structure can be represented by the following general formula (12): -[V-Rf'-VT] z -V-Rf'-V- (12) [wherein Rf' is a divalent perfluoropolyether group having a number average molecular weight of 300 to 30,000, V is independently the same as above, and T is a group represented by the following general formula (13): (wherein Z, E, and e are as defined above; U is an (e+2)-valent group having at least (e+2) Si atoms, and has a siloxane structure, a silalkylene structure, a silarylene structure, or a combination thereof, and may have a cyclic structure), and z is an integer of 0 to 5.)

[0098] In the above formula (11), Rf″ is a monovalent perfluoropolyether group having a number average molecular weight of 300 to 30,000, particularly 500 to 20,000. The perfluoropolyether group may contain a branch in the middle, and the repeating unit -C x F 2x Examples of such groups include monovalent groups having O-.

[0099] Examples of Rf″ include monovalent perfluoropolyether groups represented by the following formula: (In the formula, Y is independently an F or CF group, r is an integer of 2 to 6, k and t are each an integer of 0 to 200, preferably an integer of 0 to 100, provided that k+t is 2 to 200, preferably 3 to 150, and s is an integer of 0 to 6. Each repeating unit shown in parentheses may be bonded randomly.) (In the formula, Y is independently an F or CF group, p and q are each an integer of 0 to 200, preferably an integer of 2 to 100, with the proviso that p+q is 2 to 300, preferably 4 to 200. Each repeating unit shown in parentheses may be bonded randomly.) (wherein j is an integer of 1 to 3, and u is an integer of 1 to 200, preferably an integer of 1 to 60.)

[0100] In the above formula (12), Rf′ is a divalent perfluoropolyether group having a number average molecular weight of 300 to 30,000, particularly 500 to 20,000. The perfluoropolyether group may contain a branch in the middle, and the repeating unit -C x F 2x Examples include divalent groups having O—.

[0101] Rf′ is particularly a divalent perfluoropolyether group represented by the following formula: (In the formula, Y is independently an F or CF group, r is an integer of 2 to 6, k and t are each an integer of 0 to 200, preferably an integer of 0 to 100, with the proviso that k+t is 2 to 200, preferably 3 to 150, and s is an integer of 0 to 6.) (wherein j is an integer of 1 to 3, and u is an integer of 1 to 200, preferably an integer of 1 to 60.) (In the formula, Y is an F or CF group, j is an integer of 1 to 3, p and q are each an integer of 0 to 200, preferably an integer of 2 to 100, with the proviso that p+q is 2 to 300, preferably 4 to 200. Each repeating unit shown in parentheses may be bonded randomly.)

[0102] In the above formulas (11) and (12), V independently represents a divalent organic group (particularly a hydrocarbon group) having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, which may contain at least one atom selected from an oxygen atom, a nitrogen atom, a fluorine atom, and a silicon atom, and which may have a cyclic structure or an unsaturated bond.

[0103] Examples of V include the following: In the following formula, Ph represents a phenyl group. The bond marked with * indicates that the bond is to Rf' or Rf".

[0104] Among these, the following structure is preferred. In the following formula, Ph represents a phenyl group. The bond marked with * indicates that the bond is to Rf' or Rf".

[0105] In the above formula (12), T is a divalent group represented by the following general formula (13). (In the formula, Z, E, and e are as defined above. U is an (e+2)-valent group having at least (e+2) Si atoms, and has a siloxane structure, a silalkylene structure, a silarylene structure, or a combination thereof, and may have a cyclic structure. Note that the two bonds shown in the above formula (13) are each bonded to different Vs in formula (12).)

[0106] In the above formula (13), U is an (e+2)-valent group having at least (e+2) Si atoms, and has a siloxane structure, a silalkylene structure, a silarylene structure, or a combination thereof, and may have a cyclic structure.

[0107] Examples of U include the structures shown below. (In the formula, e, c, and W are as defined above. Each silicon atom of the unit shown in parentheses having e repeats is bonded to Z in the above formula (13), and each silicon atom of the unit shown in parentheses having two repeats is bonded to a different V in the above formula (12). The arrangement of each unit shown in parentheses may be random.)

[0108] Among the above U, the following structures are particularly preferred. (wherein e is as defined above. Each silicon atom of the unit shown in parentheses having e repeats is bonded to Z in the above formula (13), and each silicon atom of the unit shown in parentheses having two repeats is bonded to a different V in the above formula (12).)

[0109] In the above formula (12), z is an integer of 0 to 5, and is preferably 0.

[0110] Rf is monovalent 1 Examples of such materials include the following: (wherein t' is an integer of 2 to 200, preferably an integer of 2 to 100). (wherein j is an integer of 1 to 3, and u is an integer of 1 to 200, preferably an integer of 1 to 60.) (wherein t' is an integer of 2 to 200, preferably an integer of 2 to 100). (wherein t' is an integer of 2 to 200, preferably an integer of 2 to 100). (wherein t' is an integer of 2 to 200, preferably an integer of 2 to 100).

[0111] Divalent Rf 1 Examples of such materials include the following: (In the formula, r is an integer of 2 to 6, k and t are each an integer of 0 to 200, preferably an integer of 0 to 100, with the proviso that k+t is an integer of 2 to 200, preferably an integer of 3 to 150, and s is an integer of 0 to 6.) (In the formula, j is an integer of 1 to 3, p and q are each an integer of 0 to 200, preferably an integer of 2 to 100, with the proviso that p+q is 2 to 300, preferably 4 to 200. Each repeating unit shown in parentheses may be bonded randomly.) (In the formula, r is an integer of 2 to 6, k and t are each an integer of 0 to 200, preferably an integer of 0 to 100, with the proviso that k+t is an integer of 2 to 200, preferably an integer of 3 to 150, and s is an integer of 0 to 6.) (In the formula, r is an integer of 2 to 6, k and t are each an integer of 0 to 200, preferably an integer of 0 to 100, with the proviso that k+t is an integer of 2 to 200, preferably an integer of 3 to 150, and s is an integer of 0 to 6.) (In the formula, r is an integer of 2 to 6, k and t are each an integer of 0 to 200, preferably an integer of 0 to 100, with the proviso that k+t is an integer of 2 to 200, preferably an integer of 3 to 150, and s is an integer of 0 to 6.)

[0112] [Method for producing component (B)] The fluorine-containing epoxy compound represented by the above general formula (9) can be produced, for example, by the method described in JP-A-2014-80534. Specifically, first, a fluorine-containing compound A having an olefin moiety (alkenyl group) at a terminal and an organosilicon compound B having two or more, preferably three or more, SiH groups in the molecule are subjected to an addition reaction in the presence of an addition reaction catalyst under conditions that result in an excess of SiH groups, thereby synthesizing a fluorine-containing compound C having multiple SiH groups.

[0113] The fluorine-containing compound A can be particularly represented by the following general formula (14): 0 -(CH=CH2) d’ (14) [wherein, Rf 0 is a monovalent group represented by the following general formula (15) or a divalent group represented by the following general formula (16). 0 is monovalent, it is 1, and it is divalent, it is 2. 1 - (15) -V 1 -Rf'-V 1 - (16) (wherein Rf' and Rf" are as defined above. V 1 are each independently a single bond or a divalent organic group having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms, which may contain at least one atom selected from oxygen atoms, nitrogen atoms, fluorine atoms, and silicon atoms, and which may have a cyclic structure or an unsaturated bond.

[0114] In the above formulas (15) and (16), V 1 are each independently a single bond or a divalent organic group having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms, which may contain at least one atom selected from an oxygen atom, a nitrogen atom, a fluorine atom, and a silicon atom, and which may have a cyclic structure or an unsaturated bond.

[0115] Applicable V 1 Examples of such groups include the following: In the following formulae, Ph represents a phenyl group. A bond marked with an asterisk (*) indicates that the bond is to Rf' or Rf".

[0116] Examples of the monovalent fluorine-containing compound A include the following. (wherein t' is an integer of 2 to 200, preferably an integer of 2 to 100). (wherein j is an integer of 1 to 3, and u is an integer of 1 to 200, preferably an integer of 1 to 60.) (wherein t' is an integer of 2 to 200, preferably an integer of 2 to 100). (wherein t' is an integer of 2 to 200, preferably an integer of 2 to 100). (wherein t' is an integer of 2 to 200, preferably an integer of 2 to 100).

