Fluoropolyether group-containing thiol compound

Abstract

To provide a fluoropolyether group-containing thiol compound with excellent stability.SOLUTION: A fluoropolyether group-containing thiol compound according to the present disclosure comprises no ester structure and comprises two or more thiol groups selected from secondary or tertiary thiol groups.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a fluoropolyether group-containing thiol compound. [Background technology]

[0002] As a fluoropolyether group-containing thiol compound, for example, a compound having a fluoropolyether group and a primary thiol group is known (Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2006-291206 A Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present disclosure is to provide a fluoropolyether group-containing thiol compound having excellent stability. [Means for solving the problem]

[0005] The present disclosure includes the following aspects. [1] A fluoropolyether group-containing thiol compound which does not contain an ester structure and contains two or more thiol groups selected from secondary or tertiary thiol groups. [2] The fluoropolyether group-containing thiol compound according to [1], having a fluorine content of 30 mass% or more. [3] The fluoropolyether group-containing thiol compound according to [1] or [2], which contains 2 to 6 thiol groups. [4] The fluoropolyether group-containing thiol compound according to any one of [1] to [3], wherein the thiol group is a secondary thiol group. [5] The fluoropolyether group-containing thiol compound according to any one of [1] to [4], wherein the thiol groups are present on both ends of the fluoropolyether group. [6] The fluoropolyether group-containing thiol compound according to any one of [1] to [5], having a group selected from a linear or branched alkylene group, a cycloalkylene group, a phenylene group, an alkylamino group, an ether bond, a thioether bond, a carbonyl bond, and an amide bond. [7] The following formula (1) or (2): [ka] [In formula: R F1 are each independently R f1 -R F -O q - and R F2 -R f2 p -R F -O q - and R f1 each independently represents a C which may be substituted by one or more fluorine atoms; 1-16 is an alkyl group, R f2 C may be substituted with one or more fluorine atoms. 1-6 is an alkylene group, R F are each independently a divalent fluoropolyether group, p is 0 or 1; Each q is independently 0 or 1; X A each independently represents a single bond or a divalent to decavalent organic group, R S are each independently -(CR 4 (SH)-R 5 ) n -CR 1 R 2 is a monovalent group containing a group represented by -SH, R 1 is a hydrocarbon group, R 2 is a hydrogen atom or a hydrocarbon group, R 4 is a hydrogen atom or a hydrocarbon group, R 5 is a divalent hydrocarbon group, In formulas (1) and (2), at least two secondary or tertiary thiol groups are present; α1 is an integer from 1 to 9, α2 is an integer from 1 to 9, Each β is independently an integer from 1 to 9, n is an integer from 0 to 9, Formulae (1) and (2) do not contain an ester structure.] The fluoropolyether group-containing thiol compound according to any one of [1] to [6], represented by the following formula: [8] R f1 are each independently 1-16 is a perfluoroalkyl group, R f2 are each independently 1-6 is a perfluoroalkylene group. The fluoropolyether group-containing thiol compound according to [7]. [9] R F are each independently represented by the formula: -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3R Fa 6) d -(OC2F4) e -(OCF2) f - [In the formula, R Fa each independently represents a hydrogen atom, a fluorine atom, or a chlorine atom, a, b, c, d, e, and f each independently represent an integer of 0 to 200, the sum of a, b, c, d, e, and f is 1 or more, and the order of occurrence of each repeating unit enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula, with the proviso that when all RFa are hydrogen atoms or chlorine atoms, at least one of a, b, c, e, and f is 1 or more. The fluoropolyether group-containing thiol compound according to [7] or [8], wherein the fluoropolyether group-containing thiol compound is a group represented by the formula:

[10] R Fa The fluoropolyether group-containing thiol compound according to [9], wherein is a fluorine atom.

[11] R F are each independently represented by the following formula (f1), (f2), (f3), (f4), (f5), or (f6): -(OC3F6) d -(OC2F4) e - (f1) [In the formula, d is an integer of 1 to 200, and e is 0 or 1.] -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f2) [In the formula, c and d each independently represent an integer of 0 to 30, e and f each independently represent an integer of 1 to 200; The sum of c, d, e, and f is an integer of 10 to 200, The order of occurrence of each repeat unit enclosed in parentheses with the subscript c, d, e, or f is arbitrary in the formula. -(R 6 -R 7 ) g - (f3) [In the formula, R 6 is OCF2 or OC2F4, R 7 are OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12or a combination of two or three groups selected from these groups, g is an integer from 2 to 100. -(R 6 -R 7 ) g -R r -(R 7 '-R 6 ') g’ - (f4) [In the formula, R 6 is OCF2 or OC2F4, R 7 are OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of two or three groups independently selected from these groups; R 6 ' is OCF2 or OC2F4, R 7 ' is OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of two or three groups independently selected from these groups; g is an integer from 2 to 100; g' is an integer from 2 to 100, R r teeth, [ka] (In the formula, * indicates the bond position.) ]; -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f5) [In the formula, e is an integer of 1 or more and 200 or less, a, b, c, d, and f are each independently an integer of 0 or more and 200 or less, and the order of the repeating units enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula.] -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f6) [In the formula, f is an integer of 1 or more and 200 or less, a, b, c, d, and e are each independently an integer of 0 or more and 200 or less, and the order of the repeating units enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula.] The fluoropolyether group-containing thiol compound according to any one of [7] to

[10] , wherein the fluoropolyether group-containing thiol compound is a group represented by the following formula:

[12] R S is represented by the following formula (S1), (S2), or (S3): [ka] [In formula: R Sa -Z-(CR 4 (SH)-R 5 ) n -CR 1 R 2 -SH, Z is a single bond or a divalent group; R 1 is a hydrocarbon group, R 2 is a hydrogen atom or a hydrocarbon group, R 3 is a hydrogen atom or a hydrocarbon group, R 4 is a hydrogen atom or a hydrocarbon group, R 5 is a hydrocarbon group, n is an integer from 0 to 9, n1 is 1 or 2; n2 is 1, 2 or 3. The fluoropolyether group-containing thiol compound according to any one of [7] to

[11] , wherein the fluoropolyether group-containing thiol compound is a group represented by the following formula:

[13] Z is -R 11 - and R 11 is a single bond or C 1-6 is an alkylene group, The fluoropolyether group-containing thiol compound according to

[12] .

[14] R 1 is C 1-6 is an alkyl group, R 2 is a hydrogen atom or C 1-6 The fluoropolyether group-containing thiol compound according to any one of [7] to

[13] , wherein the fluoropolyether group is an alkyl group.

[15] R 3 is a hydrogen atom or C 1-6 The fluoropolyether group-containing thiol compound according to any one of

[12] to

[14] , wherein the fluoropolyether group is an alkyl group.

[16] R S The fluoropolyether group-containing thiol compound according to any one of

[12] to

[15] , wherein R is a group represented by formula (S1):

[17] R S The fluoropolyether group-containing thiol compound according to any one of

[12] to

[16] , wherein R is a group represented by formula (S2):

[18] R S The fluoropolyether group-containing thiol compound according to any one of

[12] to

[17] , wherein R is a group represented by formula (S3):

[19] The fluoropolyether group-containing thiol compound according to any one of [7] to

[18] , wherein α1, α2, and β are 1.

[20] X A is the expression: -(R 21 )m1 -(R 22 ) m2 - [In formula: R 21 is C 1-6 is an alkylene group, R 22 -O-, -CO-, -NR 23 -,-CONR 23 - or -NR 23 CO-, R 23 is a hydrogen atom or C 1-6 is an alkyl group, m1 is an integer from 0 to 10, m2 is an integer from 0 to 10, The sum of m1 and m2 is 1 or greater, R 21 and R 22 The order of occurrence of is arbitrary in the formula. The fluoropolyether group-containing thiol compound according to any one of [7] to

[19] , wherein the fluoropolyether group-containing thiol compound is a group represented by the following formula: [twenty one] The fluoropolyether group-containing thiol compound according to any one of [1] to

[20] , which has a number average molecular weight of 1,000 to 100,000. [twenty two] The fluoropolyether group-containing thiol compound according to any one of [1] to

[21] , which has a viscosity of 100 to 10,000 mPa·s. [twenty three] A curable composition comprising the fluoropolyether group-containing thiol compound according to any one of [1] to

[22] . [twenty four] The curable composition according to

[23] , further comprising a fluoropolyether group-containing unsaturated compound containing a group having a carbon-carbon double bond. [twenty five] The curable composition according to

[24] , wherein the number of the groups having a carbon-carbon double bond is 2 to 8.

[26] The curable composition according to

[24] or

[25] , wherein the group having a carbon-carbon double bond is an allyl group, a vinyl group, or a (meth)acrylic group.

[27] The curable composition according to any one of

[24] to

[26] , wherein the group having a carbon-carbon double bond is an allyl group.

[28] The curable composition according to any one of

[24] to

[27] , wherein the group having a carbon-carbon double bond is present on both ends of the fluoropolyether group.

[29] The curable composition according to any one of

[24] to

[28] , wherein the fluoropolyether group-containing unsaturated compound containing a group having a carbon-carbon double bond has a group selected from a linear or branched alkylene group, a cycloalkylene group, a phenylene group, an alkylamino group, an ether bond, a thioether bond, a carbonyl bond, and an amide bond.

[30] The fluoropolyether group-containing unsaturated compound is represented by the following formula (3) or (4): [ka] [In formula: R F1 are each independently R f1 -R F -O q - and R F2 -R f2 p -R F -O q - and R f1 each independently represents a C which may be substituted by one or more fluorine atoms; 1-16 is an alkyl group, R f2 C may be substituted with one or more fluorine atoms. 1-6 is an alkylene group, R F are each independently a divalent fluoropolyether group, p is 0 or 1; Each q is independently 0 or 1; X B each independently represents a single bond or a divalent to decavalent organic group, R D are each independently a group containing a carbon-carbon double bond, γ1 is an integer from 1 to 9, γ2 is an integer from 1 to 9, Each δ is independently an integer from 1 to 9. The curable composition according to any one of

[24] to

[29] , wherein the compound is represented by the following formula:

[31] The carbon-carbon double bond-containing group has the formula: -YA [In formula: Y is a single bond, an oxygen atom, or a divalent organic group; A is -CR 41 =CH2, R41 is independently a hydrogen atom or C 1-3 is an alkyl group. The curable composition according to

[30] , wherein the group is represented by the formula:

[32] Y is -CR 42 2- or -CO-, R 42 are each independently a hydrogen atom or C 1-6 is an alkyl group,

[31] The curable composition according to claim 1.

[33] R D is represented by the following formula (D1), (D2), (D3), (D4) or (D5): [ka] [In the formula, Y is a single bond, an oxygen atom, or a divalent organic group; A is -CR 41 =CH2, R 41 are each independently a hydrogen atom or C 1-3 is an alkyl group, X 10is independently at each occurrence a single bond or a divalent organic group; R 13 is independently at each occurrence a hydrogen atom or a monovalent organic group; t is independently in each occurrence an integer greater than or equal to 2; R 14 is independently at each occurrence a hydrogen atom or a halogen atom; R a1 may each independently in each occurrence be -Z 1 -SiR a2 p1 R a3 q1 R a4 r1 and Z 1 is independently at each occurrence a single bond, an oxygen atom, or a divalent organic group; R a2 each occurrence independently, -Z 1’ -SiR a3’ q1’ R a4’ r1’ and Z 1’ is independently at each occurrence a single bond, an oxygen atom, or a divalent organic group; R a3’ may each independently in each occurrence be -Z 2 -YA, R a4’ is independently in each occurrence a hydrogen atom, a hydroxyl group, or a monovalent organic group; Z 2 is independently in each occurrence a single bond, an oxygen atom, or a divalent organic group; q 1’ is independently at each occurrence an integer from 0 to 3; r 1’ is independently at each occurrence an integer from 0 to 3; Here, the sum of q1' and r1' is (SiR a3’ q1’ R a4’r1’ ) units, is 3, R a3 may each independently in each occurrence be -Z 2 -YA, R a4 is independently in each occurrence a hydrogen atom, a hydroxyl group, or a monovalent organic group; p1, at each occurrence, is independently an integer from 0 to 3; q1 in each occurrence is independently an integer from 0 to 3; r1, in each occurrence, is independently an integer from 0 to 3; Here, the sum of p1, q1 and r1 is (SiR a2 p1 R a3 q1 R a4 r1 ) units, is 3, R b1 may each independently in each occurrence be -Z 2 -YA, R c1 is independently in each occurrence a hydrogen atom, a hydroxyl group, or a monovalent organic group; k1, in each occurrence, is independently an integer from 0 to 3; l1 in each occurrence is independently an integer from 0 to 3; m1 in each occurrence is independently an integer from 0 to 3; Here, the sum of k1, l1, and m1 is (SiR a1 k1 R b1 l1 R c1 m1 ) units, is 3, In formula (D3), at least one -YA is present, R d1 may each independently in each occurrence be -Z 3 -CR d2 p2 R d3 q2 R d4 r2 and Z 3 is independently in each occurrence a single bond, an oxygen atom, or a divalent organic group; R d2 may each independently in each occurrence be -Z 3’ -CR d3’ q2’ R d4’ r2’ and Z 3’ is independently at each occurrence an oxygen atom or a divalent organic group; R d3’ may each independently in each occurrence be -Z 2 -YA, R d4’ is independently in each occurrence a hydrogen atom, a hydroxyl group, or a monovalent organic group; q2' is independently in each occurrence an integer from 0 to 3; r2' is independently at each occurrence an integer from 0 to 3; Here, the sum of q2' and r2' is (CR d3’ q2’ R d4’ r2’ ) units, is 3, R d3 may each independently in each occurrence be -Z 2 -YA; R d4 is independently in each occurrence a hydrogen atom, a hydroxyl group, or a monovalent organic group; p2, in each occurrence, is independently an integer from 0 to 3; q2, in each occurrence, is independently an integer from 0 to 3; r2, independently at each occurrence, is an integer from 0 to 3; Here, the sum of p2, q2 and r2 is (CR d2 p2 R d3 q2 R d4 r2 ) units, is 3, R e1may each independently in each occurrence be -Z 2 -YA, R f1 is independently in each occurrence a hydrogen atom, a hydroxyl group, or a monovalent organic group; k2 in each occurrence is independently an integer from 0 to 3; l2 in each occurrence is independently an integer from 0 to 3; m2 in each occurrence is independently an integer from 0 to 3; Here, the sum of k2, l2, and m2 is (CR d1 k2 R e1 l2 R f1 m2 ) units, is 3, In formula (D4), at least one A is present, R g1 and R h1 may each independently in each occurrence be -Z 4 -YA, -Z 4 -SiR a1 k1 R b1 l1 R c1 m1 , or -Z 4 -CR d1 k2 R e1 l2 R f1 m2 and Z 4 is independently at each occurrence a single bond, an oxygen atom, or a divalent organic group; In formula (D5), at least one A is present. The curable composition according to any one of

[31] to

[32] , wherein the group is represented by the following formula:

[34] X B are each independently represented by the following formula: -{(R 31 ) p’ -(X a ) q’}-R 32 - [In formula: R 31 is a single bond, -(CH2)s'- or an o-, m- or p-phenylene group, R 32 is a single bond, -(CH)t'- or an o-, m- or p-phenylene group, s' is an integer from 1 to 20; t' is an integer from 1 to 20; X a is -(X b ) r’ - represents Xb, in each occurrence, independently represents -O-, -CO-, -S-, o-, m- or p-phenylene group, substituted or unsubstituted C 3-10 Cycloalkylene, substituted or unsubstituted o-, m- or p-phenylene group, -CONR 34 -, -NR 34 -, -Si(R 33 )2-, -(Si(R 33 )2O) m’ -Si(R 33 )2-, and -(CH2) n’ represents a group selected from the group consisting of -, R 33 represents, independently at each occurrence, a phenyl group; C 1-6 Alkyl group or C 1-6 is an alkoxy group, R 34 each occurrence independently represents a hydrogen atom, a phenyl group, or C 1-6 is an alkyl group, m', in each occurrence, is independently an integer from 1 to 100; n', at each occurrence, is independently an integer from 1 to 20; r' is an integer from 1 to 10; p' is 0 or 1; q' is 0 or 1; Here, at least one of p' and q' is 1, and the order of the repeating units enclosed in parentheses with p' or q' is arbitrary. The curable composition according to any one of

[31] to

[33] , wherein R is a divalent group represented by the following formula:

[35] The curable composition according to any one of

[24] to

[34] , wherein a content mass ratio of the fluoropolyether group-containing thiol compound to the fluoropolyether group-containing unsaturated compound is 0.1:100 to 100:0.1.

[36] The curable composition according to any one of

[23] to

[35] , further comprising a polymerization initiator.

[37] The curable composition according to

[36] , wherein the polymerization initiator is a radical polymerization initiator.

[38] The curable composition according to

[36] or

[37] , wherein the polymerization initiator is a radical photopolymerization initiator.

[39] The curable composition according to any one of

[36] to

[38] , wherein the polymerization initiator has 1 to 3 aromatic ring structures.

[40] The curable composition according to any one of

[23] to

[39] , further comprising a fluorinated oil.

