CN118871504A

CN118871504A - Thiol compound containing fluoropolyether group

Info

Publication number: CN118871504A
Application number: CN202380022942.7A
Authority: CN
Inventors: 涩谷祥太; 东后行伦; 奥野晋吾; 佐藤友理
Original assignee: Daikin Industries Ltd
Current assignee: Daikin Industries Ltd
Priority date: 2022-02-22
Filing date: 2023-02-22
Publication date: 2024-10-29
Also published as: WO2023163068A1; TW202346474A; JP7473853B2; JP2023122578A

Abstract

The present invention provides a thiol compound containing a fluoropolyether group, wherein the thiol compound contains more than 2 thiol groups, and the thiol groups are selected from secondary thiol groups or tertiary thiol groups.

Description

Thiol compound containing fluoropolyether group

Technical Field

The present invention relates to a thiol compound containing a fluoropolyether group.

Background

As a thiol compound containing a fluoropolyether group, for example, a compound having a fluoropolyether group and a primary thiol group is known (patent document 1).

Prior art literature

Patent literature

Patent document 1: japanese patent laid-open No. 2006-29206

Disclosure of Invention

Technical problem to be solved by the invention

The purpose of the present invention is to provide a fluoropolyether group-containing thiol compound having excellent stability.

Technical scheme for solving technical problems

The present invention includes the following means.

[1] A fluoropolyether group-containing thiol compound which contains 2 or more thiol groups selected from secondary thiol groups and tertiary thiol groups.

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

[3] The fluoropolyether group-containing thiol compound according to [1] or [2], wherein 2 to 6 of the thiol groups are contained.

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

[5] A fluoropolyether group-containing thiol compound according to any one of [1] to [4], wherein the thiol groups are present on both end sides of the fluoropolyether group.

[6] The fluoropolyether group-containing thiol compound according to any one of the above [1] to [5], which 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)

wherein:

R ^F1 are each independently Rf ¹－R^F－O_q -,

R ^F2 is-Rf ² _p－R^F－O_q -,

Rf ¹ is each independently a C _1－16 alkyl group which may be substituted with 1 or more fluorine atoms,

Rf ² is a C _1－6 alkylene group which may be substituted with 1 or more fluorine atoms,

R ^F is independently a 2-valent fluoropolyether group,

P is either 0 or 1 and,

Q is each independently 0 or 1,

X ^A is independently a single bond or an organic group having a valence of 2 to 10,

R ^S are each independently a 1-valent group comprising a group shown as-CR ¹R² -SH,

R ¹ is a hydrocarbon group, and the hydrocarbon group,

R ² is a hydrogen atom or a hydrocarbon group,

In the formulae (1) and (2), at least 2 groups represented by-CR ¹R² -SH are present,

Alpha 1 is an integer of 1 to 9,

Alpha 2 is an integer of 1 to 9,

Beta is an integer of 1 to 9.

[7] The fluoropolyether group-containing thiol compound according to [6] above, wherein each Rf ¹ is independently C _1－16 perfluoroalkyl, and each Rf ² is independently C _1－6 perfluoroalkylene.

[8] The fluoropolyether group-containing thiol compound according to [6] or [7] above, wherein R ^F is each independently a group represented by the following formula:

－(OC₆F₁₂)_a－(OC₅F₁₀)_b－(OC₄F₈)_c－(OC₃R^Fa ₆)_d－(OC₂F₄)_e－(OCF₂)_f－

Wherein R ^Fa is each 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, and the sum of a, b, c, d, e and f is 1 or more, and the order in which the repeating units each denoted a, b, c, d, e or f and bracketed is present is arbitrary in the formula, but in the case where all R ^F a are hydrogen atoms or chlorine atoms, at least 1 of a, b, c, e and f is 1 or more.

[9] The fluoropolyether group-containing thiol compound as claimed in claim 8 wherein R ^Fa is a fluorine atom.

[10] A fluoropolyether group-containing thiol compound according to any one of [6] to [9] above, wherein R ^F is each independently a group represented by the following formula (f 1), (f 2), (f 3), (f 4), (f 5) or (f 6),

－(OC₃F₆)_d－(OC₂F₄)_e－(f1)

In the formula (f 1), d is an integer of 1 to 200, e is 0 or 1,

－(OC₄F₈)_c－(OC₃F₆)_d－(OC₂F₄)_e－(OCF₂)_f－(f2)

In the formula (f 2), c and d are each independently an integer of 0 to 30,

E and f are each independently integers of 1 to 200,

C. d, e and f are integers from 10 to 200,

The order in which the repeating units are represented by the subscripts c, d, e, or f and are bracketed is arbitrary in the formula,

－(R⁶－R⁷)_g－(f3)

In the formula (f 3), R ⁶ is OCF ₂ or OC ₂F₄,

R ⁷ is a group selected from OC ₂F₄、OC₃F₆、OC₄F₈、OC₅F₁₀ and OC ₆F₁₂, or a combination of 2 or 3 groups selected from these groups,

G is an integer of 2 to 100,

－(R⁶－R⁷)_g－R^r－(R^7'－R^6')_g'－(f4)

In the formula (f 4), R ⁶ is OCF ₂ or OC ₂F₄,

R ⁷ is a group selected from OC ₂F₄、OC₃F₆、OC₄F₈、OC₅F₁₀ and OC ₆F₁₂, or a combination of 2 or 3 groups independently selected from these groups,

R ^6' is OCF ₂ or OC ₂F₄,

R ^7' is a group selected from OC ₂F₄、OC₃F₆、OC₄F₈、OC₅F₁₀ and OC ₆F₁₂, or a combination of 2 or 3 groups independently selected from these groups,

G is an integer of 2 to 100,

G' is an integer of 2 to 100,

R ^r is

Wherein, represents a bonding position;

－(OC₆F₁₂)_a－(OC₅F₁₀)_b－(OC₄F₈)_c－(OC₃F₆)_d－(OC₂F₄)_e－(OCF₂)_f－(f5)

in the formula (f 5), e is an integer of 1 to 200, a, b, c, d and f are each independently an integer of 0 to 200, and the order in which the repeating units each denoted a, b, c, d, e or f and bracketed by brackets are present is arbitrary in the formula,

－(OC₆F₁₂)_a－(OC₅F₁₀)_b－(OC₄F₈)_c－(OC₃F₆)_d－(OC₂F₄)_e－(OCF₂)_f－(f6)

In the formula (f 6), f is an integer of 1 to 200, a, b, c, d and e are each independently an integer of 0 to 200, and the order in which the repeating units a, b, c, d, e or f are present in brackets is arbitrary in the formula.

[11] The fluoropolyether group-containing thiol compound according to any one of [6] to [10] above, wherein R ^S is a group represented by the following formula (S1), (S2) or (S3):

-R^Sa (S1)

-NR^Sa _n1R³ _2-n1 (S2)

-CR^Sa _n2R³ _3-n2 (S3)

in the formulas (S1), (S2) and (S3):

R ^S a is-Z-CR ¹R² -SH,

Z is a single bond or a group of valence 2,

R ¹ is a hydrocarbon group, and the hydrocarbon group,

R ² is a hydrogen atom or a hydrocarbon group,

R ³ is a hydrogen atom or a hydrocarbon group,

N1 is 1 or 2, and the number of the N-type compounds is 1 or 2,

N2 is 1, 2 or 3.

[12] The fluoropolyether group-containing thiol compound according to [11], wherein Z is-R ¹¹－R¹²－,R¹¹ a single bond or C _1－6 alkylene, R ¹² is-OCO- (CH ₂)_m) -and m is an integer of 0 to 6.

[13] A fluoropolyether group-containing thiol compound according to any one of [6] to [12] above, wherein R ¹ is a C _1－6 alkyl group and R ² is a hydrogen atom or a C _1－6 alkyl group.

[14] A fluoropolyether group-containing thiol compound according to any one of [11] to [13] above, wherein R ³ is a hydrogen atom or a C _1－6 alkyl group.

[15] The fluoropolyether group-containing thiol compound according to any one of [11] to [14], wherein R ^S is a group represented by the formula (S2) or (S3).

[16] The fluoropolyether group-containing thiol compound according to any one of [11] to [15], wherein R ^S is a group represented by the formula (S2).

[17] The fluoropolyether group-containing thiol compound according to any one of [11] to [15], wherein R ^S is a group represented by the formula (S3).

[18] The fluoropolyether group-containing thiol compound according to any one of [6] to [17], wherein α1, α2 and β are 1.

[19] The fluoropolyether group-containing thiol compound according to any one of [6] to [18] above, wherein X ^A is a group represented by the following formula:

－(R²¹)m₁－(R²²)m₂－

wherein:

r ²¹ is a C _1－6 alkylene group,

R ²² is-O- -CO-, -OCO-, -COO-, -NR ²³－、－CONR²³ -or-NR ²³ CO-,

R ²³ is a hydrogen atom or a C _1－6 alkyl group,

M1 is an integer of 0 to 10,

M2 is an integer of 0 to 10,

The sum of m1 and m2 is 1 or more,

The order of presence of R ²¹ and R ²² is arbitrary in the formula.

