Fluoropolyether-based curable composition, cured product, and article

Abstract

Provided is a fluoropolyether-based curable composition which can be used for a longer time than in the prior art, can be cured at room temperature or heat-cured, and can form a cured product having reduced hardness and good mechanical and physical properties. The fluoropolyether-based curable composition contains (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 amount of the fluorine-containing compound is less than or equal to 1 mol per secondary amino group in the component (A), and the amount of the fluorine-containing compound is less than or equal to 1 mol per secondary amino group in the component (A). And the epoxy group in the component (B) is 0.5-5 mol.

Description

Technical Field

[0001] The present invention relates to fluoropolyether-based curable compositions that are cured by the reaction of amines with epoxides, have a longer working time than conventional curable compositions, can be cured at room temperature or by heating, can form cured products with reduced hardness and good mechanical properties, cured products of the same compositions, and articles having the cured products. Background Technology

[0002] Fluoroether-based curable compositions utilizing the addition reaction of alkenyl and silyl (SiH) groups are known. For example, as curable compositions, compositions comprising a linear fluorinated polyether compound having two or more alkenyl groups in one molecule and a perfluoropolyether structure in the main chain, a fluorinated organosiloxane having two or more hydrogen atoms directly bonded to silicon atoms in one molecule, and a platinum group metal compound have been proposed (Patent Document 1, Patent Document 2 (Japanese Patent Application Publication No. 8-199070, Japanese Patent Application Publication No. 2011-201940)). Furthermore, compositions that impart self-adhesiveness by adding an organopolysiloxane having silyl and epoxy and / or trialkoxysilyl groups as a third component (adhesion enhancer) to the composition have been proposed (Patent Document 3, Patent Document 4 (Japanese Patent Application Publication No. 9-95615, Japanese Patent Application Publication No. 2011-219692)). This composition can be cured by heating for a short time, and the resulting cured product (fluorinated polyether-based cured product) has excellent solvent resistance, chemical resistance, heat resistance, low temperature properties, low moisture permeability, and electrical properties. Therefore, it has been used in various industrial fields that require these properties.

[0003] A drawback of this fluoropolyether-based curable composition is that poor curing occurs in the presence of substances containing atoms such as phosphorus, sulfur, and nitrogen. Due to this drawback, there are many applications where it is difficult to apply it; therefore, there is a need for a fluoropolyether-based curable composition that can cure even in the presence of these atoms.

[0004] Patent Document 5 (Japanese Patent Application Publication No. 2008-19398) describes a fluoropolyether-based curable composition that is cured by mixing a fluoroamide compound having a divalent perfluoropolyether group and a secondary amino group with an aniline derivative having three epoxy groups. However, this aniline derivative does not contain fluorine atoms, and therefore does not immediately exhibit compatibility with the aforementioned fluoroamide compound after mixing. Furthermore, its usable time is short, typically around 3 to 8 hours. While a short usable time is sometimes acceptable in applications requiring short-time curing at room temperature, it is preferable to sacrifice usable time in applications where the curing reaction can be accelerated by heating. Additionally, the method in Patent Document 5 tends to harden after curing, making it unsuitable for applications requiring a softer, more elastic cured product.

[0005] Patent document 6 (Japanese Patent Application Publication No. 2014-80534) describes a fluorinated epoxy compound containing monovalent or divalent perfluoropolyether groups in its main chain, which can be used as an additive to impart antifouling, water-repellent, and oil-repellent properties to the surface of thermosetting resins. However, there has been almost no research on using epoxy compounds with such characteristics as the epoxy compound in the fluorinated polyether-based curable composition described in Patent document 5, thereby obtaining a cured product with extended service life and excellent softness and elasticity.

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Application Publication No. 8-199070

[0009] Patent Document 2: Japanese Patent Application Publication No. 2011-201940

[0010] Patent Document 3: Japanese Patent Application Publication No. 9-95615

[0011] Patent Document 4: Japanese Patent Application Publication No. 2011-219692

[0012] Patent Document 5: Japanese Patent Application Publication No. 2008-19398

[0013] Patent Document 6: Japanese Patent Application Publication No. 2014-80534 Summary of the Invention

[0014] The problem that the invention aims to solve

[0015] The present invention was made in view of the above-mentioned actual situation, and aims to provide a fluoropolyether-based curable composition that has a longer service life than the past, can be cured at room temperature or by heating, can form a cured product with reduced hardness and good mechanical properties, a cured product obtained by curing the composition that is softer than the past and has excellent rubber elasticity, and an article having the cured product.

[0016] Methods for solving problems

[0017] To achieve the above objectives, the inventors conducted in-depth research and discovered that a fluorinated polyether-based curable composition containing (A) a fluorinated compound having at least two secondary amino groups in one molecule and a divalent perfluoropolyether group in the main chain, and (B) a fluorinated compound having at least two epoxy groups in one molecule and a monovalent or divalent perfluoropolyether group in the main chain, in a specific ratio, has a longer usable time. A soft, rubber-elastic cured product is obtained by room temperature curing or heating curing. Compared with Patent Document 5, the cured product has reduced hardness and good mechanical properties, thus completing the present invention.

[0018] Therefore, the present invention provides the following fluoropolyether-based curable compositions, cured compositions of the compositions, and articles having the cured compositions, which have a long service life, can be cured at room temperature or by heating, and can form cured products with good mechanical properties.

[0019] [1] A fluorinated polyether-based curable composition containing:

[0020] (A) A fluorinated compound having at least two secondary amino groups in one molecule and having a divalent perfluoropolyether group in the main chain, and

[0021] (B) A fluorinated compound having at least two epoxy groups in one molecule and having a monovalent or divalent perfluoropolyether group in the main chain: in such an amount that, relative to 1 mole of the secondary amino group in component (A), the epoxy group in component (B) is 0.5 to 5 moles.

[0022] [2] According to the fluorinated polyether-based curable composition of [1], wherein component (A) is a fluorinated compound represented by the following average formula (1),

[0023] [Chemistry 1]

[0024]

[0025] In formula (1), Rf is independently a divalent perfluoropolyether group, A is independently a divalent organic group having 1 to 12 carbon atoms and having at least one carbonyl bond, or selected from amide bond, ether bond, and ester bond, and X is independently a group formed by the following formulas (2) to (4).

[0026] [Chemistry 2]

[0027]

[0028] (where R is in the formula) 1 R is an unsubstituted or substituted monovalent hydrocarbon group. 2 Independently, it is an unsubstituted or substituted divalent hydrocarbon group. ( ) represents any one of the groups, where a is a positive number of 1 or more.

[0029] [3] The fluoropolyether-based curable composition according to [2], wherein A in the average formula (1) is independently selected from -(CH2). f -*、-(CH2) f OCH2-*, -CO-*, -(CH2) f -NR 6 -CO-*、-(CH2) f -O-CO-*, and any one of the groups represented by the following general formulas (5) and (6) (a * indicates binding with Rf, and an unmarked end indicates binding with X).

[0030] [Chemistry 3]

[0031]

[0032] (where R) 5 R is independently a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, or a trifluoromethyl group. 6 (where e is a hydrogen atom, methyl, ethyl, isopropyl, or phenyl, e is 0 or 1, and f is an integer from 1 to 9).

[0033] [4] A fluorinated polyether-based curable composition according to any one of [1] to [3], wherein component (B) is a fluorinated compound represented by the following general formula (7),

[0034] [Chemistry 4]

[0035]

[0036] In equation (7), Rf 1 Independently, it is a monovalent or divalent group with a number average molecular weight of 400–40000, possessing a fluorinated polyether structure. Rf 1 When the group is monovalent, b' is 1, b is an integer from 1 to 6, and c is an integer from 2 to 20. Rf 1When the group is divalent, 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, having a siloxane structure, a silanediol structure, a silanearyl structure, or a combination thereof, and may have a cyclic structure. Z is independently a divalent hydrocarbon group having 1 to 20 carbon atoms, may contain ether bonds or ester bonds, and may have a cyclic structure. E is independently a group represented by the following formula (I) or (II).

[0037] [Chemistry 5]

[0038]

[0039] (In formula (I), R) 3 It is an independent hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, which may contain ether or ester bonds and may have a cyclic structure.

[0040] [Chemistry 6]

[0041]

[0042] (In formula (II), R) 4 Independently, it is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms.

[0043] [5] According to the fluoropolyether-based curable composition of [4], wherein, in the formula (7), Z is independently selected from the groups represented by the following formula,

[0044] -CH2CH2-*、

[0045] -CH2CH2CH2-*、

[0046] -CH2CH2CH2CH2-*、

[0047] -CH2CH2CH2CH2CH2-*、

[0048] -CH2CH2CH2CH2CH2CH2-*、

[0049] -CH2CH2CH2CH2CH2CH2CH2-*、

[0050] -CH2CH2CH2CH2CH2CH2CH2CH2-*、

[0051] -CH2CH2CH2OCH2-*、

[0052] -CH2CH2CH2OCH2CH2OCH2-*, or

[0053] -CH2CH2CH2OCH2CH2OCH2CH2OCH2CH2-*

[0054] (In the formula, the binding terminal marked with * indicates binding with E, and the unmarked binding terminal indicates binding with Q.)

[0055] [6] According to the fluoropolyether-based curable composition described in [4] or [5], wherein, in the formula (7), the structure represented by -ZE is selected from the groups represented by the following formulas (a) to (d),

[0056] [Chemistry 7]

[0057]

[0058] (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 an integer from 2 to 20. R) 4 It is a monovalent hydrocarbon group consisting of hydrogen atoms or 1 to 20 carbon atoms, either unsubstituted or substituted.

[0059] [7] A fluoropolyether-based curable composition according to any one of [4] to [6], wherein, in the formula (7), the structure represented by -ZE is selected from the group represented by the following formula,

[0060] [Chemistry 8]

[0061] .

[0062] [8] A fluoropolyether-based curable composition according to any one of [4] to [7], wherein, in formula (7), Q is represented by the following formula,

[0063] [Chemistry 9]

[0064]

[0065] (In the formula, b1 is in Rf) 1 When the group is monovalent, the valence is an integer from 1 to 4, in Rf 1 When the group is divalent, c1 is 1, c1 is an integer from 2 to 4, and it is an integer satisfying b1 + c1 = 3 to 6. b1' in Rf 1 When the group is monovalent, it is 1 or 2; in Rf 1 When the group is divalent, c1' is 2 or 3, d1 is 0 or 1, and b1' + c1' + d1 = 4. D is a monovalent hydrocarbon group with 1 to 6 carbon atoms. The silicon atoms of the units shown in parentheses with b1 and b1' repeating units are related to Rf. 1In combination, each silicon atom of the unit shown in parentheses, which has c1 and c1' repeating units, is bonded to Z. The arrangement of the units shown in parentheses can be random.

[0066] [9] A cured product obtained by curing a fluorinated polyether curable composition according to any one of [1] to [8].

[0067]

[10] An article having a solidified substance as described in [9].

[0068]

[11] The articles described in

[10] are articles for automobiles, ships, aircraft, sports equipment, LEDs, civil engineering, chemical plants, analytical and physical and chemical equipment, living environments, communication machines, communication equipment, and railway vehicles.

[0069] The effects of the invention

[0070] The fluorinated polyether-based curable composition of the present invention uses, in a specific ratio, a fluorinated compound having at least two secondary amino groups in one molecule and a divalent perfluoropolyether group in the main chain (component (A)) and a fluorinated compound having at least two epoxy groups in one molecule and a monovalent or divalent perfluoropolyether group in the main chain as an epoxy compound reactive to the amino groups in the compound (component (B)). This results in an improved usable time compared to the curable composition described in Patent Document 5. Furthermore, by curing this composition, a cured product that is softer and has superior rubber elasticity than that of Patent Document 5 is obtained, while also exhibiting excellent chemical resistance, solvent resistance, and insulation properties. Detailed Implementation

[0071] The present invention will now be described in more detail.

[0072] [(A)Component]

[0073] The fluorinated compound of component (A) used in the fluorinated polyether-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 functions as a main agent (base oil) in the fluorinated polyether-based curable composition of the present invention.

[0074] In this invention, the degree of polymerization (or molecular weight) of a fluorinated compound, reflecting the number of repeats of the perfluorooxyalkylene units constituting the perfluoropolyether group of the main chain, can be obtained, for example, by using a fluorinated solvent as the elution solvent or by using the number-average degree of polymerization (or number-average molecular weight) converted from polystyrene in gel permeation chromatography (GPC) analysis. Furthermore, the perfluoropolyether group (Rf, Rf, described later) formed by the repeating of the perfluorooxyalkylene units constituting the main chain... 1 The number-average degree of polymerization (or number-average molecular weight) can also be determined by... 19 Calculated by F-NMR.