[41] The fluorine-containing oil has the following formula (5): R f5 -(OC4F8) a’ -(OC3F6) b’ -(OC2F4) c’ -(OCF2) d’ -R f6 (5) [In formula: R f5 C may be substituted with one or more fluorine atoms. 1-16 is an alkyl group, R f6 C may be substituted with one or more fluorine atoms. 1-16 an alkyl group, a fluorine atom, or a hydrogen atom; a', b', c', and d' are each independently an integer of 0 to 300, The order of occurrence of each repeat unit enclosed in parentheses with the subscript a', b', c', or d' is arbitrary in the formula. The curable composition according to

[40] , wherein the compound is represented by the formula:

[42] The curable composition according to any one of

[23] to

[41] , which is solvent-free.

[43] The curable composition according to any one of

[23] to

[42] , which has a viscosity of 100 to 10,000 mPa·s.

[44] A cured product obtained by curing the curable composition according to any one of

[23] to

[43] .

[45] The cured product according to

[44] , which has a weight loss of less than 50% after being kept under conditions of 65°C and 90 RH% for 72 hours.

[46] The cured product according to

[44] or

[45] , having a tensile modulus of elasticity of 0.1 to 500 MPa.

[47] The cured product according to any one of

[44] to

[46] , which is a sealing material.

[48] The cured product according to any one of

[44] to

[47] , which is an encapsulant for electronic devices.

[49] An article comprising a substrate and a layer formed on the substrate, the layer being formed by curing the curable composition according to any one of

[23] to

[43] . Effect of the Invention

[0006] The fluoropolyether group-containing thiol compound of the present disclosure has excellent stability. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] As used herein, the term "monovalent organic group" refers to a monovalent group containing carbon. The monovalent organic group may be, but is not limited to, a hydrocarbon group or a derivative thereof. The derivative of a hydrocarbon group refers to a group having one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy, etc. at the end or in the molecular chain of the hydrocarbon group. In addition, when simply referring to an "organic group", it refers to a monovalent organic group. In addition, the term "divalent organic group" refers to a divalent group containing carbon. Examples of such divalent organic groups include, but are not limited to, divalent groups obtained by further removing one hydrogen atom from an organic group. Similarly, the term "divalent to decavalent organic group" refers to a divalent to decavalent group containing carbon, and examples of such divalent to decavalent organic groups include, but are not limited to, divalent to decavalent groups obtained by further removing one to nine hydrogen atoms from an organic group.

[0008] As used herein, the term "hydrocarbon group" refers to a group containing carbon and hydrogen, which is a hydrocarbon group from which one hydrogen atom has been removed. Such a hydrocarbon group includes, but is not limited to, C 1-20 Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The above-mentioned "aliphatic hydrocarbon group" may be linear, branched, or cyclic, and may be saturated or unsaturated. The hydrocarbon group may contain one or more ring structures.

[0009] As used herein, examples of the substituent of the "hydrocarbon group" include, but are not limited to, a halogen atom, a C 1-6 Alkyl group, C 2-6 Alkenyl group, C 2-6 Alkynyl group, C 3-10 Cycloalkyl groups, C 3-10 Unsaturated cycloalkyl groups, 5-10 membered heterocyclyl groups, 5-10 membered unsaturated heterocyclyl groups, C 6-10Examples of the alkyl group include one or more groups selected from an aryl group and a 5- to 10-membered heteroaryl group.

[0010] As used herein, the term "hydrolyzable group" refers to a group that can undergo hydrolysis, i.e., a group that can be removed from the main skeleton of a compound by hydrolysis. Examples of hydrolyzable groups include -OR j , -OCOR j , -ON=CR j 2, -NR j 2, -NHR j , -NCO, halogen (wherein R j is a substituted or unsubstituted C 1-4 (representing an alkyl group) and the like.

[0011] (Fluoropolyether group-containing thiol compound) The present disclosure provides a fluoropolyether group-containing thiol compound that does not contain an ester structure and contains two or more thiol groups selected from secondary or tertiary thiol groups.

[0012] The fluoropolyether group-containing thiol compound of the present disclosure has excellent storage stability because the thiol group is a secondary or tertiary thiol group.

[0013] The secondary thiol refers to a compound in which the carbon atom to which a thiol group (SH) is bonded has one hydrocarbon group as a substituent, for example, a group represented by -CHR-SH (wherein R is a hydrocarbon group).

[0014] The above-mentioned tertiary thiol refers to a compound in which the carbon atom to which the thiol group (SH) is bonded has two hydrocarbon groups as substituents, for example, a group represented by -CR2-SH (wherein each R is independently a hydrocarbon group).

[0015] The number of thiol groups contained in the fluoropolyether group-containing thiol compound of the present disclosure may be preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more. The number of thiol groups contained in the fluoropolyether group-containing thiol compound of the present disclosure may be preferably 8 or less, for example, 7 or less or 6 or less.

[0016] In one embodiment, the number of thiol groups contained in the fluoropolyether group-containing thiol compound of the present disclosure may be preferably 2 to 8, more preferably 4 to 6. In one embodiment, the number of thiol groups contained in the fluoropolyether group-containing thiol compound of the present disclosure is 4. In another embodiment, the number of thiol groups contained in the fluoropolyether group-containing thiol compound of the present disclosure is 6. The fluoropolyether group-containing thiol compound has a plurality of thiol groups, which increases the curability.

[0017] In a preferred embodiment, the thiol groups are present on both ends of the fluoropolyether group.

[0018] In a preferred embodiment, the number of thiol groups present on both ends of the fluoropolyether group in the fluoropolyether group-containing thiol compound of the present disclosure is the same. For example, one thiol group is present on each end of the fluoropolyether group, or two thiol groups are present on each end of the fluoropolyether group. By having multiple thiol groups on both ends of the fluoropolyether group, the fluoropolyether group-containing thiol compound has higher curability, for example, 3000 mJ / cm. 3 Below that, 2000mJ / cm 3 The ultraviolet ray can be cured even with the irradiation amount below the above.

[0019] In one embodiment, the thiol group is a secondary thiol group.

[0020] In another embodiment, the thiol group is a tertiary thiol group.

[0021] In a preferred embodiment, the fluoropolyether group-containing thiol compound of the present disclosure has a group selected from a linear or branched alkylene group, a cycloalkylene group, a phenylene group, an alkylamino group, an ether bond, a thioether bond, a carbonyl bond, and an amide bond.

[0022] In one embodiment, a group selected from the linear or branched alkylene group, cycloalkylene group, phenylene group, alkylamino group, ether bond, thioether bond, carbonyl bond, and amine bond may be disposed between the fluoropolyether group and the thiol group.

[0023] The fluorine content of the fluoropolyether group-containing thiol compound of the present disclosure is preferably 30% by mass or more, more preferably 35% by mass or more, and even more preferably 40% by mass or more. The fluorine content of the fluoropolyether group-containing thiol compound of the present disclosure is preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less.

[0024] The fluorine content can be measured by elemental analysis.

[0025] The fluoropolyether group-containing thiol compound of the present disclosure is preferably soluble in a fluorine-containing solvent having an SP value in the range of 5.0 to 13.0.

[0026] Examples of the fluorine-containing solvent include perfluorohexane (SP value 5.4), hydrofluoroethers: Novec 7100 (manufactured by 3M, SP value 6.0), Novec 7300 (manufactured by 3M, SP value 6.1), Novec 7200 (manufactured by 3M, SP value 6.3), 1,3-bis(trifluoromethyl)benzene (SP value 7.6), heptafluorocyclopentene (SP value 7.6), hydrochlorofluorocarbons: AK-225 (manufactured by AGC, SP value 8.1), trifluorotoluene (SP value 8.2), hexafluoroisopropanol (SP value 9.0), and perfluorobenzene (SP value 12.7).

[0027] The above SP value can be calculated by Fedors' estimation method.

[0028] The viscosity of the fluoropolyether group-containing thiol compound of the present disclosure is preferably 100 mPa·s or more, more preferably 300 mPa·s or more, and even more preferably 500 mPa·s or more. The viscosity of the fluoropolyether group-containing thiol compound of the present disclosure is preferably 10,000 mPa·s or less, more preferably 7,000 mPa·s or less, and even more preferably 5,000 mPa·s or less.

[0029] In one embodiment, the viscosity of the fluoropolyether group-containing thiol compound of the present disclosure is 100 to 10,000 mPa·s, preferably 300 to 7,000 mPa·s, and more preferably 500 to 5,000 mPa·s.

[0030] The viscosity can be measured using a TV-10 type viscometer manufactured by Toki Sangyo Co., Ltd. (rotor No. THM1, rotation speed 1.0 rpm, measurement temperature 25° C.).

[0031] In a preferred embodiment, the fluoropolyether group-containing thiol compound of the present disclosure has the following formula (1) or (2): [ka] [In formula: R F1 are each independently Rf 1 -R F -O q - and R F2 is -Rf 2 p -R F -O q - and Rf 1 each independently represents a C which may be substituted by one or more fluorine atoms; 1-16 is an alkyl group, Rf 2 C may be substituted with one or more fluorine atoms.1-6 is an alkylene group, R F are each independently a divalent fluoropolyether group, p is 0 or 1; Each q is independently 0 or 1; X A each independently represents a single bond or a divalent to decavalent organic group, R S are each independently -(CR 4 (SH)-R 5 ) n -CR 1 R 2 is a monovalent group containing a group represented by -SH, R 1 is a hydrocarbon group, R 2 is a hydrogen atom or a hydrocarbon group, R 4 is a hydrogen atom or a hydrocarbon group, R 5 is a divalent hydrocarbon group, In formulas (1) and (2), at least two secondary or tertiary thiol groups are present; α1 is an integer from 1 to 9, α2 is an integer from 1 to 9, Each β is independently an integer from 1 to 9, n is an integer from 0 to 9, Formulae (1) and (2) do not contain an ester structure.] The compound may be represented by the formula:

[0032] In the above formula (1), R F1 is Rf 1 -R F -O q -It is.

[0033] In the above formula (2), R F2 is -Rf 2 p -R F -O q -It is.

[0034] In the above formula, Rf 1 C may be substituted with one or more fluorine atoms. 1-16 It is an alkyl group.

[0035] C which may be substituted by one or more fluorine atoms 1-16 "C" in alkyl group 1-16 The "alkyl group" may be a straight chain or a branched chain, and is preferably a straight chain or branched chain C 1-6 Alkyl groups, especially C 1-3 is preferably a straight-chain C 1-6 Alkyl groups, especially C 1-3 It is an alkyl group.

[0036] Above Rf 1 is preferably C substituted by one or more fluorine atoms 1-16 is an alkyl group, more preferably CF2H-C 1-15 A perfluoroalkylene group, more preferably C 1-16 It is a perfluoroalkyl group.

[0037] Above C 1-16 The perfluoroalkyl group may be linear or branched, and is preferably a linear or branched C 1-6 Perfluoroalkyl groups, especially C 1-3 A perfluoroalkyl group, more preferably a linear C 1-6 Perfluoroalkyl groups, especially C 1-3 A perfluoroalkyl group, specifically, -CF3, -CF2CF3, or -CF2CF2CF3.

[0038] In the above formula, Rf 2 C may be substituted with one or more fluorine atoms. 1-6 It is an alkylene group.

[0039] C which may be substituted by one or more fluorine atoms 1-6 "C" in the alkylene group 1-6The "alkylene group" may be a straight chain or a branched chain, and is preferably a straight chain or branched chain C 1-3 It is preferably a linear alkylene group. 1-3 It is an alkylene group.

[0040] Above Rf 2 is preferably C substituted by one or more fluorine atoms 1-6 is an alkylene group, more preferably C 1-6 A perfluoroalkylene group, more preferably C 1-3 It is a perfluoroalkylene group.

[0041] Above C 1-6 The perfluoroalkylene group may be linear or branched, and is preferably a linear or branched C 1-3 A perfluoroalkylene group, more preferably a linear C 1-3 A perfluoroalkylene group, specifically, -CF2-, -CF2CF2-, or -CF2CF2CF2-.

[0042] In the above formula, p is 0 or 1. In one embodiment, p is 0. In another embodiment, p is 1.

[0043] In the above formula, each q is independently 0 or 1. In one embodiment, q is 0. In another embodiment, q is 1.

[0044] In the above formulas (1) and (2), R F is independently at each occurrence a divalent fluoropolyether group.

[0045] R F is preferably -(OC h1 R Fa 2h1 ) h3 -(OC h2 R Fa 2h2-2 ) h4 - [In formula: R Fa is independently at each occurrence a hydrogen atom, a fluorine atom, or a chlorine atom; h1 is an integer from 1 to 6, h2 is an integer from 4 to 8; h3 is an integer equal to or greater than 0, h4 is an integer equal to or greater than 0, However, the number of repeating units of h3 and h4 is 1 or more, preferably 2 or more, and more preferably 5 or more, and the order of the repeating units enclosed in parentheses with h3 and h4 is arbitrary in the formula. It may contain a group represented by:

[0046] In one embodiment, R F R can be linear or branched. F is preferably of the formula: -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3R Fa 6) d -(OC2F4) e -(OCF2) f - [In formula: R Fa is independently at each occurrence a hydrogen atom, a fluorine atom, or a chlorine atom; a, b, c, d, e, and f are each independently an integer of 0 to 200, and the sum of a, b, c, d, e, and f is 1 or more. The order of the repeating units enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula. However, all R Fa is a hydrogen atom or a chlorine atom, at least one of a, b, c, e and f is 1 or greater.] It is a group represented by the following formula:

[0047] R Fa is preferably a hydrogen atom or a fluorine atom, more preferably a fluorine atom. However, all R Fais a hydrogen atom or a chlorine atom, at least one of a, b, c, e and f is 1 or greater.

[0048] Preferably, a, b, c, d, e and f may each independently be an integer of 0 to 100.

[0049] The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, and may be, for example, 15 or more or 20 or more. The sum of a, b, c, d, e and f is preferably 200 or less, more preferably 100 or less, and even more preferably 60 or less, and may be, for example, 50 or less or 30 or less.

[0050] These repeating units may be linear or branched. For example, -(OCF 12 )- may be -(OCF2CF2CF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2CF2)-, -(OCF2CF2CF(CF3)CF2CF2)-, -(OCF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF2CF(CF3))-, etc. 10 )- may be -(OCF2CF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2CF2)-, -(OCF2CF(CF3)CF2CF2)-, -(OCF2CF2CF(CF3)CF2)-, -(OCF2CF2CF2CF(CF3))-, etc. -(OC4F8)- may be any of -(OCF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3))-, -(OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)-, and -(OCF2CF(C2F5))-. -(OC3F6)- (i.e., in the above formula, R Fais a fluorine atom) may be any of -(OCF2CF2CF2)-, -(OCF(CF3)CF2)-, and -(OCF2CF(CF3))-. -(OC2F4)- may be any of -(OCF2CF2)- and -(OCF(CF3))-.

[0051] In one embodiment, the repeating unit is linear. By making the repeating unit linear, the surface slip property, abrasion resistance, etc. of the surface treatment layer can be improved.

[0052] In one embodiment, the repeating unit is a branched chain. By making the repeating unit a branched chain, the dynamic friction coefficient of the surface treatment layer can be increased.

[0053] In one embodiment, R F may include a ring structure.

[0054] The ring structure may be a three-, four-, five-, or six-membered ring as described below. [ka] [In the formula, * indicates the bond position.]

[0055] The ring structure may be preferably a four-, five-, or six-membered ring, more preferably a four-, or six-membered ring.

[0056] The repeating unit having a ring structure may preferably be the following unit. [ka] [In the formula, * indicates the bond position.]

[0057] In one embodiment, R F represents, independently in each occurrence, a group represented by any one of the following formulas (f1) to (f6). -(OC3F6) d -(OC2F4) e - (f1) [In the formula, d is an integer of 1 to 200, and e is 0 or 1.]; -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f2) [In the formula, c and d each independently represent an integer of 0 or more and 30 or less, and e and f each independently represent an integer of 1 or more and 200 or less, The sum of c, d, e, and f is 2 or more, The order of occurrence of each repeat unit enclosed in parentheses with the subscript c, d, e, or f is arbitrary in the formula. -(R 6 -R 7 ) g - (f3) [In the formula, R 6 is OCF2 or OC2F4, R 7 are OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of two or three groups independently selected from these groups; g is an integer from 2 to 100; -(R 6 -R 7 ) g -R r -(R 7’ -R 6’ ) g’ - (f4) [In the formula, R 6 is OCF2 or OC2F4, R 7 are OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of two or three groups independently selected from these groups; R 6’ is OCF2 or OC2F4, R 7’ are OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F12 or a combination of two or three groups independently selected from these groups; g is an integer from 2 to 100; g' is an integer from 2 to 100, R r teeth, [ka] (In the formula, * indicates the bond position.) ]; -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f5) [In the formula, e is an integer of 1 or more and 200 or less, a, b, c, d, and f are each independently an integer of 0 or more and 200 or less, and the order of the repeating units enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula.] -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f6) [In the formula, f is an integer of 1 or more and 200 or less, a, b, c, d, and e are each independently an integer of 0 or more and 200 or less, and the order of the repeating units enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula.]

[0058] In the above formula (f1), d is preferably an integer of 5 to 200, more preferably 10 to 100, further preferably 15 to 50, for example, an integer of 25 to 35. In one embodiment, e is 1. In another embodiment, e is 0. In the above formula (f1), OC3F6 is preferably OCF2CF2CF2, OCF2CF(CF3), or OCF(CF3)CF2, more preferably OCF2CF2CF2. OC2F4 is OCF2CF2 or OCF(CF3), preferably OCF2CF2.