[0117] Examples of the divalent fluorine-containing compound A include the following. (In the formula, r is an integer of 2 to 6, k and t are each an integer of 0 to 200, preferably an integer of 0 to 100, with the proviso that k+t is an integer of 2 to 200, preferably an integer of 3 to 150, and s is an integer of 0 to 6.) (In the formula, j is an integer of 1 to 3, p and q are each an integer of 0 to 200, preferably an integer of 2 to 100, with the proviso that p+q is 2 to 300, preferably 4 to 200. Each repeating unit shown in parentheses may be bonded randomly.) (In the formula, r is an integer of 2 to 6, k and t are each an integer of 0 to 200, preferably an integer of 0 to 100, with the proviso that k+t is an integer of 2 to 200, preferably an integer of 3 to 150, and s is an integer of 0 to 6.) (In the formula, r is an integer of 2 to 6, k and t are each an integer of 0 to 200, preferably an integer of 0 to 100, with the proviso that k+t is an integer of 2 to 200, preferably an integer of 3 to 150, and s is an integer of 0 to 6.) (In the formula, r is an integer of 2 to 6, k and t are each an integer of 0 to 200, preferably an integer of 0 to 100, with the proviso that k+t is an integer of 2 to 200, preferably an integer of 3 to 150, and s is an integer of 0 to 6.)

[0118] The organosilicon compound B can be particularly represented by the following general formula (17): Q-(H) d+e(17) (wherein Q, d, and e are as defined above. H shown in parentheses is a hydrogen atom directly bonded to the Si atom in the Q structure.)

[0119] Examples of the organosilicon compound B include the following: (In the formula, c, d, e, and W are as defined above.)

[0120] In particular, the following are preferred:

[0121] When fluorine-containing compound A is a monovalent compound and fluorine-containing compound A is reacted with organosilicon compound B in an amount such that the number of olefin moieties (alkenyl groups) in fluorine-containing compound A is d relative to the number of SiH groups (d+e) in organosilicon compound B, the structure of the resulting fluorine-containing compound C can be represented by the following general formula (18): (Rf 0 -C2H4) d -Q-(H) e (18) (wherein, Rf 0 , Q, d and e are as defined above.

[0122] When fluorine-containing compound A is a divalent compound and fluorine-containing compound A and organosilicon compound B are reacted in a molar ratio of fluorine-containing compound A:organosilicon compound B = (z+1):(z+2) (z is as defined above), the structure of the resulting fluorine-containing compound C can be represented by the following general formula (19). When z = 0, the structure is one in which organosilicon compound B is introduced at both ends of fluorine-containing compound A. (H) e -Q-[C2H4-Rf 0 -C2H4-T 1 ] z -C2H4-Rf 0 -C2H4-Q-(H) e (19) [where Q, Rf0 , e, and z are as described above. H shown in parentheses is a hydrogen atom directly bonded to the Si atom in the Q structure. 1 is represented by the following general formula (20): (wherein Q, d, and e are as defined above. H shown in parentheses is a hydrogen atom directly bonded to the Si atom in the Q structure.)

[0123] The blending ratio of the fluorine-containing compound A and the organosilicon compound B is preferably 1 to 10 mol, particularly 2 to 6 mol, of the organosilicon compound B per 1 mol of the terminal olefin moiety (alkenyl group) in the fluorine-containing compound A. In order to prevent three-dimensional crosslinking, it is desirable to carry out an addition reaction using an excess amount of the organosilicon compound B to the terminal olefin moiety (alkenyl group) of the fluorine-containing compound A, and then remove the unreacted organosilicon compound B by distillation under reduced pressure or the like. When the fluorine-containing compound A is a monovalent compound, the reaction amount of the fluorine-containing compound A and the organosilicon compound B is such that the number of olefin moieties (alkenyl groups) possessed by the fluorine-containing compound A is less than (d + e), preferably d, per molecule of the organosilicon compound B having (d + e) ​​SiH groups. Furthermore, when the fluorine-containing compound A is a divalent compound, the molar ratio of the fluorine-containing compound A:organosilicon compound B = (z + 1): (z + 2) is desirable (where z is as defined above). In addition, when the fluorine-containing compound A is a divalent compound, if necessary, an intermediate having a small z may be synthesized, and then the addition reaction may be carried out stepwise. For example, in the fluorine-containing compound C represented by the above formula (19), a compound having z = 0 is synthesized, and then 2 mol of the compound having z = 0 in the fluorine-containing compound C represented by the above formula (19) is reacted again with 1 mol of the fluorine-containing compound A to obtain a fluorine-containing compound C having z = 2. Alternatively, a component having the desired z value can be separated from a mixture having different z values ​​by any separation means. For example, only the component having z = 1 may be extracted from a mixture having z = 0 to 3 by means of preparative chromatography or the like.

[0124] The addition reaction can be carried out in the absence of a solvent, but may be carried out in the presence of a solvent if necessary. The solvent may be a commonly used organic solvent such as toluene, xylene, or isooctane. However, it is preferable that the boiling point of the solvent is equal to or higher than the target reaction temperature, that the reaction is not inhibited, and that the fluorine-containing compound C produced after the reaction is soluble at the reaction temperature. For example, partially fluorine-modified solvents such as fluorine-modified aromatic hydrocarbon solvents such as m-xylene hexafluoride and benzotrifluoride, and fluorine-modified ether solvents such as methyl perfluorobutyl ether are desirable, with m-xylene hexafluoride being particularly preferred. When a solvent is used, the amount used is not particularly limited, but is preferably 40 to 200 parts by mass, and more preferably 50 to 150 parts by mass, per 100 parts by mass of fluorine-containing compound A.

[0125] Any known addition reaction catalyst may be used. For example, a compound containing platinum, rhodium, or palladium may be used. Among these, a platinum-containing compound is preferred, and examples thereof include hexachloroplatinic (IV) acid hexahydrate, platinum carbonylvinylmethyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, platinum-octylaldehyde / octanol complex, and platinum supported on activated carbon. The amount of addition reaction catalyst to be added may be any effective amount. In particular, the amount is preferably such that the amount of metal contained is 0.1 to 5,000 ppm by mass, more preferably 1 to 1,000 ppm by mass, relative to the fluorine-containing compound A.

[0126] In the above-mentioned addition reaction, the order of adding each component is not particularly limited.For example, the method of gradually heating the mixture of fluorine-containing compound A, organosilicon compound B and addition reaction catalyst from room temperature to addition reaction temperature; the method of heating the mixture of fluorine-containing compound A, organosilicon compound B and solvent to target reaction temperature and then adding addition reaction catalyst; the method of adding fluorine-containing compound A dropwise to the mixture of organosilicon compound B and addition reaction catalyst that has been heated to target reaction temperature; the method of adding fluorine-containing compound A dropwise to the mixture of organosilicon compound B and addition reaction catalyst that has been heated to target reaction temperature; the method of adding fluorine-containing compound A dropwise to the mixture of organosilicon compound B that has been heated to target reaction temperature.Among them, the method of adding fluorine-containing compound A dropwise to the mixture of organosilicon compound B and solvent that has been heated to target reaction temperature and then adding addition reaction catalyst, or the method of adding fluorine-containing compound A dropwise to the mixture of organosilicon compound B that has been heated to target reaction temperature are particularly preferred.

[0127] The addition reaction may be carried out under conditions that are conventionally known, particularly in a dry atmosphere in air or an inert gas (such as N or Ar), at a reaction temperature of 50 to 150°C, preferably 70 to 120°C, for 0.5 to 96 hours, preferably 1 to 48 hours.

[0128] Next, an addition reaction is carried out between the SiH group of the fluorine-containing compound C obtained above and the terminal olefin moiety (alkenyl group) of compound D having a terminal olefin moiety (alkenyl group) and an epoxy group in one molecule, thereby obtaining a fluorine-containing epoxy compound represented by the above formula (9).

[0129] Compound D having a terminal olefin moiety (alkenyl group) and an epoxy group in one molecule can be particularly represented by the following general formula (21). (wherein E is the same as above. Z 1 is a single bond or a divalent hydrocarbon group having 1 to 18 carbon atoms, which may contain an ether bond or an ester bond and may have a cyclic structure.