[0075] (A) The preferred component is a fluorinated compound represented by the following average formula (1).

[0076] [Chemistry 10]

[0077]

[0078] In formula (1), Rf is independently a divalent perfluoropolyether group, A is independently a divalent organic group having 1 to 12 carbon atoms and having at least one carbonyl bond, or selected from amide bond, ether bond, and ester bond, and X is independently a group formed by the following formulas (2) to (4).

[0079] [Chemistry 11]

[0080]

[0081] (where R) 1 R is an unsubstituted or substituted monovalent hydrocarbon group. 2 (Independently an unsubstituted or substituted divalent hydrocarbon group.)

[0082] [This refers to any group where a is a positive number greater than or equal to 1.]

[0083] In the above average formula (1), X is independently a group represented by any one of the following general formulas (2) to (4).

[0084] [Chemistry 12]

[0085]

[0086] (where R) 1 R is an unsubstituted or substituted monovalent hydrocarbon group. 2 (Independently an unsubstituted or substituted divalent hydrocarbon group.)

[0087] In the above general formula (2), R 1 The group is an unsubstituted or substituted monovalent hydrocarbon group, preferably a monovalent hydrocarbon group with 1 to 12 carbon atoms, especially 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; or chloromethyl, bromoethyl, chloropropyl, trifluoropropyl, and 3,3,4,4,5,5,6,6,6-nonafluorohexyl, etc., in which part of the hydrogen atoms of these groups are replaced by halogen atoms such as fluorine, chlorine, and bromine.

[0088] In the above general formulas (2) to (4), R 2The divalent hydrocarbon group is either unsubstituted or substituted, preferably a divalent hydrocarbon group with 1 to 12 carbon atoms, especially 2 to 6. Examples include alkylene groups such as methylene, ethylene, n-propylene, isopropylene, butylene, and hexamethylene; cyclohexylene groups such as cyclohexylene; arylene groups such as phenylene, tolylene, xylene, naphthylene, and biphenylene; or groups formed by substituting part of their hydrogen atoms with halogen atoms such as fluorine.

[0089] As X, the following groups can be exemplified. Furthermore, in the following formulas, Me represents methyl and Ph represents phenyl.

[0090] [Chemistry 13]

[0091]

[0092] In the above average formula (1), A is independently a divalent organic group (especially a hydrocarbon group) having 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, and may have a carbonyl bond or at least one selected from amide bonds, ether bonds, and ester bonds. Preferably, A is selected from -(CH2). f -*、-(CH2) f OCH2-*, -CO-*, -(CH2) f -NR 6 -CO-*、-(CH2) f -O-CO-*, any one of the groups represented by the following general formulas (5) and (6). It should be noted that the binding end with * indicates binding with Rf, and the unmarked binding end indicates binding with X.

[0093] [Chemistry 14]

[0094]

[0095] (where R) 5 R is independently a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, or a trifluoromethyl group. 6 (where e is a hydrogen atom, methyl, ethyl, isopropyl, or phenyl, e is 0 or 1, and f is an integer from 1 to 9.)

[0096] As A, examples 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-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 formulas (5A), (5B), (5C), (5D), (5E), (6A), (6B), and (6C), wherein preferably groups represented by -CO-*, -CH2-NH-CO-*, -CH2CH2-NH-CO-*, or general formula (5A) or (6A). Furthermore, a binding end marked with * indicates binding with Rf, and an unmarked binding end indicates binding with X. Additionally, in the formulas, Me is methyl and Et is ethyl.

[0097] [Chemistry 15]

[0098]

[0099] In the above average formula (1), Rf is independently a divalent perfluoropolyether group containing -C x F 2x O- (where x is an integer from 1 to 6.) repeating units, for example, repeating units represented by the following formula (8) can be listed.

[0100] -(C x F 2x O) y - (8)

[0101] (In the formula, x is an integer from 1 to 6, and y is an integer from 5 to 600, preferably an integer from 10 to 400, and more preferably an integer from 30 to 200.)

[0102] As given by the above equation -C x F 2x O- indicates repeating units, such as units represented by the following formula.

[0103] -CF2O-

[0104] -CF2CF2O-

[0105] -CF2CF2CF2O-

[0106] -CF(CF3)CF2O-

[0107] -CF2CF2CF2CF2O-

[0108] -CF2CF2CF2CF2CF2CF2O-

[0109] Of these, the unit represented by the following formula is particularly preferred.

[0110] -CF2O-

[0111] -CF2CF2O-

[0112] -CF2CF2CF2O-

[0113] -CF(CF3)CF2O-

[0114] Furthermore, the repeating units in the aforementioned divalent perfluoropolyether group can be composed of one of these units alone, or can be composed of a combination of two or more of them.

[0115] Furthermore, the divalent perfluoropolyether group is preferably structured as follows.

[0116] [Chemistry 16]

[0117]

[0118] (In the formula, G is a fluorine atom or a trifluoromethyl group, p1, q1 and r1 are each integers satisfying p1≥0, q1≥0, 0≤p1+q1≤200, especially 2≤p1+q1≤150 and 0≤r1≤6 (1≤r1≤6 when p1+q1=0), k1, a1, s1, t1 and u1 are each integers satisfying 1≤k1≤3, 2≤a1≤6, 0≤s1≤100, 0≤t1≤100, 2≤s1+t1≤200, 0≤u1≤6, especially 2≤s1+t1≤200.) Let 1 be an integer ≤ 150, 0 ≤ u1 ≤ 4, and 2 ≤ s1 + t1 + u1 ≤ 150. Let v1 and w1 be integers satisfying 1 ≤ v1 ≤ 100, 1 ≤ w1 ≤ 100, and 2 ≤ v1 + w1 ≤ 200. Let z1 be an integer satisfying 1 ≤ z1 ≤ 200. Let k1', a1', and a1" be integers satisfying 1 ≤ k1' ≤ 3, 1 ≤ a1' ≤ 6, 1 ≤ a1" ≤ 6, and a1' ≠ a1" respectively. Let z1' be an integer satisfying 1 ≤ z1' ≤ 200. The repeating units shown in parentheses containing v1 and w1 can be combined randomly.

[0119] In the above average formula (1), as a specific example of Rf, an instance represented by the following formula can be shown.

[0120] [Chemistry 17]

[0121]

[0122] (In the formula, p1, q1, r1, v1, w1, z1, z1' are the same as above. s1' and t1' are each integers from 1 to 100, and s1' + t1' = 2 to 200. t1" is an integer from 2 to 100. The repeating units shown in the parentheses containing v1 and w1 can be combined randomly.)

[0123] 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. It should be noted that 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. As an average formula for the entirety of (A) components of two or more compounds containing different values ​​of the repeating number a of the main chain structure -[XA-Rf-A]-, a only needs to be a positive number of 1 or more.

[0124] As for fluorinated compounds represented by the above average formula (1), fluorinated compounds represented by the following formula are particularly preferred. It should be noted that in the formula, Me is methyl and Et is ethyl.

[0125] [Chemistry 18]

[0126]

[0127] (In the formula, s1' and t1' are each integers from 1 to 100, and s1' + t1' = integers from 2 to 200.)

[0128] [Chemistry 19]

[0129]

[0130] (In the formula, s1' and t1' are each integers from 1 to 100, and s1' + t1' = integers from 2 to 200.)

[0131] [Chemistry 20]

[0132]

[0133] (In the formula, s1' and t1' are each integers from 1 to 100, and s1' + t1' = integers from 2 to 200.)

[0134] [Chemistry 21]

[0135]

[0136] (In the formula, s1' and t1' are each integers from 1 to 100, and s1' + t1' = integers from 2 to 200.)

[0137] [Chemistry 22]

[0138]

[0139] (In the formula, s1' and t1' are each integers from 1 to 100, and s1' + t1' = integers from 2 to 200.)

[0140] [Chemistry 23]

[0141]

[0142] (In the formula, v1 and w1 are each integers from 1 to 100, and v1 + w1 = 2 to 200. The repeating units shown in the parentheses containing v1 and w1 can be combined randomly.)

[0143] [Chemistry 24]

[0144]

[0145] (In the formula, s1' and t1' are each integers from 1 to 100, and s1'+t1' is an integer from 2 to 200.)

[0146] [Chemistry 25]

[0147]

[0148] (In the formula, s1' and t1' are integers from 1 to 100, s1'+t1' is an integer from 2 to 200, and a' is a positive number greater than 1.)

[0149] (A) The amount of secondary amines in the fluorinated compound is preferably 0.002 to 0.4 mol / 100g, more preferably 0.008 to 0.3 mol / 100g. When the amount of secondary amines in the fluorinated compound is less than 0.002 mol / 100g, the degree of crosslinking becomes insufficient, which may lead to poor curing and is therefore undesirable. When the amount of secondary amines is greater than 0.4 mol / 100g, it may impair the mechanical properties of the cured product as a rubber elastomer, which is also undesirable. In this invention, the amount of secondary amines can be... 1 H-NMR determination.

[0150] (A) The viscosity (23°C) of the fluorinated compound in component (A) is 40–500,000 mPa·s, more preferably 50–300,000 mPa·s, and even more preferably in the range of 60–150,000 mPa·s. This is preferred because the cured product obtained from the fluorinated polyether-based curable composition of the present invention has suitable physical properties. Within this viscosity range, the most suitable viscosity can be selected according to the application. In the present invention, the viscosity (23°C) can be measured using a rotational viscometer or similar device (e.g., BL type, BH type, BS type, cone-plate type, rheometer, etc.).

[0151] (A) The ingredients enable the use of one of these fluorinated compounds alone or in combination of two or more.

[0152] [(B) Component]

[0153] The fluorinated compound (hereinafter also referred to as fluorinated epoxy compound) of component (B) used in the fluorinated polyether-based curable composition of the present invention is a fluorinated compound having at least two epoxy groups in one molecule and having a monovalent or divalent perfluoropolyether group in the main chain, preferably represented by the following general formula (7), and functions as a chain extender and crosslinking agent in the fluorinated polyether-based curable composition of the present invention.

[0154] [Chemistry 26]

[0155]

[0156] In equation (7), Rf 1 Independently, it is a monovalent or divalent group with a number average molecular weight of 400–40000, possessing a fluorinated polyether structure. In Rf 1 When the group is monovalent, b' is 1, b is an integer from 1 to 6, and c is an integer from 2 to 20. In Rf 1 When the group is divalent, 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, having a siloxane structure, a silanediol structure, a silanearyl structure, or a combination thereof, and may have a cyclic structure. Z is independently a divalent hydrocarbon group having 1 to 20 carbon atoms, may contain ether bonds or ester bonds, and may have a cyclic structure. E is independently a group represented by the following formula (I) or (II).

[0157] [Chemistry 27]

[0158]

[0159] (In formula (I), R) 3 It is an independent hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, which may contain ether or ester bonds and may have a cyclic structure.

[0160] [Chemistry 28]

[0161]

[0162] (In formula (II), R) 4 A monovalent hydrocarbon group consisting independently of a hydrogen atom or 1 to 20 carbon atoms, either unsubstituted or substituted.

[0163] In the above general formula (7), Rf 1When the group is monovalent, b' is 1, b is an integer from 1 to 6, preferably an integer from 1 to 4, more preferably 1, and c is an integer from 2 to 20, preferably an integer from 2 to 6, more preferably an integer from 2 to 4.

[0164] Additionally, Rf 1 When the group is divalent, b' is 2, b is 1, and c is an integer from 1 to 20, preferably an integer from 1 to 6, and more preferably an integer from 2 to 4.

[0165] Furthermore, the preferred integers are those that satisfy b+c = 3 to 6.

[0166] In the above general formula (7), E is independently a group represented by the following formula (I) or (II).

[0167] [Chemistry 29]

[0168]

[0169] (In formula (I), R) 3 It is an independent hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, which may contain ether or ester bonds and may have a cyclic structure.

[0170] [Chemistry 30]

[0171]

[0172] (In formula (II), R) 4 (A monovalent hydrocarbon group consisting independently of a hydrogen atom or 1 to 20 carbon atoms, either unsubstituted or substituted.)

[0173] In the above formula (I), R 3 The monovalent hydrocarbon group is independently composed of hydrogen atoms or 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and may contain ether bonds or ester bonds, and may have a cyclic structure. Examples of such monovalent hydrocarbon groups 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. Alternatively, halogen-substituted monovalent hydrocarbon groups such as fluoromethyl, bromoethyl, and trifluoropropyl, which have some or all of their hydrogen atoms replaced by halogen atoms such as chlorine, fluorine, or bromine, may be used. Preferably, R... 3 It is a hydrogen atom.