[0059] In the above formula (f2), e and f are each independently an integer of preferably 5 to 200, more preferably 10 to 200. The sum of c, d, e and f is preferably 5 or more, more preferably 10 or more, and may be, for example, 15 or more or 20 or more. In one embodiment, the above formula (f2) is preferably -(OCF2CF2CF2CF2) c -(OCF2CF2CF2) d -(OCF2CF2) e -(OCF2) f In another embodiment, formula (f2) is a group represented by -(OC2F4) e -(OCF2) f - may be a group represented by the formula:

[0060] In the above formula (f3), R 6 is preferably OC2F4. In the above (f3), R 7is preferably a group selected from OC2F4, OC3F6 and OC4F8, or a combination of two or three groups independently selected from these groups, and more preferably a group selected from OC3F6 and OC4F8. The combination of two or three groups independently selected from OC2F4, OC3F6 and OC4F8 is not particularly limited, and examples thereof include -OC2F4OC3F6-, -OC2F4OC4F8-, -OC3F6OC2F4-, -OC3F6OC3F6-, -OC3F6OC4F8-, -OC4F8OC4F8-, -OC4F8OC3F6-, -OC4F8OC2F4-, -OC Examples of the 2F4OC2F4OC3F6-, -OC2F4OC2F4OC4F8-, -OC2F4OC3F6OC2F4-, -OC2F4OC3F6OC3F6-, -OC2F4OC4F8OC2F4-, -OC3F6OC2F4OC2F4-, -OC3F6OC2F4OC3F6-, -OC3F6OC3F6OC2F4-, and -OC4F8OC2F4OC2F4- are mentioned. In the above formula (f3), g is preferably an integer of 3 or more, more preferably an integer of 5 or more. The above g is preferably an integer of 50 or less. In the above formula (f3), OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 may be either linear or branched, and is preferably linear. In this embodiment, the above formula (f3) is preferably -(OC2F4-OC3F6) g -or- (OC2F4-OC4F8) g -It is.

[0061] In the above formula (f4), R 6 , R 7 and g have the same meanings as those described in the above formula (f3) and have the same embodiments. 6’ , R 7’ and g' are R 6 , R 7 and g have the same meaning and behavior. r is preferably [ka] [In the formula, * indicates the bond position.] and more preferably [ka] [In the formula, * indicates the bond position.] It is.

[0062] In the above formula (f5), e is preferably an integer of 1 or more and 100 or less, more preferably an integer of 5 or more and 100 or less. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example, 10 or more and 100 or less.

[0063] In the above formula (f6), f is preferably an integer of 1 or more and 100 or less, more preferably an integer of 5 or more and 100 or less. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example, 10 or more and 100 or less.

[0064] In one embodiment, the R F is a group represented by the above formula (f1).

[0065] In one embodiment, the R F is a group represented by the above formula (f2).

[0066] In one embodiment, the R F is a group represented by the above formula (f3).

[0067] In one embodiment, the R F is a group represented by the above formula (f4).

[0068] In one embodiment, the R F is a group represented by the above formula (f5).

[0069] In one embodiment, the R F is a group represented by the above formula (f6).

[0070] Above R FIn the formula, the ratio of e to f (hereinafter referred to as "e / f ratio") is 0.1 to 10, preferably 0.2 to 5, more preferably 0.2 to 2, even more preferably 0.2 to 1.5, and even more preferably 0.2 to 0.85. By making the e / f ratio 10 or less, the slipperiness, abrasion resistance, and chemical resistance (e.g., resistance to artificial sweat) of the surface treatment layer obtained from this compound are further improved. The smaller the e / f ratio, the more improved the slipperiness and abrasion resistance of the surface treatment layer. On the other hand, by making the e / f ratio 0.1 or more, the stability of the compound can be further improved. The larger the e / f ratio, the more improved the stability of the compound.

[0071] In one embodiment, the e / f ratio is preferably 0.2 to 0.95, and more preferably 0.2 to 0.9.

[0072] In one embodiment, from the viewpoint of heat resistance, the e / f ratio is preferably 1.0 or more, and more preferably 1.0 to 2.0.

[0073] In the above fluoropolyether group-containing thiol compound, R F1 and R F2 The number average molecular weight of the portion is not particularly limited, but is, for example, 500 to 30,000, preferably 1,500 to 30,000, and more preferably 2,000 to 10,000. F1 and R F2 The number average molecular weight of 19 The value is measured by F-NMR.

[0074] R S are each independently -(CR 4 (SH)-R 5 ) n -CR 1 R 2 It is a monovalent group containing a group represented by -SH.

[0075] In a preferred embodiment, R s is -(CR 4 (SH)-R 5) n -CR 1 R 2 The group represented by -SH may be a group having a linking group selected from a linear or branched alkylene group, a cycloalkylene group, a phenylene group, an alkylamino group, an ether bond, a thioether bond, a carbonyl bond, and an amide bond bond bonded thereto.

[0076] In a preferred embodiment, R S is represented by the following formula (S1), (S2), or (S3): [ka] [In formula: R Sa -Z-(CR 3 (SH)-R 4 ) n -CR 1 R 2 -SH, Z is a single bond or a divalent group; R 1 is a hydrocarbon group, R 2 is a hydrogen atom or a hydrocarbon group, R 3 is a hydrogen atom or a hydrocarbon group, n is an integer from 0 to 9, n1 is 1 or 2; n2 is 1, 2 or 3. It may be a group represented by the formula:

[0077] R Sa -Z-(CR 3 (SH)-R 4 ) n -CR 1 R 2 -SH.

[0078] Z is a single bond or a divalent group. In one embodiment, Z is a single bond. In another embodiment, Z is a divalent organic group.

[0079] Z is preferably -R 11 -R12 -, where R 11 is a single bond or C 1-6 is an alkylene group, R 12 is a single bond or -O-(CH2) m - (m is an integer from 0 to 6). Here, -O-(CH2) m - is the right side of -(CR 3 (SH)-R 4 ) n CR 1 R 2 In a preferred embodiment, Z is -R 11 -It is.

[0080] R 11 C in 1-6 The alkylene group may be linear or branched. 1-6 The alkylene group is linear. 1-6 The alkylene group is branched.

[0081] R 11 C in 1-6 The alkylene group is preferably 1-4 It may be an alkylene group.

[0082] m is preferably an integer of 0 to 4, and more preferably 0 to 3.

[0083] In one embodiment, m is 0.

[0084] In another embodiment, m is an integer of 1 to 6, preferably an integer of 1 to 4, and more preferably an integer of 1 to 3.

[0085] R 1 is a hydrocarbon group.

[0086] R 2 is a hydrogen atom or a hydrocarbon group.

[0087] In one embodiment, R 2 is a hydrogen atom.

[0088] In another embodiment, R 2 is a hydrocarbon group.

[0089] R 1 and R 2 The hydrocarbon group in is preferably C 1-6 Alkyl groups, more preferably C 1-3 It is preferably an alkyl group, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.

[0090] R 1 and R 2 C in 1-6 The alkyl group may be linear or branched. 1-6 The alkyl group is linear. 1-6 The alkyl group is branched.

[0091] In a preferred embodiment, R 1 is C 1-6 is an alkyl group, R 2 is a hydrogen atom or C 1-6 In one embodiment, R 1 is C 1-6 is an alkyl group, R 2 is a hydrogen atom. 1 is C 1-6 is an alkyl group, R 2 is C 1-6 It is an alkyl group.

[0092] R 3 is a hydrogen atom or a hydrocarbon group.

[0093] In one embodiment, R 3 is a hydrogen atom.

[0094] In another embodiment, R 3 is a hydrocarbon group.

[0095] R 3The hydrocarbon group in is preferably C 1-6 Alkyl groups, more preferably C 1-3 It is preferably an alkyl group, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.

[0096] R 3 C in 1-6 The alkyl group may be linear or branched. 1-6 The alkyl group is linear. 1-6 The alkyl group is branched.

[0097] R 4 is a hydrogen atom or a hydrocarbon group.

[0098] In one embodiment, R 4 is a hydrogen atom.

[0099] In another embodiment, R 4 is a hydrocarbon group.

[0100] R 4 The hydrocarbon group in is preferably C 1-6 Alkyl groups, more preferably C 1-3 It is preferably an alkyl group, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.

[0101] R 4 C in 1-6 The alkyl group may be linear or branched. 1-6 The alkyl group is linear. 1-6 The alkyl group is branched.

[0102] R 5 is a divalent hydrocarbon group.

[0103] R 5 The hydrocarbon group in is preferably C 1-10 Alkylene group, more preferably C 2-8Alkylene group, more preferably C 3-6 It is an alkylene group, and even more preferably -CH(CH3)CH2CH2-.

[0104] R 5 C in 1-10 The alkylene group may be linear or branched. 1-10 The alkylene group is branched. 1-10 The alkylene group is straight-chained.

[0105] n may be an integer of 0 to 9, and preferably an integer of 1 to 3.

[0106] n1 is 1 or 2. In one embodiment, n1 is 1. In another embodiment, n1 is 2.

[0107] n2 is 1, 2 or 3. In one embodiment, n2 is 1. In another embodiment, n2 is 2. In another embodiment, n2 is 3.

[0108] In a preferred embodiment, R S is a group represented by formula (S1).

[0109] In one embodiment, R S is a group represented by formula (S2).

[0110] In one embodiment, R S is a group represented by formula (S3).

[0111] In the above formulas (1) and (2), X A The fluoropolyether moiety (R) provides water repellency and other functions. F1 and R F2 ) and a portion (R S ) is interpreted as a linker connecting the X A may be a single bond or any other group, so long as the compounds represented by formulae (1) and (2) can exist stably.

[0112] In the above formula (1), α1 is an integer from 1 to 9, and α2 is an integer from 1 to 9. These α1 and α2 are X A The sum of α1 and α2 can vary depending on the valence of X A For example, X A When X is a decavalent organic group, the sum of α1 and α2 is 10, and for example, α1 may be 9 and α2 may be 1, α1 may be 5 and α2 may be 5, or α1 may be 1 and α2 may be 9. A When is a divalent organic group, α1 and α2 are 1.

[0113] In the above formula (2), each β is independently an integer of 1 to 9. A That is, β can vary depending on the valence of X A is the valence of 1 minus 0.

[0114] X A each independently represents a single bond or a divalent to decavalent organic group.

[0115] Above X A The divalent to decavalent organic group in is preferably a divalent to octavalent organic group. In one embodiment, the divalent to decavalent organic group is preferably a divalent to tetravalent organic group, more preferably a divalent organic group. In another embodiment, the divalent to decavalent organic group is preferably a trivalent to octavalent organic group, more preferably a trivalent to hexavalent organic group.

[0116] In one embodiment, X A is a single bond or a divalent organic group, α is 1, and α2 is 1.

[0117] In one embodiment, X A is a single bond or a divalent organic group, and β is 1.

[0118] In one embodiment, X A is a trivalent to hexavalent organic group, α1 is 1, and α2 is 2 to 5.

[0119] In one embodiment, X A is a trivalent to hexavalent organic group, and β is 2 to 5.

[0120] In one embodiment, X A is a trivalent organic group, α1 is 1 and α2 is 2.

[0121] In one embodiment, X A is a trivalent organic group and β is 2.

[0122] In one embodiment, X A is a single bond or a divalent organic group, and α1, α2, and β are 1.

[0123] In a preferred embodiment, X A is the expression: -(R 21 ) m1 -(R 22 ) m2 - [In formula: R 21 is C 1-6 is an alkylene group, R 22 -O-, -CO-, -NR 23 -,-CONR 23 - or -NR 23 CO-, R 23 is a hydrogen atom or C 1-6 is an alkyl group, m1 is an integer from 0 to 10, m2 is an integer from 0 to 10, The sum of m1 and m2 is 1 or greater, R 21 and R 22 are present in any order in the formula, -(R 21 ) m1 -(R 22 ) m2 - does not contain an ester structure. Here, X is a group represented by the formula: A (Typically X AHydrogen atoms of C 1-3 Alkyl group and C 1-3 In a preferred embodiment, X A is not substituted with these groups.

[0124] In one embodiment, X A are each independently -(R 21 ) m1-1 -(R 22 ) m2 -R 24 -It is. 21 , R 22 , m1 and m2 are as defined above. 21 and R 22 The order of occurrence is arbitrary in the formula. 24 is a single bond, -(CH2) t5 - or an o-, m- or p-phenylene group, preferably -(CH2) t5 t5 is an integer of 1 to 20, preferably an integer of 2 to 6, and more preferably an integer of 2 to 3. 24 (Typically R 24 Hydrogen atoms of C 1-3 Alkyl group and C 1-3 In a preferred embodiment, R 24 is not substituted with these groups.

[0125] R 21 C in 1-6 The alkylene group may be linear or branched. 1-6 The alkylene group is linear. 1-6 The alkylene group is branched.

[0126] R 21 C in 1-6 The alkylene group is preferably 1-4 Alkylene group, more preferably C 1-2 It is an alkylene group.

[0127] R 22 -O-, -CO-, -NR 23 -,-CONR 23 - or -NR 23 It is -CO-, and preferably -O- or -CO-.

[0128] R 23 is a hydrogen atom or C 1-6 It is an alkyl group.

[0129] In one embodiment, R 23 is a hydrogen atom.

[0130] In another embodiment, R 23 is C 1-6 It is an alkyl group.

[0131] R 23 C in 1-6 The alkyl group may be linear or branched. 1-6 The alkyl group is linear. 1-6 The alkyl group is branched.

[0132] R 23 C in 1-6 The alkyl group is preferably C 1-4 Alkyl groups, more preferably C 1-2 It is preferably an alkyl group, and even more preferably a methyl group.

[0133] m1 is an integer of 0 to 10, preferably an integer of 0 to 4, and more preferably an integer of 0 to 2.

[0134] m2 is an integer of 0 to 10, preferably an integer of 0 to 2, and more preferably 0 or 1.

[0135] In one embodiment, m1 is an integer of 0 to 2, and m2 is 0 or 1.

[0136] In one embodiment, (m1,m2) is (0,1), (1,1), (2,1), or (1,0).

[0137] In a preferred embodiment, X A each independently represents a single bond, -R 21 -R 22 -R 24 -, -R 21 -R 22 -, -R 22 -R 24 -or -R 22 - (In the formula: R 21 is C 1-6 is an alkylene group, R 22 is -O- or -CO-, R 24 is C 1-6 It is an alkylene group. It is.

[0138] The number average molecular weight of the fluoropolyether group-containing thiol compound of the present disclosure may be preferably 1,000 or more, more preferably 1,500 or more, for example 2,000 or more, 4,000 or more, or 5,000 or more. The number average molecular weight of the fluoropolyether group-containing thiol compound of the present disclosure may be preferably 100,000 or less, more preferably 50,000 or less, even more preferably 30,000 or less, even more preferably 10,000 or less, for example 8,000 or less, 6,000 or less, or 5,000 or less. In this specification, the number average molecular weight of the fluoropolyether group-containing thiol compound is 19 The value is measured by F-NMR.

[0139] In one embodiment, the number average molecular weight of the fluoropolyether group-containing thiol compound of the present disclosure is 1,000 to 100,000, preferably 2,000 to 30,000, and more preferably 2,000 to 10,000.

[0140] The fluoropolyether group-containing thiol compound of the present disclosure can be produced, for example, by the following method.

[0141] The following formula (a): R S1 -X 1 -PFPE-X 1 -R S1 (a) [In formula: PFPE is a fluoropolyether group; R S1 are each independently -(CR 16 =CR 16 -R 17 ) n10 -CR 16 =CR 16 A group represented by 2, R 16 are each independently a hydrogen atom or a hydrocarbon group, preferably a hydrogen atom or C 1-10 Alkyl groups, more preferably C 2-6 is an alkyl group, R 17 are each independently a divalent hydrocarbon group, preferably C 1-10 Alkylene group, more preferably C 2-6 is an alkylene group, X 1 are each independently a single bond or a divalent organic group. and a compound represented by formula (b): R 51 -COSH (b) [In the formula, R 51 are each independently a hydrogen atom or C 1-3 An alkyl group, preferably a methyl group. and reacting a compound represented by formula (c): R S2 -X A -PFPE-X A -R S2 (c) [In formula: R S2 are each independently -(CR 4 (SCOR 51 )-R5 ) n -CR 1 R 2 -SCOR 51 is a group represented by PFPE, R 1 , R 2 , R 4 , R 5 , R 51 , X A and n are as defined above.] A compound represented by the formula:

[0142] Next, the compound represented by formula (c) is reacted with a reducing agent to obtain a compound represented by formula (d): R Sa -X A -PFPE-X A -R Sa (d) [In formula: R Sa , X A , PFPE is as defined above.] The fluoropolyether group-containing thiol compound of the present disclosure represented by the formula:

[0143] In a preferred embodiment, the reducing agent includes sodium methoxide.

[0144] (Curable composition) The present disclosure provides a curable composition comprising the fluoropolyether group-containing thiol compound of the present disclosure.

[0145] The curable composition of the present disclosure may further comprise a fluoropolyether group-containing unsaturated compound that contains a group having a carbon-carbon double bond.

[0146] (Fluoropolyether group-containing unsaturated compound) The carbon-carbon double bond-containing group is not particularly limited as long as it is a group containing a carbon-carbon double bond. Typically, the carbon-carbon double bond-containing group has a carbon-carbon double bond at a terminal.

[0147] The group having a carbon-carbon double bond is preferably an allyl group, a vinyl group, or a (meth)acrylic group, more preferably an allyl group.