[0130] In the above formula (21), Z 1is a single bond or a divalent hydrocarbon group having 1 to 18 carbon atoms, which may contain an ether bond or an ester bond and may have a cyclic structure. 1 Examples of the structures include the following. The bond marked with * indicates that it is bonded to E, and the bond without a mark indicates that it is bonded to a carbon atom. -CH2-*, -CH2CH2-*, -CH2CH2CH2-*, -CH2CH2CH2CH2CH2-*, -CH2CH2CH2CH2CH2CH2-*, -CH2CH2CH2CH2CH2CH2-*, -CH2OCH2-*, -CH2OCH2CH2OCH2-*, -CH2OCH2CH2OCH2CH2CH2-*

[0131] Examples of the compound D represented by the above formula (21) include structures represented by the following formulae (a') to (d').

[0132] In the above formula, g' is an integer of 0 to 18, preferably an integer of 0 to 13. h' is an integer of 0 to 8, i is an integer of 1 to 5, l is an integer of 0 to 9, and h'+2l+i is 0 to 18, preferably h' is an integer of 0 to 4, i is 1 or 2, l is an integer of 0 to 4, and h'+2l+i is 0 to 13. R 7 is as defined above, and is preferably a hydrogen atom or a methyl group.

[0133] Examples of the compound D having a terminal olefin moiety (alkenyl group) and an epoxy group in one molecule include the following: These compounds may be used alone or in combination of two or more.

[0134] The addition reaction of fluorine-containing compound C and compound D may be carried out according to a conventionally known method, for example, by the method described above. Preferably, the reaction is carried out in the presence of the addition reaction catalyst described above, in a dry atmosphere, in air or an inert gas (N, Ar, etc.), at a reaction temperature of 50 to 150°C, preferably 50 to 100°C, for 0.5 to 96 hours, preferably 1 to 48 hours. The reaction may be carried out in the presence of the above-mentioned solvent, if necessary.

[0135] The amount of compound D to be blended relative to fluorine-containing compound C is preferably such that the number of terminal olefin moieties (alkenyl groups) in compound D is equal to or such that the number of terminal olefin moieties (alkenyl groups) is in excess relative to the number of SiH groups in fluorine-containing compound C, and after the addition reaction, unreacted compound D is removed by distillation under reduced pressure or the like. In particular, it is desirable to carry out the reaction in an amount such that the number of terminal olefin moieties (alkenyl groups) in compound D is 1 to 5 mol, preferably 1 to 2 mol, per 1 mol of SiH groups in fluorine-containing compound C.

[0136] Particularly preferred examples of the fluorine-containing epoxy compound represented by the above general formula (9) include the compounds shown below. (wherein t' is an integer of 2 to 200, preferably an integer of 2 to 100). (wherein t' is an integer of 2 to 200, preferably an integer of 2 to 100). (wherein t' is an integer of 2 to 200, preferably an integer of 2 to 100). (wherein t' is an integer of 2 to 200, preferably an integer of 2 to 100). (wherein t' is an integer of 2 to 200, preferably an integer of 2 to 100). (wherein t' is an integer of 2 to 200, preferably an integer of 2 to 100). (wherein t' is an integer of 2 to 200, preferably an integer of 2 to 100). (wherein t' is an integer of 2 to 200, preferably an integer of 2 to 100). (wherein t' is an integer of 2 to 200, preferably an integer of 2 to 100). (wherein t' is an integer of 2 to 200, preferably an integer of 2 to 100). (wherein t' is an integer of 2 to 200, preferably an integer of 2 to 100). (wherein t' is an integer of 2 to 200, preferably an integer of 2 to 100). (wherein t' is an integer of 2 to 200, preferably an integer of 2 to 100). (wherein t' is an integer of 2 to 200, preferably an integer of 2 to 100). (In the formula, j is an integer of 1 to 3, p and q are each an integer of 0 to 200, preferably an integer of 2 to 100, with the proviso that p+q is 2 to 300, preferably 4 to 200. Each repeating unit shown in parentheses may be bonded randomly.) (In the formula, j is an integer of 1 to 3, p and q are each an integer of 0 to 200, preferably an integer of 2 to 100, with the proviso that p+q is 2 to 300, preferably 4 to 200. Each repeating unit shown in parentheses may be bonded randomly.) (In the formula, j is an integer of 1 to 3, p and q are each an integer of 0 to 200, preferably an integer of 2 to 100, with the proviso that p+q is 2 to 300, preferably 4 to 200. Each repeating unit shown in parentheses may be bonded randomly.) (In the formula, r is an integer of 2 to 6, k and t are each an integer of 0 to 200, preferably an integer of 0 to 100, with the proviso that k+t is an integer of 2 to 200, preferably an integer of 3 to 150, and s is an integer of 0 to 6.) (In the formula, r is an integer of 2 to 6, k and t are each an integer of 0 to 200, preferably an integer of 0 to 100, with the proviso that k+t is an integer of 2 to 200, preferably an integer of 3 to 150, and s is an integer of 0 to 6.) (In the formula, r is an integer of 2 to 6, k and t are each an integer of 0 to 200, preferably an integer of 0 to 100, with the proviso that k+t is an integer of 2 to 200, preferably an integer of 3 to 150, and s is an integer of 0 to 6.) (In the formula, r is an integer of 2 to 6, k and t are each an integer of 0 to 200, preferably an integer of 0 to 100, with the proviso that k+t is an integer of 2 to 200, preferably an integer of 3 to 150, and s is an integer of 0 to 6.) (In the formula, r is an integer of 2 to 6, k and t are each an integer of 0 to 200, preferably an integer of 0 to 100, with the proviso that k+t is an integer of 2 to 200, preferably an integer of 3 to 150, and s is an integer of 0 to 6.) (In the formula, r is an integer of 2 to 6, k and t are each an integer of 0 to 200, preferably an integer of 0 to 100, with the proviso that k+t is an integer of 2 to 200, preferably an integer of 3 to 150, and s is an integer of 0 to 6.) (In the formula, r is an integer of 2 to 6, k and t are each an integer of 0 to 200, preferably an integer of 0 to 100, with the proviso that k+t is an integer of 2 to 200, preferably an integer of 3 to 150, and s is an integer of 0 to 6.) (In the formula, r is an integer of 2 to 6, k and t are each an integer of 0 to 200, preferably an integer of 0 to 100, with the proviso that k+t is an integer of 2 to 200, preferably an integer of 3 to 150, and s is an integer of 0 to 6.) (In the formula, r is an integer of 2 to 6, k and t are each an integer of 0 to 200, preferably an integer of 0 to 100, with the proviso that k+t is an integer of 2 to 200, preferably an integer of 3 to 150, and s is an integer of 0 to 6.) (In the formula, r is an integer of 2 to 6, k and t are each an integer of 0 to 200, preferably an integer of 0 to 100, with the proviso that k+t is an integer of 2 to 200, preferably an integer of 3 to 150, and s is an integer of 0 to 6.) (In the formula, r is an integer of 2 to 6, k and t are each an integer of 0 to 200, preferably an integer of 0 to 100, with the proviso that k+t is an integer of 2 to 200, preferably an integer of 3 to 150, and s is an integer of 0 to 6.) (In the formula, r is an integer of 2 to 6, k and t are each an integer of 0 to 200, preferably an integer of 0 to 100, with the proviso that k+t is an integer of 2 to 200, preferably an integer of 3 to 150, and s is an integer of 0 to 6.) (In the formula, r is an integer of 2 to 6, k and t are each an integer of 0 to 200, preferably an integer of 0 to 100, with the proviso that k+t is an integer of 2 to 200, preferably an integer of 3 to 150, and s is an integer of 0 to 6.) (In the formula, r is an integer of 2 to 6, k and t are each an integer of 0 to 200, preferably an integer of 0 to 100, with the proviso that k+t is an integer of 2 to 200, preferably an integer of 3 to 150, and s is an integer of 0 to 6.)

[0137] As the epoxy compound of component (B), in addition to the fluorine-containing epoxy compound represented by the above general formula (9), epoxy compounds containing no fluorine atoms (for example, monovalent or divalent fluoropolyether structures) can also be used. For example, epoxy compounds represented by the following formula can be exemplified.

[0138] The amount of epoxy groups in the epoxy compound of component (B) is preferably 0.005 to 3 mol / 100 g, and more preferably 0.01 to 2 mol / 100 g. 1 It can be measured by H-NMR.