[20] The fluoropolyether group-containing thiol compound according to any one of [1] to [19], wherein the number average molecular weight is 1,000 ～ 100,000.

[21] The fluoropolyether group-containing thiol compound according to any one of [1] to [20], wherein the viscosity is 100 to 10000cP.

[22] A curable composition comprising a curable resin composition and a curable resin, wherein, contain: a fluoropolyether group-containing thiol compound according to any one of [1] to [21 ].

[23] The curable composition according to the above [22], wherein the curable composition further comprises a fluoropolyether group-containing unsaturated compound having a group having a carbon-carbon double bond.

[24] The curable composition according to [23], wherein the number of the groups having a carbon-carbon double bond is 2 to 8.

[25] The curable composition according to [23] or [24], wherein the group having a carbon-carbon double bond is an allyl group, a vinyl group or a (meth) acrylic group.

[26] The curable composition according to any one of [23] to [25], wherein the group having a carbon-carbon double bond is an allyl group.

[27] The curable composition according to any one of [23] to [26], wherein the group having a carbon-carbon double bond is present on both end sides of the fluoropolyether group.

[28] The curable composition according to any one of [23] to [27], wherein the fluorinated polyether group-containing unsaturated compound is a compound represented by the following formula (3) or (4):

R^F1 _γ1X^B-R^D _γ2 (3)

R^D _δ-X^B-R^F2-X^B-R^P _δ (4)

in the formulas (3) and (4):

R ^F1 are each independently Rf ¹－R^F－O_q -,

R ^F2 is-Rf ² _p－R^F－O_q -,

R ^F is independently a 2-valent fluoropolyether group,

P is either 0 or 1 and,

Q is each independently 0 or 1,

X ^B is independently a single bond or an organic group having a valence of 2 to 10,

R ^D are each independently a group comprising a carbon-carbon double bond,

Gamma 1 is an integer of 1 to 9,

Gamma 2 is an integer of 1 to 9,

Delta is an integer of 1 to 9.

[29] The curable composition according to the above [28], wherein the group containing a carbon-carbon double bond is a group represented by the following formula:

－Y－A

wherein:

y is a single bond, an oxygen atom or a 2-valent organic group,

A is-CR ⁴¹＝CH₂, and the total number of the components is,

R ⁴¹ is each independently a hydrogen atom or a C _1－3 alkyl group.

[30] The curable composition according to [28] or [29], wherein Y is-CR ⁴² ₂ -or-CO-, and R ⁴² is independently a hydrogen atom or a C _1－6 alkyl group.

[31] The curable composition according to any one of the above [28] to [30], wherein R ^D is a group represented by the following formula (D1), (D2), (D3), (D4) or (D5):

-Y-A (D1)

-SiR^a1 _k1R^b1 _llR^c1 _m1 (D3)

-CR^c1 _k2R^e1 ₁₂R^f1 _m2 (D4)

-NR^g1R^h1 (D5)

In the formulas (D1), (D2), (D3), (D4) and (D5),

Y is a single bond, an oxygen atom or a 2-valent organic group,

A is-CR ⁴¹＝CH₂, and the total number of the components is,

R ⁴¹ is each independently a hydrogen atom or a C _1－3 alkyl group,

X ¹⁰ is independently a single bond or a 2-valent organic group at each occurrence,

R ¹³ is independently in each occurrence a hydrogen atom or a 1-valent organic group,

T is an integer of2 or more independently at each occurrence,

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

R ^a1 is independently at each occurrence-Z ¹－SiR^a2 _p1R^a3 _q1R^a4 _r1,

Z ¹ is independently a single bond, an oxygen atom or a 2-valent organic group at each occurrence, R ^a2 is independently-Z ^1'－SiR^a3' _q1'R^a4' _r1' at each occurrence,

Z ^1' is independently in each occurrence a single bond, an oxygen atom or a 2-valent organic group,

R ^a3' is independently at each occurrence-Z ² -Y-A,

R ^a4' is independently at each occurrence a hydrogen atom, a hydroxyl group or a 1-valent organic group,

Z ² is independently in each occurrence a single bond, an oxygen atom or a 2-valent organic group,

Q1' is independently an integer from 0 to 3 at each occurrence,

R1' is independently an integer from 0 to 3 at each occurrence,

Here, the sum of q1 'and r1' is 3 in the (SiR ^a3' _q1'R^a4' _r1') unit,

R ^a3 is independently at each occurrence-Z ² -Y-A,

R ^a4 is independently a hydrogen atom, a hydroxyl group or a 1-valent organic group at each occurrence, p1 is independently an integer of 0 to 3 at each occurrence, q1 is independently an integer of 0 to 3 at each occurrence,

R1 is independently an integer from 0 to 3 at each occurrence,

Here, the sum of p1, q1 and r1 is 3 in the (SiR ^a2 _p1R^a3 _q1R^a4 _r1) unit,

R ^b1 is independently at each occurrence-Z ² -Y-A,

R ^c1 is independently at each occurrence a hydrogen atom, a hydroxyl group or a 1-valent organic group,

K1 is independently an integer of 0 to 3 at each occurrence,

L1 is independently an integer from 0 to 3 at each occurrence,

M1 is independently an integer of 0 to 3 at each occurrence,

Here, the sum of k1, l1 and m1 is 3 in the (SiR ^a1 _k1R^b1 _l1R^c1 _m1) unit,

In formula (D3), at least 1-Y-A is present,

R ^d1 is independently at each occurrence-Z ³－CR^d2 _p2R^d3 _q2R^d4 _r2,

Z ³ is independently in each occurrence a single bond, an oxygen atom or a 2-valent organic group,

R ^d2 is independently at each occurrence-Z ^3'－CR^d3' _q2'R^d4' _r2',

Z ^3' is independently at each occurrence an oxygen atom or a 2-valent organic group,

R ^d3' is independently at each occurrence-Z ² -Y-A,

R ^d4' is independently at each occurrence a hydrogen atom, a hydroxyl group or a 1-valent organic group,

Q2' is independently an integer from 0 to 3 at each occurrence,

R2' is independently an integer from 0 to 3 at each occurrence,

Here, the sum of q2 'and r2' is 3 in the (CR ^d3' _q2'R^d4' _r2') unit,

R ^d3 is independently at each occurrence-Z ² -Y-A;

R ^d4 is independently at each occurrence a hydrogen atom, a hydroxyl group or a 1-valent organic group;

p2 is independently an integer from 0 to 3 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;

Here, the sum of p2, q2 and r2 is 3 in the (CR ^d2 _p2R^d3 _q2R^d4 _r2) unit,

R ^e1 is independently at each occurrence-Z ² -Y-A,

R ^f1 is independently at each occurrence a hydrogen atom, a hydroxyl group or a 1-valent organic group,

K2 is independently an integer from 0 to 3 at each occurrence,

L2 is independently an integer from 0 to 3 at each occurrence,

M2 is independently an integer from 0 to 3 at each occurrence,

Here, the sum of k2, l2 and m2 is 3 in the (CR ^d1 _k2R^e1 _l2R^f1 _m2) unit,

In the formula (D4), at least 1A is present,

R ^g1 and R ^h1 are each independently of the other-Z ⁴－Y－A、－Z⁴－SiR^a1 _k1R^b1 _l1R^c1 _m1 or-Z ⁴－CR^d1 _k2R^e1 _l2R^f1 _m2,

Z ⁴ is independently in each occurrence a single bond, an oxygen atom or a 2-valent organic group,

In formula (D5), at least 1A is present.

[32] The curable composition according to any one of [28] to [31], wherein X ^B is each independently a 2-valent group represented by the following formula:

－{(R³¹)_p'－(X^a)_q'}－R³²－

[ formula:

r ³¹ is a single bond, - (CH ₂)_s' -or o-, m-or p-phenylene,

R ³² is a single bond, - (CH ₂)_t' -or o-, m-or p-phenylene,

S' is an integer of 1 to 20,

T' is an integer of 1 to 20,

X ^a represents- (X ^b)_r' -,

X ^b at each occurrence independently represents a member selected from the group consisting of-O-, -S-, ortho-, meta-, or para-phenylene substituted or unsubstituted C _3－10 cycloalkylene, substituted or unsubstituted O-, m-or p-phenylene 、－C(O)O－、－CONR³⁴－、－O－CONR³⁴－、－NR³⁴－、－Si(R³³)₂－、－(Si(R³³)₂O)_m'－Si(R³³)₂－ and- (CH ₂)_n') -groups,

R ³³ is independently at each occurrence phenyl, C _1－6 alkyl or C _1－6 alkoxy,

R ³⁴ is independently at each occurrence a hydrogen atom, phenyl or 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 of 1 to 10,

P' is either 0 or 1 and,

Q' is 0 or 1,

At least one of p 'and q' is 1, and the order in which the repeating units are present is arbitrary, with p 'or q' being indicated by brackets.

[33] The curable composition according to any one of [23] to [32], wherein the mass ratio of the fluoropolyether group-containing thiol compound to the fluoropolyether group-containing unsaturated compound is 0.1:100 to 100:0.1.