[0148] In one embodiment, the number of groups having a carbon-carbon double bond in the fluoropolyether group-containing unsaturated compound may be preferably 2 to 8, more preferably 2 to 6, and further preferably 2 to 4.

[0149] In a preferred embodiment, the group having a carbon-carbon double bond is present on both ends of the fluoropolyether group-containing unsaturated compound.

[0150] In a preferred embodiment, in the fluoropolyether group-containing unsaturated compound of the present disclosure, the number of the groups having the above-mentioned carbon-carbon double bond present at both ends of the fluoropolyether group is the same.For example, at each end of the fluoropolyether group, there is one group having a carbon-carbon double bond, or at each end of the fluoropolyether group, there are two groups having a carbon-carbon double bond.

[0151] In a preferred embodiment, the fluoropolyether group-containing unsaturated compound is represented by the following formula (3) or (4): [ka] [In formula: R F1 are each independently Rf 1 -R F -O q - and R F2 is -Rf 2 p -R F -O q - and Rf 1 each independently represents a C which may be substituted by one or more fluorine atoms; 1-16 is an alkyl group, Rf 2 C may be substituted with one or more fluorine atoms. 1-6is an alkylene group, R F are each independently a divalent fluoropolyether group, p is 0 or 1; Each q is independently 0 or 1; X B each independently represents a single bond or a divalent to decavalent organic group, R D are each independently a group containing a carbon-carbon double bond, γ1 is an integer from 1 to 9, γ2 is an integer from 1 to 9, Each δ is independently an integer from 1 to 9. It is a compound represented by the formula:

[0152] In the above formula, R F1 and R F2 R in the fluoropolyether group-containing thiol compound represented by the above formula (1) or (2) F1 and R F2 This has the same meaning as:

[0153] In the above formula, X B Each of X independently represents a single bond or a divalent to decavalent organic group. B is R D and R F1 or R F2 Therefore, the X is understood to be a linker that connects B may be any organic group as long as the compounds represented by formulas (3) and (4) can exist stably.

[0154] In the above formula, γ1 is an integer of 1 to 9, γ2 is an integer of 1 to 9, and δ is an integer of 1 to 9. These γ1, γ2, and δ are X B In formula (3), the sum of γ1 and γ2 is determined according to the valence of X B For example, X BWhen X is a decavalent organic group, the sum of γ1 and γ2 is 10, and for example, γ1 can be 9 and γ2 can be 1, γ1 can be 5 and γ2 can be 5, or γ1 can be 1 and γ2 can be 9. B When is a divalent organic group, γ1 and γ2 are 1. In formula (4), δ is X B The value is 1 less than the valence value of .

[0155] Above X B is preferably a divalent to heptavalent, more preferably a divalent to tetravalent, and further preferably a divalent organic group. B Depending on the configuration, it may be an integer between 1 and 6, an integer between 1 and 3, or 1, etc.

[0156] Above X B Examples of the formula include, but are not limited to, the following formula: -(R 31 ) p’ -(X a ) q’ -R 32 - [In formula: R 31 is a single bond, -(CH2) s’ - or an o-, m- or p-phenylene group, preferably -(CH2) s’ - and R 32 is a single bond, -(CH2) t’ - or an o-, m- or p-phenylene group, preferably -(CH2) t’ - and s' is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and even more preferably 1 or 2; t' is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3; X a is -(X b ) r’ - represents X b each occurrence independently represents -O-, -CO-, -S-, an o-, m- or p-phenylene group, a substituted or unsubstituted C 3-10Cycloalkylene, substituted or unsubstituted o-, m- or p-phenylene group, -CONR 34 -, -NR 34 -, -Si(R 33 )2-, -(Si(R 33 )2O) m’ -Si(R 33 )2-, and -(CH2) n’ represents a group selected from the group consisting of -, The above-mentioned substituents are the same as those of the above-mentioned hydrocarbon group. R 33 represents, independently at each occurrence, a phenyl group; C 1-6 Alkyl group or C 1-6 represents an alkoxy group, preferably C 1-6 an alkyl group, more preferably a methyl group; R 34 is independently at each occurrence a hydrogen atom, a phenyl group or C 1-6 represents an alkyl group (preferably a methyl group); m', in each occurrence, is independently an integer from 1 to 100, preferably an integer from 1 to 20; n', in each occurrence, is independently an integer from 1 to 20, preferably an integer from 1 to 6, more preferably an integer from 1 to 3; r' is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3; p' is 0 or 1; q' is 0 or 1, Here, at least one of p' and q' is 1, and the repeating units enclosed in parentheses with p' or q' may be present in any order. Examples of the divalent group include a divalent group represented by X B It is preferable that the copolymer does not contain an ester bond and / or a urethane bond.

[0157] R D is independently at each occurrence a group that contains a carbon-carbon double bond.

[0158] Above R DThe group containing a carbon-carbon double bond in the formula is -YA (wherein Y represents a single bond, an oxygen atom, or a divalent organic group, and A represents -CR 41 =CH2, R 41 are each independently a hydrogen atom or C 1-3 It is an alkyl group (preferably a methyl group).

[0159] The above Y represents a single bond, an oxygen atom, or a divalent organic group. Y is preferably a single bond, an oxygen atom, -CR 42 2- or -CO-, more preferably -CR 42 2-.

[0160] Above R 42 In each occurrence, each independently represents a hydrogen atom or a lower alkyl group. The lower alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group. In a preferred embodiment, R 42 is a hydrogen atom.

[0161] In a preferred embodiment, R D is represented by the following formula (D1), (D2), (D3), (D4) or (D5): [ka] [In the formula, Y is a single bond, an oxygen atom, or a divalent organic group; A is -CR 41 =CH2, R 41 are each independently a hydrogen atom or C 1-3 is an alkyl group, X 10 is independently at each occurrence a single bond or a divalent organic group; R 13 is independently at each occurrence a hydrogen atom or a monovalent organic group; t is independently in each occurrence an integer greater than or equal to 2; R 14 is independently at each occurrence a hydrogen atom or a halogen atom; R a1 may each independently in each occurrence be -Z 1 -SiR a2 p1 R a3 q1 R a4 r1 and Z 1 is independently at each occurrence a single bond, an oxygen atom, or a divalent organic group; R a2 each occurrence independently, -Z 1’ -SiR a3’ q1’ R a4’ r1’ and Z 1’ is independently at each occurrence a single bond, an oxygen atom, or a divalent organic group; R a3’ may each independently in each occurrence be -Z 2 -YA, R a4’ is independently in each occurrence a hydrogen atom, a hydroxyl group, or a monovalent organic group; Z 2 is independently in each occurrence a single bond, an oxygen atom, or a divalent organic group; q1' in each occurrence is independently an integer from 0 to 3; r1' in each occurrence is independently an integer from 0 to 3; Here, the sum of q1' and r1' is (SiR a3’ q1’ R a4’ r1’ ) units, is 3, R a3 may each independently in each occurrence be -Z 2 -YA, R a4 is independently in each occurrence a hydrogen atom, a hydroxyl group, or a monovalent organic group; p1, at each occurrence, is independently an integer from 0 to 3; q1 in each occurrence is independently an integer from 0 to 3; r1, in each occurrence, is independently an integer from 0 to 3; Here, the sum of p1, q1 and r1 is (SiR a2 p1 R a3 q1 R a4 r1 ) units, is 3, R b1 may each independently in each occurrence be -Z 2 -YA, R c1 is independently in each occurrence a hydrogen atom, a hydroxyl group, or a monovalent organic group; k1, in each occurrence, is independently an integer from 0 to 3; l1 in each occurrence is independently an integer from 0 to 3; m1 in each occurrence is independently an integer from 0 to 3; Here, the sum of k1, l1, and m1 is (SiR a1 k1 R b1 l1 R c1 m1 ) units, is 3, In formula (D3), at least one -YA is present, R d1 may each independently in each occurrence be -Z 3 -CR d2 p2 R d3 q2 R d4 r2 and Z 3 is independently in each occurrence a single bond, an oxygen atom, or a divalent organic group; R d2 may each independently in each occurrence be -Z 3’ -CR d3’ q2’ R d4’ r2’ and Z 3’is independently at each occurrence an oxygen atom or a divalent organic group; R d3’ may each independently in each occurrence be -Z 2 -YA, R d4’ is independently in each occurrence a hydrogen atom, a hydroxyl group, or a monovalent organic group; q2' is independently in each occurrence an integer from 0 to 3; r2' is independently at each occurrence an integer from 0 to 3; Here, the sum of q2' and r2' is (CR d3’ q2’ R d4’ r2’ ) units, is 3, R d3 may each independently in each occurrence be -Z 2 -YA; R d4 is independently in each occurrence a hydrogen atom, a hydroxyl group, or a monovalent organic group; p2, in each occurrence, is independently an integer from 0 to 3; q2, in each occurrence, is independently an integer from 0 to 3; r2, independently at each occurrence, is an integer from 0 to 3; Here, the sum of p2, q2 and r2 is (CR d2 p2 R d3 q2 R d4 r2 ) units, is 3, R e1 may each independently in each occurrence be -Z 2 -YA, R f1 is independently in each occurrence a hydrogen atom, a hydroxyl group, or a monovalent organic group; k2 in each occurrence is independently an integer from 0 to 3; l2 in each occurrence is independently an integer from 0 to 3; m2 in each occurrence is independently an integer from 0 to 3; Here, the sum of k2, l2, and m2 is (CR d1 k2 R e1 l2 R f1 m2 ) units, is 3, In formula (D4), at least one A is present, R g1 and R h1 may each independently in each occurrence be -Z 4 -YA, -Z 4 -SiR a1 k1 R b1 l1 R c1 m1 , or -Z 4 -CR d1 k2 R e1 l2 R f1 m2 and Z 4 is independently at each occurrence a single bond, an oxygen atom, or a divalent organic group; In formula (D5), at least one A is present. It is a group represented by the following formula:

[0162] In the above formula, X 10 is independently at each occurrence a single bond or a divalent organic group. Such a divalent organic group is preferably -R 28 -O x -R 29 -(In the formula, R 28 and R 29 each occurrence independently represents a single bond or C 1-20 is an alkylene group, and x is 0 or 1. 1-20 The alkylene group may be linear or branched, but is preferably linear. 1-20 The alkylene group is preferably 1-10 Alkylene group, more preferably C 1-6 Alkylene group, more preferably C1-3 It is an alkylene group.

[0163] In one embodiment, X 10 may each independently represent, in each occurrence, -C 1-6 Alkylene-OC 1-6 Alkylene- or -OC 1-6 It is alkylene.

[0164] In a preferred embodiment, X 10 each occurrence independently represents a single bond or a straight-chain C 1-6 An alkylene group, preferably a single bond or a straight chain C 1-3 An alkylene group, more preferably a single bond or a straight chain C 1-2 It is preferably a linear alkylene group. 1-2 It is an alkylene group.

[0165] In the above formula, R 13 is independently at each occurrence a hydrogen atom or a monovalent organic group. Such a monovalent organic group is preferably 1-20 It is an alkyl group. 1-20 The alkyl group may be straight or branched chain, but is preferably straight chain.

[0166] In a preferred embodiment, R 13 each occurrence independently represents a hydrogen atom or a straight-chain C 1-6 is an alkyl group, preferably a hydrogen atom or a straight-chain C 1-3 It is an alkyl group, preferably a hydrogen atom or a methyl group.

[0167] In the above formula, t in each occurrence is independently an integer of 2 or greater.

[0168] In a preferred embodiment, t is independently in each occurrence an integer from 2 to 10, preferably an integer from 2 to 6.

[0169] In the above formula, R 14is independently at each occurrence a hydrogen atom or a halogen atom. Such a halogen atom is preferably an iodine atom, a chlorine atom or a fluorine atom, more preferably a fluorine atom. In a preferred embodiment, R 14 is a hydrogen atom.

[0170] In the above formula, R a1 may each independently in each occurrence be -Z 1 -SiR a2 p1 R a3 q1 R a4 r1 It is.

[0171] Above Z 1 is independently a single bond, an oxygen atom, or a divalent organic group in each occurrence. 1 The structure written as is shown on the right side (SiR a2 p1 R a3 q1 R a4 r1 )

[0172] In a preferred embodiment, Z 1 is a divalent organic group.

[0173] Above Z 1 is preferably C 1-6 Alkylene group, -(CH2) z1 -O-(CH2) z2 -(wherein z1 is an integer of 0 to 6, for example, an integer of 1 to 6, and z2 is an integer of 0 to 6, for example, an integer of 1 to 6), -(CH2) z3 -Phenylene-(CH2) z4 -(wherein z3 is an integer of 0 to 6, for example, an integer of 1 to 6, and z4 is an integer of 0 to 6, for example, an integer of 1 to 6) or -(CH2) z5 -C 3-10 Cycloalkylene-(CH2) z6 - (wherein z5 is an integer of 0 to 6, for example, an integer of 1 to 6, and z6 is an integer of 0 to 6, for example, an integer of 1 to 6).1-6 The alkylene groups may be linear or branched, but are preferably linear. These groups may contain, for example, fluorine atoms, C 1-6 Alkyl group, C 2-6 Alkenyl groups, and C 2-6 It may be substituted by one or more substituents selected from alkynyl groups, but is preferably unsubstituted.

[0174] In a preferred embodiment, Z 1 is C 1-6 Alkylene group or -(CH2) z3 -Phenylene-(CH2) z4 -, preferably -phenylene-(CH2) z4 -It is.

[0175] In another preferred embodiment, the Z 1 is C 1-3 In one embodiment, Z is an alkylene group. 1 can be -CH2CH2CH2-. In another embodiment, Z 1 can be -CH2CH2-.

[0176] R a2 each occurrence independently, -Z 1’ -SiR a3’ q1’ R a4’ r1’ It is.

[0177] Above Z 1’ In each occurrence, each independently represents a single bond, an oxygen atom, or a divalent organic group. 1’ The structure written as is shown on the right side (SiR a3’ q1’ R a4’ r1’ )

[0178] In a preferred embodiment, Z 1’ is a divalent organic group.

[0179] Above Z1’ is preferably C 1-6 Alkylene group, -(CH2) z1’ -O-(CH2) z2’ - (wherein z1' is an integer of 0 to 6, for example, an integer of 1 to 6, and z2' is an integer of 0 to 6, for example, an integer of 1 to 6), or -(CH2) z3’ -Phenylene-(CH2) z4’ - (wherein z3' is an integer of 0 to 6, for example, an integer of 1 to 6, and z4' is an integer of 0 to 6, for example, an integer of 1 to 6). 1-6 The alkylene groups may be linear or branched, but are preferably linear. These groups may contain, for example, fluorine atoms, C 1-6 Alkyl group, C 2-6 Alkenyl groups, and C 2-6 It may be substituted by one or more substituents selected from alkynyl groups, but is preferably unsubstituted.

[0180] In a preferred embodiment, Z 1’ is C 1-6 Alkylene group or -(CH2) z3’ -Phenylene-(CH2) z4’ -, preferably -phenylene-(CH2) z4’ -It is. 1’ is such a group, light resistance, particularly ultraviolet light resistance, can be improved.

[0181] In another preferred embodiment, the Z 1’ is C 1-3 In one embodiment, Z is an alkylene group. 1’ can be -CH2CH2CH2-. In another embodiment, Z 1’ can be -CH2CH2-.

[0182] R a3’ may each independently in each occurrence be -Z 2 -YA.

[0183] Z 2is independently a single bond, an oxygen atom, or a divalent organic group in each occurrence. 2 The structure depicted as follows: The right side binds to (YA).

[0184] In a preferred embodiment, Z 2 is a single bond.

[0185] In a preferred embodiment, Z 2 is a divalent organic group.

[0186] Z 2 is preferably C 1-6 Alkylene group, -(CH2) z11 -O-(CH2) z12 -(wherein z11 is an integer of 0 to 6, for example, an integer of 1 to 6, and z12 is an integer of 0 to 6, for example, an integer of 1 to 6), -(CH2) z13 -Phenylene-(CH2) z14 - (wherein z13 is an integer of 0 to 6, for example, an integer of 1 to 6, and z14 is an integer of 0 to 6, for example, an integer of 1 to 6) or -(CH2) z15 -C 3-10 Cycloalkylene-(CH2) z16 - (wherein z15 is an integer of 0 to 6, for example, an integer of 1 to 6, and z16 is an integer of 0 to 6, for example, an integer of 1 to 6). 1-6 The alkylene groups may be linear or branched, but are preferably linear. These groups may contain, for example, fluorine atoms, C 1-6 Alkyl group, C 2-6 Alkenyl groups, and C 2-6 It may be substituted by one or more substituents selected from alkynyl groups, but is preferably unsubstituted.

[0187] In a preferred embodiment, Z 2 is C 1-6 Alkylene group or -(CH2) z13 -Phenylene-(CH2) z14 -, preferably -phenylene-(CH2) z14 -It is.

[0188] In another preferred embodiment, Z 2 is C 1-3 In one embodiment, Z is an alkylene group. 2 can be -CH2CH2CH2-. In another embodiment, Z 2 can be -CH2CH2-.

[0189] R a4’ is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group in each occurrence. Such monovalent organic groups are monovalent organic groups other than the above-mentioned hydrolyzable groups. Such monovalent organic groups are the same as the above-mentioned -Z 2 - is a monovalent organic group other than YA.