[0139] The amount of component (B) is such that the amount of epoxy groups in component (B) is 0.5 to 5 mol per 1 mol of thiol groups in component (A), preferably 0.7 to 2.5 mol. By using an epoxy group amount of 0.5 mol or more, it is possible to achieve a sufficient degree of crosslinking to obtain a cured product. Furthermore, by using an epoxy group amount of 5 mol or less, it is difficult for epoxy groups to remain in the resulting cured product, which is advantageous from the viewpoint of preventing changes in the physical properties of the cured product over time.

[0140] As the component (B), these fluorine-containing epoxy compounds may be used alone or in combination of two or more.

[0141] [Component (C)] Component (C) is a curing accelerator, and is used to accelerate the reaction between component (A) and component (B) and rapidly progress the curing reaction. The curing accelerator may be any known curing accelerator for epoxy resins and thiol compounds. Examples of the curing accelerator include phosphorus compounds such as triphenylphosphine, tributylphosphine, tri(p-methylphenyl)phosphine, tri(nonylphenyl)phosphine, triphenylphosphine-triphenylborane, and tetraphenylphosphine-tetraphenylborate; tertiary amine compounds such as triethylamine, benzyldimethylamine, α-methylbenzyldimethylamine, and 1,8-diazabicyclo[5.4.0]undecene-7; and imidazole compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole. urea compounds such as 1,1-dimethylurea, 1,1,3-trimethylurea, 1,1-dimethyl-3-ethylurea, 1,1-dimethyl-3-phenylurea, 1,1-diethyl-3-methylurea, 1,1-diethyl-3-phenylurea, 1,1-dimethyl-3-(3,4-dimethylphenyl)urea, 1,1-dimethyl-3-(p-chlorophenyl)urea, and 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU); amine adduct compounds such as the reaction product of an amine compound and an epoxy compound; and urea adduct compounds such as the reaction product of an amine compound and an isocyanate compound or a urea compound. Among these, solid imidazole compounds and amine adduct compounds are preferred.

[0142] The blend amount of component (C) is preferably 0.5 to 50 parts by mass, and more preferably 1 to 40 parts by mass, per 100 parts by mass of component (A). When the blend amount is 0.5 to 50 parts by mass, there is no risk of the curing rate of the composition becoming too slow or too fast during molding.

[0143] [Component (D) (Other Components)] In the fluoropolyether-based curable composition of the present invention, for the purpose of improving its practicality, various additives such as plasticizers, viscosity modifiers, flexibility-imparting agents, inorganic fillers, reaction inhibitors, ion-trapping agents, silane coupling agents, etc. may be added as needed in addition to the above-mentioned components (A), (B), and (C). The amounts of these additives added are arbitrary as long as they do not impair the object of the present invention and do not impair the properties of the composition or the physical properties of the cured product.

[0144] As the plasticizer, viscosity modifier, and flexibility-imparting agent, a polyfluorothiol compound represented by the following general formula (22) and / or a polyfluoro compound represented by the following general formulas (23) to (27) can be used.

[0145] [wherein X is the same as in the above average formula (1), and Rf 2 is a monovalent perfluoropolyether group represented by the following general formula: (wherein f2 is an integer of 2 to 200, preferably an integer of 2 to 100, and h2 is an integer of 1 to 3, and is equal to or less than the molecular weight of Rf in formula (1) of the component (A) used.)

[0146] Y 1 -O-(CF2CF2CF2O) c2 -Y 1 (23) [wherein, Y 1 are independently represented by the formula: C k2 F 2k2+1 -(k2 is an integer of 1 to 3), and c2 is an integer of 1 to 200 and is equal to or less than the molecular weight of Rf in formula (1) in the component (A) used.

[0147] Y 2 -O-(CF2O) d2 (CF2CF2O) e2 -Y 2 (24) Y 2 -O-(CF2O) d2 (CF(CF3)CF2O) e2 -Y 2 (25) Y 2 -O-(CF(CF3)CF2O) d2 -Y2 (26) (wherein, Y 2 is the above Y 1 where d2 and e2 are each integers of 1 to 200, d2+e2=2 to 200, and are equal to or less than the molecular weight of Rf in formula (1) in the component (A) used. The repeating units shown in parentheses with d2 and e2 above may be bonded randomly.

[0148] Rf 3 -(Y 3 ) c3 (27) (wherein, Rf 3 is a monovalent or divalent perfluoropolyether group, Y 3 is a monovalent organic group which may have at least one bond selected from a carbonyl bond, an amide bond, an ester bond, an ether bond and a thioester bond, and c3 is 1 or 2. 3 When Rf is monovalent, c3 is 1. 3 When is divalent, c3 is 2.)

[0149] In the above formula (22), examples of X include the same as X in the above average formula (1).

[0150] In the above formula (22), Rf 2 is a monovalent perfluoropolyether group represented by the following general formula: (In the formula, f2 is an integer of 2 to 200, preferably an integer of 2 to 100, and h2 is an integer of 1 to 3, and is equal to or less than the molecular weight of Rf in formula (1) of the component (A) used.)

[0151] Rf 2 As the above, the following are preferred. (wherein f2 is the same as above and is equal to or less than the molecular weight of Rf in formula (1) in the component (A) used.)

[0152] In the above formula (27), Rf 3 is a monovalent or divalent perfluoropolyether group, and the monovalent perfluoropolyether group is Rf in the above general formula (22). 2The divalent perfluoropolyether group may be exemplified by the same groups as Rf in the above average formula (1).

[0153] In the above formula (27), Y 3 is a monovalent organic group (particularly a hydrocarbon group) preferably having 1 to 20 carbon atoms, which may have at least one bond selected from a carbonyl bond, an amide bond, an ester bond, an ether bond, and a thioester bond, and specific examples thereof include the structures shown below. Here, Me represents a methyl group, and Et represents an ethyl group.

[0154] Specific examples of the polyfluorothiol compound represented by the general formula (22) include the following: The following f2 satisfies the above requirements.

[0155]

[0156] Specific examples of polyfluoro compounds represented by the above general formulas (23) to (27) include the following. Note that the following c2, d2, e2, the sum of d2 and e2, f2, s1', t1', the sum of s1' and t1', v1, w1, and the sum of v1 and w1 satisfy the above requirements, and the repeating units shown in parentheses with d2, e2, or v1, w1 may be bonded randomly. Furthermore, Me in the formulas is a methyl group, and Et is an ethyl group. CF3O-(CF2CF2CF2O) c2 -CF2CF3 CF3-O-(OCF2) d2 (OCF2CF2) e2 -CF3 CF3-O-(OCF2) d2 (OCF(CF3)CF2) e2 -CF3 C3F7-O-(CF(CF3)CF2O) d2 -CF2CF3

[0157] The viscosity (23°C) of the polyfluorothiol compound represented by the formula (22) and the polyfluoro compounds represented by the formulas (23) to (27) is preferably in the range of 2,000 to 200,000 mPa·s. When the polyfluorothiol compound represented by the formula (22) and the polyfluoro compounds represented by the formulas (23) to (27) are blended, the blending amount is preferably 1 to 300 parts by mass, more preferably 10 to 250 parts by mass, per 100 parts by mass of component (A).

[0158] Examples of inorganic fillers that can be added include silica powders such as fumed silica (fumed silica or dry silica), precipitated silica (wet silica), spherical silica (fused silica), sol-gel silica, and silica aerogel; various surface-treated silica powders obtained by hydrophobizing the untreated surface of the silica powder with various organochlorosilanes, organodisilazanes, cyclic organopolysilazanes, and the like; quartz powder, fused quartz powder, diatomaceous earth, reinforcing or semi-reinforcing fillers such as calcium carbonate; inorganic pigments such as titanium oxide, iron oxide, carbon black, and cobalt aluminate; heat resistance improvers such as titanium oxide, iron oxide, carbon black, cerium oxide, cerium hydroxide, zinc carbonate, magnesium carbonate, and manganese carbonate; thermal conductivity imparting agents such as alumina, boron nitride, silicon carbide, and metal powder; and conductivity imparting agents such as carbon black, silver powder, and conductive zinc white.

[0159] The reaction inhibitor is added for the purpose of improving storage stability, and is not particularly limited, and any known reaction inhibitor can be used, for example, borate ester compounds such as triisopropyl borate compounds, aluminum chelate compounds, phosphate ester compounds, barbituric acid, etc.