[0174] In equation (II) above, R 4The alkyl group is independently composed of a hydrogen atom or a carbon group with 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 8 carbon atoms, and is either unsubstituted or substituted. Examples of such monovalent alkyl groups 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. Alternatively, halogen-substituted monovalent alkyl groups, such as fluoromethyl, bromoethyl, and trifluoropropyl, may be used, where some or all of the hydrogen atoms of these alkyl groups are substituted with halogen atoms such as chlorine, fluorine, or bromine. Preferably, R... 4 It can be a hydrogen atom or a methyl group.

[0175] The structures represented by the above formula (I) or formula (II) can be exemplified by the following structures.

[0176] [Chemistry 31]

[0177]

[0178] (where R) 4 Same as above.

[0179] The preferred structure is as shown below.

[0180] [Chemistry 32]

[0181]

[0182] In the above general formula (7), Z is a divalent hydrocarbon group with 1 to 20 carbon atoms, preferably 2 to 15 carbon atoms, which can form a cyclic structure and may contain ether bonds (-O-) or ester bonds (-COO-) in the middle.

[0183] Examples of groups that can be represented by Z include those with the following structures. It should be noted that a group marked with an asterisk (*) indicates a bond to E, and an unmarked group indicates a bond to Q.

[0184] -CH2CH2-*、

[0185] -CH2CH2CH2-*、

[0186] -CH2CH2CH2CH2-*、

[0187] -CH2CH2CH2CH2CH2-*、

[0188] -CH2CH2CH2CH2CH2CH2-*、

[0189] -CH2CH2CH2CH2CH2CH2CH2-*、

[0190] -CH2CH2CH2CH2CH2CH2CH2CH2-*、

[0191] -CH2CH2CH2OCH2-*、

[0192] -CH2CH2CH2OCH2CH2OCH2-*, or

[0193] -CH2CH2CH2OCH2CH2OCH2CH2OCH2CH2-*

[0194] As a structure represented by -ZE above, for example, structures represented by the following formulas (a) to (d) can be listed.

[0195] [Chemistry 33]

[0196]

[0197] In the above formula, g is an integer from 1 to 20, preferably an integer from 2 to 15. h is an integer from 1 to 10, i is an integer from 1 to 5, l is an integer from 0 to 9, h+2l+i is 2 to 20, preferably h is an integer from 1 to 6, i is 1 or 2, l is an integer from 0 to 4, and h+2l+i is 2 to 15. R 4 As described above, hydrogen atoms or methyl groups are preferred.

[0198] The structure represented by -ZE is particularly preferred, as shown below.

[0199] [Chemistry 34]

[0200]

[0201] In the above general formula (7), Q is independently a group having at least (b+c) Si atoms with a (b+c) valence, having a siloxane structure, a silanediol structure, a silanearyl structure or a combination thereof, and may have a cyclic structure.

[0202] For example, the following structure is shown as Q.

[0203] [Chemistry 35]

[0204]

[0205] [Chemistry 36]

[0206]

[0207] [Chemistry 37]

[0208]

[0209] (In the formula, b and c are as described above. d is an integer greater than or equal to 0, preferably an integer from 0 to 10, and more preferably an integer from 0 to 6. Each silicon atom having b repeated units shown in parentheses and Rf)1 In this combination, each silicon atom of the unit shown in parentheses (with c repeating units) bonds to Z. The arrangement of the units shown in parentheses can be random.

[0210] In addition, Q can also be represented by the following formula.

[0211] [Chemistry 38]

[0212]

[0213] In the above formula, b and c are as described above. Each silicon atom of the unit shown in parentheses with b repetitions is related to Rf. 1 The silicon atom of each unit shown in parentheses with c repeating units is bonded to Z. W is a silicon atom, or a group with a (b+c) valence having a siloxane structure, a silanediol structure, a silaneryl structure, or a combination thereof.

[0214] For example, the following structures can be listed as examples of the aforementioned W.

[0215] [Chemistry 39]

[0216]

[0217] (In the formula, D is a monovalent hydrocarbon group with 1 to 6 carbon atoms, such as methyl, ethyl, propyl, etc.)

[0218] For example, the following structures can be listed as Q above.

[0219] [Chemistry 40]

[0220]

[0221] [Chemistry 41]

[0222]

[0223] [Chemistry 42]

[0224]

[0225] [Chemistry 43]

[0226]

[0227] [Chemistry 44]

[0228]

[0229] [Chemistry 45]

[0230]

[0231] Of the above Q, the following structure is particularly preferred.

[0232] [Chemistry 46]

[0233]

[0234] (In the formula, b1 is in Rf) 1 When the group is monovalent, the value is an integer from 1 to 4, more preferably 1, in Rf 1 When the group is divalent, c1 is 1, c1 is an integer from 2 to 4, and it is an integer satisfying b1 + c1 = 3 to 6. b1' in Rf 1 When the group is monovalent, it is 1 or 2, more preferably 1, in Rf 1 When the group is divalent, c1' is 1, c1' is 2 or 3, d1 is 0 or 1, and b1'+c1'+d1=4. D is a monovalent hydrocarbon group with 1 to 6 carbon atoms. The silicon atoms of each unit shown in parentheses with b1 and b1' repetitions are related to Rf. 1 In combination, each silicon atom of the unit shown in parentheses, having c1 and c1' repeating units, is bonded to Z. The arrangement of the units shown in parentheses can be random.

[0235] In the above general formula (7), Rf 1 Independently, it is a monovalent or divalent group with a number average molecular weight of 400–40000, possessing a fluorinated polyether structure. Rf 1 The number-average molecular weight is preferably in the range of 500 to 20,000. Rf 1 The number-average molecular weight can be used as, for example, by... 19 Rf calculated by F-NMR 1 The number-average molecular weight and Rf of repeating perfluorooxyalkylene units in the structure 1 The molecular weights of the linking groups in (B) are calculated from the sum of their molecular weights. Additionally, the number-average molecular weight of the entire compound of component (B) can be calculated from the molecular weights of the linked groups in (B). 1 H-NMR and 19 The terminal structure and main chain structure of F-NMR (Rf 1 The ratio is calculated from the given ratio.

[0236] Specifically, Rf 1 Preferably, it contains 1 to 500, more preferably 2 to 400, and even more preferably 4 to 200, derived from the following formula.

[0237] -C x F 2x O-

[0238] (x is an integer from 1 to 6.)

[0239] The repeated unit is represented. The repeated unit may have branches.

[0240] As the aforementioned repeating unit -C x F2x O-, for example, can be represented by the following formula.

[0241] -CF2O-

[0242] -CF2CF2O-

[0243] -CF2CF2CF2O-

[0244] -CF(CF3)CF2O-

[0245] -CF2CF(CF3)O-

[0246] -CF2CF2CF2CF2O-

[0247] -CF2CF2CF2CF2CF2O-

[0248] -CF2CF2CF2CF2CF2CF2O-

[0249] Rf 1 It may have one type of these repeating units, or it may have a combination of two or more types.

[0250] Rf with a valence of 1 1 The particularly preferred structure can be represented by the following general formula (9).

[0251] Rf”-V- (9)

[0252] (In the formula, Rf” is a monovalent perfluoropolyether group with a number average molecular weight of 300 to 30,000, and V is a divalent organic group with 2 to 20 carbon atoms, which may contain at least one of oxygen, nitrogen, fluorine and silicon atoms, and may have a cyclic structure and may have unsaturated bonds.)

[0253] Rf with a valence of 2 1 The particularly preferred structure can be represented by the following general formula (10).

[0254] -[V-Rf'-VT] z -V-Rf'-V- (10)

[0255] [In the formula, Rf' is a divalent perfluoropolyether group with a number average molecular weight of 300 to 30000, V is independently the same as above, and T is derived from the following formula (11)]

[0256] [Chemistry 47]

[0257]

[0258] (In the formula, Z, E, and c are as described above. U is a group with at least (c+2) Si atoms and a (c+2) valence, having a siloxane structure, a silanediol structure, a silanearyl structure, or a combination thereof, and may have a cyclic structure.)

[0259] [This represents a divalent group, where z is an integer from 0 to 5.]

[0260] In formula (9) above, Rf” is a monovalent perfluoropolyether group with a number average molecular weight of 300 to 30,000, particularly 500 to 20,000. This perfluoropolyether group may contain branches along its length, and examples include those with the aforementioned repeating unit -C. x F 2x A monovalent group of O-.

[0261] As for "Rf", examples of monovalent perfluoropolyether groups can be listed, represented by the following formula.

[0262] [Chemistry 48]

[0263]

[0264] (In the formula, Y is independently F or CF3 basis, r is an integer from 2 to 6, k and t are each integers from 0 to 200, preferably integers from 0 to 100, however, k+t is from 2 to 200, preferably from 3 to 150, and s is an integer from 0 to 6. The repeating units shown in parentheses can be combined randomly.)

[0265] [Chemistry 49]

[0266]

[0267] (In the formula, Y is independently F or CF3 basis, p and q are each integers from 0 to 200, preferably integers from 2 to 100, however, p+q is from 2 to 300, preferably from 4 to 200. The repeating units shown in parentheses can be randomly combined.)

[0268] [Transformation 50]

[0269]

[0270] (In the formula, j is an integer from 1 to 3, and u is an integer from 1 to 200, preferably an integer from 1 to 60.)

[0271] In formula (10) above, Rf' is a divalent perfluoropolyether group with a number-average molecular weight of 300 to 30,000, particularly 500 to 20,000. This perfluoropolyether group may contain branches along its length; examples include those having the aforementioned repeating unit -C. x F 2x O- divalent groups.

[0272] Rf' is specifically a divalent perfluoropolyether group represented by the following formula.

[0273] [Chemistry 51]

[0274]

[0275] (In the formula, Y is independently F or CF3 basis, r is an integer from 2 to 6, k and t are each integers from 0 to 200, preferably integers from 0 to 100, however, k+t is from 2 to 200, preferably 3 to 150, and s is an integer from 0 to 6.)

[0276] [Chemistry 52]

[0277]

[0278] (In the formula, j is an integer from 1 to 3, and u is an integer from 1 to 200, preferably an integer from 1 to 60.)

[0279] [Chemistry 53]

[0280]

[0281] (In the formula, Y is an F or CF3 base, j is an integer from 1 to 3, p and q are each integers from 0 to 200, preferably integers from 2 to 100, however, p+q is from 2 to 300, preferably from 4 to 200. The repeating units shown in parentheses can be combined randomly.)

[0282] In the above formulas (9) and (10), V is independently a divalent organic group (especially a hydrocarbon group) that may contain at least one selected from oxygen, nitrogen, fluorine and silicon atoms, has 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, may have a cyclic structure, and may have unsaturated bonds.

[0283] Examples of this V can be illustrated below. It should be noted that in the following formulas, Ph represents a phenyl group. A binding end marked with an asterisk (*) indicates binding with Rf” or Rf’.

[0284] [Chemistry 54]

[0285]

[0286] [Chemistry 55]

[0287]

[0288] The preferred structure is shown below. It should be noted that in the following formula, Ph represents a phenyl group. A binding end marked with an asterisk (*) indicates binding with Rf” or Rf’.

[0289] [Chemistry 56]

[0290]

[0291] In the above formula (10), T is a divalent group represented by the following formula (11).

[0292] [Chemistry 57]

[0293]

[0294] (In the formula, Z, E, and c are as described above. U is a group with a (c+2) valence having at least (c+2) Si atoms, having a siloxane structure, a silanediol structure, a silanearyl structure, or a combination thereof, and may have a cyclic structure. Furthermore, the two bonding ends shown in the above formula (11) are bonded to different V values ​​in formula (10), respectively.)

[0295] In the above formula (11), U is a group with a (c+2) valence having at least (c+2) Si atoms, having a siloxane structure, a silanediol structure, a silanearyl structure, or a combination thereof, and may have a cyclic structure.

[0296] As for this U, the following structures can be listed.

[0297] [Chem.58]

[0298]

[0299] [Chemistry 59]

[0300]

[0301] [Transformation 60]

[0302]

[0303] [Chemistry 61]

[0304]

[0305] (In the formula, c, d, and W are as described above. Each silicon atom of the unit shown in parentheses with c repetitions is bonded to Z in the above formula (11), and each silicon atom of the unit shown in parentheses with 2 repetitions is bonded to different V in the above formula (10). The arrangement of the units shown in parentheses can be random.)

[0306] Of the above-mentioned U, the following structure is particularly preferred.

[0307] [Chemistry 62]

[0308]

[0309] (In the formula, c is as described above. Each silicon atom of the unit shown in parentheses with c repetitions is bonded to Z in the above formula (11), and each silicon atom of the unit shown in parentheses with 2 repetitions is bonded to different V in the above formula (10).)