[0190] R a4’ In the above, the monovalent organic group is preferably C 1-20 is an alkyl group, more preferably C 1-6 It is preferably an alkyl group, more preferably a methyl group.

[0191] Each q1' in each occurrence is independently an integer from 0 to 3, and each r1' in each occurrence is independently an integer from 0 to 3. Here, the sum of q1' and r1' is (SiR a3’ q1’ R a4’ r1’ ) units, it is 3.

[0192] In a preferred embodiment, q1' in each occurrence is independently an integer of 1 to 3, preferably 2 or 3, and more preferably 3. In this case, r1' in each occurrence is independently an integer of 0 to 2, preferably 0 or 1, and more preferably 0.

[0193] R a3 may each independently in each occurrence be -Z 2 -YA.

[0194] R a4is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group in each occurrence. Such monovalent organic groups are monovalent organic groups other than the above-mentioned hydrolyzable groups. Such monovalent organic groups are the same as the above-mentioned -Z 2 - is a monovalent organic group other than YA.

[0195] R a4 In the above, the monovalent organic group is preferably C 1-20 is an alkyl group, more preferably C 1-6 It is preferably an alkyl group, more preferably a methyl group.

[0196] p1 is independently at each occurrence an integer from 0 to 3, q1 is independently at each occurrence an integer from 0 to 3, and r1 is independently at each occurrence an integer from 0 to 3. Here, the sum of p1, q1, and r1 is (SiR a2 p1 R a3 q1 R a4 r1 ) units, it is 3.

[0197] In one embodiment, p1 is independently in each occurrence an integer from 1 to 3, preferably 2 or 3, and more preferably 3.

[0198] In another embodiment, q1 is independently at each occurrence an integer from 1 to 3, preferably 2 or 3, and more preferably 3.

[0199] In a preferred embodiment, r1 is each independently in each occurrence an integer of 0 to 2, preferably 0 or 1, and more preferably 0.

[0200] In one embodiment, p1 is 3.

[0201] In another embodiment, q1 is 3.

[0202] In the above formula, R b1 may each independently in each occurrence be -Z 2-YA.

[0203] In the above formula, R c1 is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group in each occurrence. Such a monovalent organic group is the same as the -Z 2 - is a monovalent organic group other than YA.

[0204] R c1 In the above, the monovalent organic group is preferably C 1-20 is an alkyl group, more preferably C 1-6 It is preferably an alkyl group, more preferably a methyl group.

[0205] k1 is, independently at each occurrence, an integer from 0 to 3, l1 is, independently at each occurrence, an integer from 0 to 3, and m1 is, independently at each occurrence, an integer from 0 to 3. Here, the sum of k1, l1, and m1 is (SiR a1 k1 R b1 l1 R c1 m1 ) units, it is 3.

[0206] In one embodiment, k1 in each occurrence is independently an integer from 1 to 3, preferably 2 or 3, and more preferably 3.

[0207] In another embodiment, l1 is independently at each occurrence an integer from 1 to 3, preferably 2 or 3, and more preferably 3.

[0208] In a preferred embodiment, m1 in each occurrence is independently an integer of 0 to 2, preferably 0 or 1, and more preferably 0.

[0209] In one embodiment, k1 is 3.

[0210] In another embodiment, l1 is 3.

[0211] wherein in formula (D3), at least one -YA is present.

[0212] R d1 may each independently in each occurrence be -Z 3 -CR d2 p2 R d3 q2 R d4 r2 It is.

[0213] Z 3 is independently a single bond, an oxygen atom, or a divalent organic group in each occurrence. 3 The structure written as is shown on the right side (CR d2 p2 R d3 q2 R d4 r2 )

[0214] In a preferred embodiment, Z 3 is a divalent organic group.

[0215] Above Z 3 is preferably C 1-6 Alkylene group, -(CH2) z5 -O-(CH2) z6 -(wherein z5 is an integer of 0 to 6, for example, an integer of 1 to 6, and z6 is an integer of 0 to 6, for example, an integer of 1 to 6), -(CH2) z7 -Phenylene-(CH2) z8 -(wherein z7 is an integer of 0 to 6, for example, an integer of 1 to 6, and z8 is an integer of 0 to 6, for example, an integer of 1 to 6) or -(CH2) z9 -C 3-10 Cycloalkylene-(CH2) z10 - (wherein z9 is an integer of 0 to 6, for example, an integer of 1 to 6, and z10 is an integer of 0 to 6, for example, an integer of 1 to 6). 1-6 The alkylene groups may be linear or branched, but are preferably linear. These groups may contain, for example, fluorine atoms, C 1-6 Alkyl group, C 2-6Alkenyl groups, and C 2-6 It may be substituted by one or more substituents selected from alkynyl groups, but is preferably unsubstituted.

[0216] In a preferred embodiment, Z 3 is C 1-6 Alkylene group or -(CH2) z7 -Phenylene-(CH2) z8 -, preferably -phenylene-(CH2) z8 -It is.

[0217] In another preferred embodiment, the Z 3 is C 1-3 In one embodiment, Z is an alkylene group. 3 can be -CH2CH2CH2-. In another embodiment, Z 3 can be -CH2CH2-.

[0218] R d2 may each independently in each occurrence be -Z 3’ -CR d3’ q2’ R d4’ r2’ It is.

[0219] Z 3’ is independently a single bond, an oxygen atom, or a divalent organic group in each occurrence. 3’ The structure written as is shown on the right side (CR d3’ q2’ R d4’ r2’ )

[0220] Above Z 3’ is preferably C 1-6 Alkylene group, -(CH2) z5’ -O-(CH2) z6’ -(wherein z5' is an integer of 0 to 6, for example, an integer of 1 to 6, and z6' is an integer of 0 to 6, for example, an integer of 1 to 6), -(CH2) z7’ -Phenylene-(CH2) z8’-(wherein z7' is an integer of 0 to 6, for example, an integer of 1 to 6, and z8' is an integer of 0 to 6, for example, an integer of 1 to 6) or -(CH2) z9’ -C 3-10 Cycloalkylene-(CH2) z10’ - (wherein z9' is an integer of 0 to 6, for example, an integer of 1 to 6, and z10' is an integer of 0 to 6, for example, an integer of 1 to 6). 1-6 The alkylene groups may be linear or branched, but are preferably linear. These groups may contain, for example, fluorine atoms, C 1-6 Alkyl group, C 2-6 Alkenyl groups, and C 2-6 It may be substituted by one or more substituents selected from alkynyl groups, but is preferably unsubstituted.

[0221] In a preferred embodiment, Z 3’ is C 1-6 Alkylene group or -(CH2) z7’ -Phenylene-(CH2) z8’ -, preferably -phenylene-(CH2) z8’ -It is.

[0222] In another preferred embodiment, the Z 3’ is C 1-3 In one embodiment, Z is an alkylene group. 3’ can be -CH2CH2CH2-. In another embodiment, Z 3’ can be -CH2CH2-.

[0223] Above R d3’ may each independently in each occurrence be -Z 2 -YA.

[0224] Above R d4’ is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group in each occurrence. Such a monovalent organic group is the same as the -Z 2 - is a monovalent organic group other than YA.

[0225] Above R d4’In the above, the monovalent organic group is preferably C 1-20 is an alkyl group, more preferably C 1-6 It is preferably an alkyl group, more preferably a methyl group.

[0226] In another embodiment, R d4’ The monovalent organic group is preferably C 1-20 is an alkyl group, more preferably C 1-6 It is an alkyl group.

[0227] Each q2' in each occurrence is independently an integer from 0 to 3, and each r2' in each occurrence is independently an integer from 0 to 3. Here, the sum of q2' and r2' is (CR d3’ q2’ R d4’ r2’ ) units, it is 3.

[0228] In a preferred embodiment, q2' in each occurrence is independently an integer of 1 to 3, preferably 2 or 3, and more preferably 3. In this case, r2' in each occurrence is independently an integer of 0 to 2, preferably 0 or 1, and more preferably 0.

[0229] R d3 may each independently in each occurrence be -Z 2 -YA.

[0230] Above R d4 is independently a hydrogen atom, a hydroxyl group, or a monovalent organic group in each occurrence. Such a monovalent organic group is the same as the -Z 2 - is a monovalent organic group other than YA.

[0231] Above R d4 In the above, the monovalent organic group is preferably C 1-20 is an alkyl group, more preferably C 1-6 It is preferably an alkyl group, more preferably a methyl group.

[0232] In another embodiment, R d4The monovalent organic group is preferably C 1-20 is an alkyl group, more preferably C 1-6 It is an alkyl group.

[0233] The above p2 is independently an integer of 0 to 3 in each occurrence, q2 is independently an integer of 0 to 3 in each occurrence, and r2 is independently an integer of 0 to 3 in each occurrence. The sum of p2, q2, and r2 is (CR d2 p2 R d3 q2 R d4 r2 ) units, it is 3.

[0234] In one embodiment, p2 is independently in each occurrence an integer from 1 to 3, preferably 2 or 3, and more preferably 3.

[0235] In another embodiment, q2 is independently in each occurrence an integer from 1 to 3, preferably 2 or 3, and more preferably 3.

[0236] In a preferred embodiment, r2 is independently in each occurrence an integer from 0 to 2, preferably 0 or 1, and more preferably 0.

[0237] In one embodiment, p2 is 3.

[0238] In another embodiment, q2 is 3.

[0239] Above R e1 may each independently in each occurrence be -Z 2 -YA.

[0240] Above R f1 is independently at each occurrence a hydrogen atom, a hydroxyl group, or a monovalent organic group. Such monovalent organic groups are monovalent organic groups other than the above-mentioned hydrolyzable groups.

[0241] Above R f1In the above, the monovalent organic group is preferably C 1-20 is an alkyl group, more preferably C 1-6 It is preferably an alkyl group, more preferably a methyl group.

[0242] In another embodiment, R f1 The monovalent organic group is preferably C 1-20 is an alkyl group, more preferably C 1-6 It is an alkyl group.

[0243] The above k2 is independently an integer of 0 to 3 in each occurrence, l2 is independently an integer of 0 to 3 in each occurrence, and m2 is independently an integer of 0 to 3 in each occurrence. The sum of k2, l2 and m2 is (CR d1 k2 R e1 l2 R f1 m2 ) units, it is 3.

[0244] In one embodiment, k2 is independently in each occurrence an integer from 1 to 3, preferably 2 or 3, and more preferably 3.

[0245] In another embodiment, l2 is independently at each occurrence an integer from 1 to 3, preferably 2 or 3, and more preferably 3.

[0246] In a preferred embodiment, m2 in each occurrence is independently an integer from 0 to 2, preferably 0 or 1, and more preferably 0.

[0247] In one embodiment, k2 is 3.

[0248] In another embodiment, l2 is 3.

[0249] wherein in formula (D4), at least one -YA is present.

[0250] R g1 and Rh1 may each independently in each occurrence be -Z 4 -YA, -Z 4 -SiR a1 k1 R b1 l1 R c1 m1 , or -Z 4 -CR d1 k2 R e1 l2 R f1 m2 It is.

[0251] Z 4 In each occurrence, each independently represents a single bond, an oxygen atom, or a divalent organic group. 4 In the structure written as:, the right side is bonded (such as a -YA group).

[0252] wherein in formula (D5), at least one -YA is present.

[0253] In one embodiment, Z 4 is an oxygen atom.

[0254] In one embodiment, Z 4 is a divalent organic group.

[0255] Above Z 4 is preferably C 1-6 Alkylene group, -(CH2) z5” -O-(CH2) z6” - (wherein z5" is an integer of 0 to 6, for example, an integer of 1 to 6, and z6" is an integer of 0 to 6, for example, an integer of 1 to 6), or -(CH2) z7” -Phenylene-(CH2) z8” - (wherein z7" is an integer of 0 to 6, for example, an integer of 1 to 6, and z8" is an integer of 0 to 6, for example, an integer of 1 to 6). 1-6 The alkylene groups may be linear or branched, but are preferably linear. These groups may contain, for example, fluorine atoms, C 1-6 Alkyl group, C 2-6Alkenyl groups, and C 2-6 It may be substituted by one or more substituents selected from alkynyl groups, but is preferably unsubstituted.

[0256] In a preferred embodiment, Z 4 is C 1-6 Alkylene group or -(CH2) z7” -Phenylene-(CH2) z8” -, preferably -phenylene-(CH2) z8” -It is. 3 is such a group, light resistance, particularly ultraviolet light resistance, can be improved.

[0257] In another preferred embodiment, the Z 4 is C 1-3 In one embodiment, Z is an alkylene group. 4 can be -CH2CH2CH2-. In another embodiment, Z 4 can be -CH2CH2-.

[0258] In one embodiment, R D is a group represented by formula (D1).

[0259] In one embodiment, R D is a group represented by formula (D2).

[0260] In one embodiment, R D is a group represented by formula (D3).

[0261] In one embodiment, R D is a group represented by formula (D4).

[0262] In one embodiment, R D is a group represented by formula (D5).

[0263] The number average molecular weight of the fluoropolyether group-containing unsaturated compound of the present disclosure may be preferably 1,000 or more, more preferably 1,500 or more, for example 2,000 or more, 4,000 or more, or 5,000 or more. The number average molecular weight of the fluoropolyether group-containing unsaturated compound of the present disclosure may be preferably 100,000 or less, more preferably 50,000 or less, even more preferably 30,000 or less, even more preferably 10,000 or less, for example 8,000 or less, 6,000 or less, or 5,000 or less. In this specification, the number average molecular weight of the fluoropolyether group-containing unsaturated compound is 19 The value is measured by F-NMR.

[0264] In one embodiment, the number average molecular weight of the fluoropolyether group-containing unsaturated compound is 1,000 to 100,000, preferably 2,000 to 30,000, and more preferably 2,000 to 10,000.

[0265] The content mass ratio of the fluoropolyether group-containing thiol compound of the present disclosure to the fluoropolyether group-containing unsaturated compound is preferably 0.1:100 to 100:0.1, more preferably 5:100 to 100:5, and further preferably 10:100 to 100:10.

[0266] The curable composition of the present disclosure may further comprise a fluorinated oil.

[0267] The fluorine-containing oil is not particularly limited, but may be, for example, a fluorine-containing oil represented by the following formula (5): Rf 5 -(OC4F8) a’ -(OC3F6) b’ -(OC2F4) c’ -(OCF2) d’ -Rf 6 (5) [In formula: Rf 5 C may be substituted with one or more fluorine atoms. 1-16 is an alkyl group, Rf 6C may be substituted with one or more fluorine atoms. 1-16 an alkyl group, a fluorine atom, or a hydrogen atom; a', b', c', and d' are each independently an integer of 0 to 300, the sum of a', b', c', and d' is at least 1; The order of occurrence of each repeat unit enclosed in parentheses with the subscript a', b', c', or d' is arbitrary in the formula. It is a compound represented by the formula:

[0268] Rf 5 is an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms, preferably C 1―16 is a perfluoroalkyl.

[0269] Rf 6 is an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms, a fluorine atom, or a hydrogen atom, and is preferably 1-16 It is a perfluoroalkyl group.

[0270] In a preferred embodiment, Rf 5 and Rf 6 are each independently 1―16 More preferably, 1-3 It is a perfluoroalkyl group.

[0271] The sum of a', b', c' and d' is at least 1, preferably 1-300, and more preferably 20-300.

[0272] Among the repeating units of the above fluorinated oil, -(OC4F8)- may be any of -(OCF2CF2CF2CF2)-, -(OCF(CF3)CF2CF2)-, -(OCF2CF(CF3)CF2)-, -(OCF2CF2CF(CF3))-, -(OC(CF3)2CF2)-, -(OCF2C(CF3)2)-, -(OCF(CF3)CF(CF3))-, -(OCF(C2F5)CF2)- and (OCF2CF(C2F5))-, but is preferably -(OCF2CF2CF2CF2)-. -(OC3F6)- may be any of -(OCF2CF2CF2)-, -(OCF(CF3)CF2)- and (OCF2CF(CF3))-, but is preferably -(OCF2CF2CF2)-. -(OC2F4)- may be either -(OCF2CF2)- or (OCF(CF3))-, but is preferably -(OCF2CF2)-.

[0273] Examples of the perfluoro(poly)ether compound represented by the above general formula (5) include compounds represented by the following general formulas (5a) and (5b) (which may be one type or a mixture of two or more types). Rf 5 -(OCF2CF2CF2) b” -Rf 6 (5a) Rf 5 -(OCF2CF2CF2CF2) a” -(OCF2CF2CF2) b” -(OCF2CF2) c” -(OCF2) d” -Rf 6 (5b) In these formulas, Rf 5 and Rf 6 is as defined above; in formula (5a), b" is an integer of 1 or more and 100 or less; in formula (5b), a" and b" are each independently an integer of 0 or more and 30 or less, and c" and d" are each independently an integer of 1 or more and 300 or less. The order of occurrence of each repeating unit enclosed in parentheses with the subscripts a", b", c", and d" is arbitrary in the formula.

[0274] From another perspective, the fluorine-containing oil is represented by the general formula Rf 3 -F(where Rf 3 is C 5-16 It may be a compound represented by the formula: embedded image which is a perfluoroalkyl group. It may also be a chlorotrifluoroethylene oligomer.

[0275] The above-mentioned fluorine-containing oil may have an average molecular weight of 500 to 10000. The molecular weight of the fluorine-containing oil can be measured using GPC.