[34] The curable composition according to any one of [22] to [33], further comprising a polymerization initiator.

[35] The curable composition according to item [34], wherein the polymerization initiator is a radical polymerization initiator.

[36] The curable composition according to item [34], wherein the polymerization initiator is a radical photopolymerization initiator.

[37] The curable composition according to item [34], wherein the polymerization initiator has 1 to 3 aromatic ring structures.

[38] The curable composition according to any one of [22] to [37], further comprising a fluorine-containing oil.

[39] The curable composition according to the above [38], wherein the fluorine-containing oil is a compound represented by the following formula (5):

Rf⁵－(OC₄F₈)_a'－(OC₃F₆)_b'－(OC₂F₄)_c'－(OCF₂)_d'－Rf⁶…(5)

in formula (5):

Rf ⁵ is a C _1－16 alkyl group which may be substituted with 1 or more fluorine atoms,

Rf ⁶ is a C _1－16 alkyl group which may be substituted with 1 or more fluorine atoms, a fluorine atom or a hydrogen atom,

A ', b', c 'and d' are each independently integers of 0 to 300,

The order of the presence of the repeating units indicated by the subscripts a ', b', c 'or d' and bracketed is arbitrary in the formula.

[40] The curable composition according to any one of [22] to [39], wherein the composition is free of a solvent.

[41] The curable composition according to any one of [22] to [40], wherein the viscosity is 100 to 10000cP.

[42] A cured product of the curable composition according to any one of [22] to [41 ].

[43] The cured product of [42] above, wherein the tensile elastic modulus is 0.5 to 500MPa.

[44] The cured product according to [42] above, wherein the cured product is a sealing material.

[45] The cured product of [42] above, wherein the cured product is a sealing material for electronic devices.

[46] An article, comprising: a substrate; and a layer formed by curing the curable composition according to any one of [22] to [41] on the substrate.

[47] A compound represented by the formula (c 1),

(OH-X¹²)₂NCO-X¹¹-R^F2-X¹¹-CON(X¹²-OH)₂ (c1)

In formula (c 1):

R ^F2 is-Rf ² _p－R^F－O_q -,

R ^F is independently a 2-valent fluoropolyether group,

P is either 0 or 1 and,

Q is each independently 0 or 1,

X ¹¹ is a single bond or a 2-valent hydrocarbon group,

X ¹² is a hydrocarbon group of valence 2.

Effects of the invention

The fluoropolyether group-containing thiol compound of the present invention has excellent stability.

Detailed Description

As used herein, "1-valent organic group" refers to a 1-valent group that contains carbon. The 1-valent organic group is not particularly limited, and may be a hydrocarbon group or a derivative thereof. The derivative of the hydrocarbon group means a group having at least 1 of N, O, S, si, an amide group, a sulfonyl group, a siloxane group, a carbonyl group, a carbonyloxy group, and the like at the end of the hydrocarbon group or in the molecular chain. In the case of being merely referred to as an "organic group", 1-valent organic group is meant. In addition, "2-valent organic group" means a 2-valent group containing carbon. The 2-valent organic group is not particularly limited, and examples thereof include a 2-valent group having 1 hydrogen atom further separated from the organic group. Similarly, the "organic group having a valence of 2 to 10" refers to a group having a valence of 2 to 10 containing carbon, and the organic group having a valence of 2 to 10 is not particularly limited, and examples thereof include a group having a valence of 2 to 10, which is obtained by dropping 1 to 9 hydrogen atoms from an organic group.

As used herein, "hydrocarbon group" refers to a group containing carbon and hydrogen, and refers to a group that is separated from a hydrocarbon by 1 hydrogen atom. The hydrocarbon group is not particularly limited, and examples thereof include a C _1－20 hydrocarbon group which may be substituted with 1 or more substituents, for example, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and the like. The "aliphatic hydrocarbon group" may be any of linear, branched, and cyclic, or may be any of saturated or unsaturated. In addition, the hydrocarbon group may also contain one or more ring structures.

As the substituent of the "hydrocarbon group" used in the present specification, there are no particular restrictions, and examples thereof include 1 or more groups selected from a halogen atom, a C _1－6 alkyl group which may be substituted with 1 or more halogen atoms, a C _2－6 alkenyl group, a C _2－6 alkynyl group, a C _3－10 cycloalkyl group, a C _3－10 unsaturated cycloalkyl group, a 5-to 10-membered heterocyclic group, a 5-to 10-membered unsaturated heterocyclic group, a C _6－10 aryl group, and a 5-to 10-membered heteroaryl group.

As used herein, "hydrolyzable group" refers to a group that can undergo a hydrolysis reaction, that is, a group that can be detached from the main skeleton of a compound by a hydrolysis reaction. Examples of the hydrolyzable group include-OR ^j、－OCOR^j、－O－N＝CR^j ₂、－NR^j ₂、－NHR^j, -NCO, and halogen (in these formulae, R ^j represents a substituted OR unsubstituted C _1－4 alkyl group).

(Thiol Compound containing fluoropolyether group)

The present invention provides a fluoropolyether group-containing thiol compound having 2 or more thiol groups selected from secondary thiol groups or tertiary thiol groups.

The thiol compound containing a fluoropolyether group of the present invention has excellent storage stability because the thiol group is a secondary thiol group or a tertiary thiol group.

The secondary thiol means a compound having a hydrocarbon group having 1 carbon atom as a substituent to which a thiol group (SH) is bonded, and means, for example, a group represented by-CHR-SH (wherein R is a hydrocarbon group).

The tertiary thiol means a compound having a hydrocarbon group having 2 carbon atoms as substituents to which a thiol group (SH) is bonded, and means, for example, a group represented by-CR ₂ -SH (wherein R is each independently a hydrocarbon group).

The number of thiol groups contained in the thiol compound containing a fluoropolyether group of the present invention may be preferably 2 or more, more preferably 3 or more, and still more preferably 4 or more. The number of thiol groups contained in the thiol compound containing a fluoropolyether group of the present invention may be preferably 6 or less, for example, 5 or less or 4 or less.

In one embodiment, the number of thiol groups contained in the thiol compound containing a fluoropolyether group of the present invention may be preferably 2 to 6, more preferably 2 to 4. In one embodiment, the number of thiol groups contained in the fluoropolyether group-containing thiol compound of the present invention is 2. In another embodiment, the number of thiol groups contained in the thiol compound having a fluoropolyether group of the present invention is 4. The thiol compound containing a fluoropolyether group has a plurality of thiol groups, and thus the curing property thereof is improved.

In a preferred embodiment, the thiol groups are present at both end sides of the fluoropolyether group.

In a preferred embodiment, in the fluoropolyether group-containing thiol compound of the present invention, the number of thiol groups present on both end sides of the fluoropolyether group is the same. For example, 1 thiol group is present on each end of the fluoropolyether group, or 2 thiol groups are present on each end of the fluoropolyether group. The thiol compound containing a fluoropolyether group has a plurality of thiol groups on both end sides of the fluoropolyether group, whereby the curability is improved, and the thiol compound can be cured even with ultraviolet light having an irradiation dose of, for example, 2000mJ/cm ³ or less and further 1000mJ/cm ³ or less.

In one embodiment, the thiol group is a secondary thiol group.

In another embodiment, the thiol group is a tertiary thiol group.

The fluorine content of the thiol compound having a fluoropolyether group of the present invention is preferably 30% by mass or more, more preferably 35% by mass or more, and still more preferably 40% by mass or more. The fluorine content of the thiol compound having a fluoropolyether group of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, and still more preferably 70% by mass or less.

The fluorine content can be measured by elemental analysis.

The SP value of the fluoropolyether group-containing thiol compound of the present invention is preferably in the range of 5.0 to 13.0.

The SP value can be obtained by the estimation of Fedors.

The viscosity of the fluoropolyether group-containing thiol compound of the present invention is preferably 100cP or more, more preferably 300cP or more, and still more preferably 500cP or more. The viscosity of the fluoropolyether group-containing thiol compound of the present invention is preferably 10000cP or less, more preferably 7000cP or less, and still more preferably 5000cP or less.

In one embodiment, the viscosity of the fluoropolyether group-containing thiol compound of the present invention is 100 to 10000cP, preferably 300 to 7000cP, and more preferably 500 to 5000cP.

The viscosity can be measured by a TV-10 viscometer (rotor No. THM1, rotation speed 1.0rpm, measurement temperature 25 ℃) manufactured by Tokyo industries.

In a preferred embodiment, the fluoropolyether group-containing thiol compound of the present invention may be a compound 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 formulas (1) and (2):

R ^F1 are each independently Rf ¹－R^F－O_q -,

R ^F2 is-Rf ² _p－R^F－O_q -,

R ^F is independently a 2-valent fluoropolyether group,

P is either 0 or 1 and,

Q is each independently 0 or 1,

R ¹ is a hydrocarbon group, and the hydrocarbon group,

R ² is a hydrogen atom or a hydrocarbon group,

Alpha 1 is an integer of 1 to 9,

Alpha 2 is an integer of 1 to 9,

Beta is an integer of 1 to 9.