[0310] In the above formula (10), z is an integer from 0 to 5, preferably 0.

[0311] Rf as a 1-valent 1 For example, the following groups can be listed.

[0312] [Chemistry 63]

[0313]

[0314] (In the formula, t' is an integer from 2 to 200, preferably an integer from 2 to 100.)

[0315] [Chemistry 64]

[0316]

[0317] (In the formula, j is an integer from 1 to 3, and u is an integer from 1 to 200, preferably an integer from 1 to 60.)

[0318] [Chemistry 65]

[0319]

[0320] (In the formula, t' is an integer from 2 to 200, preferably an integer from 2 to 100.)

[0321] [Chemistry 66]

[0322]

[0323] (In the formula, t' is an integer from 2 to 200, preferably an integer from 2 to 100.)

[0324] Rf as a divalent 1 For example, the following groups can be listed.

[0325] [Chemistry 67]

[0326]

[0327] (In the formula, r is an integer from 2 to 6, k and t are each integers from 0 to 200, preferably integers from 0 to 100, however, k+t is from 2 to 200, preferably from 3 to 150. s is an integer from 0 to 6.)

[0328] [Chemistry 68]

[0329]

[0330] (In the formula, j is an integer from 1 to 3, p and q are each integers from 0 to 200, preferably integers from 2 to 100, however, p+q is from 2 to 300, preferably from 4 to 200. The repeating units shown in parentheses can be combined randomly.)

[0331] [Chemistry 69]

[0332]

[0333] (In the formula, r is an integer from 2 to 6, k and t are each integers from 0 to 200, preferably integers from 0 to 100, however, k+t is from 2 to 200, preferably from 3 to 150. s is an integer from 0 to 6.)

[0334] [Chemistry 70]

[0335]

[0336] (In the formula, r is an integer from 2 to 6, k and t are each integers from 0 to 200, preferably integers from 0 to 100, however, k+t is from 2 to 200, preferably from 3 to 150. s is an integer from 0 to 6.)

[0337] [Chemistry 71]

[0338]

[0339] (In the formula, r is an integer from 2 to 6, k and t are each integers from 0 to 200, preferably integers from 0 to 100, however, k+t is from 2 to 200, preferably from 3 to 150. s is an integer from 0 to 6.)

[0340] [(B) Manufacturing method of component]

[0341] The fluorinated epoxy compound represented by the above general formula (7) can be manufactured by, for example, the method described in Japanese Patent Application Publication No. 2014-80534. Specifically, firstly, a fluorinated compound A having an olefinic site (alkenyl group) at the end is subjected to an addition reaction with an organosilicon compound B having two or more, preferably three or more, SiH groups in the molecule in the presence of an addition reaction catalyst and under conditions where SiH groups are in excess, thereby synthesizing a fluorinated compound C having multiple SiH groups.

[0342] Fluorine compound A can be represented by the following general formula (12).

[0343] Rf 0 -(CH=CH2) b’ (12)

[0344] [In the formula, Rf] 0It is a monovalent group represented by the following general formula (13) or a divalent group represented by the following general formula (14). b' in Rf 0 When the group is monovalent, it is 1, and in Rf 0 When the group is divalent, the value is 2.

[0345] Rf”-V 1 - (13)

[0346] -V 1 -Rf'-V 1 - (14)

[0347] (In the formula, Rf' and Rf” are as described above. V) 1 The organic groups are independently single bonds, or may contain at least one selected from oxygen, nitrogen, fluorine, or silicon atoms, and have a carbon number of 1 to 18, preferably 1 to 8, divalent organic groups. They may have a cyclic structure and may have unsaturated bonds.

[0348] In equations (13) and (14) above, V 1 The organic groups are single bonds that are independent of each other, or may contain at least one of oxygen, nitrogen, fluorine or silicon atoms, and have a carbon number of 1 to 18, preferably 1 to 8, divalent organic groups. They may have a cyclic structure and may have unsaturated bonds.

[0349] As this V 1 The following groups can be exemplified. It should be noted that in the following formulas, Ph represents a phenyl group. A binding end marked with an asterisk (*) indicates binding with Rf' or Rf”.

[0350] [Chemistry 72]

[0351]

[0352] [Chemistry 73]

[0353]

[0354] Examples of fluorine-containing compounds A that are monovalent include the following compounds.

[0355] [Chemistry 74]

[0356]

[0357] (In the formula, t' is an integer from 2 to 200, preferably an integer from 2 to 100.)

[0358] [Chemistry 75]

[0359]

[0360] (In the formula, j is an integer from 1 to 3, and u is an integer from 1 to 200, preferably an integer from 1 to 60.)

[0361] [Chemistry 76]

[0362]

[0363] (In the formula, t' is an integer from 2 to 200, preferably an integer from 2 to 100.)

[0364] [Chemistry 77]

[0365]

[0366] (In the formula, t' is an integer from 2 to 200, preferably an integer from 2 to 100.)

[0367] [Chemistry 78]

[0368]

[0369] (In the formula, t' is an integer from 2 to 200, preferably an integer from 2 to 100.)

[0370] Examples of divalent fluorine-containing compounds A include the following compounds.

[0371] [Chemistry 79]

[0372]

[0373] (In the formula, r is an integer from 2 to 6, k and t are each integers from 0 to 200, preferably integers from 0 to 100, however, k+t is from 2 to 200, preferably from 3 to 150. s is an integer from 0 to 6.)

[0374] [Chemistry 80]

[0375]

[0376] (In the formula, j is an integer from 1 to 3, p and q are each integers from 0 to 200, preferably integers from 2 to 100, however, p+q is from 2 to 300, preferably from 4 to 200. The repeating units shown in parentheses can be combined randomly.)

[0377] [Chemistry 81]

[0378]

[0379] (In the formula, r is an integer from 2 to 6, k and t are each integers from 0 to 200, preferably integers from 0 to 100, however, k+t is from 2 to 200, preferably from 3 to 150. s is an integer from 0 to 6.)

[0380] [Chemistry 82]

[0381]

[0382] (In the formula, r is an integer from 2 to 6, k and t are each integers from 0 to 200, preferably integers from 0 to 100, however, k+t is from 2 to 200, preferably from 3 to 150. s is an integer from 0 to 6.)

[0383] [Chemistry 83]

[0384]

[0385] (In the formula, r is an integer from 2 to 6, k and t are each integers from 0 to 200, preferably integers from 0 to 100, however, k+t is from 2 to 200, preferably from 3 to 150. s is an integer from 0 to 6.)

[0386] Organosilicon compound B can be represented by the following general formula (15).

[0387] Q-(H) b+c (15)

[0388] (In the formula, Q, b, and c are as described above. H, shown in parentheses, represents a hydrogen atom directly bonded to the Si atom in the Q structure.)

[0389] Examples of organosilicon compound B include the following compounds.

[0390] [Chemistry 84]

[0391]

[0392] [Chemistry 85]

[0393]

[0394] [Chemistry 86]

[0395]

[0396] [Chemistry 87]

[0397]

[0398] (In the formula, b, c, d, and W are as described above.)

[0399] The following compounds are particularly preferred.

[0400] [Chemistry 88]

[0401]

[0402] [Chemistry 89]

[0403]

[0404] [Chemistry 90]

[0405]

[0406] [Chemistry 91]

[0407]

[0408] [Chemistry 92]

[0409]

[0410] [Chemistry 93]

[0411]

[0412] When a fluorinated compound A is monovalent and a fluorinated compound A and an organosilicon compound B are reacted in an amount such that the number of olefinic sites (alkenyl groups) in the fluorinated compound A is b relative to the number of SiH groups (b+c) in the organosilicon compound B, the structure of the resulting fluorinated compound C can be represented by the following general formula (16).

[0413] (Rf) 0 -C2H4) b -Q-(H) c (16)

[0414] (where Rf) 0 Q, b, and c are as described above.

[0415] When fluorine compound A is divalent, and fluorine compound A and organosilicon compound B are reacted in a mol ratio of fluorine compound A: organosilicon compound B = (z+1): (z+2) (z as described above), the structure of the resulting fluorine compound C can be represented by the following general formula (17). Furthermore, when z = 0, it becomes a structure in which organosilicon compound B is introduced into both ends of fluorine compound A.

[0416] (H) c -Q-[C2H4-Rf 0 -C2H4-T 1 ] z -C2H4-Rf 0 -C2H4-Q-(H) c (17)

[0417] [In the formula, Q and Rf] 0 c and z are as described above. The H shown in parentheses represents a hydrogen atom directly bonded to the Si atom in the Q structure. Additionally, T...1 For the following general formula (18)

[0418] [Chemistry 94]

[0419]

[0420] (In the formula, Q, b, and c are as described above. H in parentheses represents hydrogen atoms directly bonded to Si atoms in the structure.)

[0421] This indicates a divalent group.

[0422] The preferred mixing ratio of fluorinated compound A and organosilicon compound B is 1 to 10 mol, particularly 2 to 6 mol, of organosilicon compound B relative to 1 mol of the terminal olefinic group (alkenyl group) in fluorinated compound A. To prevent three-dimensional crosslinking, it is preferable to use an excess of organosilicon compound B relative to the terminal olefinic group (alkenyl group) of fluorinated compound A, and after the addition reaction, remove unreacted organosilicon compound B by vacuum distillation or the like.

[0423] When the fluorinated compound A is a monovalent compound, the reaction amount between the fluorinated compound A and the organosilicon compound B is such that the number of olefinic sites (alkenyl groups) in the fluorinated compound A is less than (b+c), preferably b, relative to the organosilicon compound B1 molecule having (b+c) SiH groups. Furthermore, when the fluorinated compound A is a divalent compound, a mol ratio of fluorinated compound A: organosilicon compound B = (z+1):(z+2) is preferred (z as described above). Moreover, when the fluorinated compound A is a divalent compound, the addition reaction can be carried out in stages after the intermediate with the smallest z value is synthesized, as needed. For example, in the fluorinated compound C represented by formula (17) above, after synthesizing a compound with z=0, 1 mol of fluorinated compound A can be reacted again in the fluorinated compound C represented by formula (17) above by reacting 2 mol of the compound with z=0, thereby obtaining a fluorinated compound C with z=2. Alternatively, from mixtures with different z values, components with the target z value can be separated using any separation method. For example, from a mixture with z = 0 to 3, preparative chromatography or similar methods can be used to extract only the component with z = 1.

[0424] The above 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. For this solvent, commonly used organic solvents such as toluene, xylene, and isooctane can be used. However, it is preferable to use solvents with a boiling point above the target reaction temperature that do not hinder the reaction and where the fluorinated compound C formed after the reaction is soluble at the reaction temperature. For example, partially fluorinated solvents such as hexafluorom-xylene, trifluorotoluene, and fluorinated ether solvents such as methyl perfluorobutyl ether are preferred, with hexafluorom-xylene being particularly preferred.

[0425] There is no particular limitation on the amount of solvent used, but it is preferably set to 40 to 200 parts by mass relative to 100 parts by mass of fluorinated compound A, and more preferably to 50 to 150 parts by mass.

[0426] Regarding the catalyst for the addition reaction, any conventionally known addition reaction catalyst can be used. For example, compounds containing platinum, rhodium, or palladium can be used. Among these, compounds containing platinum are preferred, and platinum hexachloroplatinic acid hexahydrate, platinum carbonyl vinylmethyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, platinum-octanal / octanol complex, or platinum supported on activated carbon can be used.

[0427] The amount of catalyst used in the addition reaction only needs to be an effective amount. In particular, the amount of metal contained in the fluorinated compound A can be 0.1 to 5000 ppm by mass, more preferably 1 to 1000 ppm by mass.

[0428] In the above addition reaction, there are no particular restrictions on the order of feeding the components. For example, methods include: slowly heating a mixture of fluorinated compound A, organosilicon compound B, and addition catalyst from room temperature to the addition reaction temperature; heating a mixture of fluorinated compound A, organosilicon compound B, and solvent to the target reaction temperature and then adding the addition catalyst; adding fluorinated compound A dropwise to a mixture of organosilicon compound B and addition catalyst heated to the target reaction temperature; and adding a mixture of fluorinated compound A and addition catalyst dropwise to organosilicon compound B heated to the target reaction temperature. Particularly preferred methods are those involving heating a mixture of fluorinated compound A, organosilicon compound B, and solvent to the target reaction temperature and then adding the addition catalyst, or adding a mixture of fluorinated compound A and addition catalyst dropwise to organosilicon compound B heated to the target reaction temperature.

[0429] The above addition reaction conditions can be carried out according to conventionally known methods. In particular, it is preferred to carry out the reaction in a dry atmosphere, in air or an inert gas (N2, Ar, etc.), at a reaction temperature of 50–150°C, preferably 70–120°C, for 0.5–96 hours, preferably 1–48 hours.

[0430] Secondly, by carrying out the addition reaction of the SiH group of the fluorinated compound C obtained above with the terminal olefinic group (alkenyl) of compound D which has a terminal olefinic group (alkenyl) and an epoxy group in one molecule, the fluorinated epoxy compound represented by the above formula (7) can be obtained.

[0431] Compound D, which has a terminal olefinic site (alkenyl) and an epoxy group in one molecule, can in particular be represented by the following general formula (19).

[0432] [Chem. 95]

[0433]

[0434] (In the formula, E is the same as above. Z) 1 It is a single bond or a divalent hydrocarbon group with 1 to 18 carbon atoms, and may contain ether or ester bonds, and may have a cyclic structure.

[0435] In the above equation (19), Z 1 It is a single bond or a divalent hydrocarbon group having 1 to 18 carbon atoms, and may contain ether or ester bonds, and may have a cyclic structure. Z is a group other than a single bond. 1 For example, the following structures can be listed. It should be noted that the bonding end marked with an asterisk (*) indicates bonding with an electron (E), and the unmarked bonding end indicates bonding with a carbon atom.

[0436] -CH2-*、

[0437] -CH2CH2-*、

[0438] -CH2CH2CH2-*、

[0439] -CH2CH2CH2CH2-*、

[0440] -CH2CH2CH2CH2CH2-*、

[0441] -CH2CH2CH2CH2CH2CH2-*、

[0442] -CH2OCH2-*、

[0443] -CH2OCH2CH2OCH2-*, or

[0444] -CH2OCH2CH2OCH2CH2OCH2CH2-*

[0445] As a compound D represented by the above formula (19), for example, structures represented by the following formulas (a') to (d') can be listed.

[0446] [Chemistry 96]

[0447]

[0448] In the above formula, g' is an integer from 0 to 18, preferably an integer from 0 to 13. h' is an integer from 0 to 8, i is an integer from 1 to 5, l is an integer from 0 to 9, h'+2l+i is from 0 to 18, preferably h' is an integer from 0 to 4, i is 1 or 2, l is an integer from 0 to 4, and h'+2l+i is from 0 to 13. R 4 As described above, hydrogen atoms or methyl groups are preferred.

[0449] Compound D, which has a terminal olefinic site (alkenyl group) and an epoxy group in one molecule, can be exemplified by the following compounds. This compound can be used alone or in combination of two or more.

[0450] [Chemistry 97]

[0451]

[0452] The addition reaction between fluorinated compound C and compound D can be carried out according to conventionally known methods, such as those described above. Preferably, the reaction can be carried out in the presence of the above-described addition reaction catalyst, under a dry atmosphere, in air or an inert gas (N2, Ar, etc.), at a reaction temperature of 50–150°C, preferably 50–100°C, for 0.5–96 hours, preferably 1–48 hours. The above-described solvent can be used as needed.

[0453] Regarding the amount of compound D relative to fluorinated compound C, an amount in which the number of SiH groups in fluorinated compound C and the number of terminal olefinic sites (alkenyl groups) in compound D are equal or excessive can be used. It is preferable to remove unreacted compound D by vacuum distillation or the like after the addition reaction. Specifically, it is preferable to carry out the reaction with an amount of 1 to 5 mol of terminal olefinic sites (alkenyl groups) in compound D relative to 1 mol of SiH groups in fluorinated compound C, preferably 1 to 2 mol.

[0454] As compounds represented by the above general formula (7), compounds listed below are particularly preferred.

[0455] [Chem. 98]

[0456]

[0457] (In the formula, t' is an integer from 2 to 200, preferably an integer from 2 to 100.)

[0458] [Chemistry 99]

[0459]

[0460] (In the formula, t' is an integer from 2 to 200, preferably an integer from 2 to 100.)

[0461] [Chemistry 100]

[0462]

[0463] (In the formula, t' is an integer from 2 to 200, preferably an integer from 2 to 100.)

[0464] [Chemistry 101]

[0465]

[0466] (In the formula, t' is an integer from 2 to 200, preferably an integer from 2 to 100.)

[0467] [Chemistry 102]

[0468]

[0469] (In the formula, t' is an integer from 2 to 200, preferably an integer from 2 to 100.)

[0470] [Chemistry 103]

[0471]

[0472] (In the formula, t' is an integer from 2 to 200, preferably an integer from 2 to 100.)

[0473] [Chemistry 104]

[0474]

[0475] (In the formula, t' is an integer from 2 to 200, preferably an integer from 2 to 100.)

[0476] [Chemistry 105]

[0477]

[0478] (In the formula, t' is an integer from 2 to 200, preferably an integer from 2 to 100.)

[0479] [Chemistry 106]

[0480]

[0481] (In the formula, t' is an integer from 2 to 200, preferably an integer from 2 to 100.)

[0482] [Chemistry 107]

[0483]

[0484] (In the formula, t' is an integer from 2 to 200, preferably an integer from 2 to 100.)

[0485] [Chemistry 108]

[0486]

[0487] (In the formula, t' is an integer from 2 to 200, preferably an integer from 2 to 100.)

[0488] [Chemistry 109]

[0489]

[0490] (In the formula, t' is an integer from 2 to 200, preferably an integer from 2 to 100.)

[0491] [Chemical 110]

[0492]

[0493] (In the formula, t' is an integer from 2 to 200, preferably an integer from 2 to 100.)

[0494] [Chemistry 111]

[0495]

[0496] (In the formula, t' is an integer from 2 to 200, preferably an integer from 2 to 100.)

[0497] [Chemistry 112]

[0498]

[0499] (In the formula, j is an integer from 1 to 3, p and q are each integers from 0 to 200, preferably integers from 2 to 100, however, p+q is from 2 to 300, preferably from 4 to 200. The repeating units shown in parentheses can be combined randomly.)

[0500] [Chemistry 113]

[0501]

[0502] (In the formula, j is an integer from 1 to 3, p and q are each integers from 0 to 200, preferably integers from 2 to 100, however, p+q is from 2 to 300, preferably from 4 to 200. The repeating units shown in parentheses can be combined randomly.)

[0503] [Chemistry 114]

[0504]

[0505] (In the formula, j is an integer from 1 to 3, p and q are each integers from 0 to 200, preferably integers from 2 to 100, however, p+q is from 2 to 300, preferably from 4 to 200. The repeating units shown in parentheses can be combined randomly.)

[0506] [Chemistry 115]

[0507]

[0508] (In the formula, r is an integer from 2 to 6, k and t are each integers from 0 to 200, preferably integers from 0 to 100, however, k+t is from 2 to 200, preferably from 3 to 150. s is an integer from 0 to 6.)

[0509] [Chemistry 116]

[0510]

[0511] (In the formula, r is an integer from 2 to 6, k and t are each integers from 0 to 200, preferably integers from 0 to 100, however, k+t is from 2 to 200, preferably from 3 to 150. s is an integer from 0 to 6.)

[0512] [Chemistry 117]

[0513]

[0514] (In the formula, r is an integer from 2 to 6, k and t are each integers from 0 to 200, preferably integers from 0 to 100, however, k+t is from 2 to 200, preferably from 3 to 150. s is an integer from 0 to 6.)

[0515] [Chemistry 118]

[0516]

[0517] (In the formula, r is an integer from 2 to 6, k and t are each integers from 0 to 200, preferably integers from 0 to 100, however, k+t is from 2 to 200, preferably from 3 to 150. s is an integer from 0 to 6.)

[0518] [Chemistry 119]

[0519]

[0520] (In the formula, r is an integer from 2 to 6, k and t are each integers from 0 to 200, preferably integers from 0 to 100, however, k+t is from 2 to 200, preferably from 3 to 150. s is an integer from 0 to 6.)

[0521] [Chemistry 120]

[0522]

[0523] (In the formula, r is an integer from 2 to 6, k and t are each integers from 0 to 200, preferably integers from 0 to 100, however, k+t is from 2 to 200, preferably from 3 to 150. s is an integer from 0 to 6.)

[0524] [Chemistry 121]

[0525]

[0526] (In the formula, r is an integer from 2 to 6, k and t are each integers from 0 to 200, preferably integers from 0 to 100, however, k+t is from 2 to 200, preferably from 3 to 150. s is an integer from 0 to 6.)

[0527] [Chemistry 122]

[0528]

[0529] (In the formula, r is an integer from 2 to 6, k and t are each integers from 0 to 200, preferably integers from 0 to 100, however, k+t is from 2 to 200, preferably from 3 to 150. s is an integer from 0 to 6.)

[0530] [Chemistry 123]

[0531]

[0532] (In the formula, r is an integer from 2 to 6, k and t are each integers from 0 to 200, preferably integers from 0 to 100, however, k+t is from 2 to 200, preferably from 3 to 150. s is an integer from 0 to 6.)

[0533] [Chemistry 124]

[0534]

[0535] (In the formula, r is an integer from 2 to 6, k and t are each integers from 0 to 200, preferably integers from 0 to 100, however, k+t is from 2 to 200, preferably from 3 to 150. s is an integer from 0 to 6.)

[0536] [Chemistry 125]

[0537]

[0538] (In the formula, r is an integer from 2 to 6, k and t are each integers from 0 to 200, preferably integers from 0 to 100, however, k+t is from 2 to 200, preferably from 3 to 150. s is an integer from 0 to 6.)

[0539] [Chemistry 126]

[0540]

[0541] (In the formula, r is an integer from 2 to 6, k and t are each integers from 0 to 200, preferably integers from 0 to 100, however, k+t is from 2 to 200, preferably from 3 to 150. s is an integer from 0 to 6.)

[0542] [Chemistry 127]

[0543]

[0544] (In the formula, r is an integer from 2 to 6, k and t are each integers from 0 to 200, preferably integers from 0 to 100, however, k+t is from 2 to 200, preferably from 3 to 150. s is an integer from 0 to 6.)

[0545] [Chemistry 128]

[0546]

[0547] (In the formula, r is an integer from 2 to 6, k and t are each integers from 0 to 200, preferably integers from 0 to 100, however, k+t is from 2 to 200, preferably from 3 to 150. s is an integer from 0 to 6.)

[0548] (B) The amount of epoxy groups in the fluorinated epoxy compound is preferably 0.01–0.4 mol / 100g, more preferably 0.02–0.3 mol / 100g. The amount of epoxy groups in this invention can be achieved using… 1 H-NMR determination.

[0549] The amount of component (B) in the above-mentioned formulation is 0.5 to 5 moles, preferably 0.7 to 2.5 moles, relative to 1 mole of the secondary amino group in component (A). If there are too few epoxy groups, the degree of cross-linking will be insufficient, resulting in no cured product. On the other hand, if there are too many epoxy groups, epoxy groups will easily remain in the cured product, and the physical properties of the cured product will easily change over time, which is not preferred.

[0550] (B) Components may use one of these fluorinated epoxy compounds alone, or in combination of two or more.

[0551] [(C) Ingredients (Other Ingredients)]

[0552] In the fluorinated polyether-based curable composition of the present invention, in order to improve its practicality, in addition to components (A) and (B) mentioned above, various compounding agents such as curing accelerators, plasticizers, viscosity modifiers, flexibility enhancers, inorganic fillers, and silane coupling agents can be added as needed. The amount of these additives can be arbitrary, provided that they do not impair the purpose of the present invention and do not damage the characteristics of the composition and the physical properties of the cured product.

[0553] The curing accelerator is a compound that promotes the reaction between the secondary amine in component (A) and the epoxy group in component (B) of the fluoropolyether-based curable composition of the present invention by mixing it, and is added to obtain a cured product with good physical properties in a shorter time. This allows for adjustment of the balance between usable time and heat curing time. There are no particular limitations as long as it is primarily a carboxylic anhydride or a compound with Lewis acidity.

[0554] Examples of carboxylic anhydrides that are solid at 23°C include, for instance, those that are solid at 23°C. Specifically, the following compounds can be cited as examples.

[0555] [Chemistry 129]

[0556]

[0557] Furthermore, the carboxylic anhydride can be a cyclic organopolysiloxane (i.e., a fluorinated organopolysiloxane modified carboxylic anhydride compound) having a hydrogen atom directly bonded to a silicon atom in one molecule, a perfluoroalkyl or perfluorooxyalkyl group bonded to a silicon atom by a divalent hydrocarbon group that may contain at least one selected from oxygen, nitrogen, and silicon atoms, and a cyclic carboxylic anhydride residue bonded to a silicon atom by a divalent hydrocarbon group. Examples of such compounds can be exemplified by compounds represented by the following general formula (20).