[0276] The fluorine-containing oil may be contained in an amount of, for example, 0.01 to 50 mass %, preferably 0.1 to 30 mass %, e.g., 1 to 15 mass %, relative to the curable composition of the present disclosure.

[0277] In one embodiment, the curable composition of the present disclosure is substantially free of fluorinated oil. "Substantially free of fluorinated oil" means that the composition does not contain any fluorinated oil at all, or may contain a very small amount of fluorinated oil.

[0278] The curable composition of the present disclosure may further comprise a polymerization initiator.

[0279] The polymerization initiator preferably has 1 to 3 aromatic ring structures.

[0280] The polymerization initiator is preferably a radical polymerization initiator.

[0281] The radical polymerization initiator is a compound that generates radicals by heat or light, and examples of the radical polymerization initiator include a radical thermal polymerization initiator and a radical photopolymerization initiator. In the present invention, the radical photopolymerization initiator is preferred.

[0282] Examples of the radical thermal polymerization initiator include peroxide compounds such as diacyl peroxides, such as benzoyl peroxide and lauroyl peroxide; dialkyl peroxides, such as dicumyl peroxide and di-t-butyl peroxide; peroxycarbonates, such as diisopropyl peroxydicarbonate and bis(4-t-butylcyclohexyl) peroxydicarbonate; and alkyl peresters, such as t-butyl peroxyoctoate and t-butyl peroxybenzoate; and radical-generating azo compounds, such as azobisisobutyronitrile.

[0283] Examples of the radical photopolymerization initiator include diketones such as benzyl and diacetyl, acyloins such as benzoin, acyloin ethers such as benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether, thioxanthones such as thioxanthone, 2,4-diethylthioxanthone, and thioxanthone-4-sulfonic acid, benzophenones such as 4,4'-bis(dimethylamino)benzophenone and 4,4'-bis(diethylamino)benzophenone, acetophenone, 2-(4-toluenesulfonyloxy)-2-phenylacetophenone, p-dimethylaminoacetophenone, 2,2'-dimethoxy-2-phenylacetophenone, and p-methoxy Examples of the compound include acetophenones such as acetophenone, 2-methyl[4-(methylthio)phenyl]-2-morpholino-1-propanone, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one; quinones such as anthraquinone and 1,4-naphthoquinone; aminobenzoic acids such as ethyl 2-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, (n-butoxy)ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-ethylhexyl 4-dimethylaminobenzoate; halogen compounds such as phenacyl chloride and trihalomethylphenyl sulfone; acylphosphine oxides; and peroxides such as di-t-butyl peroxide.

[0284] Examples of commercially available radical photopolymerization initiators include the following. IRGACURE 651: 2,2-dimethoxy-1,2-diphenylethan-1-one, IRGACURE 184: 1-Hydroxy-cyclohexyl-phenyl-ketone, IRGACURE 2959: 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, IRGACURE 127: 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, IRGACURE 907: 2-Methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, IRGACURE 369: 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, IRGACURE 379: 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, IRGACURE 819: Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, IRGACURE 784: bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium; IRGACURE OXE 01: 1,2-Octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], IRGACURE OXE 02: Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime), IRGACURE261, IRGACURE369, IRGACURE500, DAROCUR 1173: 2-hydroxy-2-methyl-1-phenyl-propan-1-one, DAROCUR TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, DAROCUR1116, DAROCUR2959, DAROCUR1664, DAROCUR4043, IRGACURE 754 Oxyphenylacetic acid: Mixture of 2-[2-oxo-2-phenylacetoxyethoxy]ethyl ester and oxyphenylacetic acid, 2-(2-hydroxyethoxy)ethyl ester; IRGACURE 500: A mixture of IRGACURE 184 and benzophenone (1 :1), IRGACURE 1300: a mixture of IRGACURE 369 and IRGACURE 651 (3:7), IRGACURE 1800: A mixture of CGI403 and IRGACURE 184 (1:3), IRGACURE 1870: A mixture of CGI403 and IRGACURE 184 (7:3), DAROCUR 4265: A mixture of DAROCUR TPO and DAROCUR 1173 (1:1). IRGACURE is manufactured by BASF, and DAROCUR is manufactured by Merck Japan.

[0285] The curable compositions of the present disclosure may further contain one or more other components selected from organic solvents, water, and catalysts.

[0286] The organic solvent may be a fluorine-containing organic solvent or a fluorine-free organic solvent.

[0287] Examples of the fluorine-containing organic solvent include perfluorohexane, perfluorooctane, perfluorodimethylcyclohexane, perfluorodecalin, perfluoroalkylethanol, perfluorobenzene, perfluorotoluene, perfluoroalkylamines (Fluorinert (trade name), etc.), perfluoroalkylethers, perfluorobutyltetrahydrofuran, polyfluoroaliphatic hydrocarbons (Asahiclean AC6000 (trade name)), hydrochlorofluorocarbons (Asahiclean AK-225 (trade name), etc.), hydrofluoroethers (Novec (trade name), HFE-7100 (trade name), HFE-7300 (trade name), etc.), 1,1,2,2,3,3,4-heptafluorocyclopentane, fluorine-containing alcohols, perfluoroalkyl bromides, perfluoroalkyl iodides, perfluoropolyethers (Krytox (trade name), Demnum (trade name), Fomblin (trade name), etc.), 1,3-bistrifluoromethylbenzene, 2-(perfluoroalkyl)ethyl methacrylate, 2-(perfluoroalkyl)ethyl acrylate, perfluoroalkylethylene, Freon 134a, and hexafluoropropene oligomers.

[0288] Examples of the fluorine-free organic solvent include acetone, methyl isobutyl ketone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether, pentane, hexane, heptane, octane, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, carbon disulfide, benzene, toluene, xylene, nitrobenzene, diethyl ether, dimethoxyethane, diglyme, triglyme, ethyl acetate, butyl acetate, dimethylformamide, dimethyl sulfoxide, 2-butanone, acetonitrile, benzonitrile, butanol, 1-propanol, 2-propanol, ethanol, methanol, and diacetone alcohol.

[0289] Among these, the organic solvent is preferably methyl isobutyl ketone, propylene glycol monomethyl ether, hexadecane, butyl acetate, acetone, 2-butanone, cyclohexanone, ethyl acetate, diacetone alcohol, ethanol, or 2-propanol.

[0290] The organic solvents may be used alone or in combination of two or more kinds.

[0291] The organic solvent is used in the curable composition in an amount of preferably 10 to 99% by mass, more preferably 30 to 95% by mass, and further preferably 50 to 95% by mass.

[0292] In one embodiment, the curable composition of the present disclosure is solvent-free, i.e., does not substantially contain a solvent. "Substantially does not contain a solvent" refers to a state in which no solvent is intentionally added, and a trace amount of a solvent, such as water, that is unavoidably contained may be present. For example, the content of the solvent in the curable composition of the present disclosure may be 1.0% by mass or less, 0.5% by mass or less, 0.1% by mass or less, or 0.01% by mass or less.

[0293] Examples of the catalyst include acids (eg, hydrochloric acid, acetic acid, trifluoroacetic acid, etc.), bases (eg, ammonia, triethylamine, diethylamine, etc.), transition metals (eg, Ti, Ni, Sn, etc.), and the like.

[0294] The viscosity of the curable composition of the present disclosure is preferably 100 mPa·s or more, more preferably 200 mPa·s or more, and even more preferably 300 mPa·s or more. If the viscosity is too low, the composition may be prone to dripping after application to a member. The viscosity of the curable composition of the present disclosure is preferably 10000 mPa·s or less, more preferably 7000 mPa·s or less, even more preferably 5000 mPa·s or less, even more preferably 3000 mPa·s or less, and particularly preferably less than 1000 mPa·s. If the viscosity is too high, it may be difficult to inject the composition into the fine parts of the member. By adjusting the viscosity to the above range, the composition is less prone to dripping and is easier to inject into the fine parts of the member, improving the applicability.

[0295] In one embodiment, the viscosity of the curable composition of the present disclosure is 100 to 10,000 mPa·s, preferably 200 to 7,000 mPa·s, more preferably 300 to 5,000 mPa·s, even more preferably 300 to 3,000 mPa·s, and particularly preferably 300 or more and less than 1,000 mPa·s.

[0296] In one embodiment, the curable composition of the present disclosure is a surface treatment.

[0297] The present disclosure provides a cured product obtained by curing the curable composition of the present disclosure.

[0298] The tensile modulus of the cured product of the present disclosure is preferably 0.1 to 500 MPa, more preferably 0.2 to 500 MPa, even more preferably 0.3 to 300 MPa, and even more preferably 0.4 to 100 MPa.

[0299] The tensile modulus can be measured using an autograph (Shimadzu Corporation AGS-J, load cell: 50 N, room temperature, chuck distance: 40 mm, test speed: 5.0 mm / min, test piece: width 1 cm, height 6 cm, film thickness 130 μm).

[0300] The weight loss rate (%) of the cured product of the present disclosure after being held under conditions of 65°C and 90% RH for 72 hours ((weight before holding-weight after holding) / weight before holding) x 100) is preferably less than 50%, more preferably less than 40%, even more preferably less than 20%, and particularly preferably less than 10%.

[0301] The cured product of the present disclosure is preferably a sealant.

[0302] The encapsulant is preferably an encapsulant for electronic devices.

[0303] The present disclosure includes a substrate and a layer (hereinafter also referred to as a "surface treatment layer") formed on the substrate by curing the curable composition of the present disclosure.

[0304] Substrates that can be used in the present disclosure may be made of any suitable material, such as glass, resin (which may be a natural or synthetic resin, for example, a general plastic material), OCA (Optical Clear Adhesive), polarizing plate metal, ceramics, semiconductors (silicon, germanium, etc.), electronic devices, fibers (woven fabrics, nonwoven fabrics, etc.), fur, leather, wood, ceramics, stone, etc., building materials, etc., sanitary products, etc.

[0305] In a preferred embodiment, the substrate is glass, resin, a polarizing plate, OCA (Optical Clear Adhesive) or metal, and is preferably glass, resin, a polarizing plate or OCA (Optical Clear Adhesive).

[0306] As the above glass, sapphire glass, soda-lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass, and quartz glass are preferred, and chemically strengthened soda-lime glass, chemically strengthened alkali aluminosilicate glass, and chemically bonded borosilicate glass are particularly preferred.

[0307] For example, when the article to be manufactured is an optical member, the material constituting the surface of the substrate may be a material for optical members, such as glass or transparent plastic. When the article to be manufactured is an optical member, some layer (or film), such as a hard coat layer or an anti-reflection layer, may be formed on the surface (outermost layer) of the substrate. The anti-reflection layer may be either a single-layer anti-reflection layer or a multi-layer anti-reflection layer. Examples of inorganic substances that can be used in the anti-reflection layer include SiO2, SiO, ZrO2, TiO2, TiO, Ti2O3, Ti2O5, Al2O3, Ta2O5, Ta3O5, Nb2O5, HfO2, Si3N4, CeO2, MgO, Y2O3, SnO2, MgF2, and WO3. These inorganic substances may be used alone or in combination of two or more of them (for example, as a mixture). When a multi-layer anti-reflection layer is used, it is preferable to use SiO2 and / or SiO for the outermost layer. When the product to be manufactured is an optical glass part for a touch panel, a transparent electrode, for example, a thin film using indium tin oxide (ITO) or indium zinc oxide, may be provided on a part of the surface of the substrate (glass). In addition, the substrate may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomizing film layer, a hard coating film layer, a polarizing film, a phase difference film, a liquid crystal display module, etc., depending on the specific specifications.

[0308] The shape of the substrate is not particularly limited, and may be, for example, a plate, a film, or other form. The surface region of the substrate on which the surface treatment layer is to be formed may be at least a part of the substrate surface, and may be appropriately determined according to the application and specific specifications of the product to be manufactured.

[0309] The article of the present disclosure can be produced by forming a layer of the composition of the present disclosure described above on the surface of the substrate, and optionally post-treating the layer, thereby forming a layer from the composition of the present disclosure.

[0310] The layer formation of the composition of the present disclosure can be carried out by applying the composition to the surface of a substrate so as to cover the surface. The coating method is not particularly limited. For example, a wet coating method and a dry coating method can be used.

[0311] Examples of wet coating techniques include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating and similar techniques.

[0312] Examples of dry coating methods include deposition (usually vacuum deposition), sputtering, CVD, and similar methods. Specific examples of deposition methods (usually vacuum deposition) include resistance heating, electron beam, high frequency heating such as with microwaves, ion beam, and similar methods. Specific examples of CVD methods include plasma-CVD, optical CVD, thermal CVD, and similar methods.

[0313] Furthermore, coating by atmospheric pressure plasma method is also possible.

[0314] When the dry coating method is used, the curable composition of the present disclosure may be subjected to the dry coating method as it is, or may be subjected to the dry coating method after being diluted with the above-mentioned organic solvent.

[0315] The layer formation of the curable composition of the present disclosure is preferably carried out so that the curable composition of the present disclosure is present in the layer together with a catalyst for hydrolysis and dehydration condensation. Conveniently, in the case of the wet coating method, the curable composition of the present disclosure may be diluted with a solvent, and then a catalyst may be added to the dilution of the curable composition of the present disclosure immediately before application to the substrate surface. In the case of the dry coating method, the curable composition of the present disclosure to which the catalyst has been added may be directly subjected to deposition (usually vacuum deposition) treatment, or a pellet-shaped material in which the curable composition of the present disclosure to which the catalyst has been added is impregnated into a metal porous body such as iron or copper may be subjected to deposition (usually vacuum deposition) treatment.

[0316] Any suitable acid or base can be used as the catalyst. Examples of the acid catalyst include hydrochloric acid, acetic acid, formic acid, and trifluoroacetic acid. Examples of the base catalyst include ammonia and organic amines.

[0317] The surface treatment layer included in the article of the present disclosure has lubrication properties. In addition to high lubrication properties, the surface treatment layer may have antibacterial properties, water repellency, oil repellency, antifouling properties (for example, preventing adhesion of stains such as fingerprints), waterproof properties (preventing water from penetrating into electronic parts, etc.), surface slipperiness (or lubricity, for example, wiping off stains such as fingerprints, and excellent tactile sensation to fingers), etc., depending on the composition of the composition used, and may be suitably used as a functional thin film.

[0318] In a preferred embodiment, the article of the present disclosure is useful as glass or mirror glass for vehicles, ships, or aircraft, such as automobile glass, automobile door mirrors, automobile fender mirrors, etc., or glass used in vehicle-mounted cameras, etc. In addition, it is useful as a substrate for outdoor applications, such as glass used in security cameras and convex mirrors.

[0319] Therefore, the present disclosure further relates to an optical material having the above-mentioned surface treatment layer as the outermost layer.

[0320] Preferred examples of the optical material include optical materials relating to displays and the like, such as those exemplified below, as well as a wide variety of other optical materials: for example, displays such as cathode ray tubes (CRTs; for example, personal computer monitors), liquid crystal displays, plasma displays, organic electroluminescence displays, inorganic thin-film electroluminescence dot matrix displays, rear projection displays, vacuum fluorescent displays (VFDs), field emission displays (FEDs), and other displays, protective plates for such displays, or displays whose surfaces have been treated with an anti-reflection film.

[0321] The article of the present disclosure may be, but is not limited to, an optical member. Examples of optical members include lenses for glasses, front protection plates, anti-reflection plates, polarizing plates, and anti-glare plates for displays such as PDPs and LCDs, touch panel sheets for devices such as mobile phones and personal digital assistants, disc surfaces for optical discs such as Blu-ray (registered trademark) discs, DVD discs, CD-Rs, and MOs, optical fibers, and display surfaces for watches.

[0322] The article of the present disclosure may also be a medical device or medical material.

[0323] The thickness of the layer is not particularly limited, but may be, for example, 1 nm or more, 10 nm or more, or 100 nm or more. The thickness of the layer is not particularly limited, but may be, for example, 1000 nm or less, 500 nm or less, or 100 nm or less.

[0324] The fluoropolyether group-containing thiol compound, the curable composition, and the cured product of the present disclosure have been described above in detail. However, these of the present disclosure are not limited to the above examples. EXAMPLES

[0325] The fluoropolyether group-containing thiol compound and curable composition of the present disclosure will be described in more detail through the following examples, but the present disclosure is not limited to these examples. Note that, in this embodiment, the order of the repeating units constituting the fluoropolyether is arbitrary, and the chemical formula shown below shows the average composition.

[0326] (Viscosity measurement) The viscosity of the compositions shown in Table 2, which are mixtures of a fluoropolyether group-containing unsaturated compound, a fluoropolyether group-containing thiol compound, and these with a photopolymerization initiator, was measured using a TV-10 viscometer (rotor No. THM1) manufactured by Toki Sangyo Co., Ltd. at a rotation speed of 1.0 rpm and a measurement temperature of 25°C.

[0327] (Measurement of tensile modulus) Test pieces measuring 1 cm wide and 6 cm long were cut out from the cured coatings (film thickness 130 μm) prepared from the curable compositions shown in Table 2, and the tensile modulus was measured at room temperature, with a chuck distance of 40 mm and a tensile speed of 5.0 mm / min, using an autograph (Shimadzu Corporation AGS-J, load cell: 50 N).

[0328] 1. Synthesis of allyl-containing perfluoropolyether

[0329] Synthesis Example 1 Synthesis of Compound (A-1) In a flask, 74 g of perfluoropolyether dicarboxylic acid (average composition: m = 15, n = 12) shown in the following formula (1), 33.5 mL of 1,3-bis (trifluoromethyl) benzene, 1.48 g of DMF, and 13.5 g of thionyl chloride were added and stirred, and reacted at 80 ° C for 3 hours. After distilling off the solvent, the product was ice-cooled and 11.1 g of diallylamine was added dropwise, and after the completion of the dropwise addition, the mixture was stirred overnight at room temperature. Dilute hydrochloric acid, perfluorohexane, and acetone were added to the reaction liquid to perform a liquid separation operation, and water and acetone were added for washing, and the solvent was distilled off to obtain 65 g of a perfluoropolyether compound having an allyl group shown in the following formula (A-1). 19 F-NMR measurement revealed that the number average molecular weight of this compound was 2700, and the viscosity of this compound at room temperature was 300 mPa·s. Compound (1) [ka] Compound (A-1) [ka]

[0330] Synthesis Example 2 Synthesis of Compound (A-2) 20 g of perfluoropolyether diester (average composition: m=15, n=12) represented by formula (2) and 2.64 g of 2,2-diallylpent-4-en-1-amine were added to a flask and stirred at room temperature under reduced pressure to obtain 20.5 g of a perfluoropolyether compound having an allyl group represented by formula (A-2) below. 19F-NMR measurement revealed that the number average molecular weight of this compound was 2700, and the viscosity of this compound at room temperature was 400 mPa·s. Compound (2) [ka] Compound (A-2) [ka]

[0331] Synthesis Example 3 Synthesis of Compound (A-3) According to the method described in Example 6 of JP 2016-204656, 8.52 g of a perfluoropolyether compound having an allyl group represented by the following formula (A-3) was obtained using 10 g of a perfluoropolyether diester (average composition m = 15, n = 12) represented by the formula (2) as a raw material. 19 F-NMR measurement revealed that the number average molecular weight of this compound was 2600, and the viscosity of this compound at room temperature was 300 mPa·s. Compound (A-3) [ka]

[0332] 2. Synthesis of thiol-containing perfluoropolyether

[0333] Synthesis Example 4 Synthesis of Compound (B-1) (Example 4-1) Synthesis of compound (W-1) In a flask, 5 g of perfluoropolyether diol (average composition m=8, n=7) represented by formula (3), 22 ml of 1,3-bis(trifluoromethyl)benzene, 0.30 g of tetrabutylammonium bromide, and 0.59 g of sodium hydroxide were added and heated at 60°C for 1.5 hours, after which 1.96 g of geranyl bromide was added dropwise and stirred at 70°C for 3 hours. The reaction liquid was filtered, washed with dilute hydrochloric acid, water, and saturated saline, and the solvent was removed by distillation, followed by washing with methanol to obtain 5.1 g of a perfluoropolyether compound represented by the following formula (W-1). Compound (3) [ka] Compound (W-1) [ka]

[0334] (Example 4-2) Synthesis of compound (W-2) In a reaction vessel, 8 g of the compound represented by formula (W-1) obtained in Example 4-1, 80 ml of 1,3-bis(trifluoromethyl)benzene, 2.6 g of thioacetic acid, and 0.106 g of benzyl dimethyl ketal were added, and argon was blown in to degas the mixture. The mixture was then stirred for 1 hour while being irradiated with UV light (light source: Sen Special Light Source, HL100GL-1). After washing the reaction solution with water, the solvent was distilled off, and the mixture was washed with methanol to obtain 7.8 g of a perfluoropolyether compound represented by formula (W-2) below. Compound (W-2) [ka]

[0335] (Example 4-3) Synthesis of compound (B-1) In a reaction vessel, 5 g of the compound represented by formula (W-2) obtained in Example 4-2, 15 ml of Novec7200 (manufactured by 3M), 10 ml of THF, and 2.2 ml of 28% sodium methoxide methanol solution were added and stirred at room temperature for 1 hour. Dilute hydrochloric acid was added to stop the reaction, and after separation and washing with water, the solvent was distilled off to obtain 4.3 g of a perfluoropolyether compound represented by the following formula (B-1) having a thiol group. 19 F-NMR measurement revealed that the number average molecular weight of this compound was 2000, and the viscosity of this compound at room temperature was 600 mPa s. This compound was also soluble in 1,3-bis(trifluoromethyl)benzene and perfluorobenzene. Compound (B-1) [ka]

[0336] Synthesis Example 5 Synthesis of Compound (B-2) (Example 5-1) Synthesis of compound (X-1) The same procedure as in Example 4-1 was carried out except that 2.57 g of farnesyl bromide was used instead of 1.96 g of geranyl bromide, to obtain 5.4 g of a perfluoropolyether compound represented by the following formula (X-1). Compound (X-1) [ka]

[0337] (Example 5-2) Synthesis of compound (X-2) The same procedure as in Example 4-2 was carried out except that 8g of the compound represented by (W-1) was replaced with 8g of the compound represented by (X-1), 3.67g of thioacetic acid, and 0.150g of benzyl dimethyl ketal, to obtain 8.1g of a perfluoropolyether compound represented by the following formula (X-2). Compound (X-2) [ka]

[0338] (Example 5-3) Synthesis of compound (B-2) The same procedure as in Example 4-3 was carried out except that 5 g of the compound represented by (X-2) was used instead of 5 g of the compound represented by (W-2) and 2.6 ml of 28% sodium methoxide methanol solution was used, and 3.8 g of a perfluoropolyether compound having a thiol group represented by the following formula (B-2) was obtained. 19 F-NMR measurement revealed that the number average molecular weight of this compound was 2200, and the viscosity of this compound at room temperature was 1000 mPa·s. Compound (B-2) [ka]

[0339] Synthesis Example 6 Synthesis of Compound (B-3) (Example 6-1) Synthesis of compound (Y-1) 100 g of the perfluoropolyether diester (average composition m=15, n=12) represented by formula (2) and 8.4 g of diethanolamine were added to a flask and stirred overnight at 70°C under reduced pressure to obtain 104.8 g of a perfluoropolyether compound having a hydroxyl group represented by formula (Y-1). Compound (Y-1) [ka]

[0340] (Example 6-2) Synthesis of compound (Y-2) 104.8g of the compound represented by formula (Y-1) obtained in Example 6-1, 300mL of 1,3-bis(trifluoromethyl)benzene, and 20g of triethylamine were added to a flask, and 41.5g of 2-bromopropionyl bromide was added dropwise in an ice bath and reacted overnight. After washing the reaction solution with dilute hydrochloric acid and saturated saline, the solvent was distilled off to obtain 108g of a perfluoropolyether compound having a bromo group represented by formula (Y-2). Compound (Y-2) [ka]

[0341] (Example 6-3) Synthesis of compound (Y-3) 108g of the compound represented by formula (Y-2) obtained in Example 6-2, 27.4g of potassium O-ethylxanthate, 540mL of 1,3-bis(trifluoromethyl)benzene, and 54mL of pyridine were added and reacted at room temperature overnight. After washing the reaction solution with water, the solvent was distilled off to obtain 111.7g of a perfluoropolyether compound having a xanthate group represented by formula (Y-3). Compound (Y-3) [ka]

[0342] (Example 6-4) Synthesis of compound (B-3) 110 g of the compound represented by formula (Y-3) obtained in Example 6-3, 550 mL of 1,3-bis(trifluoromethyl)benzene, and 17.1 mL of n-butylamine were added and reacted in an ice bath for 4 hours. The reaction solution was washed with dilute hydrochloric acid and saturated saline, and then added dropwise to hexane to obtain 67.2 g of a perfluoropolyether compound having a thiol group represented by formula (B-3). 19 F-NMR measurement revealed that the number average molecular weight of this compound was 3100, and the viscosity of this compound at room temperature was 2200 mPa·s. Compound (B-3) [ka]

[0343] Synthesis Example 7 Synthesis of Compound (B-4) (Example 7-1) Synthesis of compound (P-1) Into a flask, 10.0 g of a perfluoropolyether compound having an allyl group represented by formula (A-1), 30 mL of 1,3-bis(trifluoromethyl)benzene, 2.44 g of thioacetic acid, and 0.263 g of azobisisobutyronitrile were added and reacted at 80° C. The reaction liquid was washed with water to obtain 8.97 g of a perfluoropolyether compound represented by formula (P-1). Compound (P-1) [ka]

[0344] (Example 7-2) Synthesis of compound (B-4) 8.97 g of the compound represented by formula (P-1), 50 mL of Novec7200 (manufactured by 3M), and 5 mL of methanol were placed in a flask and stirred. 0.41 g of sodium was added to generate sodium methoxide, and the deprotection reaction of the acetyl group was carried out at room temperature for 1 hour. After washing the reaction solution with hydrochloric acid, the solvent was distilled off to obtain 7.53 g of a perfluoropolyether compound having a thiol group represented by (B-4). 19 F-NMR measurement revealed that the number average molecular weight of this compound was 2800, and the viscosity of this compound at room temperature was 1500 mPa·s. Compound (B-4) [ka]

[0345] Synthesis Example 8 Synthesis of Compound (A-4) (Example 8-1) Synthesis of compound (Z-1) According to Example 5-1 of Synthesis Example 5 of Japanese Patent No. 7473853, 15g of perfluoropolyether diol (average composition: m=10, n=10) of formula (3) was used as a raw material to synthesize 13.5g of perfluoropolyether compound having an allyl group represented by the following formula (Z-1). Compound (Z-1) [ka]

[0346] (Example 8-2) Synthesis of compound (A-4) According to Synthesis Example 9 of Japanese Patent No. 7473853, 2.32 g of the compound represented by formula (Z-1) was used as a raw material to obtain 2.15 g of a perfluoropolyether compound having an allyl group represented by formula (A-4). 19 F-NMR measurement revealed that the number average molecular weight of this compound was 2,400, and the viscosity of this compound was 400 cP. Compound (A-4) [ka]

[0347] Synthesis Example 9 Synthesis of Compound (B-5) (Example 9-1) Synthesis of compound (S-1) Instead of the perfluoropolyether of formula (3), 15 g of the perfluoropolyether diol (n=12) of formula (5), 44 ml of 1,3-bis(trifluoromethyl)benzene, 0.60 g of tetrabutylammonium bromide, 1.18 g of sodium hydroxide, and 3.92 g of geranyl bromide were used, and the procedure was repeated as in Example 4-1 to obtain 15.3 g of the perfluoropolyether compound represented by formula (S-1). Compound (3) [ka] Compound (S-1) [ka]

[0348] (Example 9-2) Synthesis of compound (S-2) The same procedure as in Example 4-2 was repeated except that 12 g of the compound represented by formula (S-1) was used instead of the compound represented by formula (W-1), to obtain 11.7 g of the perfluoropolyether compound represented by formula (S-2). Compound (S-2) [ka]

[0349] (Example 9-3) Synthesis of compound (B-5) In place of the compound represented by formula (W-2), 7.5 g of the compound represented by formula (S-2) was used in the same manner as in (Example 4-3), to obtain 6.3 g of a perfluoropolyether compound having a thiol group represented by formula (B-5). 19 F-NMR measurement revealed that the number average molecular weight of this compound was 2750, and the viscosity of this compound at room temperature was 950 mPa·s. Compound (B-5) [ka]

[0350] Working Example 1.Storage stability of thiol compounds 1 mL of each of the thiol group-containing perfluoropolyether compounds (B-1) to (B-5) obtained in Synthesis Examples 4 to 9 was placed in a screw tube (No. 3) and left in air at room temperature for two weeks. A horizontal line was drawn 2 cm from the bottom of the screw tube, and the screw tube was tilted sideways to compare the time it took for the liquid edge to pass the horizontal line between the initial sample and the sample after two weeks. The evaluation criteria were as follows, and the results are shown in Table 1. G: The measurement time in the 2-week sample was less than twice that of the initial sample. NG: The measurement time for the 2-week sample was more than twice that of the initial sample.

[0351] [Table 1]

[0352] 2. Preparation of curable composition and viscosity measurement The allyl group-containing perfluoropolyethers obtained in Synthesis Examples 1 to 3 and 8 and the thiol group-containing perfluoropolyethers obtained in Synthesis Examples 4 to 7 and 9 were mixed so that the equivalent weights of the allyl groups and the thiol groups matched, and 2 parts by weight of IRGACURE184 (manufactured by BASF) as a photopolymerization initiator (C) was further mixed to obtain a curable composition. The composition is shown in Table 2. Furthermore, the viscosity of these curable compositions was measured at 23°C. G: The viscosity of the composition was less than 1000 mPa·s. NG: The viscosity of the composition was 1000 mPa·s or more.

[0353] 3.Curing test The curable compositions prepared in Examples 1 to 7 and Comparative Examples 1 and 2 were applied to a glass plate as a substrate with an applicator to a film thickness of 100 μm, and then irradiated with ultraviolet light (wavelength: 365 nm) to examine whether a cured film could be produced. The irradiation dose was 2000 mJ / cm. 2 The evaluation criteria were as follows. The results are shown in Table 2. VG: A cured film was obtained and the surface was not tacky. G: Hardened and no longer flowable. NG: It did not harden and remained liquid.

[0354] 4.Water resistance test The cured film prepared in step 3 was placed in a thermohygrostat at 65°C / 90% RH and held there for 72 hours. The weight loss rate of the cured film after that was calculated and evaluated using the following formula. Weight reduction rate (%) = ((weight before holding - weight after holding) / weight before holding) x 100 The evaluation criteria were as follows. The results are shown in Table 2. VG: The weight loss of the cured film was less than 10%. G: The weight loss rate of the cured film was 10% or more and less than 50%. NG: The weight loss rate of the cured film was 50% or more. In addition, for those that were NG in the evaluation in 3, a water resistance test was not performed because a cured film could not be produced.

[0355] [Table 2]

[0356] The cured film prepared from the curable composition 1 had a tensile modulus of elasticity of 0.50 MPa.

[0357] From the results in Table 1, it was confirmed that the fluoropolyether group-containing thiol compounds (B-1) to (B-2) and (B-5) which do not contain an ester structure and have a secondary thiol group have less viscosity increase and are more stable in air than the fluoropolyether group-containing thiol compound (B-4) which has a primary thiol group. In addition, the fluoropolyether group-containing thiol compound (B-3) which has an ester structure and a secondary thiol group had less viscosity increase and was more stable in air.

[0358] From the results in Table 2, it was confirmed that Examples 1 to 7, which are compositions containing fluoropolyether group-containing thiol compounds (B-1) to (B-2) and (B-5) that do not contain an ester structure and have multiple secondary thiol groups at the terminal, further suppressed thickening and had good water resistance compared to Comparative Example 1, which is a composition containing a fluoropolyether group-containing thiol compound (B-3) that contains an ester structure and a secondary thiol group. It was also confirmed that Examples 1 to 7 suppressed thickening and had excellent ultraviolet curing properties compared to Comparative Example 2, which is a composition containing a fluoropolyether group-containing thiol compound (B-4) that has a primary thiol group. [Industrial Applicability]

[0359] The fluoropolyether group-containing thiol compound of the present disclosure can be suitably used for various applications, for example, as a coating agent.

Claims

1. A fluoropolyether group-containing thiol compound which does not contain an ester structure and contains two or more thiol groups selected from secondary or tertiary thiol groups.

2. The fluoropolyether group-containing thiol compound according to claim 1 , which has a fluorine content of 30 mass% or more.

3. The fluoropolyether group-containing thiol compound according to claim 1, which contains 2 to 6 thiol groups.

4. The fluoropolyether group-containing thiol compound according to claim 1 , wherein the thiol group is a secondary thiol group.

5. The fluoropolyether group-containing thiol compound according to claim 1 , wherein the thiol group is present on both ends of the fluoropolyether group.

6. The fluoropolyether group-containing thiol compound according to claim 1, which has a group selected from a linear or branched alkylene group, a cycloalkylene group, a phenylene group, an alkylamino group, an ether bond, a thioether bond, a carbonyl bond, and an amide bond.

7. The following formula (1) or (2): 【Chemistry 1】 [In the formula: R Ｆ１ Each independently represents Rf １ -R Ｆ -O ｑ - and R Ｆ２ is -Rf ２ ｐ -R Ｆ -O ｑ - and Rf １ each independently represents a C which may be substituted by one or more fluorine atoms; １－１６ is an alkyl group, Rf ２ C optionally substituted with one or more fluorine atoms １－６ is an alkylene group, R Ｆ are each independently a divalent fluoropolyether group, p is 0 or 1; Each q is independently 0 or 1; X Ａ each independently represents a single bond or a divalent to decavalent organic group, R Ｓ Each independently represents -(CR ４ (SH)-R ５ ) ｎ -CR １ R ２ is a monovalent group containing a group represented by -SH, R １ is a hydrocarbon group, R ２ is a hydrogen atom or a hydrocarbon group, R ４ is a hydrogen atom or a hydrocarbon group, R ５ is a divalent hydrocarbon group, In formulas (1) and (2), at least two secondary or tertiary thiol groups are present; α1 is an integer from 1 to 9, α2 is an integer from 1 to 9, Each β is independently an integer from 1 to 9; n is an integer from 0 to 9, Formulae (1) and (2) do not contain an ester structure. The fluoropolyether group-containing thiol compound according to claim 1 , represented by the formula:

8. Rf １ are each independently １－１６ is a perfluoroalkyl group, Rf ２ are each independently １－６ is a perfluoroalkylene group. The fluoropolyether group-containing thiol compound according to claim 7 .