[0160] The ion trapping agent is added to the resin composition to trap ionic impurities and prevent thermal and moisture-absorbing deterioration, and is not particularly limited and any known ion trapping agent can be used. Examples of the ion trapping agent include hydrotalcites, bismuth hydroxide compounds, and rare earth oxides.

[0161] [Method for producing fluoropolyether-based curable composition] The method for producing the fluoropolyether-based curable composition of the present invention is not particularly limited, and it can be produced by kneading the above-mentioned components.Specifically, the fluoropolyether-based curable composition of the present invention can be produced by uniformly mixing the above-mentioned components (A), (B), (C) and, if necessary, other optional components using a mixing device such as a planetary mixer, a Ross mixer, or a Hobart mixer, and, if necessary, a kneading device such as a kneader or a three-roll mill.It may also be a two-part composition that is mixed when used.

[0162] In using the fluoropolyether-based curable composition of the present invention, the composition may be dissolved to a desired concentration in an appropriate fluorine-based solvent, depending on the application and purpose, such as 1,3-bis(trifluoromethyl)benzene, Fluorinert (manufactured by 3M Corporation), perfluorobutyl methyl ether, perfluorobutyl ethyl ether, 1,1,2,2-tetrafluoroethyl methyl ether, 1,1,2,2-tetrafluoroethyl ethyl ether, 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether, hexafluoroisopropyl methyl ether, 1,1,3,3,3-pentafluoro-2-trifluoromethylpropyl methyl ether, 1,1,2,3,3,3-hexafluoropropyl methyl ether, 1,1,2,3,3,3-hexafluoropropyl ethyl ether, etc. In particular, the use of a solvent is preferred for thin film coating applications.

[0163] The produced fluoropolyether-based curable composition is preferably heated to accelerate curing and to obtain a cured product having good mechanical properties, and is preferably cured at 60° C. or higher, preferably 80 to 200° C., for a period of several tens of seconds to several days. The fluoropolyether-based curable composition of the present invention has good curability under relatively low temperature conditions, and is more preferably cured at 60 to 100° C. for 30 minutes to 4 hours.

[0164] The fluoropolyether-based curable composition of the present invention is preferably used for automobiles, ships, aircraft, space-related equipment, generators, sports equipment, lighting fixtures, organic electroluminescent (OLED) displays, LEDs, civil engineering and construction, chemical plants, analytical and physical and chemical equipment, living environments, communication devices, communication facilities, and railway vehicles.

[0165] Examples of articles containing a cured product of the fluoropolyether-based curable composition of the present invention include automobiles, aircraft, space-related equipment, sporting goods, on-board sensors, lighting fixtures, televisions, personal computers, smartphones, solar panels, wind turbines, pipes, packings, O-rings, gaskets, integrated circuits, printed wiring boards, inkjet printers, printer heads, semiconductor manufacturing equipment, organic EL (OLED) displays, LED displays, pressure vessels, cables, and interlayer insulating films. In these articles, the insulating properties, chemical resistance, low moisture permeability, and other properties possessed by the cured product of the fluoropolyether-based curable composition of the present invention are effectively utilized. The fluoropolyether-based curable composition of the present invention can also be used as a paint, antistatic agent, adhesive, coating agent, sealant, damming agent, and the like.

[0166] 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. In the following Examples, the viscosity values ​​are values ​​measured at 23°C using a rotational viscometer (BL type).

[0167] Synthesis Example 1: 1,000 g of a polymer represented by the following formula (28) (COF group amount: 0.0332 mol / 100 g) was placed in a flask, and the atmosphere in the flask was replaced with nitrogen. 102.5 g (1.33 mol) of 2-aminoethanethiol and 400 g of acetonitrile were added to the flask, and the mixture was stirred at 25° C. for 3 hours. 19 After confirming the disappearance of the acid fluoride by F-NMR, the solvent was removed by concentration under reduced pressure, and the product was filtered to obtain a fluorine-containing thiol compound represented by the following formula (29) (viscosity: 9,100 mPa / s, amount of thiol group: 0.0332 mol / 100 g). (The average value of n+m is 33) (The average value of n+m is 33)

[0168] Synthesis Example 2 Synthesis was performed in the same manner as in Synthesis Example 1, except that 158.3 g (1.33 mol) of 5-amino-2-pentanethiol was used instead of 2-aminoethanethiol, to obtain a fluorine-containing thiol compound represented by the following formula (30) (viscosity: 10,100 mPa s, amount of thiol groups: 0.0328 mol / 100 g). (The average value of n+m is 33)

[0169] Synthesis Example 3 Synthesis was performed in the same manner as in Synthesis Example 1, except that 1,000 g of a polymer represented by the following formula (31) (ester group amount: 0.0470 mol / 100 g) and 145.0 g (1.88 mol) of 2-aminoethanethiol were used instead of the polymer represented by the above formula (28), to obtain a fluorine-containing thiol compound represented by the following formula (32) (viscosity: 500 mPa s, thiol group amount: 0.0460 mol / 100 g). (n / m=0.9, n+m=45) (n / m=0.9, n+m=45, repeating units in parentheses are random.)

[0170] Synthesis Example 4 Synthesis was performed in the same manner as in Synthesis Example 1, except that 219.9 g (1.33 mol) of bis(3-mercaptopropyl)amine was used instead of 2-aminoethanethiol in Synthesis Example 1, to obtain a fluorine-containing thiol compound represented by the following formula (33) (viscosity: 7,800 mPa s, thiol group amount: 0.0646 mol / 100 g). (The average value of n+m is 33)

[0171] Synthesis Example 5: 1,000 g of the polymer represented by formula (28) (COF group amount: 0.0332 mol / 100 g) was placed in a flask, and the atmosphere in the flask was replaced with nitrogen. 26.9 g (0.35 mol) of 2-aminoethanethiol, 35.4 g (0.35 mol) of triethylamine, and 400 g of acetonitrile were added to the flask, and the mixture was stirred at 60° C. for 3 hours. 19After confirming the disappearance of the acid fluoride by F-NMR, the solvent and remaining triethylamine were removed by concentration under reduced pressure, and the product was filtered to obtain a fluorine-containing thiol compound represented by the following formula (34) (viscosity: 11,800 mPa / s, amount of thiol group: 0.0289 mol / 100 g). (The average value of a is 0.15, and the average value of n+m for each Rf in the above formula (1) is 33)

[0172] Synthesis Example 6 A flask was charged with 200 g of a polymer represented by the following formula (35) (vinyl group amount: 0.0320 mol / 100 g), and the atmosphere in the flask was replaced with nitrogen. Next, 200 g of m-xylene hexafluoride and 73.5 g (0.30 mol) of tetramethylcyclotetrasiloxane were added, and the mixture was heated to 75°C with stirring. After that, 0.08 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex (2.1 × 10 as Pt alone) was added. -6 The resulting mixture was stirred for 4 hours. After confirming the disappearance of the vinyl groups, the solvent and excess tetramethylcyclosiloxane were removed. The resulting mixture was then treated with activated carbon to obtain 149.7 g of a polymer represented by the following formula (36): (The average value of n+m is 33) (The average value of n+m is 33)

[0173] Next, 145.2 g of the polymer represented by formula (36) obtained above (SiH group amount: 0.0882 mol / 100 g) was charged into another flask, and the atmosphere inside the flask was replaced with nitrogen. 16.11 g (0.14 mol) of allyl glycidyl ether and 145.2 g of m-xylene hexafluoride were added thereto, and the temperature was raised to 70°C with stirring. 0.73 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex (1.87 × 10 as Pt alone) was then added. -5 The resulting mixture was stirred for 1 hour. After confirming the disappearance of the SiH groups, the mixture was treated with activated carbon, and the solvent and excess allyl glycidyl ether were removed by distillation under reduced pressure to obtain 150 g of a grease-like fluorine-containing epoxy compound represented by the following formula (37). The amount of epoxy groups was 0.0810 mol / 100 g. (The average value of n+m is 33)

[0174] Synthesis Example 7 A flask was charged with 200 g of a polymer represented by the following formula (38) (vinyl group amount: 0.0335 mol / 100 g), and the atmosphere in the flask was replaced with nitrogen. Next, 200 g of m-xylene hexafluoride and 78.11 g (0.32 mol) of tetramethylcyclotetrasiloxane were added, and the mixture was heated to 75°C with stirring. After that, 0.24 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex (6.2 × 10 as Pt alone) was added. -6 The resulting mixture was stirred for 2 hours. After confirming the disappearance of the vinyl groups, the solvent and excess tetramethylcyclosiloxane were removed. The resulting mixture was then treated with activated carbon to obtain 158.1 g of a polymer represented by the following formula (39): (The average value of n+m is 33) (The average value of n+m is 33)

[0175] Next, 155.0 g of the polymer represented by formula (39) obtained above (SiH group amount: 0.0929 mol / 100 g) was charged into another flask, and the atmosphere inside the flask was replaced with nitrogen. 17.8 g (0.16 mol) of allyl glycidyl ether and 155.0 g of m-xylene hexafluoride were added thereto, and the temperature was raised to 70°C with stirring. Then, 0.77 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex (1.97 × 10 as Pt alone) was added. -5 The resulting mixture was stirred for 1 hour. After confirming the disappearance of the SiH groups, the mixture was treated with activated carbon, and the solvent and excess allyl glycidyl ether were removed by distillation under reduced pressure to obtain 153 g of a grease-like fluorine-containing epoxy compound represented by the following formula (40). The amount of epoxy groups was 0.0840 mol / 100 g. (The average value of n+m is 33)

[0176] Synthesis Example 8 The same procedures as in Synthesis Example 6 were carried out, except that 17.5 g (0.14 mol) of 3-vinylcyclohexene oxide was used instead of allyl glycidyl ether, to obtain 149 g of a grease-like fluorinated epoxy compound represented by the following formula (41). The amount of epoxy groups was 0.0803 mol / 100 g. (The average value of n+m is 33)

[0177] Synthesis Example 9 The same procedures as in Synthesis Example 7 were carried out, except that 19.4 g (0.16 mol) of 3-vinylcyclohexene oxide was used instead of allyl glycidyl ether, to obtain 152 g of a grease-like fluorinated epoxy compound represented by the following formula (42). The amount of epoxy groups was 0.0833 mol / 100 g. (The average value of n+m is 33)

[0178] Synthesis Example 10: 200 g of a polymer represented by the following formula (43) (vinyl group amount: 0.0231 mol / 100 g) was charged into a flask, and the atmosphere in the flask was replaced with nitrogen. Next, 200 g of m-xylene hexafluoride and 53.77 g (0.22 mol) of tetramethylcyclotetrasiloxane were added, and the mixture was heated to 75°C with stirring. After that, 0.08 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex (2.1 × 10 as Pt alone) was added. -6 The resulting mixture was stirred for 4 hours. After confirming the disappearance of the vinyl groups, the solvent and excess tetramethylcyclosiloxane were removed. The resulting mixture was then treated with activated carbon to obtain 176.1 g of a polymer represented by the following formula (44): (The average value of n is 24) (The average value of n is 24)

[0179] Next, 150 g of the polymer represented by formula (44) obtained above (SiH group amount: 0.0658 mol / 100 g) was charged into another flask, and the atmosphere inside the flask was replaced with nitrogen. 12.57 g (0.11 mol) of allyl glycidyl ether and 150 g of m-xylene hexafluoride were added thereto, and the temperature was raised to 70°C with stirring. 0.75 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex (1.92 × 10 as Pt alone) was then added. -5 The resulting mixture was stirred for 1 hour. After confirming the disappearance of the SiH groups, the mixture was treated with activated carbon, and the solvent and excess allyl glycidyl ether were removed by distillation under reduced pressure to obtain 139 g of a grease-like fluorine-containing epoxy compound represented by the following formula (45). The amount of epoxy groups was 0.0612 mol / 100 g. (The average value of n is 24)

[0180] Synthesis Example 11 A flask was charged with 200 g of a polymer represented by the following formula (46) (vinyl group amount: 0.0239 mol / 100 g), and the atmosphere in the flask was replaced with nitrogen. Next, 200 g of m-xylene hexafluoride and 54.97 g (0.23 mol) of tetramethylcyclotetrasiloxane were added, and the mixture was heated to 75°C with stirring. After that, 0.24 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex (6.2 × 10 as Pt elemental substance) was added. -6 The resulting mixture was stirred for 4 hours. After confirming the disappearance of the vinyl groups, the solvent and excess tetramethylcyclosiloxane were removed. The resulting mixture was then treated with activated carbon to obtain 180 g of a polymer represented by the following formula (47): (The average value of n is 24) (The average value of n is 24)

[0181] Next, 150 g of the polymer represented by formula (47) obtained above (SiH group amount: 0.0677 mol / 100 g) was charged into another flask, and the atmosphere inside the flask was replaced with nitrogen. 12.92 g (0.11 mol) of allyl glycidyl ether and 150 g of m-xylene hexafluoride were added thereto, and the temperature was raised to 70°C with stirring. 0.73 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex (1.87 × 10 as Pt alone) was then added. -5 The resulting mixture was stirred for 1 hour. After confirming the disappearance of the SiH groups, the mixture was treated with activated carbon, and the solvent and excess allyl glycidyl ether were distilled off under reduced pressure to obtain 141 g of a grease-like fluorine-containing epoxy compound represented by the following formula (48). The amount of epoxy groups was 0.0629 mol / 100 g. (The average value of n is 24)

[0182] Synthesis Example 12 200 g of the polymer represented by formula (38) (vinyl group amount: 0.0335 mol / 100 g) was charged into a flask, and the atmosphere inside the flask was replaced with nitrogen. Next, 200 g of m-xylene hexafluoride and 87.0 g (0.32 mol) of 3-[(dimethylsilyl)oxy]-1,1,3,5,5-pentamethyltrisiloxane were added, and the temperature was raised to 75°C with stirring. After that, 0.24 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex (6.2 × 10 as Pt elemental substance) was added. -6 mol) was added and stirred for 2 hours. After confirming the disappearance of the vinyl groups, the solvent and excess 3-[(dimethylsilyl)oxy]-1,1,3,5,5-pentamethyltrisiloxanemethyltris(dimethylsiloxy)silane were removed by distillation under reduced pressure. The mixture was then treated with activated carbon to obtain 160 g of a polymer represented by the following formula (49): (The average value of n+m is 33)

[0183] Next, 150 g of the polymer represented by formula (49) obtained above (SiH group amount: 0.0614 mol / 100 g) was charged into another flask, and the atmosphere inside the flask was replaced with nitrogen. 11.79 g (0.10 mol) of allyl glycidyl ether and 150 g of m-xylene hexafluoride were added thereto, and the temperature was raised to 70°C with stirring. 0.73 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex (1.87 × 10 as Pt alone) was then added. -5 The resulting mixture was stirred for 1 hour. After confirming the disappearance of the SiH groups, the mixture was treated with activated carbon, and the solvent and excess allyl glycidyl ether were removed by distillation under reduced pressure to obtain 143 g of an oily fluorine-containing epoxy compound represented by the following formula (50). The amount of epoxy groups was 0.0574 mol / 100 g. (The average value of n+m is 33)

[0184] Synthesis Example 13 200 g of the polymer represented by formula (35) (vinyl group amount: 0.0320 mol / 100 g) was charged into a flask, and the atmosphere inside the flask was replaced with nitrogen. Next, 200 g of m-xylene hexafluoride and 82.0 g (0.31 mol) of 3-[(dimethylsilyl)oxy]-1,1,3,5,5-pentamethyltrisiloxane were added, and the temperature was raised to 75°C with stirring. After that, 0.10 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex (2.6 × 10 as Pt elemental substance) was added. -6 mol) was added and stirred for 3 hours. After confirming the disappearance of the vinyl groups, the solvent and excess 3-[(dimethylsilyl)oxy]-1,1,3,5,5-pentamethyltrisiloxanemethyltris(dimethylsiloxy)silane were removed by distillation under reduced pressure. The mixture was then treated with activated carbon to obtain 165 g of a polymer represented by the following formula (51): (The average value of n+m is 33)

[0185] Next, 150 g of the polymer represented by formula (51) obtained above (SiH group amount: 0.0590 mol / 100 g) was charged into another flask, and the atmosphere inside the flask was replaced with nitrogen. 11.36 g (0.10 mol) of allyl glycidyl ether and 150 g of m-xylene hexafluoride were added thereto, and the temperature was raised to 70°C with stirring. 0.76 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex (1.94 × 10 as Pt alone) was then added. -5 The resulting mixture was stirred for 1 hour. After confirming the disappearance of the SiH groups, the mixture was treated with activated carbon, and the solvent and excess allyl glycidyl ether were removed by distillation under reduced pressure to obtain 143 g of an oily fluorine-containing epoxy compound represented by the following formula (52). The amount of epoxy groups was 0.0553 mol / 100 g. (The average value of n+m is 33)

[0186] Synthesis Example 14 The same procedures as in Synthesis Example 12 were repeated, except that 12.8 g (0.10 mol) of 3-vinylcyclohexene oxide was used instead of allyl glycidyl ether, to obtain 140 g of an oily fluorinated epoxy compound represented by the following formula (53). The amount of epoxy groups was 0.0570 mol / 100 g. (The average value of n+m is 33)

[0187] [Examples 1 to 22 and Comparative Examples 1 and 2] The components used in the examples and comparative examples are as follows.

[0188] Component (A) (A1): Fluorine-containing thiol compound represented by the above formula (29) (A2): Fluorine-containing thiol compound represented by the above formula (30) (A3): Fluorine-containing thiol compound represented by the above formula (32) (A4): Fluorine-containing thiol compound represented by the above formula (33) (A5): Fluorine-containing thiol compound represented by the above formula (34) (A6): Fluorine-containing amino compound represented by the following formula (54) (amount of secondary amino group (NH) at polymer terminal: 0.0296 mol / 100 g) (The average value of a is 1.03, and the average value of n+m is 33)

[0189] (A7): Fluorine-containing amino compound represented by the following formula (55) (amount of secondary amino groups (NH) at polymer terminals: 0.0301 mol / 100 g) (The average value of n+m is 33)

[0190] Component (B) (B1): Fluorine-containing epoxy compound represented by the above formula (37) (B2): Fluorine-containing epoxy compound represented by the above formula (40) (B3): Fluorine-containing epoxy compound represented by the above formula (41) (B4): Fluorine-containing epoxy compound represented by the above formula (42) (B5): Fluorine-containing epoxy compound represented by the following formula (56) (epoxy group amount 0.1103 mol / 100 g) (n / m=0.9, n+m=45)

[0191] (B6): Fluorine-containing epoxy compound represented by the above formula (45) (B7): Fluorine-containing epoxy compound represented by the above formula (48) (B8): Fluorine-containing epoxy compound represented by the above formula (50) (B9): Fluorine-containing epoxy compound represented by the above formula (52) (B10): Fluorine-containing epoxy compound represented by the above formula (53) (B11): Epoxy compound represented by the following formula (57) (epoxy group amount 1.08 mol / 100 g)

[0192] Component (C) (C1) Amine-epoxy adduct latent curing catalyst (reaction product of an amine compound and an epoxy compound, trade name: Fujicure FXR-1081, manufactured by T&K Toka Corporation) (C2) Amine-epoxy adduct latent curing catalyst (reaction product of an amine compound and an epoxy compound, trade name: Fujicure FXR-1121, manufactured by T&K Toka Corporation) (C3) 2-phenyl-4-methyl-5-hydroxymethylimidazole (2P4MHZ-PW, manufactured by Shikoku Chemical Industries, Ltd.)

[0193] Other Components (Component (D)) (D1) Reaction inhibitor: triisopropyl borate compound (manufactured by TCI)

[0194] <Preparation of Fluoropolyether-Based Curable Composition> The above components were mixed in the amounts (parts by mass) shown in Tables 1 to 3 using a planetary mixer to obtain fluoropolyether-based curable compositions.

[0195]

[0196]

[0197]

[0198] <Confirmation of storage stability at room temperature> 10 g of each composition obtained above was placed in a glass bottle and placed in a thermostatic chamber at 25°C. After 2, 4, 8, 16, 24, 48, and 72 hours, the fluidity was measured by visual observation according to the following evaluation criteria, and the time until fluidity was lost was confirmed. The results are shown in Tables 4 to 6. [Evaluation criteria] ○: Fluidity is maintained. △: Not cured, but no fluidity. ×: Cured.

[0199]

[0200]

[0201]

[0202] The fluoropolyether-based curable compositions of Examples 1 to 22, which used any of (A1), (A2), (A3), (A4), and (A5) having a thiol group at the polymer chain terminal as the component (A), exhibited high storage stability, maintaining fluidity at 25°C for 48 hours or more, and particularly for Examples 14 to 18, 20, and 22, for 72 hours. This is advantageous because it ensures sufficient usable life for the composition when producing articles having a cured product obtained from the composition. On the other hand, in Comparative Examples 1 and 2, which used (A6) or (A7) having a secondary amino group at the polymer terminal instead of (A1), (A2), (A3), (A4), and (A5) having a thiol group at the polymer chain terminal, the compositions maintained fluidity for approximately 8 to 16 hours, but were completely cured after 24 to 48 hours, resulting in lower storage stability than Examples 1 to 22.

[0203] <Evaluation of curability of fluoropolyether-based curable compositions under heating conditions> 0.1 g of the fluoropolyether-based curable compositions of Examples 1 to 22 and Comparative Examples 1 and 2 obtained above was placed on a hot plate at 80°C. If the composition was completely cured after 30 minutes and no uncured material adhered to the surface of the cured product when touched with a spatula, it was rated as ◯, and if the curing was insufficient and no uncured material adhered to the surface when touched with a spatula, it was rated as ×. The results are shown in Tables 7 to 9.

[0204]

[0205]

[0206]

[0207] The fluoropolyether-based curable compositions of Examples 1 to 22 were all completely cured at 80° C. On the other hand, the fluoropolyether-based curable compositions of Comparative Examples 1 and 2 were inferior in storage stability to the fluoropolyether-based curable compositions of Examples 1 to 22, and also in curability at 80° C.

[0208] <Preparation of Fluoropolyether-Based Cured Products and Evaluation of Physical Properties> The fluoropolyether-based curable compositions prepared in Examples 1 to 22 and Comparative Examples 1 and 2 were immediately poured into a 2 mm thick stainless steel mold placed on a Teflon (registered trademark, the same applies hereinafter) sheet, sandwiched between other Teflon sheets, and press-cured under heating. The fluoropolyether-based curable compositions of Examples 1 to 22 were press-cured at 80°C for 2 hours, and the fluoropolyether-based curable compositions of Comparative Examples 1 and 2 were press-cured at 100°C for 6 hours. After press-curing, the 2 mm thick stainless steel mold was removed to obtain fluoropolyether-based cured products, which were then evaluated for hardness, tensile strength, and elongation at break according to JIS K 6249. The results are shown in Table 10.

[0209]

[0210] In all of the fluoropolyether-based curable compositions of Examples 1 to 22, fluoropolyether-based cured products having good mechanical properties could be obtained, as in Comparative Examples 1 and 2. The above results demonstrate that the fluoropolyether-based curable composition of the present invention combines good storage stability with good curability under relatively low temperature conditions, and can provide cured products having good mechanical properties by heat curing.

[0211] Evaluation of Electrical Properties (Insulating Properties) of Fluoropolyether-Based Cured Products: The fluoropolyether-based curable compositions prepared in Examples 1 to 22 and Comparative Examples 1 and 2 were poured immediately after preparation into a 1 mm thick stainless steel mold placed on a Teflon sheet, sandwiched between two other Teflon sheets, and then press-cured under heating. The fluoropolyether-based curable compositions of Examples 1 to 22 were press-cured at 80°C for 2 hours, and the fluoropolyether-based curable compositions of Comparative Examples 1 and 2 were press-cured at 100°C for 6 hours. After press-curing, the 1 mm thick stainless steel mold was removed from the resulting fluoropolyether-based cured products, and the volume resistivity was measured using a digital ultra-high resistance meter (5450, manufactured by ADC), and the dielectric constant (50 Hz) and dielectric loss tangent (50 Hz) were measured using an electrical insulating material C&tanδ measuring instrument (DAC-IM-D1, manufactured by Soken Denki Co., Ltd.). The results are shown in Table 11 below.

[0212]

[0213] The cured products obtained from the fluoropolyether-based curable compositions of Examples 1 to 22, like the cured products obtained from the fluoropolyether-based curable compositions of Comparative Examples 1 and 2, exhibited a sufficient level of insulation for use as cured products in articles for automobiles, ships, aircraft, space-related equipment, generators, sports equipment, lighting fixtures, organic electroluminescent (OLED) displays, LEDs, civil engineering and construction, chemical plants, analytical and physical and chemical equipment, living environments, communication devices, communication facilities, and railway vehicles.

[0214] <Evaluation of Chemical Resistance of Fluoropolyether-Based Cured Products> Dumbbell-shaped No. 6 test pieces according to JIS K 6249 and JIS K 6251 were prepared from 2 mm-thick fluoropolyether-based cured products (preparation method as described above) prepared from the fluoropolyether-based curable compositions immediately after preparation in Examples 1 to 22, and immersed in a 40% by mass aqueous sodium hydroxide solution at 25°C for 7 days. After 7 days, the dumbbell-shaped test pieces were removed, and the hardness, tensile strength, and elongation at break were evaluated in the same manner as above, and compared with the physical property values ​​(as described above) before immersion. As a result, no changes in the physical property values ​​of hardness, tensile strength, and elongation at break were observed.

[0215] <Evaluation of moisture permeability of fluoropolyether-based cured products> Using the fluoropolyether-based curable compositions immediately after preparation in Examples 1 to 22 and 1 mm-thick fluoropolyether-based cured products prepared from SIFEL2617 (manufactured by Shin-Etsu Chemical Co., Ltd.) (preparation method as described above), moisture vapor transmission rates (g / (m)) were measured under conditions of 40°C / 90% RH in accordance with JIS K 7129-1. 2 The measurement was carried out using a water vapor transmission watch L80-5000 (manufactured by Systec Illinois, Inc.). As a result, the fluoropolyether-based cured products prepared in Examples 1 to 22 all had a water vapor transmission rate of 4 g / (m 2 The water vapor permeation rate of the fluoropolyether-based cured material prepared from SIFEL2617 used in Comparative Example 3 was 5 g / (m 2 Therefore, it was shown that the fluoropolyether-based curable composition of the present invention gives a fluoropolyether-based cured product having high low moisture permeability, similar to known fluoropolyether-based curable compositions.

[0216] The above results demonstrate that the cured product of the fluoropolyether-based curable composition of the present invention has good insulating properties, chemical resistance and low moisture permeability.

Claims

1. A fluoropolyether-based curable composition containing: (A) a fluorine-containing compound having at least two thiol groups in one molecule and a divalent perfluoropolyether group in the main chain; (B) a compound having at least two epoxy groups in one molecule; and (C) a curing accelerator.

2. The fluoropolyether curable composition according to claim 1, wherein component (A) is a fluorine-containing thiol compound represented by the following average formula (1): (In the formula, Rf independently represents a divalent perfluoropolyether group; A independently represents a divalent organic group having 1 to 20 carbon atoms which may have at least one bond selected from a carbonyl bond, an amide bond, an ether bond, an ester bond, and a thioester bond; X independently represents a carbonyl bond, or a divalent to tetravalent organic group having 1 to 20 carbon atoms which may have at least one bond selected from an amide bond, an ester bond, an ether bond, and an amino bond; a is 0 or a positive number; and b independently represents an integer of 1 to 3.) 3. The fluoropolyether curable composition according to claim 2, wherein A in the average formula (1) is independently any group selected from groups represented by the following general formulas (2) to (5): (In the formula, R 1 are independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms; R 2 are independently unsubstituted or substituted divalent hydrocarbon groups having 1 to 20 carbon atoms.

4. X in the above average formula (1) is -(CH2) f -*, -(CH2) f OCH2-*,-(CH2) f -NR 5 -CH2-*, -CH(CH3)-(CH2) f -NR 5 -CH2-*, -CO-*, -(CH2) f -NR 5 -CO-*, -CH(CH3)-(CH2) f -NR 5 -CO-*, -(CH2) f 3. The fluoropolyether-based curable composition according to claim 2, wherein the fluoropolyether is any one group selected from the group consisting of —O—CO—* and groups represented by the following general formulas (6) to (8): (In the formula, R 4 are independently a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, or a trifluoromethyl group, and R 5 is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, or a phenyl group, e' is 0 or 1, and f is an integer from 1 to 12. Note that the bond marked with * indicates that it is bonded to Rf.

5. The fluoropolyether curable composition according to claim 1, wherein the thiol group in component (A) is either a primary thiol group or a secondary thiol group.

6. The fluoropolyether-based curable composition according to claim 1, wherein the amount of component (B) is such that the amount of epoxy groups in component (B) is 0.5 to 5 mol per 1 mol of thiol groups in component (A).

7. The fluoropolyether-based curable composition according to claim 1, wherein component (B) is a fluorine-containing epoxy compound represented by the following general formula (9): [wherein, Rf 1 Rf are independently monovalent or divalent groups having a fluoropolyether structure and a number average molecular weight of 400 to 40,000. 1 When Rf is monovalent, d' is 1, d is an integer of 1 to 6, and e is an integer of 2 to 20. 1 is divalent, then d' is 2, d is 1, and e is an integer from 1 to 20. Q is independently a (d+e)-valent group having at least (d+e) Si atoms, and has a siloxane structure, a silalkylene structure, a silarylene structure, or a combination thereof, and may have a cyclic structure. Z is independently a divalent hydrocarbon group having 1 to 20 carbon atoms, and may contain an ether bond or an ester bond, and may have a cyclic structure. E is independently a group represented by the following formula (I) or (II): (In the formula, R 6 are independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, which may contain an ether bond or an ester bond and may have a cyclic structure. (In the formula, R 7 are independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, v is independently 1 or 2, and the total of v is 7.

8. The fluoropolyether curable composition according to claim 7, wherein in the general formula (9), Z is independently selected from groups represented by the following formulae: -CH2CH2-*, -CH2CH2CH2-*, -CH2CH2CH2CH2-*, -CH2CH2CH2CH2CH2-*, -CH2CH2CH2CH2CH2CH2-*, -CH2CH2CH2CH2CH2CH2CH2-*, -CH2CH2CH2CH2CH2CH2CH2-*, -CH2CH2CH2OCH2-*, -CH2CH2CH2OCH2CH2OCH2CH2OCH2CH2-* (wherein the * indicates that the bond is bonded to E, and the unmarked bond indicates that the bond is bonded to Q.) 9. The fluoropolyether curable composition according to claim 7, wherein the structure represented by -ZE in the general formula (9) is selected from groups represented by the following formulas (a) to (d): (In the formula, g is an integer of 1 to 20, h is an integer of 1 to 10, i is an integer of 1 to 5, l is an integer of 0 to 9, and h+2l+i is 2 to 20. R 7 is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms.

10. The fluoropolyether curable composition according to claim 7, wherein the structure represented by -ZE in the general formula (9) is selected from groups represented by the following formulas:

11. The fluoropolyether curable composition according to claim 7, wherein in the general formula (9), Q is selected from groups represented by the following formulas: (wherein d1 is Rf 1 is an integer of 1 to 4 when Rf is monovalent; 1 is divalent, e1 is an integer of 2 to 4, and d1' is an integer that satisfies d1+e1=3 to 6. 1 is 1 or 2 when Rf is monovalent; 1 is divalent, e1' is 1, e1' is 2 or 3, f1 is 0 or 1, and d1' + e1' + f1 = 4. D is a monovalent hydrocarbon group having 1 to 6 carbon atoms. Each silicon atom of the unit shown in parentheses having d1 and d1' repeats is Rf 1 and each silicon atom of the unit shown in the parentheses having e1 and e1' repeats is bonded to Z, and the arrangement of the units shown in the parentheses may be random.

12. A fluoropolyether-based curable composition according to claim 1, wherein component (C) is at least one selected from the group consisting of phosphorus compounds, tertiary amine compounds, imidazole compounds, urea compounds, amine adduct compounds and urea adduct compounds.

13. A cured product obtained by curing the fluoropolyether-based curable composition according to any one of claims 1 to 12.

14. An article comprising the cured product of claim 13.

15. The article according to claim 14, which is for use in automobiles, ships, aircraft, space-related equipment, generators, sports equipment, lighting equipment, organic light-emitting diodes (OLEDs), LEDs, civil engineering and construction, chemical plants, analytical and physical / chemical equipment, living environments, communications equipment, communications facilities, or railway vehicles.

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