Fluoropolyether-based curable composition, cured product, and article

Abstract

Provided is a fluoropolyether-based curable composition containing: (A) a fluorine-containing compound having at least two secondary amino groups in one molecule and having a divalent perfluoropolyether group in the main chain; and (B) a fluorine-containing compound having at least two epoxy groups in one molecule and having a monovalent or divalent perfluoropolyether group in the main chain, in an amount such that the epoxy groups in component (B) are 0.5-5 moles per mole of the secondary amino groups in component (A). This fluoropolyether-based curable composition has a longer pot life than conventional compositions, can be cured at room temperature or by heating, and gives a cured product having reduced hardness and good mechanical properties.

Description

Fluoropolyether-based curable composition, cured product, and article

[0001] The present invention relates to a fluoropolyether-based curable composition that cures by the reaction of an amine with an epoxide, and that gives a cured product that has a longer pot life than conventional products, can be cured at room temperature or by heating, has reduced hardness, and has good mechanical properties; 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)). This 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. A drawback of this fluoropolyether-based curable composition is that it is known to undergo poor curing in the presence of substances containing atoms such as phosphorus, sulfur, and nitrogen. This drawback makes it 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.

[0003] 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 is incompatible with the fluorine-containing amide compound immediately after mixing, while its pot life is short, approximately 3 to 8 hours. A short pot life may be acceptable for applications requiring short curing times at room temperature. However, for applications in which the curing reaction can be accelerated by heating, a long pot life is often preferred because there is no need to sacrifice pot life for shorter curing times. Furthermore, the method of Patent Document 5 tends to produce hard cured products, making it unsuitable for applications requiring softer, more elastic cured products.

[0004] Patent Document 6 (JP 2014-80534 A) describes a fluorine-containing epoxy compound containing a monovalent or divalent perfluoropolyether group in the main chain, which is useful as an additive for imparting antifouling properties and water and oil repellency to the surface of a thermosetting resin. There has been little research into using an epoxy compound having such characteristics as an epoxy compound in the fluoropolyether-based curable composition described in Patent Document 5, and further into extending the pot life and obtaining a cured product that is soft and has excellent elasticity.

[0005] 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 Japanese Patent Laid-Open No. 2014-80534

[0006] The present invention has been made in view of the above circumstances, and aims to provide a fluoropolyether-based curable composition which has a longer pot life than conventional compositions, can be cured at room temperature or by heating, and gives a cured product with reduced hardness and good mechanical properties; a cured product which is obtainable by curing the composition and which is softer than conventional compositions and has excellent rubber elasticity; and an article comprising the cured product.

[0007] As a result of intensive research conducted by the present inventors to achieve the above-mentioned object, they have found that a fluoropolyether-based curable composition containing, in specific proportions, (A) a fluorine-containing compound having at least two secondary amino groups in one molecule and a divalent perfluoropolyether group in the main chain, and (B) a fluorine-containing compound having at least two epoxy groups in one molecule and a monovalent or divalent perfluoropolyether group in the main chain has a relatively long pot life, and can give a soft cured product having excellent rubber elasticity by room temperature curing or heat curing, and that the cured product has reduced hardness compared to that of Patent Document 5 and has good mechanical properties, which has led to the completion of the present invention.

[0008] Accordingly, the present invention provides the following fluoropolyether-based curable compositions, which have a long pot life, can be cured at room temperature or by heat curing, and give cured products with good mechanical properties, as well as cured products of the compositions and articles comprising the cured products. [1] A fluoropolyether-based curable composition containing: (A) a fluorine-containing compound having at least two secondary amino groups per molecule and a divalent perfluoropolyether group in the main chain, and (B) a fluorine-containing compound having at least two epoxy groups per molecule and a monovalent or divalent perfluoropolyether group in the main chain, in an amount such that the ratio of epoxy groups in component (B) is 0.5 to 5 moles per mole of secondary amino groups in component (A). [2] The fluoropolyether-based curable composition according to [1], wherein component (A) is a fluorine-containing compound represented by the following average formula (1): [In formula (1), Rf independently represents a divalent perfluoropolyether group, A independently represents a divalent organic group having 1 to 12 carbon atoms which may have at least one bond selected from a carbonyl bond, an amide bond, an ether bond, and an ester bond, and X independently represents a group represented by the following formulas (2) to (4): (In the formula, R 1 are independently unsubstituted or substituted monovalent hydrocarbon groups, R 2 are independently an unsubstituted or substituted divalent hydrocarbon group.) and a is a positive number of 1 or more.] [3] A in the above average formula (1) is independently -(CH2) f -*, -(CH2)f OCH2-*, -CO-*, -(CH2) f -NR 6 -CO-*, -(CH2) f The fluoropolyether-based curable composition according to [2], wherein the fluoropolyether-based curable composition is any one of groups selected from -O-CO-* and groups represented by the following general formulas (5) and (6) (the bond marked with * indicates a bond to Rf, and the bond without a mark indicates a bond to X): (In the formula, R 5 are independently a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, or a trifluoromethyl group, and R 6 represents a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, or a phenyl group, e represents 0 or 1, and f represents an integer of 1 to 9. [4] The fluoropolyether-based curable composition according to any one of [1] to [3], wherein component (B) is a fluorine-containing compound represented by the following general formula (7): [In formula (7), 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, b' is 1, b is an integer of 1 to 6, and c is an integer of 2 to 20. 1 is divalent, then b' is 2, b is 1, and c is an integer from 1 to 20. Q is independently a (b+c)-valent group having at least (b+c) 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 formula (I), R 3 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 formula (II), R 4are independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms.) [5] The fluoropolyether-based curable composition according to [4], wherein in formula (7), Z is independently selected from groups represented by the following formulas: -CH2CH2-*, -CH2CH2CH2-*, -CH2CH2CH2CH2-*, -CH2CH2CH2CH2CH2-*, -CH2CH2CH2CH2CH2CH2-*, -CH2CH2CH2CH2CH2CH2-*, -CH2CH2CH2CH2CH2CH2CH2-*, -CH2CH2CH2CH2CH2CH2CH2-*, -CH2CH2CH2CH2CH2CH2CH2-*, -CH2CH2CH2OCH2-*, -CH2CH2CH2OCH2CH2OCH2-*, or -CH2CH2CH2OCH2CH2OCH2CH2OCH2CH2OCH2CH2-* (wherein the bond marked with * is bonded to E, and the bond without a mark is bonded to Q.) [6] The fluoropolyether-based curable composition according to [4] or [5], wherein the structure represented by -ZE in formula (7) 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 4 is a hydrogen atom, or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms.) [7] The fluoropolyether-based curable composition according to any one of [4] to [6], wherein the structure represented by -ZE in formula (7) is selected from groups represented by the following formulas: [8] The fluoropolyether-based curable composition according to any one of [4] to [7], wherein in the formula (7), Q is represented by the following formula: (Wherein b1 is Rf 1 is an integer of 1 to 4 when Rf is monovalent; 1 is divalent, c1 is an integer of 2 to 4, and b1' is an integer that satisfies b1+c1=3 to 6. 1 is 1 or 2 when Rf is monovalent; 1is divalent, it is 1, c1' is 2 or 3, d1 is 0 or 1, and b1' + c1' + d1 = 4. D is a monovalent hydrocarbon group having 1 to 6 carbon atoms. Each silicon atom of the unit shown in parentheses having b1 and b1' repeats is Rf 1 and each silicon atom of the unit shown in parentheses having c1 and c1' repeats is bonded to Z, and the arrangement of the units shown in parentheses may be random.) [9] A cured product obtained by curing the fluoropolyether-based curable composition according to any one of [1] to [8].

[10] An article having the cured product according to [9].

[11] The article according to

[10] , which is for use in automobiles, ships, aircraft, sports equipment, LEDs, civil engineering and construction, chemical plants, analytical and physicochemical equipment, living environments, communication devices, communication facilities, or railway vehicles.

[0009] The fluoropolyether-based curable composition of the present invention uses a fluorine-containing compound (component (A)) having at least two secondary amino groups per molecule and a divalent perfluoropolyether group in the main chain, and an epoxy compound (component (B)) reactive with the amino groups in the compound, which is a fluorine-containing compound having at least two epoxy groups per molecule and a monovalent or divalent perfluoropolyether group in the main chain, in specific proportions, thereby exhibiting an improved pot life compared to the curable composition described in Patent Document 5. Furthermore, by curing the composition, a cured product that is softer and has better rubber elasticity than that of Patent Document 5 can be obtained, and the cured product has excellent chemical resistance, solvent resistance, and insulating properties.

[0010] 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 secondary amino groups in one molecule and a divalent perfluoropolyether group in the main chain, and acts as a main component (base oil) in the fluoropolyether-based curable composition of the present invention.

[0011] 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) in terms of polystyrene in gel permeation chromatography (GPC) analysis using a fluorine-based solvent as a developing solvent. 1 ) is the number average degree of polymerization (or number average molecular weight) 19 It can also be calculated from F-NMR.

[0012] The component (A) is preferably a fluorine-containing compound represented by the following average formula (1). [In formula (1), Rf independently represents a divalent perfluoropolyether group, A independently represents a divalent organic group having 1 to 12 carbon atoms which may have at least one bond selected from a carbonyl bond, an amide bond, an ether bond, and an ester bond, and X independently represents a group represented by the following formulas (2) to (4): (In the formula, R 1 are independently unsubstituted or substituted monovalent hydrocarbon groups, R 2 are independently unsubstituted or substituted divalent hydrocarbon groups; and a is a positive number of 1 or more.

[0013] In the above average formula (1), X is independently any of the groups represented by the following general formulae (2) to (4). (In the formula, R 1 are independently unsubstituted or substituted monovalent hydrocarbon groups, R 2 are independently unsubstituted or substituted divalent hydrocarbon groups.

[0014] In the above general formula (2), R 1is an unsubstituted or substituted monovalent hydrocarbon group, preferably having 1 to 12 carbon atoms, particularly 1 to 8. 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 have been substituted with halogen atoms such as fluorine, chlorine, and bromine, such as a chloromethyl group, bromoethyl group, chloropropyl group, trifluoropropyl group, or 3,3,4,4,5,5,6,6,6-nonafluorohexyl group.

[0015] In the above general formulas (2) to (4), R 2 is an unsubstituted or substituted divalent hydrocarbon group, preferably having 1 to 12 carbon atoms, particularly preferably 2 to 6. Examples include alkylene groups such as methylene, ethylene, n-propylene, i-propylene, butylene, and hexamethylene; 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.

[0016] Examples of X include the following groups: In the following formulae, Me represents a methyl group, and Ph represents a phenyl group.

[0017] In the average formula (1), A is independently a divalent organic group (particularly a hydrocarbon group) having 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, which may have at least one bond selected from a carbonyl bond, an amide bond, an ether bond, and an ester bond. A is -(CH2) f -*, -(CH2) f OCH2-*, -CO-*, -(CH2) f -NR 6 -CO-*, -(CH2) f -O-CO-*, or any group selected from groups represented by the following general formulas (5) and (6). 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 X. (In the formula, R 5 are independently a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, or a trifluoromethyl group, and R 6 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 9.

[0018] Examples of A include -CH2-*, -CH2CH2CH2-*, -OCH2-*, -CH2OCH2-*, -(CH2)2OCH2-*, -(CH2)3OCH2-*, -CO-*, -CH2-NH-CO-*, -CH2-N(CH3)-CO-*, -CH2-N(CH2CH3)-CO-*, -CH2CH2-NH-CO-*, -(CH2)3-NH-CO-*, -(CH2)3-N(CH3)-CO-*, -(CH2)3 Examples include -N(CH2CH3)-CO-*, -(CH2)3-N(CH(CH3)2)-CO-*, -(CH2)2-O-CO-*, -(CH2)3-O-CO-*, and groups represented by the following general formulae (5A), (5B), (5C), (5D), (5E), (6A), (6B), and (6C). Among these, -CO-*, -CH2-NH-CO-*, -CH2CH2-NH-CO-*, and groups represented by general formula (5A) or (6A) are preferred. Note that the bond marked with * indicates a bond to Rf, and the unmarked bond indicates a bond to X. Furthermore, in the formulae, Me is a methyl group, and Et is an ethyl group.

[0019] 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 (8): -(C x F 2x O) y - (8) (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.)

[0020] 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- -CF2CF2CF2CF2O- -CF2CF2CF2CF2CF2CF2O-

[0021] Among these, the units represented by the following formula are particularly preferred: -CF2O- -CF2CF2O- -CF2CF2CF2O- -CF(CF3)CF2O-

[0022] 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.

[0023] 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.

[0024] In the above average formula (1), specific examples of Rf include those represented by the following formulas. (In the formula, p1, q1, r1, 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.)

[0025] In the above average formula (1), a is a positive number of 1 or more, preferably a positive number of 1 to 3, and more preferably a positive number of 1 to 2. For each molecule of the fluorine-containing compound represented by the above average formula (1), a is an integer of 1 or more, preferably an integer of 1 to 3, and more preferably 1 or 2. However, as an average formula for the entire component (A) containing two or more compounds with different values ​​of a, which is the number of repetitions of the main chain structure -[X-A-Rf-A]-, a may be a positive number of 1 or more.

[0026] As the fluorine-containing compound represented by the above average formula (1), compounds represented by the following formula are particularly preferred: In the formula, Me is a methyl group, and Et is an ethyl group.

[0027] (In the formula, s1' and t1' are each an integer of 1 to 100, and s1' + t1' = an integer of 2 to 200.)

[0028] (In the formula, s1' and t1' are each an integer of 1 to 100, and s1' + t1' = an integer of 2 to 200.)

[0029] (In the formula, s1' and t1' are each an integer of 1 to 100, and s1' + t1' = an integer of 2 to 200.)

[0030] (In the formula, s1' and t1' are each an integer of 1 to 100, and s1' + t1' = an integer of 2 to 200.)

[0031] (In the formula, s1' and t1' are each an integer of 1 to 100, and s1' + t1' = an integer of 2 to 200.)

[0032] (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.)

[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, s1' + t1' = an integer of 2 to 200, and a' is a positive number greater than 1.)

[0035] The amount of secondary amino 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. If the amount of secondary amino groups contained in the fluorine-containing compound is less than 0.002 mol / 100g, the degree of crosslinking may be insufficient, which is undesirable, and if the amount of secondary amino groups exceeds 0.4 mol / 100g, the mechanical properties of the cured product as a rubber elastomer may be impaired, which is undesirable. In the present invention, the amount of secondary amino groups is 1 It can be measured by H-NMR.

[0036] 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.).

[0037] As the component (A), these fluorine-containing compounds can be used alone or in combination of two or more.

[0038] [Component (B)] The fluorine-containing compound (hereinafter also referred to as fluorine-containing epoxy compound) of component (B) used in the fluoropolyether-based curable composition of the present invention is a fluorine-containing compound having at least two epoxy groups in one molecule and a monovalent or divalent perfluoropolyether group in the main chain, preferably represented by the following general formula (7), and acts as a chain extender and a crosslinking agent in the fluoropolyether-based curable composition of the present invention. [In formula (7), 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, b' is 1, b is an integer of 1 to 6, and c is an integer of 2 to 20. 1 is divalent, then b' is 2, b is 1, and c is an integer from 1 to 20. Q is independently a (b+c)-valent group having at least (b+c) 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 formula (I), R 3 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 formula (II), R 4 are independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms.

[0039] In the above general formula (7), Rf 1 is monovalent, b' is 1, b is an integer of 1 to 6, preferably an integer of 1 to 4, more preferably an integer of 1, and c is an integer of 2 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 4. 1is divalent, b' is 2, b is 1, and c is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 2 to 4. Furthermore, it is preferable that b+c is an integer of 3 to 6.

[0040] In the above general formula (7), E is independently a group represented by the following formula (I) or (II). (In formula (I), R 3 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 formula (II), R 4 are independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms.

[0041] In the above formula (I), R 3 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, 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, 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. Preferably, R 3 is a hydrogen atom.

[0042] In the above formula (II), R 4are 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. Preferably, R 4 is a hydrogen atom or a methyl group.

[0043] Examples of the structure represented by the above formula (I) or (II) include the following. (In the formula, R 4 is the same as above.)

[0044] The following are preferred:

[0045] In the above general formula (7), Z is a divalent hydrocarbon group having 1 to 20 carbon atoms, preferably 2 to 15 carbon atoms, which may have a cyclic structure and may contain an ether bond (—O—) or an ester bond (—COO—).

[0046] 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-*, -CH2CH2CH2CH2CH2-*, -CH2CH2CH2CH2CH2CH2CH2-*, -CH2CH2CH2CH2CH2CH2CH2-*, -CH2CH2CH2CH2CH2CH2CH2-*, -CH2CH2CH2CH2CH2CH2CH2-*, -CH2CH2CH2OCH2-*, -CH2CH2CH2OCH2CH2OCH2-*, or -CH2CH2CH2OCH2CH2OCH2CH2OCH2CH2-*

[0047] Examples of the structure represented by -ZE include structures represented by the following formulae (a) to (d).

[0048] 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 4 is as defined above, and is preferably a hydrogen atom or a methyl group.

[0049] As the structure represented by -ZE, the following is particularly preferred.

[0050] In the general formula (7), Q is independently a (b+c)-valent group having at least (b+c) Si atoms, and has a siloxane structure, a silalkylene structure, a silarylene structure, or a combination thereof, and may have a cyclic structure.

[0051] Q may have the following structure, for example. (wherein b and c are as defined above; d 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 b repeats is Rf 1 and each silicon atom of the unit shown in parentheses having c repeats is bonded to Z. The arrangement of the units shown in parentheses may be random.

[0052] Q can also be expressed by the following formula: In the above formula, b and c are as defined above. Each silicon atom of the unit shown in parentheses having b repeats is Rf 1 and each silicon atom of the unit shown in parentheses having c repeats is bonded to Z. W is a silicon atom or a (b+c)-valent group having a siloxane structure, a silalkylene structure, a silarylene structure or a combination thereof.

[0053] 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.)

[0054] Examples of the above Q include the following structures.

[0055] Among the above Q groups, the following structures are particularly preferred. (Wherein b1 is Rf 1 When Rf is monovalent, it is an integer of 1 to 4, more preferably 1; 1 is divalent, c1 is an integer of 2 to 4, and b1' is an integer that satisfies b1+c1=3 to 6. 1 When Rf is monovalent, it is 1 or 2, more preferably 1; 1 is divalent, it is 1, c1' is 2 or 3, d1 is 0 or 1, and b1' + c1' + d1 = 4. D is a monovalent hydrocarbon group having 1 to 6 carbon atoms. Each silicon atom of the unit shown in parentheses having b1 and b1' repeats is Rf 1 and each silicon atom of the unit shown in parentheses having c1 and c1′ repeats is bonded to Z, and the arrangement of the units shown in parentheses may be random.

[0056] In the above general formula (7), 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 and19 Terminal structure and main chain structure based on F-NMR (Rf 1 ) can be calculated from the ratio.

[0057] 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.

[0058] The 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-

[0059] Rf 1 may have one of these repeating units or a combination of two or more of them.

[0060] Rf is monovalent 1 A particularly preferred structure of the above can be represented by the following general formula (9): Rf"-V- (9) (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.)