9. R Ｆ each independently represents the formula: -(OC ６ F １２ ) ａ -(OC ５ F １０ ) ｂ -(OC ４ F ８ ) ｃ -(OC ３ R Ｆａ ６ ) ｄ -(OC ２ F ４ ) ｅ -(OCF ２ ) ｆ - [In the formula, R Ｆａ are each independently a hydrogen atom, a fluorine atom or a chlorine atom, a, b, c, d, e, and f each independently represent an integer of 0 to 200, the sum of a, b, c, d, e, and f is 1 or more, and the order of the repeating units enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula, provided that all R Ｆａ is a hydrogen atom or a chlorine atom, at least one of a, b, c, e and f is 1 or more. The fluoropolyether group-containing thiol compound according to claim 7, wherein the fluoropolyether group-containing thiol compound is a group represented by the formula:

10. R Ｆａ The fluoropolyether group-containing thiol compound according to claim 9 , wherein is a fluorine atom.

11. R Ｆ each independently represents the following formula (f1), (f2), (f3), (f4), (f5), or (f6): -(OC ３ F ６ ) ｄ -(OC ２ F ４ ) ｅ - (f1) [In the formula, d is an integer from 1 to 200, and e is 0 or 1.] -(OC ４ F ８ ) ｃ -(OC ３ F ６ ) ｄ -(OC ２ F ４ ) ｅ -(OCF ２ ) ｆ - (f2) [In the formula, c and d each independently represent an integer of 0 to 30, e and f each independently represent an integer from 1 to 200; The sum of c, d, e, and f is an integer from 10 to 200, The order of occurrence of each repeat unit enclosed in parentheses with the subscript c, d, e, or f is arbitrary in the formula. -(R ６ -R ７ ) ｇ - (f3) [In the formula, R ６ is O.C.F. ２ Or O.C. ２ F ４ and R ７ , O.C. ２ F ４ , O.C. ３ F ６ , O.C. ４ F ８ , O.C. ５ F １０ and O.C. ６ F １２ or a combination of two or three groups selected from these groups, g is an integer from 2 to 100. -(R ６ -R ７ ) ｇ -R ｒ -(R ７’ -R ６’ ) ｇ’ - (f4) [In the formula, R ６ is O.C.F. ２ Or O.C. ２ F ４ and R ７ , O.C. ２ F ４ , O.C. ３ F ６ , O.C. ４ F ８ , O.C. ５ F １０ and O.C. ６ F １２ or a combination of two or three groups independently selected from these groups; R ６’ is O.C.F. ２ Or O.C. ２ F ４ and R ７’ , O.C. ２ F ４ , O.C. ３ F ６ , O.C. ４ F ８ , O.C. ５ F １０ and O.C. ６ F １２ or a combination of two or three groups independently selected from these groups; g is an integer from 2 to 100; g' is an integer from 2 to 100, R ｒ teeth, 【Chemistry 2】 (In the formula, * indicates the bond position.) is.]; -(OC ６ F １２ ) ａ -(OC ５ F １０ ) ｂ -(OC ４ F ８ ) ｃ -(OC ３ F ６ ) ｄ -(OC ２ F ４ ) ｅ -(OCF ２ ) ｆ - (f5) [In the formula, e is an integer of 1 or more and 200 or less, a, b, c, d, and f are each independently an integer of 0 or more and 200 or less, and the order of the repeating units enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula.] -(OC ６ F １２ ) ａ -(OC ５ F １０ ) ｂ -(OC ４ F ８ ) ｃ -(OC ３ F ６ ) ｄ -(OC ２ F ４ ) ｅ -(OCF ２ ) ｆ - (f6) [In the formula, f is an integer of 1 or more and 200 or less, a, b, c, d, and e are each independently an integer of 0 or more and 200 or less, and the order of the repeating units enclosed in parentheses with a, b, c, d, e, or f is arbitrary in the formula.] The fluoropolyether group-containing thiol compound according to claim 7, wherein the fluoropolyether group-containing thiol compound is a group represented by the formula:

12. R Ｓ is represented by the following formula (S1), (S2), or (S3): 【Chemistry 3】 [In the formula: R Ｓａ is -Z-(CR ４ (SH)-R ５ ) ｎ -CR １ R ２ -SH, Z is a single bond or a divalent group; R １ is a hydrocarbon group, R ２ is a hydrogen atom or a hydrocarbon group, R ３ is a hydrogen atom or a hydrocarbon group, R ４ is a hydrogen atom or a hydrocarbon group, R ５ is a hydrocarbon group, n is an integer from 0 to 9, n1 is 1 or 2; n2 is 1, 2 or 3. The fluoropolyether group-containing thiol compound according to claim 7, wherein the fluoropolyether group-containing thiol compound is a group represented by the formula:

13. Z is -R １１ - and R １１ is a single bond, or C １－６ is an alkylene group, The fluoropolyether group-containing thiol compound according to claim 12.

14. R １ is C １－６ is an alkyl group, R ２ is a hydrogen atom or C １－６ The fluoropolyether group-containing thiol compound according to claim 7, which is an alkyl group.

15. R ３ is a hydrogen atom or C １－６ The fluoropolyether group-containing thiol compound according to claim 12, which is an alkyl group.

16. R Ｓ The fluoropolyether group-containing thiol compound according to claim 12 , wherein:

17. R Ｓ The fluoropolyether group-containing thiol compound according to claim 12 , wherein:

18. R Ｓ The fluoropolyether group-containing thiol compound according to claim 12 , wherein R 1 is a group represented by formula (S3):

19. The fluoropolyether group-containing thiol compound according to claim 7 , wherein α1, α2, and β are each 1.

20. X Ａ is the formula: -(R ２１ ) ｍ１ -(R ２２ ) ｍ２ - [In the formula: R ２１ is C １－６ is an alkylene group, R ２２ is -O-, -CO-, -NR ２３ --CONR ２３ - or -NR ２３ CO-, R ２３ is a hydrogen atom or C １－６ is an alkyl group, m1 is an integer from 0 to 10, m2 is an integer from 0 to 10, The sum of m1 and m2 is 1 or more, R ２１ and R ２２ The order of occurrence of is arbitrary in the formula. The fluoropolyether group-containing thiol compound according to claim 7, wherein the fluoropolyether group-containing thiol compound is a group represented by the formula:

21. 2. The fluoropolyether group-containing thiol compound according to claim 1, wherein the number average molecular weight is 1,000 to 100,000.

22. The fluoropolyether group-containing thiol compound according to claim 1, having a viscosity of 100 to 10,000 mPa·s.

23. A curable composition comprising the fluoropolyether group-containing thiol compound according to any one of claims 1 to 22.

24. The curable composition according to claim 23, further comprising a fluoropolyether group-containing unsaturated compound that contains a group having a carbon-carbon double bond.

25. The curable composition according to claim 24, wherein the number of groups having a carbon-carbon double bond is 2 to 8.

26. The curable composition according to claim 24, wherein the group having a carbon-carbon double bond is an allyl group, a vinyl group, or a (meth)acrylic group.

27. The curable composition according to claim 24, wherein the group having a carbon-carbon double bond is an allyl group.

28. The curable composition according to claim 24, wherein the group having a carbon-carbon double bond is present on both ends of the fluoropolyether group.

29. The fluoropolyether group-containing unsaturated compound containing a group having a carbon-carbon double bond has a group selected from a linear or branched alkylene group, a cycloalkylene group, a phenylene group, an alkylamino group, an ether bond, a thioether bond, a carbonyl bond and an amide bond. The curable composition according to claim 24.

30. The fluoropolyether group-containing unsaturated compound is represented by the following formula (3) or (4): 【Chemistry 4】 [In the formula: R Ｆ１ Each independently represents Rf １ -R Ｆ -O ｑ - and R Ｆ２ is -Rf ２ ｐ -R Ｆ -O ｑ - and Rf １ each independently represents a C which may be substituted by one or more fluorine atoms; １－１６ is an alkyl group, Rf ２ C optionally substituted with one or more fluorine atoms １－６ is an alkylene group, R Ｆ are each independently a divalent fluoropolyether group, p is 0 or 1; Each q is independently 0 or 1; X Ｂ each independently represents a single bond or a divalent to decavalent organic group, R Ｄ are each independently a group containing a carbon-carbon double bond, γ1 is an integer from 1 to 9, γ2 is an integer from 1 to 9, Each δ is independently an integer from 1 to 9. The curable composition according to claim 24, wherein the compound is represented by the formula:

31. The carbon-carbon double bond-containing group has the formula: -Y-A [In the formula: Y is a single bond, an oxygen atom, or a divalent organic group; A is -CR ４１ =CH ２ and R ４１ are each independently a hydrogen atom or C １－３ is an alkyl group. The curable composition according to claim 30, wherein the group is represented by the formula:

32. Y is -CR ４２ ２ - or -CO-, R ４２ are each independently a hydrogen atom or C １－６ is an alkyl group, 32. The curable composition of claim 31.

33. R Ｄ is represented by the following formula (D1), (D2), (D3), (D4) or (D5): 【Chemistry 5】 [In the formula, Y is a single bond, an oxygen atom, or a divalent organic group; A is -CR ４１ =CH ２ and R ４１ are each independently a hydrogen atom or C １－３ is an alkyl group, X １０ is independently at each occurrence a single bond or a divalent organic group; R １３ is independently at each occurrence a hydrogen atom or a monovalent organic group; t is independently in each occurrence an integer greater than or equal to 2; R １４ is independently at each occurrence a hydrogen atom or a halogen atom; R ａ１ is independently at each occurrence -Z １ -SiR ａ２ ｐ１ R ａ３ ｑ１ R ａ４ ｒ１ and Z １ is independently at each occurrence a single bond, an oxygen atom, or a divalent organic group; R ａ２ is, independently at each occurrence, -Z １’ -SiR ａ３’ ｑ１’ R ａ４’ ｒ１’ and Z １’ is independently at each occurrence a single bond, an oxygen atom, or a divalent organic group; R ａ３’ is independently at each occurrence -Z ２ -Y-A, R ａ４’ is independently in each occurrence a hydrogen atom, a hydroxyl group, or a monovalent organic group; Z ２ is independently in each occurrence a single bond, an oxygen atom, or a divalent organic group; q1' in each occurrence is independently an integer from 0 to 3; r1' in each occurrence is independently an integer from 0 to 3; Here, the sum of q1′ and r1′ is (SiR ａ３’ ｑ１’ R ａ４’ ｒ１’ ) units is 3, R ａ３ is independently at each occurrence -Z ２ -Y-A, R ａ４ is independently in each occurrence a hydrogen atom, a hydroxyl group, or a monovalent organic group; p1, in each occurrence, is independently an integer from 0 to 3; q1 in each occurrence is independently an integer from 0 to 3; r1, independently at each occurrence, is an integer from 0 to 3; Here, the sum of p1, q1 and r1 is (SiR ａ２ ｐ１ R ａ３ ｑ１ R ａ４ ｒ１ ) units is 3, R ｂ１ is independently at each occurrence -Z ２ -Y-A, R ｃ１ is independently in each occurrence a hydrogen atom, a hydroxyl group, or a monovalent organic group; k1, in each occurrence, is independently an integer from 0 to 3; l1 in each occurrence is independently an integer from 0 to 3; m1 in each occurrence is independently an integer from 0 to 3; Here, the sum of k1, l1, and m1 is (SiR ａ１ ｋ１ R ｂ１ ｌ１ R ｃ１ ｍ１ ) units is 3, In formula (D3), at least one -Y-A is present, R ｄ１ is independently at each occurrence -Z ３ -CR ｄ２ ｐ２ R ｄ３ ｑ２ R ｄ４ ｒ２ and Z ３ is independently in each occurrence a single bond, an oxygen atom, or a divalent organic group; R ｄ２ is independently at each occurrence -Z ３’ -CR ｄ３’ ｑ２’ R ｄ４’ ｒ２’ and Z ３’ is independently at each occurrence an oxygen atom or a divalent organic group; R ｄ３’ is independently at each occurrence -Z ２ -Y-A, R ｄ４’ is independently in each occurrence a hydrogen atom, a hydroxyl group, or a monovalent organic group; q2' in each occurrence is independently an integer from 0 to 3; r2' is independently at each occurrence an integer from 0 to 3; Here, the sum of q2' and r2' is (CR ｄ３’ ｑ２’ R ｄ４’ ｒ２’ ) units is 3, R ｄ３ is independently at each occurrence -Z ２ -Y-A; R ｄ４ is independently in each occurrence a hydrogen atom, a hydroxyl group, or a monovalent organic group; p2, in each occurrence, is independently an integer from 0 to 3; q2, in each occurrence, is independently an integer from 0 to 3; r2, independently at each occurrence, is an integer from 0 to 3; Here, the sum of p2, q2 and r2 is (CR ｄ２ ｐ２ R ｄ３ ｑ２ R ｄ４ ｒ２ ) units is 3, R ｅ１ is independently at each occurrence -Z ２ -Y-A, R ｆ１ is independently in each occurrence a hydrogen atom, a hydroxyl group, or a monovalent organic group; k2 in each occurrence is independently an integer from 0 to 3; l2 in each occurrence is independently an integer from 0 to 3; m2 in each occurrence is independently an integer from 0 to 3; Here, the sum of k2, l2, and m2 is (CR ｄ１ ｋ２ R ｅ１ ｌ２ R ｆ１ ｍ２ ) units is 3, In formula (D4), at least one A is present, R ｇ１ and R ｈ１ is independently at each occurrence -Z ４ -Y-A, -Z ４ -SiR ａ１ ｋ１ R ｂ１ ｌ１ R ｃ１ ｍ１ , or -Z ４ -CR ｄ１ ｋ２ R ｅ１ ｌ２ R ｆ１ ｍ２ and Z ４ is independently at each occurrence a single bond, an oxygen atom, or a divalent organic group; In formula (D5), at least one A is present. The curable composition according to claim 30, wherein the group is represented by the formula:

34. X Ｂ are each independently represented by the following formula: -{(R ３１ ) ｐ’ -(X ａ ) ｑ’ }-R ３２ - [In the formula: R ３１ is a single bond, -(CH ２ ) ｓ’ - or an o-, m- or p-phenylene group, R ３２ is a single bond, -(CH ２ ) ｔ’ - or an o-, m- or p-phenylene group, s' is an integer from 1 to 20; t' is an integer from 1 to 20, X ａ is -(X ｂ ) ｒ’ - represents X ｂ each occurrence independently represents -O-, -CO-, -S-, o-, m- or p-phenylene group, substituted or unsubstituted C ３－１０ Cycloalkylene, a substituted or unsubstituted o-, m- or p-phenylene group, -CONR ３４ --, --NR ３４ -, -Si(R ３３ ) ２ -, -(Si(R ３３ ) ２ O) ｍ’ -Si(R ３３ ) ２ - and -(CH ２ ) ｎ’ - represents a group selected from the group consisting of R ３３ is independently at each occurrence a phenyl group; １－６ Alkyl group or C １－６ is an alkoxy group, R ３４ each occurrence independently represents a hydrogen atom, a phenyl group, or C １－６ is an alkyl group, m' in each occurrence is independently an integer from 1 to 100; n', in each occurrence, is independently an integer from 1 to 20; r' is an integer from 1 to 10; p′ is 0 or 1; q′ is 0 or 1; Here, at least one of p' and q' is 1, and the order of the repeating units enclosed in parentheses with p' or q' is arbitrary. The curable composition according to claim 30, wherein the divalent group is represented by the following formula:

35. The curable composition according to claim 24, wherein the mass ratio of the fluoropolyether group-containing thiol compound to the fluoropolyether group-containing unsaturated compound is 0.1:100 to 100:0.

1.

36. 24. The curable composition of claim 23, further comprising a polymerization initiator.

37. 37. The curable composition of claim 36, wherein the polymerization initiator is a radical polymerization initiator.

38. 37. The curable composition of claim 36, wherein the polymerization initiator is a radical photoinitiator.

39. The curable composition according to claim 36, wherein the polymerization initiator has 1 to 3 aromatic ring structures.

40. The curable composition according to claim 23, further comprising a fluorinated oil.

41. The fluorine-containing oil has the following formula (5): Rf ５ -(OC ４ F ８ ) ａ’ -(OC ３ F ６ ) ｂ’ -(OC ２ F ４ ) ｃ’ -(OCF ２ ) ｄ’ -Rf ６ ・・・(5) [In the formula: Rf ５ C optionally substituted with one or more fluorine atoms １－１６ is an alkyl group, Rf ６ C optionally substituted with one or more fluorine atoms １－１６ an alkyl group, a fluorine atom, or a hydrogen atom; a', b', c', and d' are each independently an integer of 0 to 300, The order of occurrence of each repeating unit enclosed in parentheses with the subscript a', b', c', or d' is arbitrary in the formula. The curable composition according to claim 40, wherein the compound is represented by the formula:

42. 24. The curable composition of claim 23 which is solventless.

43. The curable composition according to claim 23, having a viscosity of 100 to 10,000 mPa·s.

44. A cured product obtained by curing the curable composition according to claim 23.

45. The cured product according to claim 44, which has a weight loss of less than 50% after being held at 65°C and 90% RH for 72 hours.

46. The cured product according to claim 44, having a tensile modulus of elasticity of 0.1 to 500 MPa.

47. The cured product of claim 44, which is an encapsulant.

48. The cured product according to claim 44, which is an encapsulant for electronic devices.

49. 24. An article comprising a substrate and a layer on the substrate of the curable composition of claim 23.

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