[0558] [Chemistry 130]

[0559]

[0560] (In the formula, L is independently a monovalent perfluoropolyether group bonded to a silicon atom by a divalent linker, J is independently a cyclic carboxylic anhydride residue bonded to a silicon atom by a divalent hydrocarbon group, and R...) 8 Independently, each unit is an unsubstituted or halogenated monovalent hydrocarbon group, where t2 is an integer from 1 to 6, u2 is an integer from 1 to 4, v2 is an integer from 1 to 4, and t2+u2+v2 is an integer from 4 to 10. The repeating units shown in parentheses above can combine randomly.

[0561] In the above general formula (20), L is independently a monovalent perfluoropolyether group bonded to silicon atoms by a divalent linker, preferably a group represented by the following general formula. L is a group introduced from the viewpoint of compatibility with components (A) and (B), dispersibility and uniformity after curing.

[0562] -B-Rf 2

[0563] [In the formula, Rf] 2 The group is a monovalent perfluoropolyether group, identical to Rf” in formula (9) above, and can represent the same group as the group exemplified in Rf”. B is a divalent organic group (especially a hydrocarbon group) containing 1 to 20 carbon atoms, which may include at least one selected from oxygen, nitrogen, and silicon atoms.

[0564] As B, examples 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(C H3)2-(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, preferably -(CH2)3OCH2-*, -(CH2)3-NH-CO-*, and groups represented by the following general formulas. Furthermore, Ph represents phenyl, and Ph' represents phenylene. Additionally, the *-terminus indicates a group related to Rf. 2 The term "bonding" without an asterisk (*) indicates a bond with silicon atoms in an organohydrogen polysiloxane.

[0565] [Chemistry 131]

[0566]

[0567] In addition, in the above general formula (20), J is independently a cyclic carboxylic anhydride residue formed by the combination of a divalent hydrocarbon group and a silicon atom. Specifically, groups represented by the following general formula can be listed.

[0568] [Chemistry 132]

[0569]

[0570] In the above formula, R 9 It is a divalent hydrocarbon group with 2 to 15 carbon atoms. Specifically, examples include ethylene, propylene, and butylene, with propylene being the preferred group.

[0571] Furthermore, in the above general formula (20), R 8 The group is an unsubstituted or halogen-substituted monovalent hydrocarbon group, preferably a monovalent hydrocarbon group with 1 to 10 carbon atoms that does not contain aliphatic unsaturated bonds, more preferably a monovalent hydrocarbon group with 1 to 8 carbon atoms. Specifically, 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 formed by substituting some or all of the hydrogen atoms of these groups with halogen atoms such as fluorine, etc., preferably methyl and ethyl.

[0572] Furthermore, in the above general formula (20), t2 is an integer from 1 to 6, preferably an integer from 2 to 5; u2 is an integer from 1 to 4, preferably an integer from 1 to 3; v2 is an integer from 1 to 4, preferably an integer from 1 to 3; and t2+u2+v2 is an integer from 4 to 10, preferably an integer from 4 to 8. However, ((H)(R) 8 (SiO) unit, ((L)(R) 8 SiO) unit, and (J)(R) 8 The arrangement order of SiO units is random.

[0573] Examples of cyclic organopolysiloxanes represented by the above general formula (20) include the following compounds.

[0574] [Chemistry 133]

[0575]

[0576] (In the formula, t2' is 2 or 3, and t” is an integer from 2 to 20.)

[0577] [Chemistry 134]

[0578]

[0579] (In the formula, v2' is 2 or 3, and t” is an integer from 2 to 20.)

[0580] These carboxylic anhydrides used as curing accelerators can be used alone or in combination of two or more. In this case, the carboxylic anhydride that is solid at 23°C can be used in combination with the cyclic organopolysiloxane (fluorinated organopolysiloxane modified carboxylic anhydride compound).

[0581] As a curing accelerator, when carboxylic anhydride is incorporated, its amount is preferably 0.01 to 2 parts by mass, more preferably 0.05 to 1 part by mass, relative to 100 parts by mass of component (A). Furthermore, relative to 1 mole of secondary amino group in component (A), the cyclic carboxylic anhydride residues in the adhesion accelerator are preferably 0.005 to 0.5 moles, particularly preferably 0.05 to 0.1 moles.

[0582] As the Lewis acid-containing compound, compounds containing any one of tin, titanium, zinc, boron, ytterbium, yttrium, niobium, europium, or zirconium are preferred. Specifically, examples include ZnCl2, TiCl4, SnCl4, NbCl5, Yb(OTf)3, Y(OTf)3 (Tf being trifluoromethanesulfonyl (-S(O)2CF3)), B(C6F5)3, and the "Orgatix" series manufactured by Matsumoto Fine Chemical Co., Ltd., among which ZnCl2, TiCl4, SnCl4, and B(C6F5)3 are preferred. When mixing these Lewis acid-containing compounds as curing accelerators, the amount added can be adjusted within a range that balances usable time and heat curing time.

[0583] As plasticizers, viscosity modifiers, and flexibility enhancers, polyfluoroamino compounds represented by the following general formula (21) and / or polyfluoro compounds represented by the following general formulas (22) and (23) can be used.

[0584] [Chemistry 135]

[0585]

[0586] [In the formula, A and X are the same as above, Rf] 3 It is a monovalent perfluoropolyether group represented by the following general formula.

[0587] [Chemistry 136]

[0588]

[0589] (In the formula, f2 is an integer from 2 to 200, preferably an integer from 2 to 100, h2 is an integer from 1 to 3, and is below the molecular weight of Rf in formula (1) of the component (A) used.)

[0590] Y 1 -O-(CF2CF2CF2O) c2 -Y1 (twenty two)

[0591] [In the formula, Y] 1 Independently for the formula: C k2 F 2k2+1 - (k2 is an integer from 1 to 3) represents a group, c2 is an integer from 1 to 200, and is below the molecular weight of Rf in formula (1) of component (A) used.

[0592] Y 2 -O-(CF2O) d2 (CF2CF2O) e2 -Y 2 (twenty three)

[0593] (where Y) 2 With the above Y 1 Similarly, d2 and e2 are each integers from 1 to 200, d2 + e2 = 2 to 200, and are below the molecular weight of Rf in formula (1) of component (A). The repeating units shown in the parentheses above can be randomly combined.

[0594] In the above formula (21), A can represent the same group as A in the above average formula (1), and X can represent the same group as X in the above average formula (1).

[0595] In the above formula (21), Rf 3 It is a monovalent perfluoropolyether group represented by the following general formula.

[0596] [Chemistry 137]

[0597]

[0598] (In the formula, f2 is an integer from 2 to 200, preferably an integer from 2 to 100, h2 is an integer from 1 to 3, and is less than or equal to the molecular weight of Rf in formula (1) of the component (A) used.)

[0599] As Rf 3 Preferably, the groups shown below are preferred.

[0600] [Chemistry 138]

[0601]

[0602] (In the formula, f2 is the same as above, and is the molecular weight of Rf in formula (1) of component (A) used below.)

[0603] As a specific example of a polyfluorinated monoamine compound represented by the above general formula (21), the following examples can be cited. Furthermore, the following f2 satisfies the above necessary conditions.

[0604] [Chemistry 139]

[0605]

[0606] As specific examples of polyfluorinated compounds represented by the above general formulas (22) and (23), the following examples can be cited. Furthermore, the following c2, d2, e2 and the sum of d2 and e2 satisfy the above necessary conditions, and the repeating units shown in ( ) can be randomly combined.

[0607] CF3O-(CF2CF2CF2O) c2 -CF2CF3

[0608] CF3-O-(OCF2) d2 (OCF2CF2) e2 -CF3

[0609] The viscosity (23°C) of the polyfluoroamino compound represented by formula (21) and the polyfluoro compound represented by formulas (22) and (23) is preferably in the range of 2000 to 50000 mPa·s.

[0610] In addition, the mixing amounts of the polyfluoroamino compound represented by the above formula (21) and the polyfluoro compound represented by the above formulas (22) and (23) are each 1 to 300 parts by mass relative to 100 parts by mass of component (A), and more preferably 30 to 250 parts by mass.

[0611] As an inorganic filler, it can be used to add silica powders such as fumed silica (gas-phase silica or dry silica), settled silica (wet silica), spherical silica (fused silica), sol-gel silica, silica aerosol, etc., or various surface-treated silica powders such as silica powder, quartz powder, fused silica powder, diatomaceous earth, calcium carbonate and other reinforcing or quasi-reinforcing fillers, titanium dioxide, iron oxide, carbon black, cobalt aluminate and other inorganic pigments, titanium dioxide, iron oxide, carbon black, cerium oxide, cerium hydroxide, zinc carbonate, magnesium carbonate, manganese carbonate and other heat-resistant improving agents, alumina, boron nitride, silicon carbide, metal powder and other thermal conductivity imparting agents, carbon black, silver powder, conductive zinc oxide and other conductive imparting agents, etc.

[0612] [Method for manufacturing fluoropolyether-based curable compositions]

[0613] There are no particular limitations on the method for manufacturing the fluoropolyether-based curable composition of the present invention, and it can be manufactured by mixing the above-mentioned components. Specifically, the fluoropolyether-based curable composition of the present invention can be manufactured by uniformly mixing the above-mentioned component (A), component (B), and other optional components as needed using a planetary mixer, Ross mixer, Hobart mixer, or other mixing device, or by using a kneading device such as a kneader or a three-roller mixer as needed.

[0614] Alternatively, it can be formulated into a two-component composition that is mixed during use.

[0615] The manufactured fluorinated polyether-based curable composition can cure at room temperature, and curing can also be accelerated by adding a curing accelerator. In the absence of a curing accelerator, heating can be used to promote curing. To obtain good rubber physical properties, it is preferable to cure at 60°C or higher, preferably 80–200°C, for a period of several minutes to several days.

[0616] Furthermore, when using the fluorinated polyether-based curable composition of the present invention, the composition can be dissolved in a suitable fluorinated solvent, such as 1,3-bis(trifluoromethyl)benzene, Fluorinert (manufactured by 3M), 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., to the desired concentration, depending on its application and purpose. In particular, the solvent is preferably used in film coating applications.

[0617] The fluorinated polyether-based curable composition of the present invention is preferably used as an electrical and electronic component for automotive applications, marine applications, sporting goods applications, LED applications, civil engineering applications, chemical plant applications, semiconductor manufacturing line applications, analytical and physicochemical equipment applications, residential environment applications, communication equipment applications, communication machinery applications, aircraft applications, railway vehicle applications, portable device applications, power storage device applications, robotic applications, or lithium-ion battery applications, and more preferably as an electrical and electronic component for automotive applications, marine applications, aircraft applications, sporting goods applications, LED applications, civil engineering applications, chemical plant applications, analytical and physicochemical equipment applications, residential environment applications, communication equipment applications, communication machinery applications, communication machinery applications, and railway vehicle applications.

[0618] In particular, it is preferred to use the cured product of the fluorinated polyether-based curable composition of the present invention as an electrical and electronic component used as a gasket, filler, protective seal or coating.

[0619] Example

[0620] The following examples, embodiments, and comparative examples illustrate the invention in detail, but the invention is not limited to the examples described below. Furthermore, in the following examples, parts represent parts by mass. Additionally, in the following examples, viscosity is the value measured at 23°C using a rotational viscometer, and the amounts of vinyl groups, SiH groups, secondary amino groups, and epoxy groups are determined using... 1 Values ​​measured by H-NMR.

[0621] [Synthesis example 1]

[0622] 200 g of the polymer represented by the following formula (24) (vinyl content: 0.0320 mol / 100 g) was filled into a flask, and the flask was purged with nitrogen. Next, 200 g of hexafluorom-xylene and 73.5 g (0.30 mol) of tetramethylcyclotetrasiloxane were added. While stirring, the temperature was raised to 75 °C, and then 0.08 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex (containing 2.1 × 10⁻⁶ Pt) was added. -6 mol), and stirred for 4 hours. After confirming the disappearance of vinyl groups, the solvent and excess tetramethylcyclotetrasiloxane were removed. Then, by performing activated carbon treatment, 149.7 g of the polymer represented by the following formula (25) was obtained.

[0623] [Chemistry 140]

[0624]

[0625] (The average value of n+m is 35)

[0626] [Chemistry 141]

[0627]

[0628] (The average value of n+m is 35)

[0629] Next, 145.2 g of the polymer represented by the above formula (25) (SiH base content: 0.0882 mol / 100 g) was filled into another flask, and nitrogen was replaced in the flask. 16.11 g (0.14 mol) of allyl glycidyl ether and 145.2 g of hexafluorom-xylene were added to it. While stirring, the temperature was raised to 70 °C, and then 0.73 g of a toluene solution of platinum / 1,3-divinyltetramethyldisiloxane complex (containing 1.87 × 10⁻⁶ Pt) was added. -5The mixture was stirred for 1 hour. After confirming the disappearance of the SiH group, activated carbon treatment was performed, and the solvent and excess allyl glycidyl ether were removed by vacuum distillation to obtain 150 g of a ester-like fluorinated epoxy compound represented by the following formula (26). The amount of epoxy groups was 0.0810 mol / 100 g.