[0061] Divalent Rf 1 A particularly preferred structure can be represented by the following general formula (10): -[V-Rf'-VT] z -V-Rf'-V- (10) [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 formula (11): (wherein Z, E, and c are as defined above; U is a (c+2)-valent group having at least (c+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.)

[0062] In the above formula (9), 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-.

[0063] 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.)

[0064] In the above formula (10), 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—.

[0065] 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.)

[0066] In the above formulas (9) and (10), 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.

[0067] Examples of V include the following: In the following formula, Ph represents a phenyl group. The bond marked with * indicates that it is bonded to Rf" or Rf'.

[0068] Among these, the following structures are preferred: In the following formula, Ph represents a phenyl group. The bond marked with * indicates that the bond is to Rf" or Rf'.

[0069] In the above formula (10), T is a divalent group represented by the following formula (11). (In the formula, Z, E, and c are as defined above. U is a (c+2)-valent group having at least (c+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 (11) are each bonded to different Vs in formula (10).)

[0070] In the above formula (11), U is a (c+2)-valent group having at least (c+2) Si atoms, and has a siloxane structure, a silalkylene structure, a silarylene structure, or a combination thereof, and may have a cyclic structure.

[0071] Examples of U include the structures shown below. (In the formula, c, d, and W are as defined above. Each silicon atom of the unit shown in parentheses having c repeats is bonded to Z in formula (11), and each silicon atom of the unit shown in parentheses having two repeats is bonded to a different V in formula (10). The arrangement of each unit shown in parentheses may be random.)

[0072] Among the above U, the following structures are particularly preferred. (In the formula, c is as defined above. Each silicon atom of the unit shown in parentheses having c repeats is bonded to Z in formula (11), and each silicon atom of the unit shown in parentheses having two repeats is bonded to a different V in formula (10).)

[0073] In the above formula (10), z is an integer of 0 to 5, and is preferably 0.

[0074] 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).

[0075] 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.)

[0076] [Method for producing component (B)] The fluorine-containing epoxy compound represented by the above general formula (7) 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 such that the SiH groups are in excess, thereby synthesizing a fluorine-containing compound C having multiple SiH groups.

[0077] The fluorine-containing compound A can be particularly represented by the following general formula (12): 0 -(CH=CH2) b’ (12) [wherein, Rf 0 is a monovalent group represented by the following general formula (13) or a divalent group represented by the following general formula (14). 0 is monovalent, it is 1, and it is divalent, it is 2. 1- (13) -V 1 -Rf'-V 1 - (14) (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.

[0078] In the above formulas (13) and (14), 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.

[0079] 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".

[0080] 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).

[0081] 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.)

[0082] The organosilicon compound B can be particularly represented by the following general formula (15): Q-(H) b+c (15) (wherein Q, b, and c are as defined above. H shown in parentheses is a hydrogen atom directly bonded to the Si atom in the Q structure.)

[0083] Examples of the organosilicon compound B include the following: (In the formula, b, c, d, and W are as defined above.)

[0084] In particular, the following are preferred:

[0085] 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 b relative to the number of SiH groups (b+c) in organosilicon compound B, the structure of the resulting fluorine-containing compound C can be represented by the following general formula (16): (Rf 0 -C2H4) b -Q-(H) c (16) (wherein, Rf 0 , Q, b and c are as defined above.

[0086] When the fluorine-containing compound A is a divalent compound and the fluorine-containing compound A and the 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 (17). When z = 0, the structure is one in which the organosilicon compound B is introduced at both ends of the fluorine-containing compound A. (H) c -Q-[C2H4-Rf 0 -C2H4-T 1 ] z -C2H4-Rf 0 -C2H4-Q-(H) c (17) [wherein, Q, Rf 0 , c, 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 (18): (wherein Q, b, and c are as defined above. H shown in parentheses is a hydrogen atom directly bonded to a Si atom in the structure.)

[0087] 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 (b + c), preferably b, per molecule of the organosilicon compound B having (b + c) 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 (17), 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 (17) 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.

[0088] 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.

[0089] 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.

[0090] 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.

[0091] 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.

[0092] 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 (7).

[0093] 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 (19). (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.

[0094] In the above formula (19), 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 structure 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-*, or -CH2OCH2CH2OCH2CH2OCH2CH2-*

[0095] Examples of the compound D represented by the above formula (19) include structures represented by the following formulae (a') to (d').

[0096] 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 4 is as defined above, and is preferably a hydrogen atom or a methyl group.

[0097] 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.

[0098] 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.

[0099] 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.

[0100] Particularly preferred examples of the compound represented by the above general formula (7) 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.)

[0101] The amount of epoxy groups in the fluorine-containing epoxy compound of component (B) is preferably 0.01 to 0.4 mol / 100 g, and more preferably 0.02 to 0.3 mol / 100 g. 1 It can be measured by H-NMR.

[0102] The amount of component (B) to be added is such that the amount of epoxy groups in component (B) is 0.5 to 5 moles, preferably 0.7 to 2.5 moles, per mole of secondary amino groups in component (A). If the amount of epoxy groups is too small, the degree of crosslinking will be insufficient, making it impossible to obtain a cured product. If the amount of epoxy groups is too large, epoxy groups will tend to remain in the cured product, which is undesirable because the physical properties of the cured product will tend to change over time.

[0103] As the component (B), these fluorine-containing epoxy compounds may be used alone or in combination of two or more.

[0104] [Component (C) (Other Components)] In the fluoropolyether-based curable composition of the present invention, for the purpose of improving its practicality, various compounding agents such as a curing accelerator, a plasticizer, a viscosity modifier, a flexibility-imparting agent, an inorganic filler, a silane coupling agent, etc. may be added as needed in addition to the above-mentioned components (A) and (B). The amount of these additives to be added is optional as long as it does not impair the object of the present invention and does not impair the properties of the composition or the physical properties of the cured product.

[0105] The curing accelerator is a compound that, when added, has the effect of accelerating the reaction between the secondary amino group in component (A) and the epoxy group in component (B) in the fluoropolyether-based curable composition of the present invention, and is added to obtain a cured product with good physical properties in a shorter time. This allows the balance between the usable time and the heat curing time to be adjusted. There are no particular restrictions on the curing accelerator, as long as it is mainly either a carboxylic acid anhydride or a compound having a Lewis acidity.

[0106] Examples of the carboxylic acid anhydride include carboxylic acid anhydrides that are solid at 23° C. Specific examples include the following compounds.

[0107] The carboxylic acid anhydride may also be a cyclic organopolysiloxane (i.e., a fluorine-containing organopolysiloxane-modified carboxylic acid anhydride compound) having, in one molecule, a hydrogen atom directly bonded to a silicon atom, a perfluoroalkyl group or a perfluorooxyalkyl group bonded to a silicon atom via a divalent hydrocarbon group which may contain at least one selected from an oxygen atom, a nitrogen atom, and a silicon atom, and a cyclic carboxylic acid anhydride residue bonded to a silicon atom via a divalent hydrocarbon group. Examples of such compounds include those represented by the following general formula (20): (wherein L is independently a monovalent perfluoropolyether group bonded to a silicon atom via a divalent linking group, J is independently a cyclic carboxylic acid anhydride residue bonded to a silicon atom via a divalent hydrocarbon group, and R 8 are independently unsubstituted or halogen-substituted monovalent hydrocarbon groups, t2 is an integer of 1 to 6, u2 is an integer of 1 to 4, v2 is an integer of 1 to 4, and t2+u2+v2 is an integer of 4 to 10. The repeating units shown in the parentheses above may be bonded randomly.

[0108] In the above general formula (20), L is independently a monovalent perfluoropolyether group bonded to a silicon atom via a divalent linking group, and is preferably one represented by the following general formula: L is a group introduced from the viewpoints of compatibility with components (A) and (B), dispersibility, and uniformity after curing. -B-Rf 2 [wherein, Rf 2 is a monovalent perfluoropolyether group, is the same as Rf″ in the above formula (9), and examples thereof include the same groups as those exemplified for Rf″. B is a divalent organic group (particularly a hydrocarbon group) having 1 to 20 carbon atoms which may contain at least one atom selected from oxygen atoms, nitrogen atoms, and silicon atoms.

[0109] Examples of B include -CH2-*, -CH2CH2CH2-*, -OCH2-*, -CH2OCH2-*, -(CH2)2OCH2 -*, -(CH2)3OCH2-*, -CH2-NH-CO-*, -(CH2)3-NH-CO-*, -(CH2)3-N(CH3) -CO-*, -(CH2)3-N(CH2CH3)-CO-*, -(CH2)3-N(CH(CH3)2)-CO-*, -CH2-N (Ph)-CO-*, -(CH2)3-O-CO-*, -CH2OCH2CH2CH2-Si(CH3)2-O-Si(CH3)2- Examples include (CH2)2-*, -CO-N(CH3)-Ph'-Si(CH3)2-(CH2)2-*, -CO-N(CH2)-Ph'-Si(CH2)2-(CH2)2-Si(CH2)2-O-Si(CH2)2-(CH2)2-*, -CO-NH-Ph'-[Si(CH3)2-(CH2)2]3-CH2-*, -CO-N(CH3)-Ph'-[Si(CH3)2-(CH2)2]3-*, and groups represented by the following general formulas, of which -(CH2)3OCH2-*, -(CH2)3-NH-CO-*, and groups represented by the following general formulas are preferred. Ph represents a phenyl group, and Ph' represents a phenylene group. The bond marked with an asterisk (*) is Rf 2 A bond without an * indicates that the bond is with a silicon atom in the organohydrogenpolysiloxane.

[0110] In the general formula (20), J's are independently cyclic carboxylic acid anhydride residues bonded to a silicon atom via a divalent hydrocarbon group, and specific examples include groups represented by the following general formula:

[0111] In the above formula, R 9 is a divalent hydrocarbon group having 2 to 15 carbon atoms, and specific examples thereof include an ethylene group, a propylene group, and a butylene group, with a propylene group being preferred.

[0112] In addition, in the general formula (20), R 8are independently unsubstituted or halogen-substituted monovalent hydrocarbon groups, which contain no aliphatic unsaturated bonds and preferably have 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms. Specific examples include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, and octyl; aryl groups such as phenyl and tolyl; aralkyl groups such as benzyl and phenylethyl; and substituted monovalent hydrocarbon groups in which some or all of the hydrogen atoms of these groups have been substituted with halogen atoms such as fluorine, with methyl and ethyl being preferred.

[0113] Furthermore, in the above general formula (20), t2 is an integer of 1 to 6, preferably an integer of 2 to 5, u2 is an integer of 1 to 4, preferably an integer of 1 to 3, v2 is an integer of 1 to 4, preferably an integer of 1 to 3, and t2+u2+v2 is an integer of 4 to 10, preferably an integer of 4 to 8. However, ((H)(R 8 )SiO) units, ((L)(R 8 )SiO) units, and ((J)(R 8 The arrangement order of the SiO) units is random.

[0114] Examples of the cyclic organopolysiloxane represented by the general formula (20) include the following compounds. (In the formula, t2' is 2 or 3, and t" is an integer from 2 to 20.) (In the formula, v2' is 2 or 3, and t" is an integer from 2 to 20.)

[0115] These carboxylic acid anhydrides as curing accelerators may be used alone or in combination of two or more. In this case, the above-mentioned carboxylic acid anhydride that is solid at 23°C may be used in combination with the above-mentioned cyclic organopolysiloxane (fluorine-containing organopolysiloxane-modified carboxylic acid anhydride compound).

[0116] When a carboxylic acid anhydride is used as a curing accelerator, the amount added is preferably 0.01 to 2 parts by mass, and more preferably 0.05 to 1 part by mass, per 100 parts by mass of component (A).Furthermore, the amount of cyclic carboxylic acid anhydride residue in the adhesion promoter is preferably 0.005 to 0.5 mol, and particularly 0.05 to 0.1 mol, per 1 mol of secondary amino groups in component (A).

[0117] Preferred Lewis acidic compounds include those containing tin, titanium, zinc, boron, ytterbium, yttrium, niobium, europium, and zirconium. Specific examples include ZnCl, TiCl, SnCl, NbCl, Yb(OTf), Y(OTf) (where Tf is a trifluoromethanesulfonyl group (-S(O)CF), B(CF), and the "Orgatix" series manufactured by Matsumoto Fine Chemical Co., Ltd., with ZnCl, TiCl, SnCl, and B(CF) being preferred. When incorporating these Lewis acidic compounds as curing accelerators, the amount added can be adjusted to a range that balances the pot life and heat curing time.

[0118] As the plasticizer, viscosity modifier, and flexibility-imparting agent, a polyfluoroamino compound represented by the following general formula (21) and / or a polyfluoro compound represented by the following general formulas (22) and (23) can be used.

[0119] [wherein A and X are the same as above, and Rf 3 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.)

[0120] Y 1 -O-(CF2CF2CF2O) c2 -Y 1 (22) [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.

[0121] Y 2 -O-(CF2O) d2 (CF2CF2O) e2 -Y 2 (23) (wherein, Y 2is 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 the above parentheses may be bonded randomly.

[0122] In the above formula (21), A can be exemplified as A in the above average formula (1), and X can be exemplified as X in the above average formula (1).

[0123] In the above formula (21), Rf 3 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.)

[0124] Rf 3 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.)

[0125] Specific examples of the polyfluoromonoamino compound represented by the general formula (21) include the following: The following f2 satisfies the above requirements.

[0126]

[0127] Specific examples of polyfluoro compounds represented by the above general formulas (22) and (23) include the following. Note that c2, d2, e2, and the sum of d2 and e2 below satisfy the above requirements, and the repeating units shown in parentheses may be bonded randomly. CF3O-(CF2CF2CF2O) c2 -CF2CF3 CF3-O-(OCF2) d2 (OCF2CF2) e2 -CF3

[0128] The viscosity (23°C) of the polyfluoroamino compound represented by the formula (21) and the polyfluoro compounds represented by the formulas (22) and (23) is preferably in the range of 2,000 to 50,000 mPa·s. When the polyfluoroamino compound represented by the formula (21) and the polyfluoro compounds represented by the formulas (22) and (23) are blended, the blending amount is preferably 1 to 300 parts by mass, more preferably 30 to 250 parts by mass, per 100 parts by mass of component (A).

[0129] 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.

[0130] [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 component (A), component (B), and other optional components as needed 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.

[0131] The produced fluoropolyether-based curable composition can be cured at room temperature, and curing can be accelerated by adding a curing accelerator. Even if a curing accelerator is not used, heating is often used to accelerate curing. To obtain good rubber properties, it is preferable to cure the composition at 60°C or higher, preferably 80 to 200°C, for a period of several minutes to several days.

[0132] 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.

[0133] The fluoropolyether-based curable composition of the present invention is preferably used as electric or electronic parts for automobiles, ships, sports equipment, LEDs, civil engineering and construction, chemical plants, semiconductor production lines, analytical and physicochemical instruments, living environments, communication devices, communication facilities, aircraft, railway vehicles, portable devices, power storage devices, robots, or lithium-ion batteries, and is more preferably used for automobiles, ships, aircraft, sports equipment, LEDs, civil engineering and construction, chemical plants, analytical and physicochemical instruments, living environments, communication devices, communication facilities, and railway vehicles. In particular, electric or electronic parts using a cured product of the fluoropolyether-based curable composition of the present invention as a gasket, packing, protective seal, or coating layer are preferred.

[0134] 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, parts refer to parts by mass. In addition, in the following examples, the viscosity is a value measured at 23°C using a rotational viscometer, and the amounts of vinyl groups, SiH groups, secondary amino groups, and epoxy groups are 1 This is a value measured by H-NMR.

[0135] Synthesis Example 1 200 g of a polymer represented by the following formula (24) (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 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 (25): (The average value of n+m is 35) (The average value of n+m is 35)

[0136] Next, 145.2 g of the polymer represented by formula (25) 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 (26). The amount of epoxy groups was 0.0810 mol / 100 g. (The average value of n+m is 35)

[0137] Synthesis Example 2: 200 g of a polymer represented by the following formula (27) (vinyl group amount: 0.0335 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 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 elemental substance) was added. -6 A 1000 ml solution (containing 1000 mol) was added and stirred for 2 hours. After confirming the disappearance of the vinyl groups, the solvent and excess tetramethylcyclosiloxane were removed. The mixture was then treated with activated carbon to obtain 158.1 g of a polymer represented by the following formula (28). (The average value of n+m is 35) (The average value of n+m is 35)

[0138] Next, 155.0 g of the polymer represented by formula (28) 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. 0.77 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex (1.97 × 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 153 g of a grease-like fluorine-containing epoxy compound represented by the following formula (29). The amount of epoxy groups was 0.0840 mol / 100 g. (The average value of n+m is 35)

[0139] Synthesis Example 3 The same procedures as in Synthesis Example 1 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 (30). The amount of epoxy groups was 0.0803 mol / 100 g. (The average value of n+m is 35)

[0140] Synthesis Example 4 The same procedures as in Synthesis Example 2 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 (31). The amount of epoxy groups was 0.0833 mol / 100 g. (The average value of n+m is 35)

[0141] Synthesis Example 5 200 g of a polymer represented by the following formula (32) (vinyl group amount: 0.0231 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 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 (33): (The average value of n is 24) (The average value of n is 24)

[0142] Next, 150 g of the polymer represented by formula (33) 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 (34). The amount of epoxy groups was 0.0612 mol / 100 g. (The average value of n is 24)

[0143] Synthesis Example 6 200 g of a polymer represented by the following formula (35) (vinyl group amount: 0.0239 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 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 (36): (The average value of n is 24) (The average value of n is 24)

[0144] Next, 150 g of the polymer represented by formula (36) 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 removed by distillation under reduced pressure to obtain 141 g of a grease-like fluorine-containing epoxy compound represented by the following formula (37). The amount of epoxy groups was 0.0629 mol / 100 g. (The average value of n is 24)

[0145] Synthesis Example 7 200 g of the polymer represented by formula (27) (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 (38). (The average value of n+m is 35)

[0146] Next, 150 g of the polymer represented by formula (38) 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 (39). The amount of epoxy groups was 0.0574 mol / 100 g. (The average value of n+m is 35)

[0147] Synthesis Example 8 200 g of the polymer represented by formula (24) (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 alone) 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 (40): (The average value of n+m is 35)

[0148] Next, 150 g of the polymer represented by formula (40) 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. Then, 0.76 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex (1.94 × 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 143 g of an oily fluorine-containing epoxy compound represented by the following formula (41). The amount of epoxy groups was 0.0553 mol / 100 g. (The average value of n+m is 35)

[0149] Synthesis Example 9 The same procedures as in Synthesis Example 7 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 (42). The amount of epoxy groups was 0.0571 mol / 100 g. (The average value of n+m is 35)

[0150] [Example 1] 90 parts of (A1) a polymer represented by the following formula (43) (viscosity 4,900 mPa s, amount of secondary amino groups at the polymer terminal 0.0296 mol / 100 g) and 10 parts of (A2) a polymer represented by the following formula (44) (viscosity 24,920 mPa s, amount of secondary amino groups at the polymer terminal 0.0301 mol / 100 g) were kneaded together, and then 43.1 parts of (B1) a fluorine-containing epoxy group compound represented by the above formula (26) (epoxy group amount 0.0810 mol / 100 g) were added and kneaded to obtain a fluoropolyether-based curable composition. (The average value of a is 1.03, and the average value of n+m is 35)

[0151] (The average value of n+m is 35)

[0152] [Example 2] A fluoropolyether-based curable composition was obtained in the same manner as in Example 1, except that 60 parts by mass of (A1) the polymer represented by the above formula (43), 40 parts by mass of (A2) the polymer represented by the above formula (44), and 43.3 parts by mass of (B1) the fluorine-containing epoxy compound represented by the above formula (26) were used.

[0153] [Example 3] A fluoropolyether-based curable composition was obtained in the same manner as in Example 1, except that 40 parts by mass of (A1) the polymer represented by the above formula (43), 60 parts by mass of (A2) the polymer represented by the above formula (44), and 43.5 parts by mass of (B1) the fluorine-containing epoxy compound represented by the above formula (26) were used.

[0154] [Example 4] A fluoropolyether-based curable composition was obtained in the same manner as in Example 1, except that 100 parts by mass of (A1) the polymer represented by the above formula (43) and 43.0 parts by mass of (B1) the fluorine-containing epoxy compound represented by the above formula (26) were used.

[0155] [Example 5] A fluoropolyether-based curable composition was obtained in the same manner as in Example 1, except that 100 parts by mass of (A2) the polymer represented by the above formula (44) and 43.8 parts by mass of (B1) the fluorine-containing epoxy compound represented by the above formula (26) were used.

[0156] [Example 6] A fluoropolyether-based curable composition was obtained in the same manner as in Example 1, except that 42.7 parts of (B2) a fluorine-containing epoxy compound represented by the above formula (29) (epoxy group amount: 0.0840 mol / 100 g) was used instead of the fluorine-containing epoxy compound (B1) in Example 1.

[0157] [Example 7] A fluoropolyether-based curable composition was obtained in the same manner as in Example 4, except that 43.3 parts by mass of (B2) a fluorine-containing epoxy compound represented by the above formula (29) was used instead of (B1) the fluorine-containing epoxy compound in Example 4.

[0158] [Example 8] A fluoropolyether-based curable composition was obtained in the same manner as in Example 1, except that 43.3 parts of (B3) a fluorine-containing epoxy compound represented by the above formula (30) (epoxy group amount: 0.0803 mol / 100 g) was used instead of (B1) the fluorine-containing epoxy compound in Example 1.

[0159] [Example 9] A fluoropolyether-based curable composition was obtained in the same manner as in Example 4, except that 43.9 parts of (B3) a fluorine-containing epoxy compound represented by the above formula (30) was used instead of (B1) a fluorine-containing epoxy compound.

[0160] [Example 10] A fluoropolyether-based curable composition was obtained in the same manner as in Example 1, except that 42.8 parts of (B4) a fluorine-containing epoxy compound represented by the above formula (31) (epoxy group amount: 0.0833 mol / 100 g) was used instead of the fluorine-containing epoxy compound (B1) in Example 1.

[0161] [Example 11] A fluoropolyether-based curable composition was obtained in the same manner as in Example 1, except that 33.0 parts of (B5) a fluorine-containing epoxy compound (epoxy group amount 0.1103 mol / 100 g) represented by the following formula (45) was used instead of the fluorine-containing epoxy compound (B1) in Example 1. (n / m=0.9, n+m=45)

[0162] [Example 12] A fluoropolyether-based curable composition was obtained in the same manner as in Example 4, except that 32.9 parts of (B5) a fluorine-containing epoxy compound represented by the above formula (45) was used instead of (B1) a fluorine-containing epoxy compound.

[0163] [Example 13] A fluoropolyether-based curable composition was obtained in the same manner as in Example 4, except that (B6) the fluorine-containing epoxy compound represented by the above formula (34) (epoxy group amount 0.0612 mol / 100 g) was used in place of the fluorine-containing epoxy compound (B1) in Example 4.

[0164] [Example 14] A fluoropolyether-based curable composition was obtained in the same manner as in Example 4, except that (B7) the fluorine-containing epoxy compound represented by the above formula (37) (epoxy group amount 0.0629 mol / 100 g) was used in place of the fluorine-containing epoxy compound (B1) in Example 4, in an amount of 60.0 parts by mass.

[0165] [Example 15] A fluoropolyether-based curable composition was obtained in the same manner as in Example 1, except that 62.7 parts of (B8) a fluorine-containing epoxy compound represented by the above formula (39) (epoxy group amount: 0.0574 mol / 100 g) was used instead of the fluorine-containing epoxy compound (B1) in Example 1.

[0166] [Example 16] A fluoropolyether-based curable composition was obtained in the same manner as in Example 4, except that 62.8 parts by mass of (B8) a fluorine-containing epoxy compound represented by the above formula (39) was used instead of (B1) the fluorine-containing epoxy compound in Example 4.

[0167] [Example 17] A fluoropolyether-based curable composition was obtained in the same manner as in Example 1, except that (B9) 62.0 parts of a fluorine-containing epoxy compound (epoxy group amount 0.0553 mol / 100 g) represented by the above formula (41) was used instead of the fluorine-containing epoxy compound (B1).

[0168] [Example 18] A fluoropolyether-based curable composition was obtained in the same manner as in Example 4, except that 62.1 parts by mass of (B9) a fluorine-containing epoxy compound represented by the above formula (41) was used instead of (B1) a fluorine-containing epoxy compound.

[0169] [Example 19] A fluoropolyether-based curable composition was obtained in the same manner as in Example 1, except that 62.9 parts of (B10) a fluorine-containing epoxy compound represented by the above formula (42) (epoxy group amount: 0.0571 mol / 100 g) was used instead of the fluorine-containing epoxy compound (B1).

[0170] [Example 20] A fluoropolyether-based curable composition was obtained in the same manner as in Example 4, except that 63.0 parts by mass of (B10) a fluorine-containing epoxy compound represented by the above formula (42) was used instead of (B1).

[0171] Comparative Example 1 A fluoropolyether-based curable composition was obtained in the same manner as in Example 1, except that 2.74 parts by mass of (B11) an epoxy compound represented by the following formula (46) was used instead of (B1).

[0172] [Comparative Example 2] A fluoropolyether-based curable composition was obtained in the same manner as in Example 4, except that 2.73 parts by mass of (B11) the epoxy compound represented by the above formula (28) was used instead of (B1).

[0173] [Comparative Example 3] A fluoropolyether-based curable composition was obtained in the same manner as in Example 5, except that 2.78 parts by mass of (B11) the epoxy compound represented by the above formula (28) was used instead of (B1).

[0174] <Measurement of pot life at room temperature> Each composition was placed in a thermostatic chamber at 25°C, and the time until fluidity was lost was measured by visual observation after 2, 4, 8, 16, and 24 hours. The results are shown in Tables 1 to 3. [Evaluation criteria] ○: Fluidity is maintained. △: Not cured, but no fluidity. ×: Cured.

[0175]

[0176]

[0177]

[0178] The fluoropolyether-based curable compositions of Examples 1 to 20, which used a fluorine-containing epoxy compound as component (B), maintained fluidity for approximately 8 to 16 hours at 25° C. Comparative Examples 1 to 3, which used the same component (A) as Examples 1, 4, and 5, resulted in shorter pot lives than the corresponding Examples 1, 4, and 5.

[0179] <Preparation of fluoropolyether-based cured products and evaluation of physical properties> The fluoropolyether-based curable compositions prepared in Examples 1 to 20 and Comparative Examples 1 to 3 were each poured into a 2 mm thick stainless steel mold placed on a Teflon (registered trademark, the same applies hereinafter) sheet immediately after preparation, sandwiched between other Teflon sheets, and press-cured at 100°C for 6 hours. After press-curing, the 2 mm thick stainless steel mold was removed, and the physical properties of the resulting fluoropolyether-based cured products were evaluated in accordance with JIS K 6249. The results are shown in Table 4.

[0180]

[0181] The fluoropolyether curable compositions of Examples 1 to 20, which used fluorine-containing epoxy compounds (B1) to (B10) as component (B), all resulted in cured products with good rubber elasticity. Compared to these cured products, the cured products obtained from the fluoropolyether curable compositions of Comparative Examples 1 to 3, which were prepared using fluorine-free epoxy compound (B11) as component (B), were significantly harder and had poorer rubber elasticity. From these results, it was found that the fluoropolyether curable compositions of Examples 1 to 20 had long pot lives, and the resulting cured products were soft and had excellent rubber elasticity.

Claims

1. A fluoropolyether-based curable composition containing: (A) a fluorine-containing compound having at least two secondary amino groups in each molecule and a divalent perfluoropolyether group in the main chain; and (B) a fluorine-containing compound having at least two epoxy groups in each molecule and a monovalent or divalent perfluoropolyether group in the main chain, in an amount such that the epoxy groups in component (B) are 0.5 to 5 moles per mole of secondary amino groups in component (A).

2. The fluoropolyether-based curable composition according to claim 1, wherein component (A) is a fluorine-containing compound represented by the following average formula (1): [In formula (1), Rf is independently a divalent perfluoropolyether group, A is independently a carbonyl bond or a divalent organic group having 1 to 12 carbon atoms which may have at least one bond selected from an amide bond, an ether bond, and an ester bond, and X is independently a group represented by the following formulas (2) to (4): (In the formula, R 1 are independently unsubstituted or substituted monovalent hydrocarbon groups; R 2 are independently an unsubstituted or substituted divalent hydrocarbon group; and a is a positive number of 1 or more.

3. A in the above average formula (1) is independently -(CH2) f -*, -(CH2) f OCH2-*, -CO-*, -(CH2) f -NR 6 -CO-*, -(CH2) f The fluoropolyether-based curable composition according to claim 2, which is any group selected from -O-CO-* and groups represented by the following general formulas (5) and (6) (wherein the bond marked with * is bonded to Rf, and the bond without a mark is bonded to X). (In the formula, R 5 are independently a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, or a trifluoromethyl group; R 6 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 9.

4. The fluoropolyether-based curable composition according to claim 1, wherein the component (B) is a fluorine-containing compound represented by the following general formula (7): [In formula (7), Rf 1 Rf is independently a monovalent or divalent group having a fluoropolyether structure and a number average molecular weight of 400 to 40,000. 1 When Rf is monovalent, b' is 1, b is an integer from 1 to 6, and c is an integer from 2 to 20. 1 is divalent, then b' is 2, b is 1, and c is an integer from 1 to 20. Q is independently a (b+c)-valent group having at least (b+c) 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, which 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 formula (I), R 3 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 formula (II), R 4 are independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms.

5. The fluoropolyether curable composition according to claim 4, wherein in formula (7), Z is independently selected from groups represented by the following formulae: -CH2CH2-*, -CH2CH2CH2-*, -CH2CH2CH2CH2-*, -CH2CH2CH2CH2CH2CH2-*, -CH2CH2CH2CH2CH2CH2CH2-*, -CH2CH2CH2CH2CH2CH2CH2-*, -CH2CH2CH2CH2CH2CH2CH2-*, -CH2CH2CH2CH2CH2CH2CH2-*, -CH2CH2CH2OCH2-*, -CH2CH2CH2OCH2CH2OCH2-*, or -CH2CH2CH2OCH2CH2OCH2CH2OCH2CH2OCH2CH2-* (wherein the bond marked with * is bonded to E, and the bond without a mark is bonded to Q.) 6. The fluoropolyether curable composition according to claim 4, wherein the structure represented by -ZE in the formula (7) is selected from groups represented by the following formulas (a) to (d): (In the formula, g is an integer from 1 to 20, h is an integer from 1 to 10, i is an integer from 1 to 5, l is an integer from 0 to 9, and h+2l+i is 2 to 20. R 4 is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms.

7. The fluoropolyether curable composition according to claim 4, wherein in the formula (7), the structure represented by -ZE is selected from groups represented by the following formulas:

8. The fluoropolyether curable composition according to claim 4, wherein in formula (7), Q is represented by the following formula: (Wherein, b1 is Rf 1 is an integer from 1 to 4 when Rf is monovalent; 1 is divalent, c1 is an integer of 2 to 4, and b1' is an integer that satisfies b1+c1=3 to 6. 1 is 1 or 2 when Rf is monovalent; 1 is divalent, c1' is 2 or 3, d1 is 0 or 1, and b1'+c1'+d1=4. D is a monovalent hydrocarbon group having 1 to 6 carbon atoms. Each silicon atom of the unit shown in parentheses having b1 and b1' repetitions is Rf 1 and each silicon atom of the unit shown in the brackets having c1 and c1′ repeats is bonded to Z, and the arrangement of the units shown in the brackets may be random.

9. A cured product obtained by curing the fluoropolyether curable composition according to any one of claims 1 to 8.

10. An article comprising the cured product according to claim 9.

11. The article according to claim 10, which is for use in automobiles, ships, aircraft, sporting goods, LEDs, civil engineering and construction, chemical plants, analytical and physicochemical instruments, living environments, communication devices, communication facilities, and railway cars.