In the above formula (1), R ^F1 is Rf ¹－R^F－O_q -.

In the above formula (2), R ^F2 is-Rf ² _p－R^F－O_q -.

In the above formula, rf ¹ is a C _1－16 alkyl group which may be substituted with 1 or more fluorine atoms.

The "C _1－16 alkyl group" in the C _1－16 alkyl group which may be substituted with 1 or more fluorine atoms may be a straight-chain or branched-chain C _1－6 alkyl group, particularly a C _1－3 alkyl group, and more particularly a straight-chain C _1－6 alkyl group, particularly a C _1－3 alkyl group.

The above-mentioned Rf ¹ is preferably a C _1－16 alkyl group substituted with 1 or more fluorine atoms, more preferably a CF ₂H－C_1－15 perfluoroalkylene group, and still more preferably a C _1－16 perfluoroalkyl group.

The C _1－16 perfluoroalkyl group may be linear or branched, and is preferably a linear or branched C _1－6 perfluoroalkyl group, particularly a C _1－3 perfluoroalkyl group, more preferably a linear C _1－6 perfluoroalkyl group, particularly a C _1－3 perfluoroalkyl group, and particularly-CF ₃、－CF₂CF₃ or-CF ₂CF₂CF₃.

In the above formula, rf ² is a C _1－6 alkylene group which may be substituted with 1 or more fluorine atoms.

The "C _1－6 alkylene group" in the C _1－6 alkylene group which may be substituted with 1 or more fluorine atoms may be a linear or branched C _1－3 alkylene group, and is preferably a linear C _1－3 alkylene group.

The above-mentioned Rf ² is preferably a C _1－6 alkylene group substituted with 1 or more fluorine atoms, more preferably a C _1－6 perfluoroalkylene group, and still more preferably a C _1－3 perfluoroalkylene group.

The C _1－6 perfluoroalkylene group may be linear or branched, and is preferably linear or branched C _1－3 perfluoroalkylene group, more preferably linear C _1－3 perfluoroalkylene group, and particularly-CF ₂－、－CF₂CF₂ -or-CF ₂CF₂CF₂ -.

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

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

In the above formulas (1) and (2), R ^F is independently a 2-valent fluoropolyether group at each occurrence.

R ^F may preferably contain a group represented by the following formula.

－(OC_h1R^Fa _2h1)_h3－(OC_h2R^Fa _2h2－2)_h4－

[ Formula:

R ^Fa is independently a hydrogen atom, a fluorine atom or a chlorine atom at each occurrence,

H1 is an integer of 1 to 6,

H2 is an integer of 4 to 8,

H3 is an integer of 0 or more,

H4 is an integer of 0 or more,

Wherein the total of h3 and h4 is 1 or more, preferably 2 or more, more preferably 5 or more, and the order of the presence of the repeating units denoted by h3 and h4 and bracketed is arbitrary in the formula. ]

In one embodiment, R ^F is linear or branched. R ^F is preferably a group of the formula.

[ Formula:

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 presence of the repeating units noted a, b, c, d, e or f and bracketed is arbitrary in the formula. However, in the case where all R ^Fa are hydrogen atoms or chlorine atoms, at least 1 of a, b, c, e and f is 1 or more. ]

R ^Fa is preferably a hydrogen atom or a fluorine atom, more preferably a fluorine atom. However, in the case where all R ^Fa are hydrogen atoms or chlorine atoms, at least 1 of a, b, c, e and f is 1 or more.

A. b, c, d, e and f are preferably each independently integers from 0 to 100.

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

These repeating units may be linear or branched. For example, - (OC ₆F₁₂) -may be －(OCF₂CF₂CF₂CF₂CF₂CF₂)－、－(OCF(CF₃)CF₂CF₂CF₂CF₂)－、－(OCF₂CF(CF₃)CF₂CF₂CF₂)－、－(OCF₂CF₂CF(CF₃)CF₂CF₂)－、－(OCF₂CF₂CF₂CF(CF₃)CF₂)－、－(OCF₂CF₂CF₂CF₂CF(CF₃))－ or the like. - (OC ₅F₁₀) -may be －(OCF₂CF₂CF₂CF₂CF₂)－、－(OCF(CF₃)CF₂CF₂CF₂)－、－(OCF₂CF(CF₃)CF₂CF₂)－、－(OCF₂CF₂CF(CF₃)CF₂)－、－(OCF₂CF₂CF₂CF(CF₃))－, etc. - (OC ₄F₈) -may be any of －(OCF₂CF₂CF₂CF₂)－、－(OCF(CF₃)CF₂CF₂)－、－(OCF₂CF(CF₃)CF₂)－、－(OCF₂CF₂CF(CF₃))－、－(OC(CF₃)₂CF₂)－、－(OCF₂C(CF₃)₂)－、－(OCF(CF₃)CF(CF₃))－、－(OCF(C₂F₅)CF₂)－ and- (OCF ₂CF(C₂F₅)) -. - (OC ₃F₆) - (i.e. wherein R ^Fa is a fluorine atom in the above formula) may be any of- (OCF ₂CF₂CF₂)－,－(OCF(CF₃)CF₂) -and- (OCF ₂CF(CF₃)) -. - (OC ₂F₄) -may be any of- (OCF ₂CF₂) -and- (OCF (CF ₃)) -.

In one embodiment, the repeating unit is linear. By making the repeating unit linear, the surface slidability, wear durability, and the like of the surface treatment layer can be improved.

In one embodiment, the repeating unit is branched. By forming the repeating unit into a branched chain, the coefficient of dynamic friction of the surface treatment layer can be increased.

In one embodiment, R ^F may comprise a ring structure.

The above-mentioned ring structure may be a three-membered ring, a four-membered ring, a five-membered ring or a six-membered ring as follows.

[ Wherein, the formula (I) represents a bonding position. ]

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

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

[ Wherein, the formula (I) represents a bonding position. ]

In one embodiment, each occurrence of R ^F is independently a group represented by any one of formulas (f 1) to (f 6) below.

－(OC₃F₆)_d－(OC₂F₄)_e－(f1)

In the formula (f 1), d is an integer of 1 to 200, and e is 0 or 1.]

－(OC₄F₈)_c－(OC₃F₆)_d－(OC₂F₄)_e－(OCF₂)_f－(f2)

[ In formula (f 2), c and d are each independently an integer of 0 to 30, e and f are each independently an integer of 1 to 200,

C. The sum of d, e and f is more than 2,

The order of presence of the repeating units indicated by subscripts c, d, e, or f and bracketed is arbitrary in the formula. ]

－(R⁶－R⁷)_g－(f3)

[ In formula (f 3), R ⁶ is OCF ₂ or OC ₂F₄,

G is an integer of 2 to 100. ]

－(R⁶－R⁷)_g－R^r－(R^7'－R^6')_g'－(f4)

[ In formula (f 4), R ⁶ is OCF ₂ or OC ₂F₄,

R ^6' is OCF ₂ or OC ₂F₄,

G is an integer of 2 to 100,

G' is an integer of 2 to 100,

R ^r is

(Wherein, represents a bonding position.)

In the formula (f 5), e is an integer of 1 to 200, a, b, c, d and f are each independently an integer of 0 to 200, and the order of the presence of the repeating units denoted by a, b, c, d, e or f and bracketed is arbitrary in the formula. ]

In the formula (f 6), f is an integer of 1 to 200, a, b, c, d and e are each independently an integer of 0 to 200, and the order of the presence of the repeating units denoted by a, b, c, d, e or f and bracketed is arbitrary in the formula. ]

In the above formula (f 1), d is preferably an integer of 5 to 200, more preferably an integer of 10 to 100, still more 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 (f 1), OC ₃F₆ is preferably OCF ₂CF₂CF₂、OCF₂CF(CF₃) or OCF (CF ₃)CF₂), more preferably OCF ₂CF₂CF₂.OC₂F₄ is OCF ₂CF₂ or OCF (CF ₃), and still more preferably OCF ₂CF₂.

In the above formula (f 2), e and f are each independently an integer of preferably 5 to 200, more preferably an integer of 10 to 200. The sum of c, d, e and f is preferably 5 or more, more preferably 10 or more, and may be 15 or more or 20 or more, for example. In one embodiment, the formula (f 2) is preferably a group represented by －(OCF₂CF₂CF₂CF₂)_c－(OCF₂CF₂CF₂)_d－(OCF₂CF₂)_e－(OCF₂)_f－. In another embodiment, formula (f 2) may be a group represented by- (OC ₂F₄)_e－(OCF₂)_f -).

In the above formula (f 3), R ⁶ is preferably OC ₂F₄. In the above (f 3), R ⁷ is preferably a group selected from OC ₂F₄、OC₃F₆ and OC ₄F₈, or a combination of 2 or 3 groups independently selected from these groups, more preferably a group selected from OC ₃F₆ and OC ₄F₈. The combination of 2 or 3 groups independently selected from OC ₂F₄、OC₃F₆ and OC ₄F₈ is not particularly limited, and examples thereof include －OC₂F₄OC₃F₆－、－OC₂F₄OC₄F₈－、－OC₃F₆OC₂F₄－、－OC₃F₆OC₃F₆－、－OC₃F₆OC₄F₈－、－OC₄F₈OC₄F₈－、－OC₄F₈OC₃F₆－、－OC₄F₈OC₂F₄－、－OC₂F₄OC₂F₄OC₃F₆－、－OC₂F₄OC₂F₄OC₄F₈－、－OC₂F₄OC₃F₆OC₂F₄－、－OC₂F₄OC₃F₆OC₃F₆－、－OC₂F₄OC₄F₈OC₂F₄－、－OC₃F₆OC₂F₄OC₂F₄－、－OC₃F₆OC₂F₄OC₃F₆－、－OC₃F₆OC₃F₆OC₂F₄－ and-OC ₄F₈OC₂F₄OC₂F₄ -. In the above formula (f 3), g is preferably an integer of 3 or more, more preferably an integer of 5 or more. The above g is preferably an integer of 50 or less. In the above formula (f 3), OC ₂F₄、OC₃F₆、OC₄F₈、OC₅F₁₀ and OC ₆F₁₂ may be any of linear or branched chains, and are preferably linear. In this embodiment, the above formula (f 3) is preferably- (OC ₂F₄－OC₃F₆)_g -or- (OC ₂F₄－OC₄F₈)_g -).

In the above formula (f 4), R ⁶、R⁷ and g have the same meanings as those described in the above formula (f 3). The meanings of R ^6'、R^7' and g' are the same as those of R ⁶、R⁷ and g described in the above formula (f 3), respectively, and the same manner is adopted. R ^r is preferably

Wherein, represents a bonding position;

More preferably

Wherein, the bond position is represented.

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

In the above formula (f 6), f is preferably an integer of 1 to 100, more preferably an integer of 5 to 100. a. The sum of b, c, d, e and f is preferably 5 or more, more preferably 10 or more, for example, 10 or more and 100 or less.

In one embodiment, R ^F is a group represented by the formula (f 1).

In one embodiment, R ^F is a group represented by the formula (f 2).

In one embodiment, R ^F is a group represented by the formula (f 3).

In one embodiment, R ^F is a group represented by the formula (f 4).

In one embodiment, R ^F is a group represented by the formula (f 5).

In one embodiment, R ^F is a group represented by the above formula (f 6).

In R ^F, 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, still more preferably 0.2 to 1.5, and still more preferably 0.2 to 0.85. By setting the e/f ratio to 10 or less, slidability, abrasion durability, and chemical resistance (e.g., durability against artificial sweat) of the surface-treated layer obtained from the compound can be further improved. The smaller the e/f ratio is, the more slidability and wear durability of the surface-treated layer are improved. On the other hand, by setting the e/f ratio to 0.1 or more, the stability of the compound can be further improved. The greater the e/f ratio, the greater the stability of the compound.

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

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

In the above-mentioned fluoropolyether group-containing thiol compound, the number average molecular weight of the R ^F1 and R ^F2 portions is not particularly limited, and may be, for example, 500 to 30,000, preferably 1,500 to 30,000, and more preferably 2,000 to 10,000. In the present specification, the number average molecular weights of R ^F1 and R ^F2 are values measured by ¹⁹ F-NMR.

R ^S is a group represented by the following formula (S1), (S2) or (S3).

-R^Sa (S1)

-NR^Sa _n1R³ _2-n1 (S2)

-CR^Sa _n2R³ _3-n2 (S3)

[ Formula:

R ^Sa is-Z-CR ¹R² -SH,

Z is a single bond or a group of valence 2,

R ¹ is a hydrocarbon group, and the hydrocarbon group,

R ² is a hydrogen atom or a hydrocarbon group,

R ³ is a hydrogen atom or a hydrocarbon group,

N1 is 1 or 2, and the number of the N-type compounds is 1 or 2,

N2 is 1, 2 or 3.]

R ^Sa is-Z-CR ¹R² -SH.

Z is a single bond or a 2-valent group. In one embodiment, Z is a single bond. In another embodiment, Z is a 2-valent organic group.

Z is preferably-R ¹¹－R¹² -. Wherein R ¹¹ is a single bond or C _1－6 alkylene, R ¹² is-OC (O) - (CH ₂)_m - (m is an integer of 0 to 6). Wherein the right side of-OC (O) - (CH ₂)_m -is bonded to CR ¹R² -SH.

The C _1－6 alkylene group in R ¹¹ may be straight or branched. In one embodiment, the C _1－6 alkylene is straight chain. In another embodiment, the C _1－6 alkylene is branched.

The C _1－6 alkylene in R ¹¹ may preferably be C _1－4 alkylene.

M is preferably an integer of 0 to 4, more preferably 0 to 3.

In one embodiment, m is 0.

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

R ¹ is a hydrocarbon group.

R ² is a hydrogen atom or a hydrocarbon group.

In one embodiment, R ² is a hydrogen atom.

In another embodiment, R ² is hydrocarbyl.

The hydrocarbyl group in R ¹ and R ² is preferably a C _1－6 alkyl group, more preferably a C _1－3 alkyl group, still more preferably a methyl or ethyl group, and still more preferably a methyl group.

The C _1－6 alkyl groups in R ¹ and R ² may be straight chain or branched. In one embodiment, the C _1－6 alkyl is straight chain. In another embodiment, the C _1－6 alkyl is branched.

In a preferred embodiment, R ¹ is C _1－6 alkyl and R ² is a hydrogen atom or C _1－6 alkyl. In one embodiment, R ¹ is C _1－6 alkyl and R ² is a hydrogen atom. In another embodiment, R ¹ is C _1－6 alkyl and R ² is C _1－6 alkyl.

R ³ is a hydrogen atom or a hydrocarbon group.

In one embodiment, R ³ is a hydrogen atom.

In another embodiment, R ³ is hydrocarbyl.

The hydrocarbon group in R ³ is preferably a C _1－6 alkyl group, more preferably a C _1－3 alkyl group, still more preferably a methyl group or an ethyl group, and still more preferably a methyl group.

The C _1－6 alkyl group in R ³ may be straight chain or branched. In one embodiment, the C _1－6 alkyl is straight chain. In another embodiment, the C _1－6 alkyl is branched.

N1 is 1 or 2. In one embodiment, n1 is 1. In another embodiment, n1 is 2.

N2 is 1, 2 or 3. In one embodiment, n2 is 1. In another embodiment, n2 is 2. In another embodiment, n2 is 3.

In a preferred embodiment, R ^S is a group of formula (S2) or (S3).

In one embodiment, R ^S is a group of formula (S2).

In one embodiment, R ^S is a group of formula (S3).

In the above formulas (1) and (2), X ^A can be understood as a connecting portion connecting the fluoropolyether portion (R ^F1 and R ^F2) providing the water repellency and the like and the portion (R ^S) providing the binding energy with the base material. Accordingly, the X ^A may be a single bond or any group as long as the compounds represented by the formulas (1) and (2) can exist stably.

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 vary according to the valence of X ^A. The sum of α1 and α2 is the same as the valence of X ^A. For example, in the case where X ^A is a 10-valent organic group, the sum of α1 and α2 is 10, and for example, α1 may be 9 and α2 may be 1, α1 may be 5 and α2 may be 5, or α1 may be 1 and α2 may be 9. In addition, in the case where X ^A is a 2-valent organic group, α1 and α2 are 1.

In the above formula (2), β is an integer of 1 to 9, respectively. Beta may vary depending on the valence of X ^A. That is, β is a value obtained by subtracting 1 from the valence of X ^A.

X ^A is independently a single bond or an organic group having a valence of 2 to 10.

The organic group having a valence of 2 to 10 in X ^A is preferably an organic group having a valence of 2 to 8. In one embodiment, the 2-10 valent organic group is preferably a 2-4 valent organic group, and more preferably a 2 valent organic group. In another embodiment, the 2-10 valent organic group is preferably a 3-8 valent organic group, and more preferably a 3-6 valent organic group.

In one embodiment, X ^A is a single bond or a 2-valent organic group, α is 1, and α2 is 1.

In one embodiment, X ^A is a single bond or a 2-valent organic group, and β is 1.

In one embodiment, X ^A is a 3-6 valent organic group, α1 is 1, and α2 is 2-5.

In one embodiment, X ^A is a 3-6 valent organic group and β is 2-5.

In one embodiment, X ^A is a 3 valent organic group, α1 is 1, and α2 is 2.

In one embodiment, X ^A is a 3 valent organic group and β is 2.

In one embodiment, X ^A is a single bond or a 2-valent organic group, and α1, α2, and β are 1.

In a preferred embodiment, X ^A is a group of the formula.

－(R²¹)_m1－(R²²)_m2－

[ Formula:

r ²¹ is a C _1－6 alkylene group,

R ²² is-O- -CO-, -OCO-, -COO-, -NR ²³－、－CONR²³ -or-NR ²³ CO-,

R ²³ is a hydrogen atom or a C _1－6 alkyl group,

M1 is an integer of 0 to 10,

M2 is an integer of 0 to 10,

The sum of m1 and m2 is 1 or more,

The order of presence of R ²¹ and R ²² is arbitrary in the formula. ]

Wherein X ^A (typically a hydrogen atom of X ^A) may be substituted with 1 or more substituents selected from the group consisting of a fluorine atom, a C _1－3 alkyl group and a C _1－3 fluoroalkyl group. In a preferred embodiment, X ^A is not substituted with these groups.

In one embodiment, X ^A is independently- (R ²¹)_m1－1－(R²²)_m2－R²⁴－.R²¹、R²², m1 and m2 have the same meaning as described above. R ²¹ and R ²² are in any order of presence in the formula. R ²⁴ represents a single bond, - (CH ₂)_t5 -or o-, m-or p-phenylene, preferably- (CH ₂)_t5 -. T5 is an integer from 1 to 20, preferably from 2 to 6, more preferably from 2 to 3. Wherein R ²⁴ (typically a hydrogen atom of R ²⁴) may be substituted with 1 or more substituents selected from fluorine atom, C _1－3 alkyl and C _1－3 fluoroalkyl groups. In a preferred embodiment, R ²⁴ is not substituted with these groups.

The C _1－6 alkylene group in R ²¹ may be straight or branched. In one embodiment, the C _1－6 alkylene is straight chain. In another embodiment, the C _1－6 alkylene is branched.

The C _1－6 alkylene group in R ²¹ is preferably a C _1－4 alkylene group, more preferably a C _1－2 alkylene group.

R ²² is-O- -CO-, -OCO-, -COO-, -NR ²³－、－CONR²³ -or-NR ²³ CO-, preferably-O-, -CO-; -OCO-or-COO-, more preferably-O-or-CO-.

R ²³ is a hydrogen atom or a C _1－6 alkyl group.

In one embodiment, R ²³ is a hydrogen atom.

In another embodiment, R ²³ is C _1－6 alkyl.

The C _1－6 alkyl group in R ²³ may be straight chain or branched. In one embodiment, the C _1－6 alkyl is straight chain. In another embodiment, the C _1－6 alkyl is branched.

The C _1－6 alkyl group in R ²³ is preferably a C _1－4 alkyl group, more preferably a C _1－2 alkyl group, and still more preferably a methyl group.

M1 is an integer of 0 to 10, preferably an integer of 0 to 4, and more preferably an integer of 0 to 2.

M2 is an integer of 0 to 10, preferably an integer of 0 to 2, more preferably 0 or 1.

In one embodiment, m1 is an integer from 0 to 2, and m2 is 0 or 1.

In one embodiment, (m 1, m 2) is (0, 1), (1, 1), (2, 1) or (1, 0).

In a preferred embodiment, X ^A is each independently a single bond,

－R²¹－R²²－R²⁴－、

－R²¹－R²²－、

-R ²²－R²⁴ -, or

－R²²－。

(Wherein:

r ²¹ is a C _1－6 alkylene group,

R ²² is-O-or-CO-,

R ²⁴ is C _1－6 alkylene. )

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

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

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

Reacting a compound represented by the following formula (a) with a compound represented by the formula (b) to obtain a compound represented by the formula (c).

R⁵¹OCO-X¹-PFPE-X¹-COOR⁵¹ (a)

[ Formula:

The PFPE is a fluoropolyether group,

R ⁵¹ is each independently a hydrogen atom or a C _1－3 alkyl group, preferably methyl,

X ¹ is each independently a single bond or a 2-valent organic group. ]

HN(X²-OH)₂ (b)

[ Wherein X ² is each independently a 2-valent organic group. ]

(OH-X²)₂NCO-X¹-PFPE-X¹-CON(X²-OH)₂ (c)

[ Wherein PFPE, X ¹ and X ² have the same meanings as described above. ]

In addition, the X ¹ -CO-moiety corresponds to X ^A of formula (2).

Then, the compound represented by the formula (c) is reacted with the compound represented by the formula (d) to obtain the compound represented by the formula (e).

[ Formula:

hal ¹ is a halogen atom, preferably a bromine atom,

Hal ² is a halogen atom, preferably a bromine atom,

R ⁵² is a hydrocarbon group. ]

[ Wherein PFPE, X ¹、X²、R⁵² and Hal ² have the same meanings as described above. ]

In addition, R ⁵² corresponds to R ¹,－X² -O-CO-moiety of formula (2) corresponds to Z of formula (S2).

Then, the compound represented by the formula (e) is reacted with the compound represented by the formula (f) to obtain the compound represented by the formula (g).

[ Wherein R ⁵³ is a C _1－6 alkyl group, preferably a methyl group or an ethyl group, particularly preferably an ethyl group. ]

[ Wherein PFPE, X ¹、X²、R⁵² and R ⁵³ have the same meanings as described above. ]

Thereafter, the compound represented by the formula (g) is treated with an alkylamine, preferably n-butylamine, to obtain the fluoropolyether group-containing thiol compound of the present invention represented by the formula (h).

[ Wherein PFPE, X ¹、X² and R ⁵² have the same meanings as described above. ]

The compound represented by the above formula (c) is a production intermediate useful for producing the fluoropolyether group-containing thiol compound of the present invention. Accordingly, the present invention provides a compound represented by the following formula (c 1).

(OH-X¹²)₂NCO-X¹¹-R^F2-X¹¹-CON(X¹²-OH)₂ (c1)

[ Formula (c 1):

R ^F2 is-Rf ² _p－R^F－O_q -,

R ^F is independently a 2-valent fluoropolyether group,

P is either 0 or 1 and,

Q is each independently 0 or 1,

X ¹¹ is a single bond or a 2-valent hydrocarbon group,

X ¹² is a hydrocarbon group of valence 2. ]

R ^F2 has the same meaning as R ^F2 in the above formulae (1) and (2).

The above-mentioned hydrocarbon group having a valence of 2 is preferably R ⁶¹－R⁶²－R⁶³.

[ Formula:

R ⁶¹ is a single bond or C _1－6 alkylene,

R ⁶² is a single bond or a phenylene group,

R ⁶³ is a single bond or C _1－6 alkylene,

But does not include the case where all are single bonds. ]

The above-mentioned C _1－6 alkylene group may be straight chain or branched. Preferably, the C _1－6 alkylene group is straight chain.

X ¹¹ is preferably a single bond.

X ¹² is preferably C _1-6 alkylene.

As another method, the following method can be cited.

The compound represented by the formula (k) can be obtained by reacting the compound represented by the formula (i) with the compound represented by the formula (j).

HO-X¹-PFPE-X¹-OH (i)

[ Wherein X ¹ has the same meaning as described above. ]

[ Wherein R ⁵² has the same meaning as described above. ]

[ Wherein PFPE, X ¹ and R ⁵² have the same meanings as described above. ]

As another method, the following method can be mentioned.

The compound represented by the formula (o) can be obtained by reacting the compound represented by the formula (m) with the compound represented by the formula (n).

Hal³-X³-CH＝CH₂ (m)

[ Formula: hal ³ is a halogen atom, preferably bromine,

X ³ is each independently a single bond or a 2-valent organic group, preferably methylene. ]

CH₂＝CH-X³-O-X¹-PFPE-X¹-O-X³-CH＝CH₂ (n)

[ Wherein PFPE, X ¹ and X ³ have the same meanings as described above. ]

Thereafter, the compound represented by the formula (o) is ring-opened using, for example, hydrochloric acid to obtain the compound represented by the formula (p).

[ Wherein PFPE, X ¹ and X ³ have the same meanings as described above. ]

Then, the compound represented by the formula (p) is reacted with the compound represented by the formula (j), whereby the compound represented by the formula (q) can be obtained.

[ Wherein R ⁵² has the same meaning as described above. ]

[ Wherein PFPE, X ¹、X³ and R ⁵² have the same meanings as described above. ]

(Curable composition)

The present invention provides a curable composition containing the fluoropolyether group-containing thiol compound of the present invention.

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.

(Unsaturated Compound containing fluoropolyether group)

The group having a carbon-carbon double bond is not particularly limited as long as it contains a carbon-carbon double bond. Typical groups containing a carbon-carbon double bond have a carbon-carbon double bond at the end.

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

In one embodiment, the number of groups having a carbon-carbon double bond in the fluorinated polyether group-containing unsaturated compound may be preferably 2 to 8, more preferably 2 to 6, and still more preferably 2 to 4.

In a preferred embodiment, the above-mentioned group having a carbon-carbon double bond is present at both end sides of the unsaturated compound having a fluoropolyether group.

In a preferred embodiment, in the unsaturated compound containing a fluoropolyether group of the present invention, the number of groups having a carbon-carbon double bond present on both end sides of the fluoropolyether group is the same. For example, 1 group having a carbon-carbon double bond is present on each end side of the fluoropolyether group, or 2 groups having a carbon-carbon double bond are present on each end side of the fluoropolyether group.

In a preferred embodiment, the fluorinated polyether group-containing unsaturated compound 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 ₆ (4)

[ Formula (3) and (4):

R ^F1 are each independently Rf ¹－R^F－O_q -,

R ^F2 is-Rf ² _p－R^F－O_q -,

R ^F is independently a 2-valent fluoropolyether group,

P is either 0 or 1 and,

Q is each independently 0 or 1,

R ^D are each independently a group having a carbon-carbon double bond,

Gamma 1 is an integer of 1 to 9,

Gamma 2 is an integer of 1 to 9,

Delta is an integer of 1 to 9. ]

In the above formula, R ^F1 and R ^F2 have the same meanings as R ^F1 and R ^F2 in the fluoropolyether group-containing thiol compound represented by the above formula (1) or (2).

In the above formula, X ^B independently represents a single bond or an organic group having a valence of 2 to 10. The X ^B is understood to be a connection part connecting R ^D to R ^F1 or R ^F2. Accordingly, the X ^B may be any organic group as long as it is a group that stabilizes the compounds represented by the formulas (3) and (4).

In the above formula, γ1 is an integer of 1to 9, γ2 is an integer of 1to 9, and δ is an integer of 1to 9. These γ1, γ2 and δ are determined in accordance with the valence of X ^B, and in the formula (3), the sum of γ1 and γ2 is the value of the valence of X ^B. For example, in the case where X ^B is a 10-valent organic group, the sum of γ1 and γ2 is 10, and for example, γ1 may be 9 and γ2 may be 1, γ1 may be 5 and γ2 may be 5, or γ1 may be 1 and γ2 may be 9. In addition, in the case where X ^B is a 2-valent organic group, γ1 and γ2 are 1. In the formula (4), δ is a value obtained by subtracting 1 from the value of the valence of X ^B.

The above-mentioned X ^B is preferably a 2-7-valent, more preferably a 2-4-valent, and still more preferably a 2-valent organic group. γ1, γ2 and δ may be an integer of 1 to 6, an integer of 1 to 3, 1 or the like according to X ^B.

Examples of X ^B are not particularly limited, and examples thereof include a 2-valent group represented by the following formula.

－(R³¹)_p'－(X^a)_q'－R³²－

[ Formula:

R ³¹ represents a single bond, - (CH ₂)_s' -or o-, m-or p-phenylene, preferably- (CH ₂)_s' -,

R ³² represents a single bond, - (CH ₂)_t' -or o-, m-or p-phenylene, preferably- (CH ₂)_t' -,

S' is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, still more preferably 1 or 2,

T' is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3, X ^a represents- (X ^b)_r' -,

The substituent is the same as the substituent of the hydrocarbon group,

R ³³ in each occurrence independently represents phenyl, C _1－6 alkyl or C _1－6 alkoxy, preferably C _1－6 alkyl, more preferably methyl,

R ³⁴ in each occurrence independently represents a hydrogen atom, a phenyl group or a C _1－6 alkyl group (preferably methyl),

M' is independently an integer from 1 to 100, preferably an integer from 1 to 20,

N' is independently an integer from 1 to 20, preferably an integer from 1 to 6, more preferably an integer from 1 to 3,

R' is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3,

P' is either 0 or 1 and,

Q' is 0 or 1,

Wherein at least one of p 'and q' is 1, and the order in which the repeating units are present is arbitrary, with p 'or q' being indicated by brackets. ]

R ^D is in each case independently a radical having a carbon-carbon double bond.

The group having a carbon-carbon double bond in R ^D is-Y-A (wherein Y represents a single bond, an oxygen atom or a 2-valent organic group, A is-CR ⁴¹＝CH₂,R⁴¹ each independently represents a hydrogen atom or a C _1-3 alkyl group (preferably methyl)).

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

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

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

-Y-A (D1)

-SiR^a1 _k1R^b1R^c1 _m1 (D3)

-CR^d1 _k2R^e1 ₁₂R^f1 _m2 (D4)

-NR^g1R^h1 (D5)

[ In the formulae (D1), (D2), (D3), (D4) and (D5),

Y is a single bond, an oxygen atom or a 2-valent organic group,

A is-CR ⁴¹＝CH₂, and the total number of the components is,

R ⁴¹ is each independently a hydrogen atom or a C _1-3 alkyl group,

T is an integer of2 or more independently at each occurrence,

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

R ^a1 is independently at each occurrence-Z ¹－SiR^a2 _p1R^a3 _q1R^a4 _r1,

Z ¹ is independently in each occurrence a single bond, an oxygen atom or a 2-valent organic group,

R ^a2 is independently at each occurrence-Z ^1'－SiR^a3' _q1'R^a4' _r1',

R ^a3' is independently at each occurrence-Z ² -Y-A,

Q1 'is independently an integer of 0 to 3 at each occurrence, r1' is independently an integer of 0 to 3 at each occurrence,

Wherein the sum of q1 'and r1' is 3 in the (SiR ^a3' _q1'R^a4' _r1') unit,

R ^a3 is independently at each occurrence-Z ² -Y-A,

R ^a4 is independently at each occurrence a hydrogen atom, a hydroxyl group or a 1-valent organic group,

P1 is independently an integer from 0 to 3 at each occurrence,

Q1 is independently an integer of 0 to 3 at each occurrence, r1 is independently an integer of 0 to 3 at each occurrence,

Wherein the sum of p1, q1 and r1 is 3 in the (SiR ^a2 _p1R^a3 _q1R^a4 _r1) unit,

R ^b1 is independently at each occurrence-Z ² -Y-A,

K1 is independently an integer of 0 to 3 at each occurrence,

L1 is independently an integer from 0 to 3 at each occurrence, m1 is independently an integer from 0 to 3 at each occurrence,

Wherein the sum of k1, l1 and m1 is 3 in the (SiR ^a1 _k1R^b1 _l1R^c1 _m1) unit,

In formula (D3), at least 1-Y-A is present,

R ^d1 is independently at each occurrence-Z ³－CR^d2 _p2R^d3 _q2R^d4 _r2,

R ^d2 is independently at each occurrence-Z ^3'－CR^d3' _q2'R^d4' _r2',

R ^d3' is independently at each occurrence-Z ² -Y-A,

Q2' is independently an integer from 0 to 3 at each occurrence,

R2' is independently an integer from 0 to 3 at each occurrence,

Wherein the sum of q2 'and r2' is 3 in the (CR ^d3' _q2'R^d4' _r2') unit,

R ^d3 is independently at each occurrence-Z ² -Y-A;

p2 is independently an integer from 0 to 3 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;

Wherein the sum of p2, q2 and r2 is 3 in the (CR ^d2 _p2R^d3 _q2R^d4 _r2) unit,

R ^e1 is independently at each occurrence-Z ² -Y-A,

K2 is independently an integer from 0 to 3 at each occurrence,

L2 is independently an integer from 0 to 3 at each occurrence,

M2 is independently an integer from 0 to 3 at each occurrence,

Wherein the sum of k2, l2 and m2 is 3 in the (CR ^d1 _k2R^e1 _l2R^f1 _m2) unit,

In the formula (D4), at least 1A is present,

R ^g1 and R ^h1 are each independently at each occurrence-Z ⁴－Y－A、－Z⁴－SiR^a1 _k1R^b1 _l1R^c1 _m1, or-Z ⁴－CR^d1 _k2R^e1 _l2R^f1 _m2,

In formula (D5), at least 1A is present. ]

In the above formula, X ¹⁰ is independently a single bond or a 2-valent organic group at each occurrence. The 2-valent organic group is preferably-R ²⁸－O_x－R²⁹ - (wherein R ²⁸ and R ²⁹ are each independently a single bond or C _1－20 alkylene group at each occurrence and x is 0 or 1). The C _1－20 alkylene group may be straight or branched, preferably straight. The C _1－20 alkylene group is preferably a C _1－10 alkylene group, more preferably a C _1－6 alkylene group, and even more preferably a C _1－3 alkylene group.

In one embodiment, X ¹⁰ is independently at each occurrence-C _1－6 alkylene-O-C _1－6 alkylene-or-O-C _1－6 alkylene-.

In a preferred embodiment, X ¹⁰ is independently at each occurrence a single bond or a linear C _1－6 alkylene group, preferably a single bond or a linear C _1－3 alkylene group, more preferably a single bond or a linear C _1－2 alkylene group, and even more preferably a linear C _1－2 alkylene group.

In the above formula, R ¹³ is independently a hydrogen atom or a 1-valent organic group at each occurrence. The 1-valent organic group is preferably a C _1－20 alkyl group. The C _1－20 alkyl group may be straight or branched, preferably straight.

In a preferred embodiment, R ¹³ is independently at each occurrence a hydrogen atom or a linear C _1－6 alkyl group, preferably a hydrogen atom or a linear C _1－3 alkyl group, preferably a hydrogen atom or a methyl group.

In the above formula, t is an integer of 2 or more independently at each occurrence.

In a preferred embodiment, t is independently an integer from 2 to 10, preferably an integer from 2 to 6, at each occurrence.

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

In the above formula, R ^a1 is independently-Z ¹－SiR^a2 _p1R^a3 _q1R^a4 _r1 at each occurrence.

Each occurrence of Z ¹ is independently a single bond, an oxygen atom, or a 2-valent organic group. The right side of the structure hereinafter denoted as Z ¹ is bonded to (SiR ^a2 _p1R^a3 _q1R^a4 _r1).

In a preferred embodiment, Z ¹ is a 2-valent organic group.

The above-mentioned Z ¹ is preferably C _1－6 alkylene, - (CH ₂)_z1－O－(CH₂)_z2 - (wherein, Z1 is an integer of 0 to 6, for example an integer of 1 to 6), 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), 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, Z6 is an integer of 0 to 6, for example an integer of 1 to 6). The C _1－6 alkylene may be straight chain or branched, preferably straight chain, these groups may be substituted with 1 or more substituents selected from the group consisting of fluorine atom, C _1－6 alkyl, C _2－6 alkenyl and C _2－6 alkynyl, but are preferably unsubstituted.

In a preferred embodiment, Z ¹ is C _1－6 alkylene or- (CH ₂)_z3 -phenylene- (CH ₂)_z4) -, preferably-phenylene- (CH ₂)_z4 -).

In another preferred embodiment, Z ¹ is C _1－3 alkylene. In one embodiment, Z ¹ may be-CH ₂CH₂CH₂ -. In another embodiment, Z ¹ may be-CH ₂CH₂ -.

R ^a2 is independently-Z ^1'－SiR^a3' _q1'R^a4' _r1' at each occurrence.

Each occurrence of Z ^1' is independently a single bond, an oxygen atom, or a 2-valent organic group. The right side of the structure hereinafter denoted as Z ^1' is bonded to (SiR ^a3' _q1'R^a4' _r1').

In a preferred embodiment, Z ^1' is a 2-valent organic group.

The above-mentioned Z ^1' is preferably C _1－6 alkylene, - (CH ₂)_z1'－O－(CH₂)_z2' - (wherein, Z1 'is an integer of 0 to 6, for example an integer of 1 to 6), 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). The C _1－6 alkylene group may be straight or branched, preferably straight, and these groups may be substituted, preferably unsubstituted, with 1 or more substituents selected from the group consisting of a fluorine atom, a C _1－6 alkyl group, a C _2－6 alkenyl group and a C _2－6 alkynyl group.

In a preferred embodiment, Z ^1' is C _1－6 alkylene or- (CH ₂)_z3' -phenylene- (CH ₂)_z4') -, preferably-phenylene- (CH ₂)_z4'－.Z^1') is a group which can further improve the light resistance, particularly the ultraviolet resistance.

In another preferred embodiment, Z ^1' is C _1－3 alkylene. In one embodiment, Z ^1' may be-CH ₂CH₂CH₂ -. In another embodiment, Z ^1' may be-CH ₂CH₂ -.

R ^a3' is independently at each occurrence-Z ² -Y-A.

Z ² is independently a single bond, an oxygen atom, or a 2-valent organic group at each occurrence. The right side of the structure designated as Z ² hereinafter is bonded to (Y-A).

In a preferred embodiment, Z ² is a 2-valent organic group.

Z ² is preferably C _1－6 alkylene, - (CH ₂)_z11－O－(CH₂)_z12 - (wherein Z11 is an integer of 0 to 6, for example an integer of 1 to 6), -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), 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.) the C _1－6 alkylene may be linear or branched, preferably, these groups may be substituted, preferably unsubstituted, with 1 or more substituents selected from fluorine atom, C _1－6 alkyl, C _2－6 alkenyl and C _2－6 alkynyl.

In a preferred embodiment, Z ² is C _1－6 alkylene or- (CH ₂)_z13 -phenylene- (CH ₂)_z14) -, preferably-phenylene- (CH ₂)_z14 -).

In another preferred embodiment, Z ² is C _1－3 alkylene. In one embodiment, Z ² may be-CH ₂CH₂CH₂ -. In another embodiment, Z ² may be-CH ₂CH₂ -.

R ^a4' is independently at each occurrence a hydrogen atom, a hydroxyl group or a 1-valent organic group. The 1-valent organic group is a 1-valent organic group other than the above-described hydrolyzable groups. The 1-valent organic group is a 1-valent organic group other than the above-mentioned-Z ² -Y-A.

In R ^a4', the 1-valent organic group is preferably a C _1－20 alkyl group, more preferably a C _1－6 alkyl group, and still more preferably a methyl group.

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. Wherein the sum of q1 'and r1' is 3 in the (SiR ^a3' _q1'R^a4' _r1') unit.

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

R ^a3 is independently at each occurrence-Z ² -Y-A.

R ^a4 is independently at each occurrence a hydrogen atom, a hydroxyl group or a 1-valent organic group. The 1-valent organic group is a 1-valent organic group other than the above-described hydrolyzable groups. The 1-valent organic group is a 1-valent organic group other than the above-mentioned-Z ² -Y-A.

In R ^a4, the 1-valent organic group is preferably a C _1－20 alkyl group, more preferably a C _1－6 alkyl group, and still more preferably a methyl group.

P1 is an integer of 0 to 3 independently at each occurrence, q1 is an integer of 0 to 3 independently at each occurrence, and r1 is an integer of 0 to 3 independently at each occurrence. Wherein the sum of p1, q1 and r1 is 3 in the (SiR ^a2 _p1R^a3 _q1R^a4 _r1) unit.

In one embodiment, p1 is independently an integer from 1 to 3, preferably 2 or 3, more preferably 3, at each occurrence.

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

In a preferred embodiment, r1 is independently an integer from 0 to 2, preferably 0 or 1, more preferably 0, at each occurrence.

In one embodiment, p1 is 3.

In another embodiment, q1 is 3.

In the above formula, R ^b1 is independently-Z ² -Y-A at each occurrence.

In the above formula, R ^c1 is independently a hydrogen atom, a hydroxyl group, or a 1-valent organic group at each occurrence. The 1-valent organic group is a 1-valent organic group other than the above-mentioned-Z ² -Y-A.

In R ^c1, the 1-valent organic group is preferably a C _1－20 alkyl group, more preferably a C _1－6 alkyl group, and still more preferably a methyl group.

K1 is an integer of 0 to 3 independently at each occurrence, l1 is an integer of 0 to 3 independently at each occurrence, and m1 is an integer of 0 to 3 independently at each occurrence. Wherein the sum of k1, l1 and m1 is 3 in the (SiR ^a1 _k1R^b1 _l1R^c1 _m1) unit.

In one embodiment, k1 is independently an integer from 1 to 3, preferably 2 or 3, more preferably 3, at each occurrence.

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

In a preferred embodiment, m1 is independently an integer from 0 to 2, preferably 0 or 1, more preferably 0, at each occurrence.

In one embodiment, k1 is 3.

In another embodiment, l1 is 3.

Wherein in formula (D3), at least 1-Y-A is present.

R ^d1 is independently-Z ³－CR^d2 _p2R^d3 _q2R^d4 _r2 at each occurrence.

Z ³ is independently a single bond, an oxygen atom, or a 2-valent organic group at each occurrence. The right side of the structure denoted as Z ³ below is bonded to (CR ^d2 _p2R^d3 _q2R^d4 _r2).

In a preferred embodiment, Z ³ is a 2-valent organic group.

The above-mentioned Z ³ is preferably C _1－6 alkylene, - (CH ₂)_z5－O－(CH₂)_z6 - (wherein Z5 is an integer of 0 to 6, for example an integer of 1 to 6), 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, 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),. The C _1－6 alkylene may be straight chain or branched, preferably straight chain, these groups may be substituted with 1 or more substituents selected from the group consisting of fluorine atom, C _1－6 alkyl, C _2－6 alkenyl and C _2－6 alkynyl, preferably are unsubstituted.

In a preferred embodiment, Z ³ is C _1－6 alkylene or- (CH ₂)_z7 -phenylene- (CH ₂)_z8) -, preferably-phenylene- (CH ₂)_z8 -).

In another preferred embodiment, Z ³ is C _1－3 alkylene. In one embodiment, Z ³ may be-CH ₂CH₂CH₂ -. In another embodiment, Z ³ may be-CH ₂CH₂ -.

R ^d2 is independently-Z ^3'－CR^d3' _q2'R^d4' _r2' at each occurrence.

Z ^3' is independently a single bond, an oxygen atom, or a 2-valent organic group at each occurrence. The right side of the structure denoted as Z ^3' below is bonded to (CR ^d3' _q2'R^d4' _r2').

The above-mentioned Z ^3' is preferably C _1－6 alkylene, - (CH ₂)_z5'－O－(CH₂)_z6' - (wherein, Z5 'is an integer of 0 to 6, for example an integer of 1 to 6), 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), 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). The C _1－6 alkylene may be straight chain or branched, preferably straight chain, these groups may be substituted, for example, preferably unsubstituted, with 1 or more substituent selected from the group consisting of fluorine atom, C _1－6 alkyl, C _2－6 alkenyl and C _2－6 alkynyl.

In a preferred embodiment, Z ^3' is C _1－6 alkylene or- (CH ₂)_z7' -phenylene- (CH ