Thiol compound containing fluoropolyether group

Abstract

The purpose of the present invention is to provide a fluorinated polyether group-containing thiol compound having excellent stability. This fluorinated polyether group-containing thiol compound does not contain an ester structure, and contains two or more thiol groups selected from a secondary thiol group and a tertiary thiol group.

Description

Technical Field

[0001] The present invention relates to thiol compounds containing fluorinated polyether groups. Background Art

[0002] As a thiol compound containing a fluorinated polyether group, for example, a compound having a fluorinated polyether group and a primary thiol group is known (Patent Document 1).

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Publication No. 2006-291206 Summary of the invention

[0006] Technical problem to be solved by the invention

[0007] An object of the present invention is to provide a thiol compound containing a fluorinated polyether group having excellent stability.

[0008] Technical solutions for solving technical problems

[0009] The present invention includes the following aspects.

[0010] [1] A fluorinated polyether group-containing thiol compound having no ester structure and containing two or more thiol groups selected from secondary thiol groups and tertiary thiol groups.

[0011] [2] The fluorinated polyether group-containing thiol compound according to [1], wherein the fluorine content is 30% by mass or more.

[0012] [3] The fluorinated polyether group-containing thiol compound according to [1] or [2], comprising 2 to 6 thiol groups.

[0013] [4] The fluoropolyether-based thiol compound according to any one of [1] to [3], wherein the thiol group is a secondary thiol group.

[0014] [5] The fluoropolyether-based thiol compound according to any one of [1] to [4], wherein the thiol group is present on both end sides of the fluoropolyether group.

[0015] [6] The fluoropolyether-based thiol compound according to any one of [1] to [5], 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.

[0016] [7] The fluoropolyether-based thiol compound according to any one of [1] to [6], which is represented by the following formula (1) or (2).

[0017] RF1 α1 -X A -R S α2 (1)

[0018] R S β -X A -R F2 -X A -R S β (2)

[0019] [Wherein,

[0020] R F1 R f1 -R F -O q -

[0021] R F2 For -R f2 p -R F -O q -

[0022] R f1 are each independently C which may be substituted with one or more fluorine atoms 1－16 alkyl,

[0023] R f2 is C which may be substituted by one or more fluorine atoms 1－6 Alkylene,

[0024] R F are each independently a divalent fluorinated polyether group,

[0025] p is 0 or 1,

[0026] q is independently 0 or 1,

[0027] X A are each independently a single bond or a 2- to 10-valent organic group,

[0028] R S Each independently includes -(CR 4 (SH)-R 5 ) n -CR 1 R 2 - a monovalent group represented by a group represented by SH,

[0029] R 1 is a hydrocarbon group,

[0030] R 2 is a hydrogen atom or a hydrocarbon group,

[0031] R 4 is a hydrogen atom or a hydrocarbon group,

[0032] R 5 is a divalent hydrocarbon group,

[0033] In formula (1) and (2), there are at least two secondary or tertiary thiol groups,

[0034] α1 is an integer from 1 to 9,

[0035] α2 is an integer from 1 to 9,

[0036] β is an integer of 1 to 9 independently.

[0037] n is an integer from 0 to 9,

[0038] Formulas (1) and (2) do not contain ester structures.]

[0039] [8] The fluorinated polyether group-containing thiol compound according to [7],

[0040] R f1 C 1－16 Perfluoroalkyl,

[0041] R f2 C 1－6 Perfluoroalkylene.

[0042] [9] The fluorinated polyether group-containing thiol compound as shown in [7] or [8], wherein R F They are independently of each other and are of 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 - the group shown.

[0043] [Where R Fa are independently a hydrogen atom, a fluorine atom or a chlorine atom,

[0044] a, b, c, d, e and f are each independently an integer of 0 to 200, the sum of a, b, c, d, e and f is 1 or more, the order of existence of the repeating units marked with a, b, c, d, e or f and enclosed in parentheses in the formula is arbitrary, wherein in all R Fa When it is a hydrogen atom or a chlorine atom, at least one of a, b, c, e and f is 1 or more.]

[0045]

[10] The fluorinated polyether group-containing thiol compound according to [9], wherein R Fa A fluorine atom.

[0046]

[11] The fluorinated polyether group-containing thiol compound according to any one of [7] to

[10] , wherein R F Each independently represents a group represented by the following formula (f1), (f2), (f3), (f4), (f5) or (f6).

[0047] -(OC 3 F 6 ) d -(OC 2 F 4 ) e - (f1)

[0048] [Wherein, d is an integer of 1 to 200, and e is 0 or 1.]

[0049] -(OC 4 F 8 ) c -(OC 3 F 6 ) d -(OC 2 F 4 ) e -(OCF 2 ) f -(f2)

[0050] [wherein, c and d are each independently an integer of 0 to 30,

[0051] e and f are each independently an integer of 1 to 200,

[0052] The sum of c, d, e and f is an integer from 10 to 200,

[0053] The order of presence of the repeating units marked with the subscript c, d, e or f and enclosed in parentheses is arbitrary in the formula.]

[0054] -(R 6 -R 7 ) g - (f3)

[0055] [Where R6 For OCF 2 or OC 2 F 4 ,

[0056] R 7 For OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 or a combination of two or three groups selected from these groups,

[0057] g is an integer from 2 to 100.]

[0058] -(R 6 -R 7 ) g -R r -(R 7' -R 6' ) g' - (f4)

[0059] [Where R 6 For OCF 2 or OC 2 F 4 ,

[0060] R 7 For OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 or a combination of 2 or 3 groups independently selected from these groups,

[0061] R 6' For OCF 2 or OC 2 F 4 ,

[0062] R 7' For OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5F 10 and OC 6 F 12 or a combination of 2 or 3 groups independently selected from these groups,

[0063] g is an integer from 2 to 100,

[0064] g' is an integer from 2 to 100,

[0065] R r for:

[0066]

[0067] (Where * indicates the bonding position.)]

[0068] -(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)

[0069] [In the formula, e is an integer from 1 to 200, a, b, c, d and f are each independently an integer from 0 to 200, and the order of existence of each repeating unit marked with a, b, c, d, e or f and enclosed in parentheses is arbitrary in the formula.]

[0070] -(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)

[0071] [In the formula, f is an integer from 1 to 200, a, b, c, d and e are each independently an integer from 0 to 200, and the order of existence of each repeating unit marked with a, b, c, d, e or f and enclosed in parentheses is arbitrary in the formula.]

[0072]

[12] The fluorinated polyether group-containing thiol compound according to any one of [7] to

[11] , wherein R S It is a group represented by the following formula (S1), (S2) or (S3).

[0073] -R Sa (S1)

[0074] -UR Sa n1 R 3 2-n1 (S2)

[0075] -CR Sa n2 R 3 3-n2 (S3)

[0076] [Wherein,

[0077] R Sa Z-(CR 4 (SH)-R 5 ) n -CR 1 R 2 -SH,

[0078] Z is a single bond or a divalent group,

[0079] R 1 is a hydrocarbon group,

[0080] R 2 is a hydrogen atom or a hydrocarbon group,

[0081] R 3 is a hydrogen atom or a hydrocarbon group,

[0082] R 4 is a hydrogen atom or a hydrocarbon group,

[0083] R 5 is a hydrocarbon group,

[0084] n is an integer from 0 to 9,

[0085] n1 is 1 or 2,

[0086] n2 is 1, 2, or 3.]

[0087]

[13] The fluorinated polyether group-containing thiol compound according to

[12] , wherein

[0088] Z is -R 11 -

[0089] R 11 is a single bond or C 1－6 Alkylene.

[0090]

[14] The fluorinated polyether group-containing thiol compound according to any one of [7] to

[13] , wherein R 1 C 1－6 Alkyl, R 2 A hydrogen atom or C 1－6 alkyl.

[0091]

[15] The fluorinated polyether group-containing thiol compound according to any one of

[12] to

[14] , wherein R 3 A hydrogen atom or C 1－6 alkyl.

[0092]

[16] The fluorinated polyether group-containing thiol compound according to any one of

[12] to

[15] , wherein R S It is a group represented by formula (S1).

[0093]

[17] The fluorinated polyether group-containing thiol compound according to any one of

[12] to

[16] , wherein R S It is a group represented by formula (S2).

[0094]

[18] The fluorinated polyether group-containing thiol compound according to any one of

[12] to

[17] , wherein R S It is a group represented by formula (S3).

[0095]

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

[18] , wherein α1, α2 and β are 1.

[0096]

[20] The fluorinated polyether group-containing thiol compound according to any one of [7] to

[19] , wherein X A Formula: -(R 21 ) m1 -(R 22 ) m2 - the group shown.

[0097] [Wherein,

[0098] R 21 C 1－6 Alkylene,

[0099] R 22 -O-, -CO-, -NR 23 -、-CONR 23 -or-NR23 CO-,

[0100] R 23 A hydrogen atom or C 1－6 alkyl,

[0101] m1 is an integer from 0 to 10,

[0102] m2 is an integer from 0 to 10,

[0103] The sum of m1 and m2 is greater than 1,

[0104] R 21 and R 22 The order in which the terms are present in the formula is arbitrary.]

[0105]

[21] The fluorinated polyether group-containing thiol compound according to any one of [1] to

[20] , wherein R F is a group represented by the following formula (f1) or (f2), X A Formula: -(R 21 ) m1 -(R 22 ) m2 - shown group, and R S A compound which is a group represented by the following formula (S1) or (S2).

[0106] R S β -X A -R F2 -X A -R S β (2)

[0107] [R F2 Rf 2 p -R F -O q -

[0108] R 2 is C which may be substituted by one or more fluorine atoms 1－6 Alkylene,

[0109] R F are each independently a divalent fluorinated polyether group,

[0110] p is 0 or 1,

[0111] q is independently 0 or 1,

[0112] X A are each independently a single bond or a 2- to 10-valent organic group,

[0113] R S Each independently includes -(CR 4 (SH)-R 5 ) n -CR 1 R 2 - a monovalent group represented by a group represented by SH,

[0114] R 1 is a hydrocarbon group,

[0115] R 2 is a hydrogen atom or a hydrocarbon group,

[0116] R 4 is a hydrogen atom or a hydrocarbon group,

[0117] R 5 is a divalent hydrocarbon group,

[0118] In (2), there are at least 2 secondary or tertiary thiol groups,

[0119] α1 is an integer from 1 to 9,

[0120] α2 is an integer from 1 to 9,

[0121] β is an integer of 1 to 9 independently.

[0122] n is an integer from 0 to 9,

[0123] Formula (2) does not contain an ester structure.]

[0124] -(OC 3 F 6 ) d -(OC 2 F 4 ) e - (f1)

[0125] [Wherein, d is an integer of 1 to 200, and e is 0 or 1.]

[0126] -(OC 4 F 8 ) c -(OC 3 F 6 ) d -(OC 2 F 4 ) e -(OCF 2 ) f -(f2)

[0127] [wherein, c and d are each independently an integer of 0 to 30,

[0128] e and f are each independently an integer of 1 to 200,

[0129] The sum of c, d, e and f is an integer from 10 to 200,

[0130] The order of presence of the repeating units marked with the subscript c, d, e or f and enclosed in parentheses is arbitrary in the formula.]

[0131] Formula - (R 21 ) m1 -(R 22 ) m2 -middle,

[0132] R 21 C 1－6 Alkylene,

[0133] R 22 -O-, -CO-, -NR 23 -、-CONR 23 -or-NR 23 CO-,

[0134] R 23 A hydrogen atom or C 1－6 alkyl,

[0135] m1 is an integer from 0 to 10,

[0136] m2 is an integer from 0 to 10,

[0137] The sum of m1 and m2 is greater than 1,

[0138] R 21 and R 22 The order in which is present in the formula is arbitrary.

[0139] -R Sa (S1)

[0140] -NR Sa n1 R 3 2－n1 (S2)

[0141]

[22] The fluorinated polyether group-containing thiol compound according to any one of [1] to

[21] , wherein the number average molecular weight is 1,000 to 100,000.

[0142]

[23] The fluorinated polyether group-containing thiol compound according to any one of [1] to

[22] , wherein the viscosity is 100 to 10,000 mPa·s.

[0143]

[24] A curable composition comprising the fluoropolyether-based thiol compound according to any one of [1] to

[23] .

[0144]

[25] The curable composition according to

[24] , further comprising a fluorinated polyether group-containing unsaturated compound having a group having a carbon-carbon double bond.

[0145]

[26] The curable composition according to

[25] , wherein the number of the groups having carbon-carbon double bonds is 2 to 8.

[0146]

[27] The curable composition according to

[25] or

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

[0147]

[28] The curable composition according to any one of

[25] to

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

[0148]

[29] The curable composition according to any one of

[25] to

[28] , wherein the group having a carbon-carbon double bond is present on both end sides of the fluoropolyether group.

[0149]

[30] A curable composition as described in any one of

[25] to

[29] , wherein the unsaturated compound containing a fluorinated polyether group and 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.

[0150]

[31] The curable composition according to any one of

[25] to

[30] , wherein

[0151] The above-mentioned fluorinated polyether group-containing unsaturated compound is a compound represented by the following formula (3) or (4).

[0152] R F1 V1 -X B -R D γ2 (3)

[0153] R D δ -Y B -R F2 -Y B -R D δ (3)

[0154] [Wherein,

[0155] R F1 R f1 -R F -O q -

[0156] R F2 For -R f2 p -R F -O q -

[0157] R f1 are each independently C which may be substituted with one or more fluorine atoms 1－16 alkyl,

[0158] R f2 is C which may be substituted by one or more fluorine atoms 1－6 Alkylene,

[0159] R F are each independently a divalent fluorinated polyether group,

[0160] p is 0 or 1,

[0161] q is independently 0 or 1,

[0162] X B are each independently a single bond or a 2- to 10-valent organic group,

[0163] R D are each independently a group having a carbon-carbon double bond,

[0164] γ1 is an integer from 1 to 9,

[0165] γ2 is an integer from 1 to 9,

[0166] δ is independently an integer of 1 to 9.]

[0167]

[32] The curable composition according to

[31] , wherein

[0168] The above-mentioned group having a carbon-carbon double bond is a group represented by the formula: -YA.

[0169] [Wherein,

[0170] Y is a single bond, an oxygen atom or a divalent organic group,

[0171] A is -CR 41 =CH 2 ,

[0172] R 41 are independently a hydrogen atom or a C 1-3 alkyl.]

[0173]

[33] The curable composition according to

[32] , wherein

[0174] Y is -CR 42 2-or-CO-,

[0175] R 42 are independently a hydrogen atom or a C 1-6 alkyl.

[0176]

[34] The curable composition according to any one of

[32] to

[33] , wherein

[0177] R D It is a group represented by the following formula (D1), (D2), (D3), (D4) or (D5).

[0178] -YA (D1)

[0179]

[0180] -SiR a1 k1 R b1 11 R c1 m1 (D3)

[0181] -CR d1 k2 R e1 12 R f1 m2 (D4)

[0182] -NR g1 R h1 (D5)

[0183] [Wherein,

[0184] Y is a single bond, an oxygen atom or a divalent organic group,

[0185] A is -CR 41 =CH 2 ,

[0186] R 41 are independently a hydrogen atom or a C 1-3 alkyl,

[0187] X 10 is independently a single bond or a divalent organic group at each occurrence,

[0188] R 13 is independently a hydrogen atom or a monovalent organic group at each occurrence,

[0189] t is independently an integer greater than 2 at each occurrence,

[0190] R 14is independently a hydrogen atom or a halogen atom at each occurrence,

[0191] R a1 -Z independently at each occurrence 1 -SiR a2 p1 R a3 q1 R a4 r1 ,

[0192] Z 1 is independently a single bond, an oxygen atom or a divalent organic group at each occurrence,

[0193] R a2 Each time it occurs, it is independently -Z 1' -SiR a3' q1' R a4' r1' ,

[0194] Z 1' is independently a single bond, an oxygen atom or a divalent organic group at each occurrence,

[0195] R a3 'In each occurrence, it is independently -Z 2 -Y-A,

[0196] R a4' is independently a hydrogen atom, a hydroxyl group or a monovalent organic group at each occurrence,

[0197] Z 2 is independently a single bond, an oxygen atom or a divalent organic group at each occurrence,

[0198] q 1' is independently an integer from 0 to 3 at each occurrence,

[0199] r 1' is independently an integer from 0 to 3 at each occurrence,

[0200] Among them, the sum of q1' and r1' is (SiR a3' q1' R a4' r1' ) unit is 3,

[0201] R a3 Each time it occurs, it is independently -Z 2 -Y-A,

[0202] R a4Each occurrence is independently a hydrogen atom, a hydroxyl group or a monovalent organic group, p1 is independently an integer of 0 to 3 each occurrence, q1 is independently an integer of 0 to 3 each occurrence, r1 is independently an integer of 0 to 3 each occurrence,

[0203] Among them, the sum of p1, q1 and r1 is (SiR a2 p1 R a3 q1 R a4 r1 ) unit is 3,

[0204] R b1 Each time it occurs, it is independently -Z 2 -Y-A,

[0205] R c1 Each occurrence is independently a hydrogen atom, a hydroxyl group or a monovalent organic group, k1 is independently an integer of 0 to 3 each time it occurs, l1 is independently an integer of 0 to 3 each time it occurs, m1 is independently an integer of 0 to 3 each time it occurs,

[0206] Among them, the sum of k1, l1 and m1 is (SiR a1 k1 R b1 l1 R c1 m1 ) unit is 3, in formula (D3), there is at least one -Y-A,

[0207] R d1 Each time it occurs, it is independently -Z 3 -CR d2 p2 R d3 q2 R d4 r2 ,

[0208] Z 3 Each occurrence is independently a single bond, an oxygen atom or a divalent organic group, R d2 Each time it occurs, it is independently -Z 3' -CR d3' q2' R d4' r2' ,

[0209] Z 3' is independently an oxygen atom or a divalent organic group at each occurrence,

[0210] R d3'Each time it occurs, it is independently -Z 2 -Y-A,

[0211] R d4' is independently a hydrogen atom, a hydroxyl group or a monovalent organic group at each occurrence,

[0212] q2' is independently an integer from 0 to 3 at each occurrence,

[0213] r2' is independently an integer from 0 to 3 at each occurrence,

[0214] Among them, the sum of q2' and r2' is (CR d3' q2' R d4' r2' ) unit is 3,

[0215] R d3 Each time it occurs, it is independently -Z 2 -Y-A,

[0216] R d4 is independently a hydrogen atom, a hydroxyl group or a monovalent organic group at each occurrence,

[0217] p2 is independently an integer from 0 to 3 at each occurrence.

[0218] q2 is independently an integer from 0 to 3 at each occurrence,

[0219] r2 is independently an integer from 0 to 3 at each occurrence,

[0220] Among them, the sum of p2, q2 and r2 is (CR d2 p2 R d3 q2 R d4 r2 ) unit is 3,

[0221] R e1 Each time it occurs, it is independently -Z 2 -Y-A,

[0222] R f1 is independently a hydrogen atom, a hydroxyl group or a monovalent organic group at each occurrence,

[0223] k2 is independently an integer from 0 to 3 at each occurrence.

[0224] l2 is an integer from 0 to 3 independently at each occurrence.

[0225] m2 is independently an integer from 0 to 3 at each occurrence.

[0226] Among them, the sum of k2, l2 and m2 is (CR d1 k2 R e1 l2 R f1 m2 ) unit is 3,

[0227] In formula (D4), there is at least one A,

[0228] R g1 and R h1 Each time it occurs, it is independently -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 ,

[0229] Z 4 Each occurrence is independently a single bond, an oxygen atom or a divalent organic group, and in formula (D5), there is at least one A.]

[0230]

[35] The curable composition according to any one of

[32] to

[34] , wherein

[0231] X B Each independently represents the following formula: 31 ) p' -(X a ) q'}-R 32 - The divalent group shown.

[0232] [Wherein,

[0233] R 31 is a single bond, -(CH 2 )s'-or o-phenylene, m-phenylene or p-phenylene,

[0234] R 32 is a single bond, -(CH 2 )t'-or o-phenylene, m-phenylene or p-phenylene,

[0235] s' is an integer from 1 to 20,

[0236] t' is an integer from 1 to 20,

[0237] X a Indicates - (X b ) r' -

[0238] Xb, at each occurrence, independently represents -O-, -CO-, -S-, o-phenylene, m-phenylene or p-phenylene, substituted or unsubstituted C 3－10 Cycloalkylene, substituted or unsubstituted o-phenylene, m-phenylene or p-phenylene, -CONR 34 -, -NR 34 -、-Si(R 33 ) 2 -、-(Si(R 33 ) 2 O) m' -Si(R 33 ) 2 - and - (CH 2 ) n' - in the group,

[0239] R 33 Each occurrence is independently phenyl, C 1-6 Alkyl or C 1-6 Alkoxy,

[0240] R 34 Each occurrence is independently a hydrogen atom, a phenyl group or a C 1-6 alkyl,

[0241] m' is independently an integer from 1 to 100 at each occurrence,

[0242] n' is independently an integer from 1 to 20 at each occurrence,

[0243] r' is an integer from 1 to 10,

[0244] p' is 0 or 1,

[0245] q' is 0 or 1,

[0246] In which at least one of p' and q' is 1, the order of existence of each repeating unit marked with p' or q' and enclosed in parentheses is arbitrary.]

[0247]

[36] The curable composition according to any one of

[31] to

[35] , wherein

[0248] The above-mentioned unsaturated compound containing a fluorinated polyether group is included in the compound represented by the above formula (4): F is a group represented by the following formula (f1), R D is a group represented by the following formula (D1), (D2), (D3), (D4) or (D5), XB Each independently represents the following formula: 31 ) p′ -(X a ) q′}-R 32 -a compound having a divalent group as shown,

[0249] -(OC 3 F 6 ) d -(OC 2 F 4 ) e - (f1)

[0250] [Wherein, d is an integer of 1 to 200, and e is 0 or 1.]

[0251] -YA (D1)

[0252]

[0253] -SiR a1 k1 R b1 11 R c1 m1 (D3)

[0254] -CR d1 k2 R e1 12 R f1 m2 (D4)

[0255] -NR g1 R h1 (D5)

[0256] [Wherein,

[0257] Y is a single bond, an oxygen atom or a divalent organic group,

[0258] A is -CR 41 =CH 2 ,

[0259] R 41 are independently a hydrogen atom or a C 1-3 alkyl,

[0260] X 10 is independently a single bond or a divalent organic group at each occurrence,

[0261] R 13 is independently a hydrogen atom or a monovalent organic group at each occurrence,

[0262] t is independently an integer greater than 2 at each occurrence,

[0263] R 14 is independently a hydrogen atom or a halogen atom at each occurrence,

[0264] R a1 Each time it occurs, it is independently -Z 1 -SiR a2 p1 R a3 q1 R a4 r1 ,

[0265] Z 1 is independently a single bond, an oxygen atom or a divalent organic group at each occurrence,

[0266] R a2 Each time it occurs, it is independently -Z 1' -SiR a3' q1' R a4' r1' ,

[0267] Z 1' is independently a single bond, an oxygen atom or a divalent organic group at each occurrence,

[0268] R a3' Each time it occurs, it is independently -Z 2 -Y-A,

[0269] R a4' is independently a hydrogen atom, a hydroxyl group or a monovalent organic group at each occurrence,

[0270] Z 2 is independently a single bond, an oxygen atom or a divalent organic group at each occurrence,

[0271] q1' is independently an integer from 0 to 3 at each occurrence,

[0272] r1' is independently an integer from 0 to 3 at each occurrence,

[0273] Among them, the sum of q1' and r1' is (SiR a3' q1' R a4' r1' ) unit is 3,

[0274] R a3 Each time it occurs, it is independently -Z 2 -Y-A,

[0275] Ra4 is independently a hydrogen atom, a hydroxyl group or a monovalent organic group at each occurrence,

[0276] p1 is an integer from 0 to 3 independently at each occurrence.

[0277] q1 is an integer from 0 to 3 independently at each occurrence.

[0278] r1 is independently an integer from 0 to 3 each time it appears.

[0279] Among them, the sum of p1, q1 and r1 is (SiR a2 p1 R a3 q1 R a4 r1 ) unit is 3,

[0280] R b1 Each time it occurs, it is independently -Z 2 -Y-A,

[0281] R c1 is independently a hydrogen atom, a hydroxyl group or a monovalent organic group at each occurrence,

[0282] k1 is independently an integer from 0 to 3 each time it appears.

[0283] l1 is an integer from 0 to 3 independently at each occurrence.

[0284] m1 is independently an integer from 0 to 3 at each occurrence.

[0285] Among them, the sum of k1, l1 and m1 is (SiR a1 k1 R b1 l1 R c1 m1 ) unit is 3,

[0286] In formula (D3), there is at least one -Y-A,

[0287] R d1 Each time it occurs, it is independently -Z 3 -CR d2 p2 R d3 q2 R d4 r2 ,

[0288] Z 3 is independently a single bond, an oxygen atom or a divalent organic group at each occurrence,

[0289] R d2 Each time it occurs, it is independently -Z 3' -CR d3' q2' R d4' r2' ,

[0290] Z 3' is independently an oxygen atom or a divalent organic group at each occurrence,

[0291] R d3' Each time it occurs, it is independently -Z 2 -Y-A,

[0292] R d4' is independently a hydrogen atom, a hydroxyl group or a monovalent organic group at each occurrence,

[0293] q2' is independently an integer from 0 to 3 at each occurrence,

[0294] r2' is independently an integer from 0 to 3 at each occurrence,

[0295] Among them, the sum of q2' and r2' is (CR d3' q2' R d4' r2' ) unit is 3,

[0296] R d3 Each time it occurs, it is independently -Z 2 -Y-A,

[0297] R d4 is independently a hydrogen atom, a hydroxyl group or a monovalent organic group at each occurrence,

[0298] p2 is independently an integer from 0 to 3 at each occurrence.

[0299] q2 is independently an integer from 0 to 3 at each occurrence,

[0300] r2 is independently an integer from 0 to 3 at each occurrence,

[0301] Among them, the sum of p2, q2 and r2 is (CR d2 p2 R d3 q2 R d4 r2 ) unit is 3,

[0302] R e1 Each time it occurs, it is independently -Z 2 -Y-A,

[0303] R f1 is independently a hydrogen atom, a hydroxyl group or a monovalent organic group at each occurrence,

[0304] k2 is independently an integer from 0 to 3 at each occurrence.

[0305] l2 is an integer from 0 to 3 independently at each occurrence.

[0306] m2 is independently an integer from 0 to 3 at each occurrence.

[0307] Among them, the sum of k2, l2 and m2 is (CR d1 k2 R e1 l2 R f1 m2 ) unit is 3,

[0308] In formula (D4), there is at least one A,

[0309] R g1 and R h1 Each time it occurs, it is independently -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 ,

[0310] Z 4 is independently a single bond, an oxygen atom or a divalent organic group at each occurrence,

[0311] In formula (D5), there is at least one A.]

[0312] -{(R 31 ) p' -(X a ) q'}-R 32 -

[0313] [Wherein,

[0314] R 31 is a single bond, -(CH 2 ) s' - or o-phenylene, m-phenylene or p-phenylene,

[0315] R 32 is a single bond, -(CH 2 ) t' - or o-phenylene, m-phenylene or p-phenylene,

[0316] s' is an integer from 1 to 20,

[0317] t' is an integer from 1 to 20,

[0318] X a Indicates - (X b ) r' -

[0319] X b Each occurrence independently represents a substituted or unsubstituted C 3－10 Cycloalkylene, substituted or unsubstituted o-phenylene, m-phenylene or p-phenylene, -CONR 34 -, -NR 34 -、-Si(R 33 ) 2 -、-(Si(R 33 ) 2 O) m' -Si(R 33 ) 2 - and - (CH 2 ) n' - in the group,

[0320] R 33 Each occurrence is independently phenyl, C 1－6 Alkyl or C 1－6 Alkoxy,

[0321] R 34 Each occurrence is independently a hydrogen atom, a phenyl group or a C 1－6 alkyl,

[0322] m' is independently an integer from 1 to 100 at each occurrence,

[0323] n' is independently an integer from 1 to 20 at each occurrence,

[0324] r' is an integer from 1 to 10,

[0325] p' is 0 or 1,

[0326] q' is 0 or 1,

[0327] In which at least one of p' and q' is 1, the order of existence of each repeating unit marked with p' or q' and enclosed in parentheses is arbitrary.]

[0328]

[37] The curable composition according to any one of

[25] to

[36] , wherein the mass ratio of the fluorinated polyether group-containing thiol compound to the fluorinated polyether group-containing unsaturated compound is 0.1:100 to 100:0.1.

[0329]

[38] The curable composition according to any one of

[24] to

[37] , further comprising a polymerization initiator.

[0330]

[39] The curable composition according to

[38] , wherein the polymerization initiator is a free radical polymerization initiator.

[0331]

[40] The curable composition according to

[38] or

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

[0332]

[41] The curable composition according to any one of

[38] to

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

[0333]

[42] The curable composition according to any one of

[25] to

[41] , further comprising a fluorinated oil.

[0334]

[43] The curable composition according to

[42] , wherein the fluorinated oil is a compound represented by the following formula (5).

[0335] R f5 -(OC 4 F 8 ) a' -(OC 3 F 6 ) b' -(OC 2 F 4 ) c' -(OCF 2 ) d' -R f6 ···(5)

[0336] [Wherein,

[0337] R f5 is C which may be substituted by one or more fluorine atoms 1－16 alkyl,

[0338] R f6 is C which may be substituted by one or more fluorine atoms 1－16 an alkyl group, a fluorine atom or a hydrogen atom,

[0339] a', b', c' and d' are each independently an integer of 0 to 300,

[0340] The order of presence of the repeating units marked with the indices a', b', c' or d' and enclosed in parentheses is arbitrary in the formula.]

[0341]

[44] The curable composition according to any one of

[25] to

[43] , which is a solvent-free curable composition.

[0342]

[45] The curable composition according to any one of

[25] to

[44] , wherein the viscosity is 100 to 10,000 mPa·s.

[0343]

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

[25] to

[45] .

[0344]

[47] The cured product according to

[46] , wherein the weight loss rate after being kept at 65°C and 90 RH% for 72 hours is less than 50%.

[0345]

[48] ​​The cured product according to

[46] or

[47] , wherein the tensile elastic modulus is 0.1 to 500 MPa.

[0346]

[49] The cured product according to any one of

[46] to

[48] , which is a packaging material.

[0347]

[50] The cured product according to any one of

[46] to

[49] , which is a packaging material for electronic devices.

[0348]

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

[25] to

[45] .

[0349] Effects of the Invention

[0350] The fluorinated polyether group-containing thiol compound of the present invention is excellent in stability. DETAILED DESCRIPTION

[0351] When used in this specification, "monovalent organic group" refers to a monovalent group containing carbon. The monovalent organic group is not particularly limited, and may be a hydrocarbon group or a derivative thereof. The so-called derivative of the hydrocarbon group refers to a group having one or more N, O, S, Si, amide group, sulfonyl group, siloxane group, carbonyl group, carbonyloxy group, etc. at the end of the hydrocarbon group or in the molecular chain. Among them, when it is simply written as "organic group", it means a monovalent organic group. In addition, "divalent organic group" refers to a divalent group containing carbon. As the divalent organic group, it is not particularly limited, and a divalent group further separated from one hydrogen atom can be listed. Similarly, "2- to 10-valent organic group" refers to a 2- to 10-valent group containing carbon, and as the 2- to 10-valent organic group, it is not particularly limited, and a 2- to 10-valent group further separated from 1 to 9 hydrogen atoms can be listed.

[0352] As used in this specification, a "hydrocarbon group" is a group containing carbon and hydrogen, and refers to a group in which one hydrogen atom is separated from a hydrocarbon. The hydrocarbon group is not particularly limited, and examples thereof include C 1－20 Hydrocarbon groups, such as aliphatic hydrocarbon groups, aromatic hydrocarbon groups, etc. The above-mentioned "aliphatic hydrocarbon groups" can be any of linear, branched or cyclic, and can also be any of saturated or unsaturated. In addition, the hydrocarbon group can contain one or more ring structures.

[0353] As used in the present specification, the substituent of the "hydrocarbon group" is not particularly limited, and examples thereof include halogen atoms, C 1－6 Alkyl, C 2－6 Alkenyl, C 2－6 Alkynyl, C 3－10 Cycloalkyl, C 3－10 unsaturated cycloalkyl, 5- to 10-membered heterocyclic group, 5- to 10-membered unsaturated heterocyclic group, C 6－10 One or more of an aryl group and a 5- to 10-membered heteroaryl group.

[0354] When used in this specification, "hydrolyzable group" refers to a group that can undergo a hydrolysis reaction, that is, a group that can be separated from the main skeleton of a compound by a hydrolysis reaction. Examples of hydrolyzable groups include -OR j , -OCOR j 、-O-N=CR j 2 , -NR j 2 , -NHR j , -NCO, halogen (in these formulas, R j represents substituted or unsubstituted C1－4 Alkyl) etc.

[0355] (Fluorinated polyether group-containing thiol compound)

[0356] The present invention provides a thiol compound containing a fluorinated polyether group which does not contain an ester structure and contains two or more thiol groups selected from secondary thiol groups or tertiary thiol groups.

[0357] The fluorinated polyether group-containing thiol compound of the present invention has excellent storage stability because the thiol group is a secondary thiol group or a tertiary thiol group.

[0358] The secondary thiol refers to a compound in which the carbon atom to which the 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).

[0359] The tertiary thiol is a compound in which the carbon atom to which the thiol group (SH) is bonded has two hydrocarbon groups as substituents, for example, -CR 2 A group represented by -SH (wherein each R is independently a hydrocarbon group).

[0360] The number of thiol groups contained in the fluorinated polyether group-containing thiol compound of the present invention is preferably 2 or more, more preferably 3 or more, and further preferably 4 or more. Furthermore, the number of thiol groups contained in the fluorinated polyether group-containing thiol compound of the present invention is preferably 8 or less, for example, 7 or less or 6 or less.

[0361] In one embodiment, the number of thiol groups contained in the fluorinated polyether group-containing thiol compound of the present invention is preferably 2 to 8, more preferably 4 to 6. In one embodiment, the number of thiol groups contained in the fluorinated polyether group-containing thiol compound of the present invention is 4. In another embodiment, the number of thiol groups contained in the fluorinated polyether group-containing thiol compound of the present invention is 6. When the fluorinated polyether group-containing thiol compound has a plurality of thiol groups, the curability is improved.

[0362] In a preferred embodiment, the thiol groups are present on both end sides of the fluoropolyether group.

[0363] In a preferred embodiment, in the thiol compound containing a fluorinated polyether group of the present invention, the number of the thiol groups present at both ends of the fluorinated polyether group is the same. For example, there is one thiol group at each end of the fluorinated polyether group, or there are two thiol groups at each end of the fluorinated polyether group. The thiol compound containing a fluorinated polyether group has a plurality of thiol groups at both ends of the fluorinated polyether group, and the curing property is further improved, even if the curing temperature is 3000 mJ / cm 3 Below, even 2000mJ / cm 3 The following irradiation doses of ultraviolet rays can also cure.

[0364] In one embodiment, the thiol group is a secondary thiol group.

[0365] In another embodiment, the thiol group is a tertiary thiol group.

[0366] In a preferred embodiment, the fluorinated polyether group-containing thiol compound of the present invention 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.

[0367] In one embodiment, the above-mentioned 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 may be disposed between the fluoropolyether group and the thiol group.

[0368] The fluorine content of the fluorinated polyether group-containing thiol compound of the present invention is preferably 30% by mass or more, more preferably 35% by mass or more, and further preferably 40% by mass or more. In addition, the fluorine content of the fluorinated polyether group-containing thiol compound of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, and further preferably 70% by mass or less.

[0369] The above-mentioned fluorine content can be measured by elemental analysis.

[0370] The fluorinated polyether group-containing thiol compound of the present invention is preferably soluble in a fluorinated solvent having an SP value within a range of 5.0 to 13.0.

[0371] Examples of the fluorinated solvent include perfluorohexane (SP value 5.4), hydrofluoroether: Novec 7100 (produced by 3M Company, SP value 6.0), Novec 7300 (produced by 3M Company, SP value 6.1), Novec 7200 (produced by 3M Company, SP value 6.3), 1,3-bis(trifluoromethyl)benzene (SP value 7.6), heptafluorocyclopentene (SP value 7.6), hydrochlorofluorocarbon: AK-225 (produced by AGC Corporation, SP value 8.1), trifluorotoluene (SP value 8.2), hexafluoroisopropanol (SP value 9.0) and perfluorobenzene (SP value 12.7).

[0372] The above SP value can be calculated by Fedors's estimation method.

[0373] The viscosity of the thiol compound containing a fluorinated polyether group of the present invention is preferably 100 mPa·s or more, more preferably 300 mPa·s or more, and further preferably 500 mPa·s or more. Furthermore, the viscosity of the thiol compound containing a fluorinated polyether group of the present invention is preferably 10000 mPa·s or less, more preferably 7000 mPa·s or less, and further preferably 5000 mPa·s or less.

[0374] In one embodiment, the viscosity of the fluorinated polyether group-containing thiol compound of the present invention is 100 to 10,000 mPa·s, preferably 300 to 7,000 mPa·s, and more preferably 500 to 5,000 mPa·s.

[0375] The above viscosity can be measured using a TV-10 viscometer manufactured by Toki Sangyo Co., Ltd. (rotor No. THM1, rotation speed 1.0 rpm, measurement temperature 25° C.).

[0376] In a preferred embodiment, the fluorinated polyether group-containing thiol compound of the present invention may be a compound represented by the following formula (1) or (2).

[0377] R F1 α1 -X A -R S α2 (1)

[0378] R S β -X A -R F2 -X A -R S β (2)

[0379] [Wherein,

[0380] R F1 Rf 1 -R F -O q -

[0381] R F2 Rf 2 p -R F -O q -

[0382] R 1 are each independently C which may be substituted with one or more fluorine atoms 1－16 alkyl,

[0383] R 2 is C which may be substituted by one or more fluorine atoms 1－6 Alkylene,

[0384] R F are each independently a divalent fluorinated polyether group,

[0385] p is 0 or 1,

[0386] q is independently 0 or 1,

[0387] XA are each independently a single bond or a 2- to 10-valent organic group,

[0388] R S Each independently includes -(CR 4 (SH)-R 5 ) n -CR 1 R 2 - a monovalent group represented by a group represented by SH,

[0389] R 1 is a hydrocarbon group,

[0390] R 2 is a hydrogen atom or a hydrocarbon group,

[0391] R 4 is a hydrogen atom or a hydrocarbon group,

[0392] R 5 is a divalent hydrocarbon group,

[0393] In formula (1) and (2), there are at least two secondary or tertiary thiol groups,

[0394] α1 is an integer from 1 to 9,

[0395] α2 is an integer from 1 to 9,

[0396] β is an integer of 1 to 9 independently.

[0397] n is an integer from 0 to 9,

[0398] Formulas (1) and (2) do not contain ester structures.]

[0399] In the above formula (1), R F1 Rf 1 -R F -O q -

[0400] In the above formula (2), R F2 Rf 2 p -R F -O q -

[0401] In the above formula, Rf 1 is C which may be substituted by one or more fluorine atoms 1－16 alkyl.

[0402] The above C may be substituted with one or more fluorine atoms 1－16 The "C" in the alkyl 1－16 The "alkyl" may be a straight chain or a branched chain, preferably a straight chain or a branched chain C1－6 Alkyl groups, especially C 1－3 Alkyl, more preferably a straight chain C 1－6 Alkyl groups, especially C 1－3 alkyl.

[0403] The above Rf 1 Preferably, C is substituted with one or more fluorine atoms. 1－16 Alkyl, more preferably CF 2 H-C 1－15 Perfluoroalkylene, more preferably C 1－16 Perfluoroalkyl.

[0404] C 1－16 The perfluoroalkyl group may be a straight chain or a branched chain, preferably a straight chain or a branched chain C 1－6 Perfluoroalkyl, especially C 1－3 Perfluoroalkyl, more preferably linear C 1－6 Perfluoroalkyl, especially C 1－3 Perfluoroalkyl, specifically -CF 3 , -CF 2 CF 3 or -CF 2 CF 2 CF 3 .

[0405] In the above formula, Rf 2 is C which may be substituted by one or more fluorine atoms 1－6 Alkylene.

[0406] The above C may be substituted with one or more fluorine atoms 1－6 The "C" in the alkylene 1－6 The "alkylene" may be a straight chain or a branched chain, preferably a straight chain or a branched chain C 1－3 Alkylene, more preferably linear C 1－3 Alkylene.

[0407] The above Rf 2 Preferably, C is substituted with one or more fluorine atoms. 1－6 Alkylene, more preferably C 1－6 Perfluoroalkylene, more preferably C 1－3 Perfluoroalkylene.

[0408] C 1－6 The perfluoroalkylene group may be a linear or branched group, preferably a linear or branched C 1－3 Perfluoroalkylene, more preferably linear C 1－3 Perfluoroalkylene, specifically -CF 2 -, -CF 2 CF2 -or-CF 2 CF 2 CF 2 -

[0409] In the above formula, p is 0 or 1. In one embodiment, p is 0. In another embodiment, p is 1.

[0410] In the above formula, q is independently 0 or 1. In one embodiment, q is 0. In another embodiment, q is 1.

[0411] In the above formulas (1) and (2), R F Each occurrence is independently a divalent fluorinated polyether group.

[0412] R F Preferably include the following: - (OC h1 R Fa 2h1 ) h3 -(OC h2 R Fa 2h2－2 ) h4 - the group shown.

[0413] [Wherein,

[0414] R Fa is independently a hydrogen atom, a fluorine atom or a chlorine atom at each occurrence,

[0415] h1 is an integer from 1 to 6,

[0416] h2 is an integer from 4 to 8,

[0417] h3 is an integer greater than 0,

[0418] h4 is an integer greater than 0,

[0419] The total of h3 and h4 is 1 or more, preferably 2 or more, and more preferably 5 or more, and the order of existence of each repeating unit marked with h3 and h4 and enclosed in parentheses in the formula is arbitrary.]

[0420] In one approach, R F It can be straight chain or branched. F Preferably the formula is:

[0421] -(OC 6 F 12 ) a -(OC 5 F 10 ) b -(OC 4 F 8 ) c -(OC3 R Fa 6 ) d -(OC 2 F 4 ) e -(OCF 2 ) f - the group shown.

[0422] [Wherein,

[0423] R Fa is independently a hydrogen atom, a fluorine atom or a chlorine atom at each occurrence,

[0424] 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 existence of each repeating unit marked with a, b, c, d, e or f and enclosed in parentheses in the formula is arbitrary. Fa When it is a hydrogen atom or a chlorine atom, at least one of a, b, c, e and f is 1 or more.]

[0425] R Fa Preferably, it is a hydrogen atom or a fluorine atom, and more preferably, it is a fluorine atom. Fa When it is a hydrogen atom or a chlorine atom, at least one of a, b, c, e and f is 1 or more.

[0426] It is preferred that a, b, c, d, e and f are each independently an integer of 0 to 100.

[0427] The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, 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, further preferably 60 or less, for example, 50 or less or 30 or less.

[0428] These repeating units may be straight-chain or branched. 6 F 12 )-can be-(OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 )-、-(OCF(CF 3 )CF 2 CF 2 CF 2 CF 2 )-、-(OCF 2 CF(CF 3 )CF 2 CF2 CF 2 )-, -(OCF 2 CF 2 CF(CF 3 )CF 2 CF 2 )-, -(OCF 2 CF 2 CF 2 CF(CF 3 )CF 2 )-, -(OCF 2 CF 2 CF 2 CF 2 CF(CF 3 ))-, etc. -(OC 5 F 10 )- can be -(OCF 2 CF 2 CF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 CF 2 CF 2 )-, -(OCF 2 CF(CF 3 )CF 2 CF 2 )-, -(OCF 2 CF 2 CF(CF 3 )CF 2 )-, -(OCF 2 CF 2 CF 2 CF(CF 3 ))-, etc. -(OC 4 F 8 )- can be -(OCF 2 CF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 CF 2 )-, -(OCF 2 CF(CF 3 )CF 2 )-, -(OCF 2 CF 2 CF(CF 3 ))-, -(OC(CF 3 ) 2 CF 2)-, -(OCF 2 C(CF 3 ) 2 )-, -(OCF(CF 3 )CF(CF 3 ))-, -(OCF(C 2 F 5 )CF 2 )- and -(OCF 2 CF(C 2 F 5 ))-. -(OC 3 F 6 )-(i.e., in the above formula, R Fa is a fluorine atom) can be -(OCF 2 CF 2 CF 2 )-, -(OCF(CF 3 )CF 2 )- and -(OCF 2 CF(CF 3 ))-. -(OC 2 F 4 )- can be -(OCF 2 CF 2 )- and -(OCF(CF 3 ))-.

[0429] In one mode, the above repeating unit is linear. By making the above repeating unit linear, the surface slidability, wear durability, etc. of the surface treatment layer can be improved.

[0430] In one mode, the above repeating unit is branched. By making the above repeating unit branched, the dynamic friction coefficient of the surface treatment layer can be increased.

[0431] In one mode, R F can include a ring structure.

[0432] The above ring structure can be the following three-membered ring, four-membered ring, five-membered ring or six-membered ring.

[0433]

[0434] [In the formula, * represents the bonding position.]

[0435] The above ring structure is preferably a four-membered ring, five-membered ring or six-membered ring, more preferably a four-membered ring or six-membered ring.

[0436] The repeating unit having a ring structure is preferably the following unit.

[0437]

[0438] [Wherein, * represents the bonding position.]

[0439] In one approach, R F Each occurrence is independently a group represented by any one of the following formulae (f1) to (f6).

[0440] -(OC 3 F 6 ) d -(OC 2 F 4 ) e - (f1)

[0441] [Wherein, d is an integer of 1 to 200, and e is 0 or 1.]

[0442] -(OC 4 F 8 ) c -(OC 3 F 6 ) d -(OC 2 F 4 ) e -(OCF 2 ) f -(f2)

[0443] [wherein, c and d are each independently an integer from 0 to 30, e and f are each independently an integer from 1 to 200,

[0444] The sum of c, d, e and f is greater than 2,

[0445] The order of presence of the repeating units marked with the subscript c, d, e or f and enclosed in parentheses is arbitrary in the formula.]

[0446] -(R 6 -R 7 ) g - (f3)

[0447] [Where R 6 For OCF 2 or OC 2 F 4 ,

[0448] R 7 For OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F12 or a combination of 2 or 3 groups independently selected from these groups,

[0449] g is an integer from 2 to 100.]

[0450] -(R 6 -R 7 ) g -R r -(R 7' -R 6' ) g' - (f4)

[0451] [Where R 6 For OCF 2 or OC 2 F 4 ,

[0452] R 7 For OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 or a combination of 2 or 3 groups independently selected from these groups,

[0453] R 6' For OCF 2 or OC 2 F 4 ,

[0454] R 7' For OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 or a combination of 2 or 3 groups independently selected from these groups,

[0455] g is an integer from 2 to 100,

[0456] g' is an integer from 2 to 100,

[0457] R r for:

[0458]

[0459] (Where * indicates the bonding position.)]

[0460] -(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)

[0461] [In the formula, e is an integer from 1 to 200, a, b, c, d and f are each independently an integer from 0 to 200, and the order of existence of each repeating unit marked with a, b, c, d, e or f and enclosed in parentheses is arbitrary in the formula.]

[0462] -(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)

[0463] [In the formula, f is an integer from 1 to 200, a, b, c, d and e are each independently an integer from 0 to 200, and the order of existence of each repeating unit marked with a, b, c, d, e or f and enclosed in parentheses is arbitrary in the formula.]

[0464] In the above formula (f1), d is preferably an integer of 5 to 200, more preferably an integer of 10 to 100, further preferably an integer of 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), OC 3 F 6 OCF is preferred2 CF 2 CF 2 、OCF 2 CF(CF 3 ) or OCF(CF 3 )CF 2 , preferably OCF 2 CF 2 CF 2 .OC 2 F 4 For OCF 2 CF 2 or OCF(CF 3 ), preferably OCF 2 CF 2 .

[0465] In the above formula (f2), e and f are preferably independently integers of 5 to 200, more preferably integers of 10 to 200. Furthermore, the sum of c, d, e and f is preferably 5 or more, more preferably 10 or more, for example, 15 or more or 20 or more. In one embodiment, the above formula (f2) is preferably -(OCF 2 CF 2 CF 2 CF 2 ) c -(OCF 2 CF 2 CF 2 ) d -(OCF 2 CF 2 ) e -(OCF 2 ) f In another embodiment, formula (f2) can be -(OC 2 F 4 ) e -(OCF 2 ) f - the group shown.

[0466] In the above formula (f3), R 6 Preferably OC 2 F 4 In (f3) above, R 7 Preferably selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 or a combination of two or three groups independently selected from these groups, more preferably selected from OC 3 F 6and OC 4 F 8 As a group from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 The combination of two or three groups independently selected from the group is not particularly limited, and examples thereof include -OC 2 F 4 OC 3 F 6 -、-OC 2 F 4 OC 4 F 8 -、-OC 3 F 6 OC 2 F 4 -、-OC 3 F 6 OC 3 F 6 -、-OC 3 F 6 OC 4 F 8 -、-OC 4 F 8 OC 4 F 8 -、-OC 4 F 8 OC 3 F 6 -、-OC 4 F 8 OC 2 F 4 -、-OC 2 F 4 OC 2 F 4 OC 3 F 6 -、-OC 2 F 4 OC 2 F 4 OC 4 F 8 -、-OC 2 F 4 OC 3 F 6 OC 2 F 4 -、-OC 2 F 4 OC 3 F 6 OC 3 F 6-、-OC 2 F 4 OC 4 F 8 OC 2 F 4 -、-OC 3 F 6 OC 2 F 4 OC 2 F 4 -、-OC 3 F 6 OC 2 F 4 OC 3 F 6 -、-OC 3 F 6 OC 3 F 6 OC 2 F 4 - and - OC 4 F 8 OC 2 F 4 OC 2 F 4 In the above formula (f3), g is preferably an integer greater than 3, and more preferably an integer greater than 5. The above g is preferably an integer less than 50. In the above formula (f3), OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 It may be a straight chain or a branched chain, and is preferably a straight chain. In this embodiment, the above formula (f3) is preferably -(OC 2 F 4 -OC 3 F 6 ) g -or-(OC 2 F 4 -OC 4 F 8 ) g -

[0467] 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 form. 6' , R 7' and g' respectively have the same meanings as R described in the above formula (f3). 6, R 7 Same as g, in the same way. r Preferably:

[0468]

[0469] [Wherein, * represents the bonding position.]

[0470] More preferably:

[0471]

[0472] [Wherein, * represents the bonding position.]

[0473] In the above formula (f5), e is preferably an integer of 1 to 100, more preferably an integer of 5 to 100. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example, 10 to 100.

[0474] In the above formula (f6), f is preferably an integer of 1 to 100, more preferably an integer of 5 to 100. The sum of a, b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example, 10 to 100.

[0475] In one embodiment, the above R F It is a group represented by the above formula (f1).

[0476] In one embodiment, the above R F It is a group represented by the above formula (f2).

[0477] In one embodiment, the above R F It is a group represented by the above formula (f3).

[0478] In one embodiment, the above R F It is a group represented by the above formula (f4).

[0479] In one embodiment, the above R F It is a group represented by the above formula (f5).

[0480] In one embodiment, the above R F It is a group represented by the above formula (f6).

[0481] In the above R FIn the embodiment of the present invention, 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, further preferably 0.2 to 1.5, and further more preferably 0.2 to 0.85. By making the e / f ratio less than 10, the sliding property, wear durability and chemical resistance (for example, durability to artificial sweat) of the surface treatment layer obtained from the compound are further improved. The smaller the e / f ratio, the higher the sliding property and wear durability of the surface treatment layer. On the other hand, by making the e / f ratio greater than 0.1, the stability of the compound can be further improved. The larger the e / f ratio, the higher the stability of the compound.

[0482] In one embodiment, the e / f ratio is preferably 0.2 to 0.95, more preferably 0.2 to 0.9.

[0483] In one embodiment, from the viewpoint of heat resistance, the e / f ratio is preferably 1.0 or more, more preferably 1.0 to 2.0.

[0484] In the above-mentioned thiol compound containing a fluorinated polyether group, R F1 and R F2 The number average molecular weight of the moiety is not particularly limited, and 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 is 19 The value measured by F-NMR.

[0485] R S Each independently includes -(CR 4 (SH)-R 5 ) n -CR 1 R 2 A monovalent group of a group represented by -SH.

[0486] In a preferred embodiment, R s Can be in - (CR 4 (SH)-R 5 ) n -CR 1 R 2 A group represented by -SH to which 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 is bonded as a linking group.

[0487] In a preferred embodiment, R S The group may be a group represented by the following formula (S1), (S2) or (S3).

[0488] -R Sa(S1)

[0489] -NR Sa n1 R 3 2-n1 (S2)

[0490] -CR Sa n2 R 3 3-n2 (S3)

[0491] [Wherein,

[0492] R Sa Z-(CR 3 (SH)-R 4 ) n -CR 1 R 2 -SH,

[0493] Z is a single bond or a divalent group,

[0494] R 1 is a hydrocarbon group,

[0495] R 2 is a hydrogen atom or a hydrocarbon group,

[0496] R 3 is a hydrogen atom or a hydrocarbon group,

[0497] n is an integer from 0 to 9,

[0498] n1 is 1 or 2,

[0499] n2 is 1, 2, or 3.]

[0500] R Sa Z-(CR 3 (SH)-R 4 ) n -CR 1 R 2 -SH.

[0501] 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.

[0502] Z is preferably -R 11 -R 12 -. In the formula, R 11 is a single bond or C 1－6 Alkylene, R 12 is a single bond or -O-(CH 2 ) m -(m is an integer from 0 to 6). 2 )m The right side of - and -(CR 3 (SH)-R 4 ) n CR 1 R 2 -SH bonding. No ester bond is formed on the left side. In a preferred embodiment, Z is -R 11 -

[0503] R 11 C 1－6 The alkylene group may be a straight chain or a branched chain. 1－6 In another embodiment, the alkylene group is a straight chain. 1－6 The alkylene group is a branched chain.

[0504] R 11 C 1－6 The alkylene group is preferably C 1－4 Alkylene.

[0505] m is preferably an integer of 0-4, more preferably an integer of 0-3.

[0506] In one embodiment, m is zero.

[0507] In another embodiment, m is an integer of 1-6, preferably an integer of 1-4, and more preferably an integer of 1-3.

[0508] R 1 It is a hydrocarbon group.

[0509] R 2 It is a hydrogen atom or a hydrocarbon group.

[0510] In one approach, R 2 A hydrogen atom.

[0511] In another embodiment, R 2 It is a hydrocarbon group.

[0512] R 1 and R 2 The hydrocarbon group is preferably C 1－6 Alkyl, more preferably C 1－3 The alkyl group is more preferably a methyl group or an ethyl group, and even more preferably a methyl group.

[0513] R 1 and R 2 C 1－6 The alkyl group may be a straight chain or a branched chain. 1－6 In another embodiment, the alkyl group is a straight chain. 1－6 The alkyl group is a branched chain.

[0514] In a preferred embodiment, R 1 C1－6 Alkyl, R 2 A hydrogen atom or C 1－6 In one embodiment, R 1 C 1－6 Alkyl, R 2 In another embodiment, R 1 C 1－6 Alkyl, R 2 C 1－6 alkyl.

[0515] R 3 It is a hydrogen atom or a hydrocarbon group.

[0516] In one approach, R 3 A hydrogen atom.

[0517] In another embodiment, R 3 It is a hydrocarbon group.

[0518] R 3 The hydrocarbon group is preferably C 1－6 Alkyl, more preferably C 1－3 The alkyl group is more preferably a methyl group or an ethyl group, and even more preferably a methyl group.

[0519] R 3 C 1－6 The alkyl group may be a straight chain or a branched chain. 1－6 In another embodiment, the alkyl group is a straight chain. 1－6 The alkyl group is a branched chain.

[0520] R 4 It is a hydrogen atom or a hydrocarbon group.

[0521] In one approach, R 4 A hydrogen atom.

[0522] In another embodiment, R 4 It is a hydrocarbon group.

[0523] R 4 The hydrocarbon group is preferably C 1－6 Alkyl, more preferably C 1－3 The alkyl group is more preferably a methyl group or an ethyl group, and even more preferably a methyl group.

[0524] R 4 C 1－6 The alkyl group may be a straight chain or a branched chain. 1－6 In another embodiment, the alkyl group is a straight chain. 1－6 The alkyl group is a branched chain.

[0525] R 5 It is a divalent hydrocarbon group.

[0526] R 5 The hydrocarbon group is preferably C 1－10 Alkylene, more preferably C 2－8 Alkylene, more preferably C 3－6 Alkylene, more preferably -CH(CH 3 )CH 2 CH 2 -

[0527] R 5 C 1－10 The alkylene group may be a straight chain or a branched chain. 1－10 In another embodiment, the alkylene group is branched. 1－10 An alkylene group is a straight chain.

[0528] n may be an integer of 0-9, and preferably an integer of 1-3.

[0529] n1 is 1 or 2. In one embodiment, n1 is 1. In another embodiment, n1 is 2.

[0530] n2 is 1, 2 or 3. In one embodiment, n2 is 1. In another embodiment, n2 is 2. In another embodiment, n2 is 3.

[0531] In a preferred embodiment, R S It is a group represented by formula (S1).

[0532] In one approach, R S It is a group represented by formula (S2).

[0533] In one approach, R S It is a group represented by formula (S3).

[0534] In the above formulas (1) and (2), X A It can be understood that the fluoropolyether portion (R F1 and R F2 ), and a portion providing bonding capability to a substrate (R S Therefore, as long as the compounds represented by formula (1) and (2) can exist stably, the X A It may be a single bond or an arbitrary group.

[0535] In the above formula (1), α1 is an integer of 1 to 9, and α2 is an integer of 1 to 9. These α1 and α2 may correspond to X A The sum of α1 and α2 is equal to X A For example, in X AWhen X is a devalent organic group, the sum of α1 and α2 is 10, for example, α1 is 9 and α2 is 1, α1 is 5 and α2 is 5, or α1 is 1 and α2 is 9. A When it is a divalent organic group, α1 and α2 are 1.

[0536] In the above formula (2), β is independently an integer of 1 to 9. β may correspond to X A That is, β is X A The value of the valence minus 1.

[0537] X A Each independently represents a single bond or a di- to decavalent organic group.

[0538] The above X A The 2- to 10-valent organic group is preferably a 2- to 8-valent organic group. In one embodiment, the 2- to 10-valent organic group is preferably a 2- to 4-valent organic group, more preferably a 2-valent organic group. In another embodiment, the 2- to 10-valent organic group is preferably a 3- to 8-valent organic group, more preferably a 3- to 6-valent organic group.

[0539] In one approach, X A is a single bond or a divalent organic group, α is 1, and α2 is 1.

[0540] In one approach, X A is a single bond or a divalent organic group, and β is 1.

[0541] In one approach, X A It is a tri- to hexavalent organic group, α1 is 1, and α2 is 2-5.

[0542] In one approach, X A It is a trivalent to hexavalent organic group, and β is 2 to 5.

[0543] In one approach, X A It is a trivalent organic group, α1 is 1, and α2 is 2.

[0544] In one approach, X A It is a trivalent organic group, and β is 2.

[0545] In one approach, X A is a single bond or a divalent organic group, and α1, α2 and β are 1.

[0546] In a preferred embodiment, X A Formula: -(R 21 ) m1 -(R 22 ) m2 - the group shown.

[0547] [Wherein,

[0548] R 21 C 1－6 Alkylene,

[0549] R 22 -O-, -CO-, -NR 23 -、-CONR 23 -or-NR 23 CO-,

[0550] R 23 A hydrogen atom or C 1－6 alkyl,

[0551] m1 is an integer from 0 to 10,

[0552] m2 is an integer from 0 to 10,

[0553] The sum of m1 and m2 is greater than 1,

[0554] R 21 and R 22 The order of existence in the formula is arbitrary.

[0555] -(R 21 ) m1 -(R 22 ) m2 - Does not contain ester structure.]

[0556] Here, X A (Typically X A The hydrogen atoms) may be selected from fluorine atoms, C 1－3 Alkyl and C 1－3 In a preferred embodiment, X A Not substituted by these groups.

[0557] In one approach, X A Each independently is -(R 21 ) m1－1 -(R 22 ) m2 -R 24 -. R 21 , R 22 , m1 and m2 have the same meanings as above. 21 and R 22 The order of existence of R in the formula is arbitrary. 24 Represents a single bond, -(CH 2 ) t5 - or o-phenylene, m-phenylene or p-phenylene, preferably -(CH 2 ) 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 The hydrogen atoms) may be selected from fluorine atoms, C 1－3 Alkyl and C 1－3 In a preferred embodiment, R 24 Not substituted by these groups.

[0558] R 21 C 1－6 The alkylene group may be a straight chain or a branched chain. 1－6 In another embodiment, the alkylene group is a straight chain. 1－6 The alkylene group is a branched chain.

[0559] R 21 C 1－6 The alkylene group is preferably C 1－4 Alkylene, more preferably C 1－2 Alkylene.

[0560] R 22 -O-, -CO-, -NR 23 -、-CONR 23 -or-NR 23 CO-, preferably -O- or -CO-.

[0561] R 23 A hydrogen atom or C 1－6 alkyl.

[0562] In one approach, R 23 A hydrogen atom.

[0563] In another embodiment, R 23 C 1－6 alkyl.

[0564] R 23 C 1－6 The alkyl group may be a straight chain or a branched chain. 1－6 In another embodiment, the alkyl group is a straight chain. 1－6 The alkyl group is a branched chain.

[0565] R 23 C 1－6 The alkyl group is preferably C 1－4 Alkyl, more preferably C 1－2 The alkyl group is more preferably a methyl group.

[0566] m1 is an integer of 0-10, preferably an integer of 0-4, and more preferably an integer of 0-2.

[0567] m2 is an integer of 0 to 10, preferably an integer of 0 to 2, and more preferably 0 or 1.

[0568] In one embodiment, m1 is an integer of 0 to 2, and m2 is 0 or 1.

[0569] In one embodiment, (m1, m2) is (0, 1), (1, 1), (2, 1) or (1, 0).

[0570] In a preferred embodiment, X A Respectively and independently:

[0571] single bond,

[0572] -R 21 -R 22 -R 24 -

[0573] -R 21 -R 22 -

[0574] -R 22 -R 24 -,or

[0575] -R 22 -

[0576] (Where,

[0577] R 21 C 1－6 Alkylene,

[0578] R 22 is -O- or -CO-,

[0579] R 24 C 1－6 Alkylene.)

[0580] The number average molecular weight of the thiol compound containing a fluorinated polyether group of the present invention is 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. Furthermore, the number average molecular weight of the thiol compound containing a fluorinated polyether group of the present invention is preferably 100,000 or less, more preferably 50,000 or less, further preferably 30,000 or less, further 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 thiol compound containing a fluorinated polyether group is represented by 19 The value measured by F-NMR.

[0581] In one embodiment, the number average molecular weight of the fluorinated polyether group-containing thiol compound of the present invention is 1,000 to 100,000, preferably 2,000 to 30,000, more preferably 2,000 to 10,000.

[0582] The fluorinated polyether group-containing thiol compound of the present invention can be produced, for example, by the following method.

[0583] The compound represented by the following formula (a) is reacted with the compound represented by the following formula (b) to obtain the compound represented by the following formula (c).

[0584] R S1 -X 1 PFPE-X 1 -R S1 (a)

[0585] [Wherein,

[0586] PFPE is a fluoropolyether-based

[0587] R S1 Each independently is -(CR 16 =CR 16 -R 17 ) n10 -CR 16 =CR 16 2 The groups shown,

[0588] R 16 are independently a hydrogen atom or a hydrocarbon group, preferably a hydrogen atom or a C 1－10 Alkyl, more preferably C 2－6 alkyl,

[0589] R 17 are independently a divalent hydrocarbon group, preferably C 1－10 Alkylene, more preferably C 2－6 Alkylene,

[0590] X 1 Each independently represents a single bond or a divalent organic group.]

[0591] R 51 -COSH(b)

[0592] [Where R 51 are independently a hydrogen atom or a C 1－3 Alkyl, preferably methyl.]

[0593] R S2 -X A PFPE-X A -R S2 (c)

[0594] [Wherein,

[0595] R S2 Each independently is -(CR 4 (SCOR 51 )-R 5 ) n -CR 1 R 2 -SCOR 51 The groups shown,

[0596] PFPE, R 1 , R 2 , R 4 , R 5 , R 51 , X A and n have the same meaning as above.]

[0597] Next, the compound represented by the formula (c) is reacted with a reducing agent to obtain the fluorinated polyether group-containing thiol compound of the present invention represented by the formula (d).

[0598] R Sa -X A PFPE-X A -R Sa (d)

[0599] [Where R Sa , X A PFPE has the same meaning as above.]

[0600] In a preferred embodiment, the reducing agent may be sodium methoxide.

[0601] (Curable composition)

[0602] The present invention provides a curable composition containing the fluorinated polyether group-containing thiol compound of the present invention.

[0603] The curable composition of the present invention may further contain a fluorinated polyether group-containing unsaturated compound containing a group having a carbon-carbon double bond.

[0604] (Unsaturated compound containing fluorinated polyether group)

[0605] The above-mentioned group having a carbon-carbon double bond is not particularly limited as long as it is a group having a carbon-carbon double bond. Typically, the group having a carbon-carbon double bond has a carbon-carbon double bond at a terminal.

[0606] The group having a carbon-carbon double bond is preferably an allyl group, a vinyl group or a (meth)acryloyl group, and more preferably an allyl group.

[0607] In one embodiment, the number of groups having a carbon-carbon double bond in the fluorinated polyether group-containing unsaturated compound is preferably 2 to 8, more preferably 2 to 6, and even more preferably 2 to 4.

[0608] In a preferred embodiment, the above-mentioned group having a carbon-carbon double bond is present on both end sides of the fluorinated polyether group-containing unsaturated compound.

[0609] In a preferred embodiment, in the fluorinated polyether group-containing unsaturated compound of the present invention, the number of the above-mentioned groups having carbon-carbon double bonds present at both ends of the fluorinated polyether group is the same. For example, there is one group having a carbon-carbon double bond at each end of the fluorinated polyether group, or there are two groups having carbon-carbon double bonds at each end of the fluorinated polyether group.

[0610] In a preferred embodiment, the fluorinated polyether group-containing unsaturated compound is a compound represented by the following formula (3) or (4).

[0611] R F1 γ1 -X B -R D γ2 (3)

[0612] R D δ -X B -R F2 -X B -R D δ (3)

[0613] [Wherein,

[0614] R F1 Rf 1 -R F -O q -

[0615] R F2 Rf 2 p -R F -O q -

[0616] R 1 are each independently C which may be substituted with one or more fluorine atoms 1－16 alkyl,

[0617] R 2 is C which may be substituted by one or more fluorine atoms 1－6 Alkylene,

[0618] R Fare each independently a divalent fluorinated polyether group,

[0619] p is 0 or 1,

[0620] q is independently 0 or 1,

[0621] X B are each independently a single bond or a 2- to 10-valent organic group,

[0622] R D are each independently a group having a carbon-carbon double bond,

[0623] γ1 is an integer from 1 to 9,

[0624] γ2 is an integer from 1 to 9,

[0625] δ is independently an integer of 1 to 9.]

[0626] In the above formula, R F1 and R F2 The meaning of R is the same as that of R of the thiol compound containing a fluorinated polyether group represented by the above formula (1) or (2). F1 and R F2 same.

[0627] In the above formula, X B Each independently represents a single bond or a di- to decavalent organic group. B It can be understood as R D With R F1 or R F2 Therefore, as long as the compounds represented by formula (3) and (4) can exist stably, the X B It can be any organic group.

[0628] 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 determined according to X B The valence of is determined by, in formula (3), the sum of γ1 and γ2 is X B For example, in X B When X is a devalent organic group, the sum of γ1 and γ2 is 10, for example, γ1 is 9 and γ2 is 1, γ1 is 5 and γ2 is 5, or γ1 is 1 and γ2 is 9. B When X is a divalent organic group, γ1 and γ2 are 1. In formula (4), δ is B The value of the valence minus 1.

[0629] The above X B It is preferably a divalent to heptavalent organic group, more preferably a divalent to tetravalent organic group, and still more preferably a divalent organic group. BCorrespondingly, it can be an integer of 1 to 6, an integer of 1 to 3, or 1, etc.

[0630] As the above X B Examples of are not particularly limited, and include the following formula: 31 ) p' -(X a ) q' -R 32 - The divalent group shown.

[0631] [Wherein,

[0632] R 31 Represents a single bond, -(CH 2 ) s' - or o-phenylene, m-phenylene or p-phenylene, preferably -(CH 2 ) s' -

[0633] R 32 Represents a single bond, -(CH 2 ) t' - or o-phenylene, m-phenylene or p-phenylene, preferably -(CH 2 ) t' -

[0634] 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,

[0635] 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 Indicates - (X b ) r' -

[0636] X b Each occurrence independently represents a substituted or unsubstituted C 3－10 Cycloalkylene, substituted or unsubstituted o-phenylene, m-phenylene or p-phenylene, -CONR 34 -, -NR 34 -、-Si(R 33 ) 2 -、-(Si(R 33 ) 2 O) m' -Si(R 33 ) 2 - and - (CH 2 ) n' - group,

[0637] The substituents mentioned above have the same meanings as the substituents of the above-mentioned hydrocarbon groups.

[0638] R 33 Each occurrence independently represents phenyl, C 1－6 Alkyl or C 1－6 Alkoxy, preferably C 1－6 Alkyl, more preferably methyl,

[0639] R 34 Each occurrence independently represents a hydrogen atom, a phenyl group or a C 1－6 an alkyl group (preferably a methyl group),

[0640] m' is independently an integer of 1 to 100, preferably an integer of 1 to 20, at each occurrence.

[0641] n' is independently an integer of 1 to 20 at each occurrence, preferably an integer of 1 to 6, more preferably an integer of 1 to 3,

[0642] r' is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3,

[0643] p' is 0 or 1,

[0644] q' is 0 or 1,

[0645] In which at least one of p' and q' is 1, the order of existence of each repeating unit marked with p' or q' and enclosed in parentheses is arbitrary.]

[0646] X B Preferably, no ester bonds and / or urethane bonds are present.

[0647] R D Each occurrence is independently a group having a carbon-carbon double bond.

[0648] The above R D The group having a carbon-carbon double bond is -YA (wherein Y represents a single bond, an oxygen atom or a divalent organic group, and A is -CR 41 =CH 2 , R 41 are independently a hydrogen atom or a C 1-3 A group represented by an alkyl group (preferably a methyl group).

[0649] The above-mentioned 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 -.

[0650] The above R42 Each occurrence of is independently 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 A hydrogen atom.

[0651] In a preferred embodiment, R D It is a group represented by the following formula (D1), (D2), (D3), (D4) or (D5).

[0652] -YA (D1)

[0653]

[0654] -SiR a1 k1 R b1 11 R c1 m1 (D3)

[0655] -CR d1 k2 R e1 12 R f1 m2 (D4)

[0656] -NR g1 R h1 (D5)

[0657] [Wherein,

[0658] Y is a single bond, an oxygen atom or a divalent organic group,

[0659] A is -CR 41 =CH 2 ,

[0660] R 41 are independently a hydrogen atom or a C 1-3 alkyl,

[0661] X 10 is independently a single bond or a divalent organic group at each occurrence,

[0662] R 13 is independently a hydrogen atom or a monovalent organic group at each occurrence,

[0663] t is independently an integer greater than 2 at each occurrence,

[0664] R 14 is independently a hydrogen atom or a halogen atom at each occurrence,

[0665] Ra1 -Z independently at each occurrence 1 -SiR a2 p1 R a3 q1 R a4 r1 ,

[0666] Z 1 is independently a single bond, an oxygen atom or a divalent organic group at each occurrence,

[0667] R a2 Each time it occurs, it is independently -Z 1' -SiR a3' q1' R a4' r1' ,

[0668] Z 1' is independently a single bond, an oxygen atom or a divalent organic group at each occurrence,

[0669] R a3' Each time it occurs, it is independently -Z 2 -Y-A,

[0670] R a4' is independently a hydrogen atom, a hydroxyl group or a monovalent organic group at each occurrence,

[0671] Z 2 is independently a single bond, an oxygen atom or a divalent organic group at each occurrence,

[0672] q1' is independently an integer from 0 to 3 at each occurrence,

[0673] r1' is independently an integer from 0 to 3 at each occurrence,

[0674] Among them, the sum of q1' and r1' is (SiR a3' q1' R a4' r1' ) unit is 3,

[0675] R a3 Each time it occurs, it is independently -Z 2 -Y-A,

[0676] R a4 is independently a hydrogen atom, a hydroxyl group or a monovalent organic group at each occurrence,

[0677] p1 is an integer from 0 to 3 independently at each occurrence.

[0678] q1 is an integer from 0 to 3 independently at each occurrence.

[0679] r1 is independently an integer from 0 to 3 each time it appears.

[0680] Among them, the sum of p1, q1 and r1 is (SiR a2 p1 R a3 q1 R a4 r1 ) unit is 3,

[0681] R b1 Each time it occurs, it is independently -Z 2 -Y-A,

[0682] R c1 is independently a hydrogen atom, a hydroxyl group or a monovalent organic group at each occurrence,

[0683] k1 is independently an integer from 0 to 3 each time it appears.

[0684] l1 is an integer from 0 to 3 independently at each occurrence.

[0685] m1 is independently an integer from 0 to 3 at each occurrence.

[0686] Among them, the sum of k1, l1 and m1 is (SiR a1 k1 R b1 l1 R c1 m1 ) unit is 3,

[0687] In formula (D3), there is at least one -Y-A,

[0688] R d1 Each time it occurs, it is independently -Z 3 -CR d2 p2 R d3 q2 R d4 r2 ,

[0689] Z 3 is independently a single bond, an oxygen atom or a divalent organic group at each occurrence,

[0690] R d2 Each time it occurs, it is independently -Z 3' -CR d3' q2' R d4' r2' ,

[0691] Z 3' is independently an oxygen atom or a divalent organic group at each occurrence,

[0692] R d3' Each time it occurs, it is independently -Z 2 -Y-A,

[0693] R d4' is independently a hydrogen atom, a hydroxyl group or a monovalent organic group at each occurrence,

[0694] q2' is independently an integer from 0 to 3 at each occurrence,

[0695] r2' is independently an integer from 0 to 3 at each occurrence,

[0696] Among them, the sum of q2' and r2' is (CR d3' q2' R d4' r2' ) unit is 3,

[0697] R d3 Each time it occurs, it is independently -Z 2 -Y-A,

[0698] R d4 is independently a hydrogen atom, a hydroxyl group or a monovalent organic group at each occurrence,

[0699] p2 is independently an integer from 0 to 3 at each occurrence.

[0700] q2 is independently an integer from 0 to 3 at each occurrence,

[0701] r2 is independently an integer from 0 to 3 at each occurrence,

[0702] Among them, the sum of p2, q2 and r2 is (CR d2 p2 R d3 q2 R d4 r2 ) unit is 3,

[0703] R e1 Each time it occurs, it is independently -Z 2 -Y-A,

[0704] R f1 is independently a hydrogen atom, a hydroxyl group or a monovalent organic group at each occurrence,

[0705] k2 is independently an integer from 0 to 3 at each occurrence.

[0706] l2 is an integer from 0 to 3 independently at each occurrence.

[0707] m2 is independently an integer from 0 to 3 at each occurrence,

[0708] Among them, the sum of k2, l2 and m2 is (CR d1 k2 R e1 l2 R f1 m2 ) unit is 3,

[0709] In formula (D4), there is at least one A,

[0710] R g1 and R h1 Each time it occurs, it is independently -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 ,

[0711] Z 4 Each occurrence is independently a single bond, an oxygen atom or a divalent organic group, and in formula (D5), there is at least one A.]

[0712] In the above formula, X 10 Each occurrence is independently a single bond or a divalent organic group. The divalent organic group is preferably -R 28 -O x -R 29 -(where R 28 and R 29 Each occurrence is independently a single bond or C 1－20 alkylene, x is 0 or 1). 1－20 The alkylene group may be a straight chain or a branched chain, and is preferably a straight chain. 1－20 The alkylene group is preferably C 1－10 Alkylene, more preferably C 1－6 Alkylene, more preferably C 1－3 Alkylene.

[0713] In one approach, X 10Each time it occurs, it is independently -C 1－6 Alkylene-O-C 1－6 Alkylene-or-O-C 1－6 Alkylene-.

[0714] In a preferred embodiment, X 10 Each occurrence is independently a single bond or a linear C 1－6 Alkylene, preferably a single bond or straight chain C 1－3 Alkylene, more preferably a single bond or straight chain C 1－2 Alkylene, more preferably a straight chain C 1－2 Alkylene.

[0715] In the above formula, R 13 Each occurrence is independently a hydrogen atom or a monovalent organic group. The monovalent organic group is preferably C 1－20 Alkyl. 1－20 The alkyl group may be a linear chain or a branched chain, and is preferably a linear chain.

[0716] In a preferred embodiment, R 13 Each occurrence is independently a hydrogen atom or a linear C 1－6 Alkyl, preferably a hydrogen atom or a straight-chain C 1－3 The alkyl group is preferably a hydrogen atom or a methyl group.

[0717] In the above formula, t is independently an integer greater than 2 at each occurrence.

[0718] In a preferred embodiment, t is independently an integer of 2 to 10, preferably an integer of 2 to 6, at each occurrence.

[0719] In the above formula, R 14 Each occurrence of is independently a hydrogen atom or a halogen atom. The 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 A hydrogen atom.

[0720] In the above formula, R a1 Each time it occurs, it is independently -Z 1 -SiR a2 p1 R a3 q1 R a4 r1 .

[0721] The above Z 1 Each occurrence is independently a single bond, an oxygen atom or a divalent organic group. 1 The right side of the structure is a2p1 R a3 q1 R a4 r1 ) bonding.

[0722] In a preferred embodiment, Z 1 It is a divalent organic group.

[0723] The above Z 1 Preferably C 1－6 Alkylene, -(CH 2 ) z1 -O-(CH 2 ) 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), -(CH 2 ) z3 -phenylene-(CH 2 ) 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 -(CH 2 ) z5 -C 3－10 Cycloalkylene-(CH 2 ) 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 group may be a straight chain or a branched chain, preferably a straight chain. These groups may be selected from, for example, fluorine atoms, C 1－6 Alkyl, C 2－6 Alkenyl and C 2－6 One or more substituents in the alkynyl group may be substituted, but preferably the alkynyl group is unsubstituted.

[0724] In a preferred embodiment, Z 1 C 1－6 Alkylene or -(CH 2 ) z3 -phenylene-(CH 2 ) z4 -, preferably -phenylene-(CH 2 ) z4 -

[0725] In another preferred embodiment, the above Z 1 C 1－3 In one embodiment, Z 1 Can be -CH 2 CH 2 CH 2 -. In another way, Z 1 Can be -CH2 CH 2 -

[0726] R a2 Each time it occurs, it is independently -Z 1' -SiR a3' q1' R a4' r1' .

[0727] The above Z 1' Each occurrence is independently a single bond, an oxygen atom or a divalent organic group. 1' The right side of the structure is a3' q1' R a4' r1' ) bonding.

[0728] In a preferred embodiment, Z 1' It is a divalent organic group.

[0729] The above Z 1' Preferably C 1－6 Alkylene, -(CH 2 ) z1' -O-(CH 2 ) 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 -(CH 2 ) z3' -phenylene-(CH 2 ) 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 group may be a straight chain or a branched chain, preferably a straight chain. These groups may be selected from, for example, fluorine atoms, C 1－6 Alkyl, C 2－6 Alkenyl and C 2－6 One or more substituents in the alkynyl group may be substituted, but preferably the alkynyl group is unsubstituted.

[0730] In a preferred embodiment, Z 1' C 1－6 Alkylene or -(CH 2 ) z3' -phenylene-(CH 2 ) z4' -, preferably -phenylene-(CH 2 ) z4' -. In Z 1' In the case of such a group, light resistance, particularly ultraviolet resistance, can be further improved.

[0731] In a preferred embodiment, the above Z 1' C 1－3 In one embodiment, Z 1' Can be -CH 2 CH 2 CH 2 -. In another way, Z 1' Can be -CH 2 CH 2 -

[0732] R a3' Each time it occurs, it is independently -Z 2 -Y-A.

[0733] Z 2 Each occurrence is independently a single bond, an oxygen atom or a divalent organic group. 2 The right side of the structure is bonded to (Y-A).

[0734] In a preferred embodiment, Z 2 For a single key.

[0735] In a preferred embodiment, Z 2 It is a divalent organic group.

[0736] Z 2 Preferably C 1－6 Alkylene, -(CH 2 ) z11 -O-(CH 2 ) 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), -(CH 2 ) z13 -phenylene-(CH 2 ) 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 -(CH 2 ) z15 -C 3－10 Cycloalkylene-(CH 2 ) 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 group may be a straight chain or a branched chain, preferably a straight chain. These groups may be selected from, for example, fluorine atoms, C 1－6 Alkyl, C 2－6 Alkenyl and C 2－6One or more substituents in the alkynyl group may be substituted, but preferably the alkynyl group is unsubstituted.

[0737] In a preferred embodiment, Z 2 C 1－6 Alkylene or -(CH 2 ) z13 -phenylene-(CH 2 ) z14 -, preferably -phenylene-(CH 2 ) z14 -

[0738] In another preferred embodiment, Z 2 C 1－3 In one embodiment, Z 2 Can be -CH 2 CH 2 CH 2 -. In another way, Z 2 Can be -CH 2 CH 2 -

[0739] R a4' Each occurrence is independently a hydrogen atom, a hydroxyl group or a monovalent organic group. The monovalent organic group is a monovalent organic group other than the above-mentioned hydrolyzable group. The monovalent organic group is a monovalent organic group other than the above-mentioned -Z 2 A monovalent organic group other than -Y-A.

[0740] In R a4' The monovalent organic group is preferably C 1－20 Alkyl, more preferably C 1－6 The alkyl group is more preferably a methyl group.

[0741] q1' is independently an integer of 0 to 3 at each occurrence, and r1' is independently an integer of 0 to 3 at each occurrence. The sum of q1' and r1' is (SiR a3' q1' R a4' r1' ) unit is 3.

[0742] In a preferred embodiment, q1' is independently an integer of 1 to 3, preferably 2 or 3, and more preferably 3, at each occurrence. In this case, r1' is independently an integer of 0 to 2, preferably 0 or 1, and more preferably 0, at each occurrence.

[0743] R a3 Each time it occurs, it is independently -Z 2 -Y-A.

[0744] Ra4 Each occurrence is independently a hydrogen atom, a hydroxyl group or a monovalent organic group. The monovalent organic group is a monovalent organic group other than the above-mentioned hydrolyzable group. The monovalent organic group is a monovalent organic group other than the above-mentioned -Z 2 A monovalent organic group other than -Y-A.

[0745] In R a4 The monovalent organic group is preferably C 1－20 Alkyl, more preferably C 1－6 The alkyl group is more preferably a methyl group.

[0746] p1 is independently an integer from 0 to 3 at each occurrence, q1 is independently an integer from 0 to 3 at each occurrence, and r1 is independently an integer from 0 to 3 at each occurrence. The sum of p1, q1 and r1 is (SiR a2 p1 R a3 q1 R a4 r1 ) unit is 3.

[0747] In one embodiment, p1 is independently an integer of 1 to 3, preferably 2 or 3, and more preferably 3, at each occurrence.

[0748] In another embodiment, q1 is independently an integer of 1 to 3, preferably 2 or 3, and more preferably 3, at each occurrence.

[0749] In a preferred embodiment, r1 is independently an integer of 0 to 2 at each occurrence, preferably 0 or 1, and more preferably 0.

[0750] In one embodiment, p1 is 3.

[0751] In another embodiment, q1 is 3.

[0752] In the above formula, R b1 Each time it occurs, it is independently -Z 2 -Y-A.

[0753] In the above formula, R c1 Each occurrence is independently a hydrogen atom, a hydroxyl group or a monovalent organic group. The monovalent organic group is excluding the above-mentioned -Z 2 A monovalent organic group other than -Y-A.

[0754] R c1 The monovalent organic group is preferably C 1－20 Alkyl, more preferably C 1－6 The alkyl group is more preferably a methyl group.

[0755] k1 is independently an integer from 0 to 3 at each occurrence, l1 is independently an integer from 0 to 3 at each occurrence, and m1 is independently an integer from 0 to 3 at each occurrence. The sum of k1, l1 and m1 is (SiR a1 k1 R b1 l1 R c1 m1 ) unit is 3.

[0756] In one embodiment, k1 is independently an integer of 1 to 3, preferably 2 or 3, and more preferably 3, at each occurrence.

[0757] In another embodiment, l1 is independently an integer of 1 to 3, preferably 2 or 3, and more preferably 3, at each occurrence.

[0758] In a preferred embodiment, m1 is independently an integer of 0 to 2 at each occurrence, preferably 0 or 1, and more preferably 0.

[0759] In one embodiment, k1 is 3.

[0760] In another embodiment, l1 is 3.

[0761] However, in formula (D3), there is at least one -Y-A.

[0762] R d1 Each time it occurs, it is independently -Z 3 -CR d2 p2 R d3 q2 R d4 r2 .

[0763] Z 3 Each occurrence is independently a single bond, an oxygen atom or a divalent organic group. 3 The right side of the structure is the same as (CR d2 p2 R d3 q2 R d4 r2 ) bonding.

[0764] In a preferred embodiment, Z 3 It is a divalent organic group.

[0765] The above Z 3 Preferably C 1－6 Alkylene, -(CH 2 ) z5 -O-(CH 2 )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), -(CH 2 ) z7 -phenylene-(CH 2 ) 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 -(CH 2 ) z9 -C 3－10 Cycloalkylene-(CH 2 ) 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 group may be a straight chain or a branched chain, preferably a straight chain. These groups may be selected from, for example, fluorine atoms, C 1－6 Alkyl, C 2－6 Alkenyl and C 2－6 One or more substituents in the alkynyl group may be substituted, but preferably the alkynyl group is unsubstituted.

[0766] In a preferred embodiment, Z 3 C 1－6 Alkylene or -(CH 2 ) z7 -phenylene-(CH 2 ) z8 -, preferably -phenylene-(CH 2 ) z8 -

[0767] In another preferred embodiment, the above Z 3 C 1－3 In one embodiment, Z 3 Can be -CH 2 CH 2 CH 2 -. In another way, Z 3 Can be -CH 2 CH 2 -

[0768] R d2 Each time it occurs, it is independently -Z 3' -CR d3' q2' R d4' r2' .

[0769] Z 3' Each occurrence is independently a single bond, an oxygen atom or a divalent organic group. 3'The right side of the structure is the same as (CR d3' q2' R d4' r2' ) bonding.

[0770] The above Z 3' Preferably C 1－6 Alkylene, -(CH 2 ) z5' -O-(CH 2 ) 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), -(CH 2 ) z7' -phenylene-(CH 2 ) 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 -(CH 2 ) z9' -C 3－10 Cycloalkylene-(CH 2 ) 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 group may be a straight chain or a branched chain, preferably a straight chain. These groups may be selected from, for example, fluorine atoms, C 1－6 Alkyl, C 2－6 Alkenyl and C 2－6 One or more substituents in the alkynyl group may be substituted, but preferably the alkynyl group is unsubstituted.

[0771] In a preferred embodiment, Z 3' C 1－6 Alkylene or -(CH 2 ) z7' -phenylene-(CH 2 ) z8' -, preferably -phenylene-(CH 2 ) z8' -

[0772] In another preferred embodiment, the above Z 3' C 1－3 In one embodiment, Z 3' Can be -CH 2 CH 2 CH 2 -. In another way, Z 3' Can be -CH 2 CH 2 -

[0773] The above R d3' Each time it occurs, it is independently -Z 2 -Y-A.

[0774] The above R d4' Each occurrence is independently a hydrogen atom, a hydroxyl group or a monovalent organic group. The monovalent organic group is excluding the above-mentioned -Z 2 A monovalent organic group other than -Y-A.

[0775] The above R d4' The monovalent organic group is preferably C 1－20 Alkyl, more preferably C 1－6 The alkyl group is more preferably a methyl group.

[0776] In another embodiment, R d4' is a monovalent organic group, preferably C 1－20 Alkyl, more preferably C 1－6 alkyl.

[0777] q2' is independently an integer from 0 to 3 at each occurrence, and r2' is independently an integer from 0 to 3 at each occurrence. The sum of q2' and r2' is (CR d3' q2' R d4' r2' ) unit is 3.

[0778] In a preferred embodiment, q2' is independently an integer of 1 to 3, preferably 2 or 3, and more preferably 3, at each occurrence. In this case, r2' is independently an integer of 0 to 2, preferably 0 or 1, and more preferably 0, at each occurrence.

[0779] R d3 Each time it occurs, it is independently -Z 2 -Y-A.

[0780] The above R d4 Each occurrence is independently a hydrogen atom, a hydroxyl group or a monovalent organic group. The monovalent organic group is excluding the above-mentioned -Z 2 A monovalent organic group other than -Y-A.

[0781] The above R d4 The monovalent organic group is preferably C 1－20 Alkyl, more preferably C 1－6 The alkyl group is more preferably a methyl group.

[0782] In another embodiment, R d4 is a monovalent organic group, preferably C 1－20 Alkyl, more preferably C 1－6alkyl.

[0783] The above p2 is independently an integer of 0 to 3 at each occurrence, q2 is independently an integer of 0 to 3 at each occurrence, and r2 is independently an integer of 0 to 3 at each occurrence. The sum of p2, q2 and r2 is (CR d2 p2 R d3 q2 R d4 r2 ) unit is 3.

[0784] In one embodiment, p2 is independently an integer of 1 to 3, preferably 2 or 3, and more preferably 3, at each occurrence.

[0785] In another embodiment, q2 is independently an integer of 1 to 3, preferably 2 or 3, and more preferably 3, at each occurrence.

[0786] In a preferred embodiment, r2 is independently an integer of 0 to 2 at each occurrence, preferably 0 or 1, and more preferably 0.

[0787] In one embodiment, p2 is 3.

[0788] In another embodiment, q2 is 3.

[0789] The above R e1 Each time it occurs, it is independently -Z 2 -Y-A.

[0790] The above R f1 Each occurrence of is independently a hydrogen atom, a hydroxyl group or a monovalent organic group. The monovalent organic group is a monovalent organic group other than the above-mentioned hydrolyzable group.

[0791] The above R f1 The monovalent organic group is preferably C 1－20 Alkyl, more preferably C 1－6 The alkyl group is more preferably a methyl group.

[0792] In another embodiment, R f1 is a monovalent organic group, preferably C 1－20 Alkyl, more preferably C 1－6 alkyl.

[0793] The above k2 is independently an integer of 0 to 3 at each occurrence, l2 is independently an integer of 0 to 3 at each occurrence, and m2 is independently an integer of 0 to 3 at each occurrence. The sum of k2, l2 and m2 is (CR d1 k2 R e1l2 R f1 m2 ) unit is 3.

[0794] In one embodiment, k2 is independently an integer of 1 to 3, preferably 2 or 3, and more preferably 3, at each occurrence.

[0795] In another embodiment, l2 is independently an integer of 1 to 3, preferably 2 or 3, and more preferably 3, at each occurrence.

[0796] In a preferred embodiment, m2 is independently an integer of 0 to 2 at each occurrence, preferably 0 or 1, and more preferably 0.

[0797] In one embodiment, k2 is 3.

[0798] In another embodiment, l2 is 3.

[0799] However, in formula (D4), there is at least one -Y-A.

[0800] R g1 and R h1 Each time it occurs, it is independently -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 .

[0801] Z 4 Each occurrence is independently a single bond, an oxygen atom or a divalent organic group. 4 The right side of the structure is bonded to (-Y-A group, etc.).

[0802] However, in formula (D5), there is at least one -Y-A.

[0803] In one approach, Z 4 For oxygen atoms.

[0804] In one approach, Z 4 It is a divalent organic group.

[0805] The above Z 4 Preferably C 1－6 Alkylene, -(CH 2) z5” -O-(CH 2 ) 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 -(CH 2 ) z7” -phenylene-(CH 2 ) 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 group may be a straight chain or a branched chain, preferably a straight chain. These groups may be selected from, for example, fluorine atoms, C 1－6 Alkyl, C 2－6 Alkenyl and C 2－6 One or more substituents in the alkynyl group may be substituted, but preferably the alkynyl group is unsubstituted.

[0806] In a preferred embodiment, Z 4 C 1－6 Alkylene or -(CH 2 ) z7” -phenylene-(CH 2 ) z8” -, preferably -phenylene-(CH 2 ) z8” -. In Z 3 In the case of such a group, light resistance, particularly ultraviolet resistance, can be further improved.

[0807] In another preferred embodiment, the above Z 4 C 1－3 In one embodiment, Z 4 Can be -CH 2 CH 2 CH 2 -. In another way, Z 4 Can be -CH 2 CH 2 -

[0808] In one approach, R D It is a group represented by formula (D1).

[0809] In one approach, R D It is a group represented by formula (D2).

[0810] In one approach, R D It is a group represented by formula (D3).

[0811] In one approach, R D It is a group represented by formula (D4).

[0812] In one approach, R D It is a group represented by formula (D5).

[0813] The number average molecular weight of the unsaturated compound containing a fluorinated polyether group of the present invention is 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. Furthermore, the number average molecular weight of the unsaturated compound containing a fluorinated polyether group of the present invention is preferably 100,000 or less, more preferably 50,000 or less, further preferably 30,000 or less, further 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 unsaturated compound containing a fluorinated polyether group is represented by 19 The value measured by F-NMR.

[0814] In one embodiment, the number average molecular weight of the fluorinated polyether group-containing unsaturated compound is 1,000 to 100,000, preferably 2,000 to 30,000, and more preferably 2,000 to 10,000.

[0815] The mass ratio of the fluorinated polyether group-containing thiol compound of the present invention to the fluorinated polyether group-containing unsaturated compound is preferably 0.1:100 to 100:0.1, more preferably 5:100 to 100:5, and even more preferably 10:100 to 100:10.

[0816] The curable composition of the present invention may further contain fluorine-containing oil.

[0817] The fluorine-containing oil is not particularly limited, and may be, for example, a compound represented by the following formula (5).

[0818] R 5 -(OC 4 F 8 ) a' -(OC 3 F 6 ) b' -(OC 2 F 4 ) c' -(OCF 2 ) d' -Rf 6 ···(5)

[0819] [Wherein,

[0820] R 5 is C which may be substituted by one or more fluorine atoms 1－16 alkyl,

[0821] R6 is C which may be substituted by one or more fluorine atoms 1－16 an alkyl group, a fluorine atom or a hydrogen atom,

[0822] a', b', c' and d' are each independently an integer of 0 to 300,

[0823] The sum of a', b', c' and d' is at least 1,

[0824] The order of presence of the repeating units marked with the indices a', b', c' or d' and enclosed in parentheses is arbitrary in the formula.]

[0825] R 5 is an alkyl group having 1 to 16 carbon atoms which may be substituted with 1 or more fluorine atoms, preferably C 1―16 of perfluoroalkyl.

[0826] R 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, preferably C 1－16 Perfluoroalkyl.

[0827] In a preferred embodiment, Rf 5 and Rf 6 C 1―16 A perfluoroalkyl group, more preferably C 1－3 Perfluoroalkyl.

[0828] The sum of a', b', c' and d' is at least 1, preferably 1-300, more preferably 20-300.

[0829] In the repeating unit of the above fluorinated oil, -(OC 4 F 8 )-can be-(OCF 2 CF 2 CF 2 CF 2 )-、-(OCF(CF 3 )CF 2 CF 2 )-、-(OCF 2 CF(CF 3 )CF 2 )-、-(OCF 2 CF 2 CF(CF 3 ))-、-(OC(CF 3 ) 2 CF 2 )-、-(OCF 2 C(CF 3 ) 2)-、-(OCF(CF 3 )CF(CF 3 ))-、-(OCF(C 2 F 5 )CF 2 )- and (OCF 2 CF(C 2 F 5 ))-, preferably -(OCF 2 CF 2 CF 2 CF 2 )-. -(OC 3 F 6 )-can be-(OCF 2 CF 2 CF 2 )-、-(OCF(CF 3 )CF 2 )- and (OCF 2 CF(CF 3 ))-, preferably -(OCF 2 CF 2 CF 2 )-. -(OC 2 F 4 )-can be-(OCF 2 CF 2 )- and (OCF(CF 3 ))-, preferably -(OCF 2 CF 2 )-.

[0830] Examples of the perfluoro(poly)ether compound represented by the general formula (5) include compounds represented by any one of the following general formulas (5a) and (5b) (the compounds may be one or a mixture of two or more).

[0831] R 5 -(OCF 2 CF 2 CF 2 ) b” -Rf 6 ···(5a)

[0832] R 5 -(OCF 2 CF 2 CF 2 CF 2 ) a” -(OCF 2 CF 2 CF 2 ) b” -(OCF2 CF 2 ) c” -(OCF 2 ) d” -Rf 6 ···(5b)

[0833] In these formulas, Rf 5 and Rf 6 As above; in formula (5a), b" is an integer greater than 1 and less than 100; in formula (5b), a" and b" are each independently an integer greater than 0 and less than 30, and c" and d" are each independently an integer greater than 1 and less than 300. The order of existence of each repeating unit marked with subscripts a", b", c", d" and enclosed in parentheses in the formula is arbitrary.

[0834] From another perspective, the fluorinated oil may be of the general formula Rf 3 -F(where Rf 3 C 5－16 Furthermore, it may be a chlorotrifluoroethylene oligomer.

[0835] The 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.

[0836] The curable composition of the present invention may contain, for example, 0.01 to 50% by mass, preferably 0.1 to 30% by mass, for example 1 to 15% by mass of the fluorinated oil, based on the mass of the curable composition of the present invention.

[0837] In one embodiment, the curable composition of the present invention contains substantially no fluorinated oil. Substantially containing no fluorinated oil means that the composition contains no fluorinated oil at all or may contain a very small amount of fluorinated oil.

[0838] The curable composition of the present invention may further contain a polymerization initiator.

[0839] The polymerization initiator preferably has 1 to 3 aromatic ring structures.

[0840] The above-mentioned polymerization initiator is preferably a radical polymerization initiator.

[0841] The radical polymerization initiator is a compound that generates radicals by heat or light, and examples thereof include a radical thermal polymerization initiator and a radical photopolymerization initiator. In the present invention, the radical photopolymerization initiator is preferred.

[0842] Examples of the above-mentioned free radical thermal polymerization initiator include: diacyl peroxides such as benzoyl peroxide and lauroyl peroxide, dialkyl peroxides such as dicumyl peroxide and di-tert-butyl peroxide, peroxy carbonates such as diisopropyl peroxydicarbonate and di(4-tert-butylcyclohexyl) peroxydicarbonate, peroxy alkyl peroxides such as tert-butyl peroxyoctanoate and tert-butyl peroxybenzoate, and free radical generating azo compounds such as azobisisobutyronitrile.

[0843] Examples of the free 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 benzophenone, 4,4'-bis(dimethylamino)benzophenone, and 4,4'-bis(diethylamino)benzophenone; acetophenone, 2-(4-toluenesulfonyloxy)-2-phenylacetophenone, p-dimethylaminoacetophenone, 2,2'-dimethoxy-2- Acetophenones such as phenylacetophenone, p-methoxyacetophenone, 2-methyl[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane-1-one, etc.; quinones such as anthraquinone and 1,4-naphthoquinone, etc.; aminobenzoic acids such as ethyl 2-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (n-butoxy)ethyl 4-dimethylaminobenzoate, isopentyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, etc.; halogen-containing compounds such as phenacyl chloride and trihalomethylphenyl sulfone, acylphosphine oxides, peroxides such as di-tert-butyl peroxide, etc.

[0844] Examples of commercially available products of the radical photopolymerization initiator include the following.

[0845] IRGACURE 651: 2,2-dimethoxy-1,2-diphenylethane-1-one,

[0846] IRGACURE 184: 1-Hydroxy-cyclohexyl-phenyl-ketone,

[0847] IRGACURE 2959: 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one,

[0848] IRGACURE 127: 2-Hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propane-1-one,

[0849] IRGACURE 907: 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one,

[0850] IRGACURE 369: 2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,

[0851] IRGACURE 379: 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone,

[0852] IRGACURE 819: Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide,

[0853] IRGACURE 784: Bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium,

[0854] IRGACURE OXE 01: 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyl oxime)],

[0855] IRGACURE OXE 02: Ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyl oxime),

[0856] IRGACURE261, IRGACURE369, IRGACURE500,

[0857] DAROCUR 1173: 2-hydroxy-2-methyl-1-phenyl-propane-1-one, DAROCUR TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide,

[0858] DAROCUR1116, DAROCUR2959, DAROCUR1664, DAROCUR4043,

[0859] IRGACURE 754 Oxyphenylacetic acid: a mixture of 2-[2-oxo-2-phenylacetoxyethoxy]ethyl ester, oxyphenylacetic acid, and 2-(2-hydroxyethoxy)ethyl ester,

[0860] IRGACURE 500: a mixture of IRGACURE 184 and benzophenone (1:1), IRGACURE 1300: a mixture of IRGACURE 369 and IRGACURE 651 (3:7),

[0861] 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).

[0862] Among them, IRGACURE is a product of BASF, and DAROCUR is a product of Merck Japan.

[0863] In one embodiment, the curable composition of the present invention is a solvent-free composition, that is, substantially free of solvent. "Substantially free of solvent" means that a solvent is not intentionally added, and a trace amount of an inevitably contained solvent, such as water, may exist. For example, the content of the solvent in the curable composition of the present invention may be 1.0 mass % or less, 0.5 mass % or less, 0.1 mass % or less, or 0.01 mass % or less.

[0864] The viscosity of the curable composition of the present invention is preferably 100 mPa·s or more, more preferably 200 mPa·s or more, and further preferably 300 mPa·s or more. When the viscosity is too low, dripping may sometimes occur after coating on the component. In addition, the viscosity of the curable composition of the present invention is preferably 10000 mPa·s or less, more preferably 7000 mPa·s or less, further preferably 5000 mPa·s or less, further preferably 3000 mPa·s or less, and particularly preferably less than 1000 mPa·s. When the viscosity is too high, injection into fine parts of the component sometimes becomes difficult. By adjusting to the above-mentioned viscosity, dripping is not easy to occur, and it is easy to inject into fine parts of the component, which can improve the coating property.

[0865] In one embodiment, the viscosity of the curable composition of the present invention is 100 to 10,000 mPa·s, preferably 200 to 7,000 mPa·s, more preferably 300 to 5,000 mPa·s, further preferably 300 to 3,000 mPa·s, and particularly preferably 300 mPa·s or more and less than 1,000 mPa·s.

[0866] In one embodiment, the curable composition of the present invention is a surface treatment agent.

[0867] The present invention provides a cured product obtained by curing the curable composition of the present invention.

[0868] The tensile modulus of elasticity of the cured product of the present invention is preferably 0.1 to 500 MPa, more preferably 0.2 to 500 MPa, further preferably 0.3 to 300 MPa, and further preferably 0.4 to 100 MPa.

[0869] The tensile modulus can be measured using a precision universal tester (AGS-J manufactured by Shimadzu Corporation, 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).

[0870] The weight loss rate (%) of the cured product of the present invention after being kept at 65°C and 90% RH for 72 hours (((weight before keeping - weight after keeping) / weight before keeping) × 100) is preferably less than 50%, more preferably less than 40%, further preferably less than 20%, and particularly preferably less than 10%.

[0871] The cured product of the present invention is preferably a packaging material.

[0872] The above-mentioned packaging material is preferably a packaging material for electronic devices.

[0873] The present invention includes a substrate and a layer formed on the substrate by curing the curable composition of the present invention (hereinafter also referred to as a "surface treatment layer").

[0874] The substrate that can be used in the present invention can be composed of, for example, glass, resin (which can be natural or synthetic resin, such as a common plastic material), OCA (Optical Clear Adhesive), polarizing plate metal, ceramics, semiconductors (silicon, germanium, etc.), electronic devices, fibers (textiles, non-woven fabrics, etc.), fur, leather, wood, ceramics, stone, building components, sanitary products, and any other suitable materials.

[0875] In a preferred embodiment, the substrate is glass, resin, polarizing plate, OCA (Optical Clear Adhesive) or metal, preferably glass, resin, polarizing plate or OCA (Optical Clear Adhesive).

[0876] As the above-mentioned 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.

[0877] For example, when the object to be manufactured is an optical component, the material constituting the surface of the substrate may be a material for optical components, such as glass or transparent plastic. In addition, when the object to be manufactured is an optical component, the surface (outermost layer) of the substrate may be formed with certain layers (or films), such as a hard coating layer or an anti-reflection layer. The anti-reflection layer may be a single-layer anti-reflection layer or a multi-layer anti-reflection layer. Examples of inorganic substances that can be used for the anti-reflection layer include SiO 2 、SiO、ZrO 2 、TiO 2 、TiO、Ti 2 O 3 、Ti 2 O 5 、Al 2 O 3 、 2 O 5 、 3 O 5 , Nb 2 O 5 , HfO 2 、Si 3 N 4 、CeO 2 ,MgO,Y 2 O 3 SnO 2 MgF 2 , WO 3 These inorganic substances can be used alone or in combination (e.g., in the form of a mixture). When a multilayer antireflection layer is formed, it is preferred that the outermost layer use SiO 2 And / or SiO. When the desired article is an optical glass component for a touch screen, part of the surface of the substrate (glass) may have a transparent electrode, such as a thin film of indium tin oxide (ITO) or indium zinc oxide. In addition, the substrate may have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomized film layer, a hard coating layer, a polarizing film, a phase difference film, and a liquid crystal display module, etc., depending on its specific style.

[0878] The shape of the above-mentioned substrate is not particularly limited, for example, can be plate-like, film, other forms. In addition, the surface area of ​​the substrate that wants to form the surface treatment layer is at least a portion of the substrate surface, can be appropriately determined according to the purpose of the article that wants to be manufactured and specific styles etc.

[0879] The article of the present invention can be produced by forming a layer of the composition of the present invention on the surface of the substrate and, if necessary, post-treating the layer to form a layer of the composition of the present invention.

[0880] When forming a layer of the composition of the present invention, the composition can be applied to the surface of the substrate in a manner that covers the surface. The covering method is not particularly limited. For example, a wet covering method and a dry covering method can be used.

[0881] The surface treatment layer included in the article of the present invention has slippery properties. In addition to high slippery properties, the surface treatment layer may also have antibacterial properties, water repellency, oil repellency, antifouling properties (for example, preventing the adhesion of dirt such as fingerprints), water repellency (preventing water from entering electronic components, etc.), surface sliding properties (or lubricity, such as the ability to wipe off dirt such as fingerprints or excellent touch to fingers), etc., depending on the composition of the composition used, and is suitable for use as a functional film.

[0882] In a preferred embodiment, the article of the present invention is useful in glass or mirrored glass for vehicles, ships or aircraft, such as automobile glass, automobile door mirrors or automobile side mirrors, or glass for vehicle-mounted cameras, etc. Furthermore, it is useful in glass used for surveillance cameras or substrates for outdoor use such as curved road reflectors.

[0883] Therefore, the present invention further relates to an optical material having the above-mentioned surface treatment layer as the outermost layer.

[0884] As optical materials, in addition to the optical materials related to displays etc. exemplified below, it is also preferred to cite a variety of optical materials, for example: cathode ray tubes (CRT, such as computer monitors), liquid crystal displays, plasma displays, organic EL displays, inorganic thin film EL dot matrix displays, rear projection displays, fluorescent display tubes (VFD), field emission displays (FED, Field Emission Display) and the like or protective plates of these displays, or materials having an anti-reflection film treated on their surfaces.

[0885] The articles of the present invention are not particularly limited and may be optical components. Examples of optical components include the following articles: lenses of glasses, etc.; front protective plates, anti-reflection plates, polarizing plates, anti-glare plates of displays such as PDP and LCD; touch screens of devices such as mobile phones and portable information terminals; disc surfaces of optical discs such as Blu-ray (registered trademark) discs, DVD discs, CD-R, MO, etc.; optical fibers; display surfaces of clocks, etc.

[0886] Furthermore, the article of the present invention may be a medical device or a medical material.

[0887] The thickness of the above layer is not particularly limited, and may be, for example, 1 nm or more, 10 nm or more, or 100 nm or more. Also, the thickness of the above layer is not particularly limited, and may be 1000 nm or less, 500 nm or less, or 100 nm or less.

[0888] The fluorinated polyether group-containing thiol compound, curable composition, cured product, etc. of the present invention have been described in detail above, but the present invention is not limited to the above examples.

[0889] Example

[0890] The thiol compound containing a fluorinated polyether group and the curable composition of the present invention are specifically described by the following examples, but the present invention is not limited to these examples. In this example, the order of existence of the repeating units constituting the fluorinated polyether is arbitrary, and the chemical formula shown below represents the average composition.

[0891] (Viscosity measurement)

[0892] The viscosity of the fluorinated polyether group-containing unsaturated compound, the fluorinated polyether group-containing thiol compound, and the composition shown in Table 2 obtained by mixing them 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.

[0893] (Determination of tensile elastic modulus)

[0894] A test piece having a width of 1 cm and a length of 6 cm was cut out from a cured coating film (film thickness of 130 μm) made of the curable composition shown in Table 2, and the tensile modulus was measured at room temperature with a clamp spacing of 40 mm and a tensile speed of 5.0 mm / min using a precision universal tester (AGS-J manufactured by Shimadzu Corporation, load cell: 50 N).

[0895] 1. Synthesis of allyl-containing perfluoropolyether

[0896] Synthesis Example 1 Synthesis of Compound (A-1)

[0897] In a flask, 74 g of perfluoropolyether dicarboxylic acid (average composition: m=15, n=12) represented by 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, 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. After the addition was completed, the mixture was stirred overnight at room temperature. Dilute hydrochloric acid, perfluorohexane, and acetone were added to the reaction solution, and a liquid separation operation was performed. After washing with water and acetone, the solvent was distilled off to obtain 65 g of a perfluoropolyether compound having an allyl group represented by the following formula (A-1). According to 19 According to F-NMR measurement, the number average molecular weight of the compound is 2700, and the viscosity of the compound at room temperature is 300 mPa·s.

[0898] Compound (1)

[0899]

[0900] Compound (A-1)

[0901]

[0902] Synthesis Example 2 Synthesis of Compound (A-2)

[0903] 20 g of the perfluoropolyether diester represented by formula (2) (average composition: m=15, n=12) 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 the following formula (A-2). 19 According to F-NMR measurement, the number average molecular weight of the compound is 2700, and the viscosity of the compound at room temperature is 400 mPa·s.