[0630] [Chemistry 142]

[0631]

[0632] (The average value of n+m is 35)

[0633] [Synthesis example 2]

[0634] 200 g of the polymer represented by the following formula (27) (vinyl content: 0.0335 mol / 100 g) was filled into a flask, and the flask was purged with nitrogen. Next, 200 g of hexafluorom-xylene and 78.11 g (0.32 mol) of tetramethylcyclotetrasiloxane were added. While stirring, the temperature was raised to 75 °C, and then 0.24 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex (containing 6.2 × 10⁻⁶ Pt) was added. -6 mol), and stirred for 2 hours. After confirming the disappearance of vinyl groups, the solvent and excess tetramethylcyclotetrasiloxane were removed. Then, by performing activated carbon treatment, 158.1 g of the polymer represented by the following formula (28) was obtained.

[0635] [Chemistry 143]

[0636]

[0637] (The average value of n+m is 35)

[0638] [Chemistry 144]

[0639]

[0640] (The average value of n+m is 35)

[0641] Next, 155.0 g of the polymer represented by the above formula (28) (SiH base content: 0.0929 mol / 100 g) was filled into another flask, and nitrogen was replaced inside the flask. 17.8 g (0.16 mol) of allyl glycidyl ether and 155.0 g of hexafluorom-xylene were added to it. While stirring, the temperature was raised to 70 °C, and then 0.77 g of a toluene solution of platinum / 1,3-divinyltetramethyldisiloxane complex (containing 1.97 × 10⁻⁶ Pt) was added. -5mol), stirred for 1 hour. After confirming the disappearance of the SiH group, activated carbon treatment was performed, and the solvent and excess allyl glycidyl ether were removed by vacuum distillation to obtain 153 g of a ester-like fluorinated epoxy compound represented by the following formula (29). The amount of epoxy groups was 0.0840 mol / 100 g.

[0642] [Chemistry 145]

[0643]

[0644] (The average value of n+m is 35)

[0645] [Synthesis example 3]

[0646] In Synthesis Example 1, except that 17.5 g (0.14 mol) of 3-vinylcyclohexene oxide was used instead of allyl glycidyl ether, all other steps were performed in the same manner as in Synthesis Example 1, and 149 g of a ester-like fluorinated epoxy compound represented by the following formula (30) was obtained. The amount of epoxy groups was 0.0803 mol / 100 g.

[0647] [Chemistry 146]

[0648]

[0649] (The average value of n+m is 35)

[0650] [Synthesis Example 4]

[0651] In Synthesis Example 2, except that 19.4 g (0.16 mol) of 3-vinylcyclohexene oxide was used instead of allyl glycidyl ether, all other steps were performed in the same manner as in Synthesis Example 2, and 152 g of a ester-like fluorinated epoxy compound represented by the following formula (31) was obtained. The amount of epoxy groups was 0.0833 mol / 100 g.

[0652] [Chemistry 147]

[0653]

[0654] (The average value of n+m is 35)

[0655] [Synthesis example 5]

[0656] 200 g of the polymer represented by the following formula (32) (vinyl content: 0.0231 mol / 100 g) was filled into a flask, and the flask was nitrogen-purged. Next, 200 g of hexafluorom-xylene and 53.77 g (0.22 mol) of tetramethylcyclotetrasiloxane were added. While stirring, the temperature was raised to 75 °C, and then 0.08 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex (containing 2.1 × 10⁻⁶ Pt) was added. -6mol), and stirred for 4 hours. After confirming the disappearance of vinyl groups, the solvent and excess tetramethylcyclotetrasiloxane were removed. Then, by performing activated carbon treatment, 176.1 g of the polymer represented by the following formula (33) was obtained.

[0657] [Chemistry 148]

[0658]

[0659] (The average value of n is 24)

[0660] [Chemistry 149]

[0661]

[0662] (The average value of n is 24)

[0663] Next, 150 g of the polymer (SiH base content: 0.0658 mol / 100 g) represented by the above formula (33) was filled into another flask, and nitrogen replacement was performed inside the flask. 12.57 g (0.11 mol) of allyl glycidyl ether and 150 g of hexafluorom-xylene were added to it. While stirring, the temperature was raised to 70 °C, and then 0.75 g of a toluene solution of platinum / 1,3-divinyltetramethyldisiloxane complex (containing 1.92 × 10⁻⁶ Pt) was added. -5 mol), and stirred for 1 hour. After confirming the disappearance of the SiH group, activated carbon treatment was performed, and the solvent and excess allyl glycidyl ether were removed by vacuum distillation to obtain 139 g of a ester-like fluorinated epoxy compound represented by the following formula (34). The amount of epoxy groups was 0.0612 mol / 100 g.

[0664] [Chemistry 150]

[0665]

[0666] (The average value of n is 24)

[0667] [Synthesis example 6]

[0668] 200 g of the polymer represented by the following formula (35) (vinyl content: 0.0239 mol / 100 g) was filled into a flask, and the flask was purged with nitrogen. Next, 200 g of hexafluorom-xylene and 54.97 g (0.23 mol) of tetramethylcyclotetrasiloxane were added. While stirring, the temperature was raised to 75 °C, and then 0.24 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex (containing 6.2 × 10⁻⁶ Pt) was added. -6mol), and stirred for 4 hours. After confirming the disappearance of vinyl groups, the solvent and excess tetramethylcyclotetrasiloxane were removed. Then, by performing activated carbon treatment, 180 g of the polymer represented by the following formula (36) was obtained.

[0669] [Chemistry 151]

[0670]

[0671] (The average value of n is 24)

[0672] [Chemistry 152]

[0673]

[0674] (The average value of n is 24)

[0675] Next, 150 g of the polymer (SiH base content: 0.0677 mol / 100 g) represented by the above formula (36) was filled into another flask, and nitrogen was replaced in the flask. 12.92 g (0.11 mol) of allyl glycidyl ether and 150 g of hexafluorom-xylene were added to it. While stirring, the temperature was raised to 70 °C, and then 0.73 g of a toluene solution of platinum / 1,3-divinyltetramethyldisiloxane complex (containing 1.87 × 10⁻⁶ Pt) was added. -5 mol), and stirred for 1 hour. After confirming the disappearance of the SiH group, activated carbon treatment was performed, and the solvent and excess allyl glycidyl ether were removed by vacuum distillation to obtain 141 g of a ester-like fluorinated epoxy compound represented by the following formula (37). The amount of epoxy groups was 0.0629 mol / 100 g.

[0676] [Chemistry 153]

[0677]

[0678] (The average value of n is 24)

[0679] [Synthesis Example 7]

[0680] 200 g of the polymer represented by the above formula (27) (vinyl content: 0.0335 mol / 100 g) was filled into a flask, and the flask was purged with nitrogen. Next, 200 g of hexafluorom-xylene and 87.0 g (0.32 mol) of 3-[(dimethylsilyl)oxy]-1,1,3,5,5-pentamethyltrisiloxane were added. While stirring, the temperature was raised to 75 °C, and then 0.24 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex (containing 6.2 × 10⁻⁶ Pt) was added. -6mol), and stirred for 2 hours. After confirming the disappearance of vinyl groups, the solvent and excess 3-[(dimethylsilyl)oxy]-1,1,3,5,5-pentamethyltrisiloxanemethyltris(dimethylsiloxy)silane were removed by vacuum distillation. Then, 160 g of the polymer represented by the following formula (38) was obtained by activated carbon treatment.

[0681] [Chemistry 154]

[0682]

[0683] (The average value of n+m is 35)

[0684] Next, 150 g of the polymer (SiH base content: 0.0614 mol / 100 g) represented by the above formula (38) was filled into another flask, and nitrogen was replaced in the flask. 11.79 g (0.10 mol) of allyl glycidyl ether and 150 g of hexafluorom-xylene were added to it. While stirring, the temperature was raised to 70 °C, and then 0.73 g of a toluene solution of platinum / 1,3-divinyltetramethyldisiloxane complex (containing 1.87 × 10⁻⁶ mol of Pt) was added. -5 mol), and stirred for 1 hour. After confirming the disappearance of the SiH group, activated carbon treatment was performed, and the solvent and excess allyl glycidyl ether were removed by vacuum distillation to obtain 143 g of a ester-like fluorinated epoxy compound represented by the following formula (39). The amount of epoxy groups was 0.0574 mol / 100 g.

[0685] [Chemistry 155]

[0686]

[0687] (The average value of n+m is 35)

[0688] [Synthesis example 8]

[0689] 200 g of the polymer represented by the above formula (24) (vinyl content: 0.0320 mol / 100 g) was filled into a flask, and the flask was purged with nitrogen. Next, 200 g of hexafluorom-xylene and 82.0 g (0.31 mol) of 3-[(dimethylsilyl)oxy]-1,1,3,5,5-pentamethyltrisiloxane were added. While stirring, the temperature was raised to 75 °C, and then 0.10 g of a toluene solution of platinum / 1,3-divinyl-tetramethyldisiloxane complex (containing 2.6 × 10⁻⁶ Pt) was added. -6mol), and stirred for 3 hours. After confirming the disappearance of vinyl groups, the solvent and excess 3-[(dimethylsilyl)oxy]-1,1,3,5,5-pentamethyltrisiloxanemethyltris(dimethylsiloxy)silane were removed by vacuum distillation. Then, 165 g of the polymer represented by the following formula (40) was obtained by activated carbon treatment.

[0690] [Chemistry 156]

[0691]

[0692] (The average value of n+m is 35)

[0693] Next, 150 g of the polymer (SiH base content: 0.0590 mol / 100 g) represented by the above formula (40) was filled into another flask, and nitrogen replacement was performed inside the flask. 11.36 g (0.10 mol) of allyl glycidyl ether and 150 g of hexafluorom-xylene were added to it. While stirring, the temperature was raised to 70 °C, and then 0.76 g of a toluene solution of platinum / 1,3-divinyltetramethyldisiloxane complex (containing 1.94 × 10⁻⁶ Pt) was added. -5 mol), and stirred for 1 hour. After confirming the disappearance of the SiH group, activated carbon treatment was performed, and the solvent and excess allyl glycidyl ether were removed by vacuum distillation to obtain 143 g of an oily fluorinated epoxy compound represented by the following formula (41). The amount of epoxy groups was 0.0553 mol / 100 g.

[0694] [Chemistry 157]

[0695]

[0696] (The average value of n+m is 35)

[0697] [Synthesis Example 9]

[0698] In Synthesis Example 7, except that 12.8 g (0.10 mol) of 3-vinylcyclohexene oxide was used instead of allyl glycidyl ether, all other steps were performed in the same manner as in Synthesis Example 7, and 40 g of an oily fluorinated epoxy compound represented by the following formula (42) was obtained. The amount of epoxy groups was 0.0571 mol / 100 g.

[0699] [Chemistry 158]

[0700]

[0701] (The average value of n+m is 35)

[0702] [Example 1]

[0703] By mixing 90 parts of (A1) polymer represented by the following formula (43) (viscosity 4900 mPa·s, secondary amino content at the polymer end 0.0296 mol / 100g) and 10 parts of (A2) polymer represented by the following formula (44) (viscosity 24920 mPa·s, secondary amino content at the polymer end 0.0301 mol / 100g), and then adding 43.1 parts of (B1) fluorinated epoxy compound represented by the above formula (26) (epoxy content 0.0810 mol / 100g), a fluorinated polyether curable composition was obtained.

[0704] [Chemistry 159]

[0705]

[0706] (The average value of a is 1.03, and the average value of n+m is 35)

[0707] [Chemistry 160]

[0708]

[0709] (The average value of n+m is 35)

[0710] [Example 2]

[0711] In Example 1, a fluorinated polyether curable composition was obtained by the same method as in Example 1, except that 60 parts by mass of the polymer represented by formula (43) above (A1), 40 parts by mass of the polymer represented by formula (44) above (A2), and 43.3 parts by mass of the fluorinated epoxy compound represented by formula (26) above (B1).

[0712] [Example 3]

[0713] In Example 1, except for 40 parts by mass of the polymer represented by formula (43) above (A1), 60 parts by mass of the polymer represented by formula (44) above (A2), and 43.5 parts by mass of the fluorinated epoxy compound represented by formula (26) above, a fluorinated polyether curable composition was obtained by the same method as in Example 1.

[0714] [Example 4]

[0715] In Example 1, except for 100 parts by mass of the polymer represented by formula (43) above (A1) and 43.0 parts by mass of the fluorinated epoxy compound represented by formula (26) above, a fluorinated polyether curable composition was obtained by the same method as in Example 1.

[0716] [Example 5]

[0717] In Example 1, except for 100 parts by mass of the polymer represented by formula (44) above (A2) and 43.8 parts by mass of the fluorinated epoxy compound represented by formula (26) above, a fluorinated polyether curable composition was obtained by the same method as in Example 1.

[0718] [Example 6]

[0719] In Example 1, except that 42.7 parts of fluorinated epoxy compound (B2) represented by the above formula (29) (epoxy group content 0.0840 mol / 100 g) were used instead of fluorinated epoxy compound (B1), a fluorinated polyether curable composition was obtained by the same method as in Example 1.

[0720] [Example 7]

[0721] In Example 4, except for 43.3 parts by weight of fluorinated epoxy compound (B2) represented by the above formula (29) used instead of fluorinated epoxy compound (B1), a fluorinated polyether curable composition was obtained by the same method as in Example 4.

[0722] [Example 8]

[0723] In Example 1, except that 43.3 parts of fluorinated epoxy compound (B3) represented by the above formula (30) (epoxy group content 0.0803 mol / 100 g) were used instead of fluorinated epoxy compound (B1), a fluorinated polyether curable composition was obtained by the same method as in Example 1.

[0724] [Example 9]

[0725] In Example 4, except for 43.9 parts of fluorinated epoxy compound (B3) represented by the above formula (30) used instead of fluorinated epoxy compound (B1), a fluorinated polyether curable composition was obtained by the same method as in Example 4.

[0726] [Example 10]

[0727] In Example 1, except that 42.8 parts of (B4) fluorinated epoxy compound represented by the above formula (31) (epoxy group content 0.0833 mol / 100 g) were used instead of (B1) fluorinated epoxy compound, a fluorinated polyether curable composition was obtained by the same method as in Example 1.

[0728] [Example 11]

[0729] In Example 1, except that 33.0 parts of (B5) fluorinated epoxy compound represented by the following formula (45) (epoxy group content 0.1103 mol / 100 g) were used instead of (B1) fluorinated epoxy compound, a fluorinated polyether curable composition was obtained by the same method as in Example 1.

[0730] [Chemistry 161]

[0731]

[0732] (n / m = 0.9, n + m = 45)

[0733] [Example 12]

[0734] In Example 4, except for 32.9 parts of fluorinated epoxy compound (B5) represented by the above formula (45) used instead of fluorinated epoxy compound (B1), a fluorinated polyether curable composition was obtained by the same method as in Example 4.

[0735] [Example 13]

[0736] In Example 4, except that 60.7 parts by weight of fluorinated epoxy compound (B6) represented by the above formula (34) (epoxy group content 0.0612 mol / 100 g) was used instead of fluorinated epoxy compound (B1), a fluorinated polyether curable composition was obtained by the same method as in Example 4.

[0737] [Example 14]

[0738] In Example 4, except that 60.0 parts by weight of fluorinated epoxy compound (B7) represented by the above formula (37) (epoxy group content 0.0629 mol / 100 g) was used instead of fluorinated epoxy compound (B1), a fluorinated polyether curable composition was obtained by the same method as in Example 4.

[0739] [Example 15]

[0740] In Example 1, except that 62.7 parts of fluorinated epoxy compound (B8) represented by the above formula (39) (epoxy group content 0.0574 mol / 100 g) were used instead of fluorinated epoxy compound (B1), a fluorinated polyether curable composition was obtained by the same method as in Example 1.

[0741] [Example 16]

[0742] In Example 4, except for 62.8 parts by weight of (B8) fluorinated epoxy compound represented by the above formula (39) used instead of (B1), a fluorinated polyether curable composition was obtained by the same method as in Example 4.

[0743] [Example 17]

[0744] In Example 1, except for 62.0 parts of (B9) fluorinated epoxy compound represented by the above formula (41) (epoxy group content 0.0553 mol / 100 g) used instead of (B1), a fluorinated polyether curable composition was obtained by the same method as in Example 1.

[0745] [Example 18]

[0746] In Example 4, except for 62.1 parts by weight of (B9) fluorinated epoxy compound represented by the above formula (41) used instead of (B1), a fluorinated polyether curable composition was obtained by the same method as in Example 4.

[0747] [Example 19]

[0748] In Example 1, except that 62.9 parts of (B10) fluorinated epoxy compound represented by the above formula (42) (epoxy group content 0.0571 mol / 100 g) were used instead of (B1) fluorinated epoxy compound, a fluorinated polyether curable composition was obtained by the same method as in Example 1.

[0749] [Example 20]

[0750] In Example 4, except for 63.0 parts by weight of (B10) fluorinated epoxy compound represented by the above formula (42) used instead of (B1) fluorinated epoxy compound, a fluorinated polyether curable composition was obtained by the same method as in Example 4.

[0751] [Comparative Example 1]

[0752] In Example 1, except for 2.74 parts by weight of epoxy compound (B11) represented by the following formula (46) used instead of fluorinated epoxy compound (B11), a fluorinated polyether curable composition was obtained in the same manner as in Example 1.

[0753]

[0754] [Comparative Example 2]

[0755] In Example 4, except for 2.73 parts by weight of the epoxy compound represented by the above formula (28) (B11) used instead of the fluorinated epoxy compound (B11), a fluorinated polyether curable composition was obtained in the same manner as in Example 4.

[0756] [Comparative Example 3]

[0757] In Example 5, except for 2.78 parts by mass of the epoxy compound represented by the above formula (28) (B11) used instead of the fluorinated epoxy compound (B1), a fluorinated polyether-based curable composition was obtained in the same manner as in Example 5.

[0758] <Determination of usability time at room temperature>

[0759] Each composition was placed in a constant temperature bath at 25°C, and the time until loss of fluidity was determined by visual observation after 2, 4, 8, 16, and 24 hours. The results are shown in Tables 1–3.

[0760] [Evaluation Criteria]

[0761] ○: Liquidity was maintained.

[0762] △: Not solidified, but not fluid.

[0763] ×: Curing.

[0764] [Table 1]

[0765]

[0766] [Table 2]

[0767]

[0768] [Table 3]

[0769]

[0770] The fluorinated polyether-based curable compositions of Examples 1-20, which used a fluorinated epoxy compound as component (B), maintained fluidity for approximately 8-16 hours at 25°C. Comparative Examples 1-3, which used the same component (A) as Examples 1, 4, and 5, showed shorter usable times compared to their corresponding Examples 1, 4, and 5.

[0771] <Preparation and Physical Property Evaluation of Fluoropolyether-Based Cured Products>

[0772] The fluoropolyether-based curable compositions prepared immediately after Example 1-20 and Comparative Examples 1-3 were cast into a 2mm thick stainless steel mold placed on a sheet of Teflon (registered trademark, hereinafter the same). The molds were then clamped with another sheet of Teflon and pressure-cured at 100°C for 6 hours. After pressure curing, the 2mm thick stainless steel mold was removed, and the physical properties of the resulting fluoropolyether-based cured products were evaluated according to JIS K 6249. The results are shown in Table 4.

[0773] [Table 4]

[0774]

[0775] The fluorinated polyether-based curable compositions of Examples 1-20, which used fluorinated epoxy compounds (B1) to (B10) as component (B), all resulted in cured products with good rubber elasticity. Compared with these cured products, the cured products of the fluorinated polyether-based curable compositions of Comparative Examples 1-3, which used fluorine-free epoxy compounds (B11) as component (B), had higher hardness and lower rubber elasticity.

[0776] The results above show that the fluorinated polyether-based curable compositions of Examples 1 to 20 have a long service life, and the cured products are soft and have excellent rubber elasticity.

Claims

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

2. The fluorinated polyether-based curable composition according to claim 1, wherein, (A) The component is a fluorinated compound represented by the following average formula (1), [Chemistry 1] In formula (1), Rf is independently a divalent perfluoropolyether group, A is independently a divalent organic group having 1 to 12 carbon atoms and having at least one carbonyl bond, or selected from amide bonds, ether bonds, and ester bonds, X is independently any group represented by the following formulas (2) to (4), and a is a positive number of 1 or more. [Chemistry 2] In the formula, R 1 R is an unsubstituted or substituted monovalent hydrocarbon group. 2 It is an unsubstituted or substituted divalent hydrocarbon group.

3. The fluorinated polyether-based curable composition according to claim 2, wherein, In the average formula (1), A is independently selected from -(CH2). f -*、-(CH2) f OCH2-*, -CO-*, -(CH2) f -NR 6 -CO-*、-(CH2) f -O-CO-*, and any one of the groups represented by the following general formulas (5) and (6), where the *-tethering end indicates binding to Rf, and the unmarked tethering end indicates binding to X. [Chemistry 3] In the formula, R 5 R is independently a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, or a trifluoromethyl group. 6 It can be a hydrogen atom, methyl, ethyl, isopropyl or phenyl, e is 0 or 1, and f is an integer from 1 to 9.

4. The fluorinated polyether-based curable composition according to claim 1, wherein, (B) The component is a fluorinated compound represented by the following general formula (7), [Chemistry 4] In equation (7), Rf 1 Rf is a monovalent or divalent group with a number average molecular weight of 400 to 40,000 that independently has a fluorinated polyether structure. 1 When the group is monovalent, b' is 1, b is an integer from 1 to 6, c is an integer from 2 to 20, and Rf 1 When the group is divalent, b' is 2, b is 1, and c is an integer from 1 to 20; Q is independently a divalent group having at least (b+c) Si atoms, having a siloxane structure, a silanediol structure, a silanearyl structure, or a combination thereof, and may have a cyclic structure; Z is independently a divalent hydrocarbon group having 1 to 20 carbon atoms, may contain ether bonds or ester bonds, and may have a cyclic structure; E is independently a group represented by the following formula (I) or (II). [Chemistry 5] In equation (I), R 3 Independently composed of a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, it may contain ether or ester bonds and may have a cyclic structure. [Chemistry 6] In equation (II), R 4 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 claim 4, wherein, In equation (7), Z is independently selected from the groups represented by the following formula. -CH2CH2-*、 -CH2CH2CH2-*、 -CH2CH2CH2CH2-*、 -CH2CH2CH2CH2CH2-*、 -CH2CH2CH2CH2CH2CH2-*、 -CH2CH2CH2CH2CH2CH2CH2-*、 -CH2CH2CH2CH2CH2CH2CH2CH2-*、 -CH2CH2CH2OCH2-*、 -CH2CH2CH2OCH2CH2OCH2-*, or -CH2CH2CH2OCH2CH2OCH2CH2OCH2CH2-* In the formula, the terminal marked with * indicates a connection to E, and the unmarked terminal indicates a connection to Q.

6. The fluorinated polyether-based curable composition according to claim 4, wherein, In equation (7), the structure represented by -ZE is selected from the groups represented by equations (a) to (d) below. [Chemistry 7] 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, h+2l+i is an integer from 2 to 20, and R 4 It is a monovalent hydrocarbon group consisting of hydrogen atoms or 1 to 20 carbon atoms, either unsubstituted or substituted.

7. The fluorinated polyether-based curable composition according to claim 4, wherein, In equation (7), the structure represented by -ZE is selected from the groups represented by the following formula. [Chemistry 8] 。 8. The fluoropolyether-based curable composition according to claim 4, wherein, In equation (7), Q is represented by the following equation: [Chemistry 9] In the formula, b1 is in Rf 1 When the group is monovalent, the valence is an integer from 1 to 4, in Rf 1 When the group is divalent, c1 is 1, c1 is an integer from 2 to 4, and they are integers satisfying b1 + c1 = 3 to 6, b1' in Rf 1 When the group is monovalent, it is 1 or 2, in Rf 1 When the group is divalent, c1' is 2 or 3, d1 is 0 or 1, and b1'+c1'+d1=4. D is a monovalent hydrocarbon group with 1 to 6 carbon atoms. The silicon atoms of the units shown in parentheses with b1 and b1' repeating units are related to Rf. 1 In combination, each silicon atom of the unit shown in parentheses, which has c1 and c1' repeating units, is bonded to Z, and the arrangement of the units shown in parentheses can be random.

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

10. An article having the solidified product according to claim 9.

11. The article according to claim 10, which is for automobiles, ships, aircraft, sports equipment, LEDs, civil engineering, chemical plants, analytical and physicochemical equipment, living environments, communication machines, communication equipment, and railway vehicles.

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