[0904] Compound (2)

[0905]

[0906] Compound (A-2)

[0907]

[0908] Synthesis Example 3 Synthesis of Compound (A-3)

[0909] According to the method described in Example 6 of Japanese Patent Application Laid-Open No. 2016-204656, 10 g of the perfluoropolyether diester represented by formula (2) (average composition m=15, n=12) was used as a raw material to obtain 8.52 g of a perfluoropolyether compound having an allyl group represented by the following formula (A-3). 19 According to F-NMR measurement, the number average molecular weight of the compound is 2600, and the viscosity of the compound at room temperature is 300 mPa·s.

[0910] Compound (A-3)

[0911]

[0912] 2. Synthesis of thiol-containing perfluoropolyether

[0913] Synthesis Example 4 Synthesis of Compound (B-1) (Example 4-1) Synthesis of Compound (W-1)

[0914] In a flask, 5 g of the 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. Then, 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 distilled off. Then, the mixture was washed with methanol to obtain 5.1 g of a perfluoropolyether compound represented by the following formula (W-1).

[0915] Compound (3)

[0916]

[0917] Compound (W-1)

[0918]

[0919] (Example 4-2) Synthesis of Compound (W-2)

[0920] 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 benzoin diethyl ether were added to a reaction container, and argon gas was introduced for degassing. Then, the mixture was stirred for 1 hour while being irradiated with UV light (light source: HL100GL-1 manufactured by SEN Special Light Source Co., Ltd.). After the reaction solution was washed 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 the following formula (W-2).

[0921] Compound (W-2)

[0922]

[0923] (Example 4-3) Synthesis of Compound (B-1)

[0924] 5 g of the compound represented by formula (W-2) obtained in Example 4-2, 15 ml of Novec 7200 (produced by 3M), 10 ml of THF, and 2.2 ml of 28% sodium methoxide methanol solution were added to a reaction container and stirred at room temperature for 1 hour. Dilute hydrochloric acid was added to terminate the reaction, and after separation and water washing, 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 According to F-NMR measurement, the number average molecular weight of the compound is 2000, and the viscosity of the compound at room temperature is 600 mPa·s. In addition, the compound is soluble in 1,3-bis(trifluoromethyl)benzene and perfluorobenzene.

[0925] Compound (B-1)

[0926]

[0927] Synthesis Example 5 Synthesis of Compound (B-2) (Example 5-1) Synthesis of Compound (X-1)

[0928] 5.4 g of a perfluoropolyether compound represented by the following formula (X-1) was obtained in the same manner as in Example 4-1 except that 2.57 g of farnesyl bromide was used instead of 1.96 g of geranyl bromide.

[0929] Compound (X-1)

[0930]

[0931] (Example 5-2) Synthesis of Compound (X-2)

[0932] The same operation as in Example 4-2 was carried out except that 8 g of the compound represented by (W-1) was replaced with 8 g of the compound represented by (X-1), 3.67 g of thioacetic acid, and 0.150 g of benzoin diethyl ether to obtain 8.1 g of a perfluoropolyether compound represented by the following formula (X-2).

[0933] Compound (X-2)

[0934]

[0935] (Example 5-3) Synthesis of Compound (B-2)

[0936] The same operation as in Example 4-3 was carried out except that 5 g of the compound represented by (X-2) and 2.6 ml of a 28% sodium methoxide methanol solution were used instead of 5 g of the compound represented by (W-2) to obtain 3.8 g of a perfluoropolyether compound represented by the following formula (B-2) having a thiol group. 19 According to F-NMR measurement, the number average molecular weight of the compound is 2200, and the viscosity of the compound at room temperature is 1000 mPa·s.

[0937] Compound (B-2)

[0938]

[0939] Synthesis Example 6 Synthesis of Compound (B-3) (Example 6-1) Synthesis of Compound (Y-1)

[0940] 100 g of the perfluoropolyether diester represented by formula (2) (average composition m=15, n=12) and 8.4 g of diethanolamine were added to a flask and stirred at 70° C. overnight under reduced pressure to obtain 104.8 g of a perfluoropolyether compound having a hydroxyl group represented by formula (Y-1).

[0941] Compound (Y-1)

[0942]

[0943] (Example 6-2) Synthesis of Compound (Y-2)

[0944] 104.8 g of the compound represented by formula (Y-1) obtained in Example 6-1, 300 mL of 1,3-bis(trifluoromethyl)benzene, and 20 g of triethylamine were added to a flask, and 41.5 g of 2-bromopropionyl bromide was added dropwise in an ice bath to react overnight. The reaction solution was washed with dilute hydrochloric acid and saturated brine, and the solvent was distilled off to obtain 108 g of a perfluoropolyether compound having a bromine group represented by formula (Y-2).

[0945] Compound (Y-2)

[0946]

[0947] (Example 6-3) Synthesis of Compound (Y-3)

[0948] 108 g of the compound represented by formula (Y-2) obtained in Example 6-2, 27.4 g of potassium O-ethylxanthate, 540 mL of 1,3-bis(trifluoromethyl)benzene, and 54 mL of pyridine were added, and the reaction was carried out at room temperature overnight. After the reaction solution was washed with water, the solvent was distilled off to obtain 111.7 g of a perfluoropolyether compound having a xanthate group represented by formula (Y-3).

[0949] Compound (Y-3)

[0950]

[0951] (Example 6-4) Synthesis of Compound (B-3)

[0952] 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 the mixture was 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 According to F-NMR measurement, the number average molecular weight of the compound is 3100, and the viscosity of the compound at room temperature is 2200 mPa·s.

[0953] Compound (B-3)

[0954]

[0955] Synthesis Example 7 Synthesis of Compound (B-4) (Example 7-1) Synthesis of Compound (P-1)

[0956] 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 to a flask and reacted at 80° C. The reaction solution was washed with water to obtain 8.97 g of a perfluoropolyether compound represented by formula (P-1).

[0957] Compound (P-1)

[0958]

[0959] (Example 7-2) Synthesis of Compound (B-4)

[0960] 8.97 g of the compound represented by formula (P-1), 50 mL of Novec7200 (produced 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 According to F-NMR measurement, the number average molecular weight of the compound is 2800, and the viscosity of the compound at room temperature is 1500 mPa·s.

[0961] Compound (B-4)

[0962]

[0963] Synthesis Example 8 Synthesis of Compound (A-4) (Example 8-1) Synthesis of Compound (Z-1)

[0964] According to Example 5-1 of Synthesis Example 5 of Japanese Patent No. 7473853, 15 g of a perfluoropolyether diol of formula (3) (average composition: m=10, n=10) was used as a raw material to synthesize 13.5 g of a perfluoropolyether compound having an allyl group represented by the following formula (Z-1).

[0965] Compound (Z-1)

[0966]

[0967] (Example 8-2) Synthesis of Compound (A-4)

[0968] 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 According to F-NMR measurement, the number average molecular weight of the compound was 2400, and the viscosity of the compound was 400 cP.

[0969] Compound (A-4)

[0970]

[0971] Synthesis Example 9 Synthesis of Compound (B-5) (Example 9-1) Synthesis of Compound (S-1)

[0972] The same operation as in Example 4-1 was carried out except that 15 g of a perfluoropolyether diol (n=12) of the 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 in place of the perfluoropolyether of the formula (3) to obtain 15.3 g of a perfluoropolyether compound represented by the formula (S-1).

[0973] Compound (3)

[0974] HOCH 2 CF 2 CF 2 O)CF 2 CF 2 CF 2 O) n CF 2 CF 2 CH 2 CH 2 OH

[0975] Compound (S-1)

[0976]

[0977] (Example 9-2) Synthesis of Compound (S-2)

[0978] 11.7 g of a perfluoropolyether compound represented by formula (S-2) was obtained in the same manner as in Example 4-2 except that 12 g of the compound represented by formula (S-1) was used instead of the compound represented by formula (W-1).

[0979] Compound (S-2)

[0980]

[0981] (Example 9-3) Synthesis of Compound (B-5)

[0982] The same procedure as in Example 4-3 was carried out except that 7.5 g of the compound represented by formula (S-2) was used instead of the compound represented by formula (W-2) to obtain 6.3 g of a perfluoropolyether compound having a thiol group represented by formula (B-5). 19 According to F-NMR measurement, the number average molecular weight of the compound is 2750, and the viscosity of the compound at room temperature is 950 mPa·s.

[0983] Compound (B-5)

[0984]

[0985] Example

[0986] 1. Storage stability of thiol compounds

[0987] Take 1 mL of each of the thiol-containing perfluoropolyether compounds (B-1) to (B-5) obtained in Synthesis Examples 4 to 9 in a spiral tube (No. 3) and place it in air at room temperature for 2 weeks. Draw a horizontal line on the spiral tube at 2 cm from the bottom, tilt the spiral tube horizontally, and compare the time it takes for the sample liquid end to pass through the horizontal line for the initial sample and the sample after 2 weeks. The evaluation criteria are as follows, and the results are shown in Table 1.

[0988] G: The measurement time of the sample after 2 weeks is less than twice that of the initial sample.

[0989] NG: The measurement time of the sample after 2 weeks is more than twice that of the initial sample.

[0990] [Table 1]

[0991] Compound stability B－1 G B－2 G B－3 G B－4 NG B－5 G

[0992] 2. Preparation of curable composition and viscosity measurement

[0993] The allyl group-containing perfluoropolyether obtained in Synthesis Examples 1 to 3 and 8 and the thiol group-containing perfluoropolyether obtained in Synthesis Examples 4 to 7 and 9 were mixed in a manner that the equivalents of the allyl group and the thiol group were matched, and 2 parts by weight of the photopolymerization initiator (C) IRGACURE 184 (produced by BASF) were further mixed to obtain a curable composition. The composition is shown in Table 2. In addition, the viscosity of these curable compositions at 23° C. was measured.

[0994] G: The viscosity of the composition is lower than 1000 mPa·s.

[0995] NG: The viscosity of the composition is 1000 mPa·s or more.

[0996] 3. Curing test

[0997] 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 a film thickness of 100 μm using an applicator and irradiated with ultraviolet light (wavelength: 365 nm) to investigate whether a cured film could be produced. The irradiation dose was set to 2000 mJ / cm 2 The evaluation criteria are as follows, and the results are shown in Table 2.

[0998] VG: A cured film was obtained with no wrinkles on the surface.

[0999] G: Solidified and no longer flowing.

[1000] NG: Unable to solidify and in liquid state.

[1001] 4. Water resistance test

[1002] The cured film prepared in 3. was placed in a constant temperature and humidity chamber at 65°C / 90 RH% and kept for 72 hours. The weight reduction rate of the cured film thereafter was calculated using the following formula and evaluated.

[1003] Weight reduction rate (%) = ((weight before maintenance - weight after maintenance) / weight before maintenance) × 100

[1004] The evaluation criteria are as follows, and the results are shown in Table 2.

[1005] VG: The weight loss of the cured film was less than 10%.

[1006] G: The weight reduction rate of the cured film is 10% or more and less than 50%.

[1007] NG: The weight reduction rate of the cured film is 50% or more.

[1008] In addition, for the samples evaluated as NG in 3., since a cured film could not be formed, the water resistance test was not conducted.

[1009] [Table 2]

[1010]

[1011] The tensile elastic modulus of the cured film obtained from the curable composition 1 was 0.50 MPa.

[1012] From the results in Table 1, it can be confirmed that the thiol compounds (B-1) to (B-2) and (B-5) containing fluorinated polyether groups without an ester structure and having a secondary thiol group have suppressed viscosity increase and excellent stability in air compared with the thiol compound (B-4) containing a fluorinated polyether group having a primary thiol group. In addition, the thiol compound (B-3) containing a fluorinated polyether group having an ester structure and a secondary thiol group has suppressed viscosity increase and excellent stability in air.

[1013] According to the results in Table 2, it can be confirmed that Examples 1 to 7, which are compositions containing thiol compounds (B-1) to (B-2) and (B-5) containing fluorinated polyether groups without an ester structure and having multiple secondary thiol groups at the ends, have further suppressed thickening and good water resistance compared to Comparative Example 1, which is a composition containing a thiol compound (B-3) containing a fluorinated polyether group containing an ester structure and a secondary thiol group. In addition, Examples 1 to 7 have suppressed thickening and excellent ultraviolet curability compared to Comparative Example 2, which is a composition containing a thiol compound (B-4) containing a primary thiol group.

[1014] Industrial Applicability

[1015] The fluorinated polyether group-containing thiol compound of the present invention is suitably used in various applications, for example, it is suitable as a coating agent.

Claims

1. A thiol compound containing a fluorinated polyether group, characterized in that: It does not contain an ester structure and contains two or more thiol groups selected from secondary thiol groups or tertiary thiol groups.

2. The thiol compound containing a fluorinated polyether group according to claim 1, characterized in that The fluorine content is 30% by mass or more.

3. The thiol compound containing a fluorinated polyether group according to claim 1, characterized in that Contains 2 to 6 thiol groups.

4. The thiol compound containing a fluorinated polyether group according to claim 1, characterized in that The thiol group is a secondary thiol group.

5. The thiol compound containing a fluorinated polyether group according to claim 1, characterized in that The thiol groups are present on both end sides of the fluoropolyether group.

6. The thiol compound containing a fluorinated polyether group according to claim 1, characterized in that It 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 thiol compound containing a fluorinated polyether group according to claim 1, characterized in that It is represented by the following formula (1) or (2): R F1 α1 -X A -R S α2 (1) R S β -X A -R F2 -X A -R S β (2) In the formula, R F1 Rf 1 -R F -O q - R F2 is -Rf 2 p -R F -O q -, R 1 are each independently C which may be substituted with one or more fluorine atoms 1－16 alkyl, R 2 is C which may be substituted by one or more fluorine atoms 1－6 Alkylene, R F are each independently a divalent fluorinated polyether group, p is 0 or 1, q is independently 0 or 1, X A are each independently a single bond or a 2- to 10-valent organic group, R S Each independently includes -(CR 4 (SH)-R 5 ) n -CR 1 R 2 - a monovalent group represented by 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 formula (1) and (2), there are at least two secondary or tertiary thiol groups, α1 is an integer from 1 to 9, α2 is an integer from 1 to 9, β is an integer of 1 to 9 independently. n is an integer from 0 to 9, Formulas (1) and (2) do not contain an ester structure.

8. The thiol compound containing a fluorinated polyether group according to claim 7, characterized in that R 1 C 1－16 Perfluoroalkyl, R 2 C 1－6 Perfluoroalkylene.

9. The thiol compound containing a fluorinated polyether group according to claim 7, characterized in that R F They are independently of the formula: -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3R Fa 6) d -(OC2F4) e -(OCF2) f - the group shown, In the formula, R Fa are independently 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, the sum of a, b, c, d, e and f is 1 or more, the order of existence of the repeating units marked with a, b, c, d, e or f and enclosed in parentheses in the formula is arbitrary, wherein in all R Fa When it is a hydrogen atom or a chlorine atom, at least one of a, b, c, e and f is 1 or more.

10. The thiol compound containing a fluorinated polyether group according to claim 9, characterized in that R Fa A fluorine atom.

11. The thiol compound containing a fluorinated polyether group according to claim 7, characterized in that R F are independently a group represented by the following formula (f1), (f2), (f3), (f4), (f5) or (f6), -(OC3F6) d -(OC2F4) e - (f1) In formula (f1), d is an integer of 1 to 200, and e is 0 or 1; <h2 style=";text-align:left;direction:ltr">(OC4F8)<h2 style=";text-align:left;direction:ltr"> c <h2 style=";text-align:left;direction:ltr"> (OC3F6)<h2 style=";text-align:left;direction:ltr"> d <h2 style=";text-align:left;direction:ltr"> (OC2F4)<h2 style=";text-align:left;direction:ltr"> e <h2 style=";text-align:left;direction:ltr"> (OCF2)<h2 style=";text-align:left;direction:ltr"> f <h2 style=";text-align:left;direction:ltr"> -(f2) In formula (f2), c and d are each independently an integer of 0 to 30, e and f are each independently an integer of 1 to 200, The sum of c, d, e and f is an integer from 10 to 200, The order of presence of the repeating units marked with superscript c, d, e or f and enclosed in brackets in the formula is arbitrary; -(R 6 -R 7 ) g - (f3) In formula (f3), R 6 For OCF2 or OC2F4, R 7 is selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 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 For OCF2 or OC2F4, R 7 is selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of 2 or 3 groups independently selected from these groups, R 6 ' is OCF2 or OC2F4, R 7 ' is selected from OC2F4, OC3F6, OC4F8, OC5F 10 and OC6F 12 or a combination of 2 or 3 groups independently selected from these groups, g is an integer from 2 to 100, g' is an integer from 2 to 100, R r for: In the formula, * represents the bonding position; -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f5) In formula (f5), e is an integer from 1 to 200, a, b, c, d and f are each independently an integer from 0 to 200, and the order of existence of each repeating unit marked with a, b, c, d, e or f and enclosed in parentheses is arbitrary in the formula; -(OC6F 12 ) a -(OC5F 10 ) b -(OC4F8) c -(OC3F6) d -(OC2F4) e -(OCF2) f - (f6) In formula (f6), f is an integer from 1 to 200, a, b, c, d and e are each independently an integer from 0 to 200, and the order of existence of each repeating unit marked with a, b, c, d, e or f and enclosed in parentheses is arbitrary in the formula.

12. The thiol compound containing a fluorinated polyether group according to claim 7, characterized in that R S is a group represented by the following formula (S1), (S2) or (S3), -R Sa (S1) -NR Sa n1 R 3 2-n1 (S2) -CR Sa n2 R 3 3-n2 (S3) 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.

13. The thiol compound containing a fluorinated polyether group according to claim 12, characterized in that Z is -R 11 -, R 11 is a single bond or C 1-6 Alkylene.

14. The thiol compound containing a fluorinated polyether group according to claim 7, characterized in that R 1 C 1-6 Alkyl, R 2 A hydrogen atom or C 1-6 alkyl.

15. The thiol compound containing a fluorinated polyether group according to claim 12, characterized in that R 3 A hydrogen atom or C 1-6 alkyl.

16. The thiol compound containing a fluorinated polyether group according to claim 12, characterized in that R S It is a group represented by formula (S1).

17. The thiol compound containing a fluorinated polyether group according to claim 12, characterized in that R S It is a group represented by formula (S2).

18. The thiol compound containing a fluorinated polyether group according to claim 12, characterized in that R S It is a group represented by formula (S3).

19. The thiol compound containing a fluorinated polyether group according to claim 7, characterized in that α1, α2 and β are 1.

20. The thiol compound containing a fluorinated polyether group according to claim 7, characterized in that X A Formula: -(R 21 ) m1 -(R 22 ) m2 - the group shown, In the formula, R 21 C 1－6 Alkylene, R 22 -O-, -CO-, -NR 23 -、-CONR 23 -or-NR 23 CO-, R 23 A hydrogen atom or C 1－6 alkyl, m1 is an integer from 0 to 10, m2 is an integer from 0 to 10, The sum of m1 and m2 is greater than 1, R 21 and R 22 The order in which is present in the formula is arbitrary.

21. The thiol compound containing a fluorinated polyether group according to claim 1, characterized in that In the compound represented by the following formula (2), R F is a group represented by the following formula (f1) or (f2), X A Formula: -(R 21 ) m1 -(R 22 ) m2 - shown group, and R S A compound represented by a group of the following formula (S1) or (S2), R S β -X A -R F2 -X A -R S β (2) In formula (2), R F2 Rf 2 p -R F -O q - R 2 is C which may be substituted by one or more fluorine atoms 1－6 Alkylene, R F are each independently a divalent fluorinated polyether group, p is 0 or 1, q is independently 0 or 1, X A are each independently a single bond or a 2- to 10-valent organic group, R S Each independently includes -(CR 4 (SH)-R 5 ) n -CR 1 R 2 - a monovalent group represented by 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 (2), there are at least 2 secondary or tertiary thiol groups, α1 is an integer from 1 to 9, α2 is an integer from 1 to 9, β is an integer of 1 to 9 independently. n is an integer from 0 to 9, Formula (2) does not contain an ester structure, -(OC3F6) d -(OC2F4) e - (f1) In formula (f1), d is an integer of 1 to 200, e is 0 or 1, <h2 style=";text-align:left;direction:ltr">(OC4F8)<h2 style=";text-align:left;direction:ltr"> c <h2 style=";text-align:left;direction:ltr"> (OC3F6)<h2 style=";text-align:left;direction:ltr"> d <h2 style=";text-align:left;direction:ltr"> (OC2F4)<h2 style=";text-align:left;direction:ltr"> e <h2 style=";text-align:left;direction:ltr"> (OCF2)<h2 style=";text-align:left;direction:ltr"> f <h2 style=";text-align:left;direction:ltr"> -(f2) In formula (f2), c and d are each independently an integer of 0 to 30, e and f are each independently an integer of 1 to 200, The sum of c, d, e and f is an integer from 10 to 200, The order of the repeating units marked with the subscript c, d, e or f and enclosed in parentheses is arbitrary in the formula. Formula - (R 21 ) m1 -(R 22 ) m2 -middle, R 21 C 1－6 Alkylene, R 22 -O-, -CO-, -NR 23 -、-CONR 23 -or-NR 23 CO-, R 23 A hydrogen atom or C 1－6 alkyl, m1 is an integer from 0 to 10, m2 is an integer from 0 to 10, The sum of m1 and m2 is greater than 1, R 21 and R 22 The order of existence in the formula is arbitrary. -R Sa (S1), -NR Sa n1 R 3 2－n1 (S2)。 22. The thiol compound containing a fluorinated polyether group according to claim 1, characterized in that The number average molecular weight is 1,000 to 100,000.

23. The thiol compound containing a fluorinated polyether group according to claim 1, characterized in that The viscosity is 100 to 10000 mPa·s.

24. A curable composition, characterized in that A thiol compound comprising a fluorinated polyether group according to any one of claims 1 to 23.

25. The curable composition according to claim 24, characterized in that It also contains a fluorinated polyether group-containing unsaturated compound having a group having a carbon-carbon double bond.

26. The curable composition according to claim 25, characterized in that The number of the groups having carbon-carbon double bonds is 2 to 8.

27. The curable composition according to claim 25, wherein The group having a carbon-carbon double bond is an allyl group, a vinyl group or a (meth)acryloyl group.

28. The curable composition according to claim 25, wherein The group having a carbon-carbon double bond is an allyl group.

29. The curable composition according to claim 25, characterized in that The group having a carbon-carbon double bond is present on both end sides of the fluoropolyether group.

30. The curable composition according to claim 25, wherein The fluorinated polyether group-containing unsaturated compound including 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.

31. The curable composition according to claim 25, wherein The unsaturated compound containing a fluorinated polyether group is a compound represented by the following formula (3) or (4): R F1 γ1 -X B -R D γ2 3) R D δ -X B -R F2 -X B -R D δ (4) In the formula, R F1 Rf 1 -R F -O q - R F2 is -Rf 2 p -R F -O q -, R 1 are each independently C which may be substituted with one or more fluorine atoms 1－16 alkyl, R 2 is C which may be substituted by one or more fluorine atoms 1－6 Alkylene, R F are each independently a divalent fluorinated polyether group, p is 0 or 1, q is independently 0 or 1, X B are each independently a single bond or a 2- to 10-valent organic group, R D are each independently a group having a carbon-carbon double bond, γ1 is an integer from 1 to 9, γ2 is an integer from 1 to 9, δ is an integer of 1-9 respectively independently.

32. The curable composition according to claim 31, wherein The group having a carbon-carbon double bond is a group represented by the formula: -YA, In the formula, Y is a single bond, an oxygen atom or a divalent organic group, A is -CR 41 =CH2, R 41 are independently a hydrogen atom or a C 1-3 alkyl.

33. The curable composition according to claim 32, wherein Y is -CR 42 2- or -CO-, R 42 are independently a hydrogen atom or a C 1-6 alkyl.

34. The curable composition according to claim 31, wherein R D is a group represented by the following formula (D1), (D2), (D3), (D4) or (D5), -YA (D1) -SiR a1 k1 R b1 l1 R c1 m1 (D3) -CR d1 k2 R el l2 R fl m2 (D4) -NR g1 R h1 (D5) In the formula, Y is a single bond, an oxygen atom or a divalent organic group, A is -CR 41 =CH2, R 41 are independently a hydrogen atom or a C 1-3 alkyl, X 10 is independently a single bond or a divalent organic group at each occurrence, R 13 is independently a hydrogen atom or a monovalent organic group at each occurrence, t is independently an integer greater than 2 at each occurrence, R 14 is independently a hydrogen atom or a halogen atom at each occurrence, R a1 -Z independently at each occurrence 1 -SiR a2 p1 R a3 q1 R a4 r1 , Z 1 is independently a single bond, an oxygen atom or a divalent organic group at each occurrence, R a2 Each time it occurs, it is independently -Z 1' -SiR a3' q1' R a4' r1' , Z 1' is independently a single bond, an oxygen atom or a divalent organic group at each occurrence, R a3' Each time it occurs, it is independently -Z 2 -Y-A, R a4' is independently a hydrogen atom, a hydroxyl group or a monovalent organic group at each occurrence, Z 2 is independently a single bond, an oxygen atom or a divalent organic group at each occurrence, q1' is independently an integer from 0 to 3 at each occurrence, r1' is independently an integer from 0 to 3 at each occurrence, Among them, the sum of q1' and r1' is (SiR a3' q1' R a4' r1' ) unit is 3, R a3 Each time it occurs, it is independently -Z 2 -Y-A, R a4 is independently a hydrogen atom, a hydroxyl group or a monovalent organic group at each occurrence, p1 is an integer from 0 to 3 independently at each occurrence. q1 is an integer from 0 to 3 independently at each occurrence. r1 is independently an integer from 0 to 3 each time it appears. Among them, the sum of p1, q1 and r1 is (SiR a2 p1 R a3 q1 R a4 r1 ) unit is 3, R b1 Each time it occurs, it is independently -Z 2 -Y-A, R c1 is independently a hydrogen atom, a hydroxyl group or a monovalent organic group at each occurrence, k1 is independently an integer from 0 to 3 each time it appears. l1 is an integer from 0 to 3 independently at each occurrence. m1 is independently an integer from 0 to 3 at each occurrence. Among them, the sum of k1, l1 and m1 is (SiR a1 k1 R b1 l1 R c1 m1 ) unit is 3, In formula (D3), there is at least one -Y-A, R d1 Each time it occurs, it is independently -Z 3 -CR d2 p2 R d3 q2 R d4 r2 , Z 3 is independently a single bond, an oxygen atom or a divalent organic group at each occurrence, R d2 Each time it occurs, it is independently -Z 3' -CR d3' q2' R d4' r2' , Z 3' is independently an oxygen atom or a divalent organic group at each occurrence, R d3' Each time it occurs, it is independently -Z 2 -Y-A, R d4' is independently a hydrogen atom, a hydroxyl group or a monovalent organic group at each occurrence, q2' is independently an integer from 0 to 3 at each occurrence, r2' is independently an integer from 0 to 3 at each occurrence, Among them, the sum of q2' and r2' is (CR d3' q2' R d4' r2' ) unit is 3, R d3 Each time it occurs, it is independently -Z 2 -Y-A, R d4 is independently a hydrogen atom, a hydroxyl group or a monovalent organic group at each occurrence, p2 is an integer from 0 to 3 independently at each occurrence. q2 is independently an integer from 0 to 3 at each occurrence, r2 is independently an integer from 0 to 3 at each occurrence, Among them, the sum of p2, q2 and r2 is (CR d2 p2 R d3 q2 R d4 r2 ) unit is 3, R e1 Each time it occurs, it is independently -Z 2 -Y-A, R f1 is independently a hydrogen atom, a hydroxyl group or a monovalent organic group at each occurrence, k2 is independently an integer from 0 to 3 at each occurrence. l2 is an integer from 0 to 3 independently at each occurrence. m2 is independently an integer from 0 to 3 at each occurrence. Among them, the sum of k2, l2 and m2 is (CR d1 k2 R e1 l2 R f1 m2 ) unit is 3, In formula (D4), there is at least one A, R g1 and R h1 Each time it occurs, it is independently -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 , Z 4 is independently a single bond, an oxygen atom or a divalent organic group at each occurrence, In formula (D5), at least one A exists.

35. The curable composition according to claim 31, wherein X B Each independently represents the following formula: 31 ) p' -(X a ) q' }-R 32 - the divalent group shown, In the formula, R 31 is a single bond, -(CH2) s' - or o-phenylene, m-phenylene or p-phenylene, R 32 is a single bond, -(CH2) t' - or o-phenylene, m-phenylene or p-phenylene, s' is an integer from 1 to 20, t' is an integer from 1 to 20, X a Indicates - (X b ) r' - X b Each occurrence independently represents a substituted or unsubstituted C 3－10 Cycloalkylene, substituted or unsubstituted o-phenylene, m-phenylene or p-phenylene, -CONR 34 -, -NR 34 -、-Si(R 33 )2-、-(Si(R 33 )2O) m' -Si(R 33 )2- and -(CH2) n' - in the group, R 33 Each occurrence is independently phenyl, C 1-6 Alkyl or C 1-6 Alkoxy, R 34 Each occurrence is independently a hydrogen atom, a phenyl group or a C 1-6 alkyl, m' is independently an integer from 1 to 100 at each occurrence, n' is independently an integer from 1 to 20 at each occurrence, r' is an integer from 1 to 10, p' is 0 or 1, q' is 0 or 1, However, at least one of p′ and q′ is 1, and the order of existence of the repeating units indicated by p′ or q′ and enclosed in parentheses is arbitrary.

36. The curable composition according to claim 31, characterized in that The unsaturated compound containing a fluorinated polyether group is included in the compound represented by formula (4): F is a group represented by the following formula (f1), RD is a group represented by the following formula (D1), (D2), (D3), (D4) or (D5), X B Each independently represents the following formula: 31 ) p′ -(X a ) q′ }-R 32 -a compound having a divalent group as shown, -(OC3F6) d -(OC2F4) e - (f1) In formula (f1), d is an integer of 1 to 200, and e is 0 or 1; -YA (D1) -SiR al k1 R b1 l1 R c1 m1 (D3) -CR d1 k2 R e1 l2 R fl m2 (D4) -NR g1 R h1 (D5) In formulas (D1), (D2), (D3), (D4) and (D5), Y is a single bond, an oxygen atom or a divalent organic group, A is -CR 41 =CH2, R 41 are independently a hydrogen atom or a C 1-3 alkyl, X 10 is independently a single bond or a divalent organic group at each occurrence, R 13 is independently a hydrogen atom or a monovalent organic group at each occurrence, t is independently an integer greater than 2 at each occurrence, R 14 is independently a hydrogen atom or a halogen atom at each occurrence, R a1 Each time it occurs, it is independently -Z 1 -SiR a2 p1 R a3 q1 R a4 r1 , Z 1 is independently a single bond, an oxygen atom or a divalent organic group at each occurrence, R a2 Each time it occurs, it is independently -Z 1' -SiR a3' q1' R a4' r1' , Z 1' is independently a single bond, an oxygen atom or a divalent organic group at each occurrence, R a3' Each time it occurs, it is independently -Z 2 -Y-A, R a4 'is independently a hydrogen atom, a hydroxyl group or a monovalent organic group at each occurrence, Z 2 is independently a single bond, an oxygen atom or a divalent organic group at each occurrence, q1' is independently an integer from 0 to 3 at each occurrence, r1' is independently an integer from 0 to 3 at each occurrence, Among them, the sum of q1' and r1' is (SiR a3' q1' R a4' r1' ) unit is 3, R a3 Each time it occurs, it is independently -Z 2 -Y-A, R a4 is independently a hydrogen atom, a hydroxyl group or a monovalent organic group at each occurrence, p1 is an integer from 0 to 3 independently at each occurrence. q1 is an integer from 0 to 3 independently at each occurrence. r1 is independently an integer from 0 to 3 each time it appears. Among them, the sum of p1, q1 and r1 is (SiR a2 p1 R a3 q1 R a4 r1 ) unit is 3, R b1 Each time it occurs, it is independently -Z 2 -Y-A, R c1 is independently a hydrogen atom, a hydroxyl group or a monovalent organic group at each occurrence, k1 is independently an integer from 0 to 3 each time it appears. l1 is an integer from 0 to 3 independently at each occurrence. m1 is independently an integer from 0 to 3 at each occurrence. Among them, the sum of k1, l1 and m1 is (SiR a1 k1 R b1 l1 R c1 m1 ) unit is 3, In formula (D3), there is at least one -Y-A, R d1 Each time it occurs, it is independently -Z 3 -CR d2 p2 R d3 q2 R d4 r2 , Z 3 is independently a single bond, an oxygen atom or a divalent organic group at each occurrence, R d2 Each time it occurs, it is independently -Z 3 '-CR d3' q2' R d4' r2' , Z 3' is independently an oxygen atom or a divalent organic group at each occurrence, R d3' Each time it occurs, it is independently -Z 2 -Y-A, R d4 'is independently a hydrogen atom, a hydroxyl group or a monovalent organic group at each occurrence, q2' is independently an integer from 0 to 3 at each occurrence, r2' is independently an integer from 0 to 3 at each occurrence, Among them, the sum of q2' and r2' is (CR d3' q2' R d4' r2' ) unit is 3, R d3 Each time it occurs, it is independently -Z 2 -Y-A, R d4 is independently a hydrogen atom, a hydroxyl group or a monovalent organic group at each occurrence, p2 is an integer from 0 to 3 independently at each occurrence. q2 is independently an integer from 0 to 3 at each occurrence, r2 is independently an integer from 0 to 3 at each occurrence, Among them, the sum of p2, q2 and r2 is (CR d2 p2 R d3 q2 R d4 r2 ) unit is 3, R e1 Each time it occurs, it is independently -Z 2 -Y-A, R f1 is independently a hydrogen atom, a hydroxyl group or a monovalent organic group at each occurrence, k2 is independently an integer from 0 to 3 at each occurrence. l2 is an integer from 0 to 3 independently at each occurrence. m2 is independently an integer from 0 to 3 at each occurrence. Among them, the sum of k2, l2 and m2 is (CR d1 k2 R e1 l2 R f1 m2 ) unit is 3, In formula (D4), there is at least one A, R g1 and R h1 Each time it occurs, it is independently -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 , Z 4 is independently a single bond, an oxygen atom or a divalent organic group at each occurrence, In formula (D5), there is at least one A; Formula - {(R 31 ) p' -(X a ) q' }-R 32 -middle, R 31 is a single bond, -(CH2) s' - or o-phenylene, m-phenylene or p-phenylene, R 32 is a single bond, -(CH2) t' - or o-phenylene, m-phenylene or p-phenylene, s' is an integer from 1 to 20, t' is an integer from 1 to 20, X a Indicates - (X b ) r' - X b Each occurrence independently represents a substituted or unsubstituted C 3－10 Cycloalkylene, substituted or unsubstituted o-phenylene, m-phenylene or p-phenylene, -CONR 34 -, -NR 34 -、-Si(R 33 )2-、-(Si(R 33 )2O) m' -Si(R 33 )2- and -(CH2) n' - in the group, R 33 Each occurrence is independently phenyl, C 1－6 Alkyl or C 1－6 Alkoxy, R 34 Each occurrence is independently a hydrogen atom, a phenyl group or a C 1－6 alkyl, m' is independently an integer from 1 to 100 at each occurrence, n' is independently an integer from 1 to 20 at each occurrence, r' is an integer from 1 to 10, p' is 0 or 1, q' is 0 or 1, However, at least one of p' and q' is 1, and the order of existence of each repeating unit indicated by p' or q' and enclosed in parentheses is arbitrary.

37. The curable composition according to claim 25, wherein The mass ratio of the thiol compound containing a fluorinated polyether group to the unsaturated compound containing a fluorinated polyether group is 0.1:100 to 100:0.

1.

38. The curable composition according to claim 24, wherein It also contains a polymerization initiator.

39. The curable composition according to claim 38, wherein The polymerization initiator is a free radical polymerization initiator.

40. The curable composition according to claim 39, wherein The polymerization initiator is a free radical photopolymerization initiator.

41. The curable composition according to claim 38, wherein The polymerization initiator has 1 to 3 aromatic ring structures.

42. The curable composition according to claim 24, wherein Also contains fluorinated oil.

43. The curable composition according to claim 42, characterized in that The fluorine-containing oil is a compound represented by the following formula (5): Rf 5 -(OC4F8) a' -(OC3F6) b' -(OC2F4) c' -(OCF2) d' -Rf 6 ···(5) In the formula, R 5 is C which may be substituted by one or more fluorine atoms 1－16 alkyl, R 6 is C which may be substituted by 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 presence of the individual repeating units marked with the subscript a', b', c' or d' and enclosed in parentheses is arbitrary in the formula.

44. The curable composition according to claim 24, wherein It is a solvent-free curable composition.

45. The curable composition according to claim 24, wherein The viscosity is 100 to 10000 mPa·s.

46. ​​A solidified product, characterized in that This is a cured product obtained by curing the curable composition according to claim 24.

47. The cured product according to claim 46, wherein The weight loss rate after being kept at 65°C and 90 RH% for 72 hours was less than 50%.

48. The cured product according to claim 46, wherein The tensile elastic modulus is 0.1 to 500 MPa.

49. The cured product according to claim 46, wherein It is a packaging material.

50. The cured product according to claim 46, wherein It is a packaging material for electronic devices.

51. An article, characterized in that A layer comprising a substrate and a layer formed by curing the curable composition according to claim 24 on the substrate.

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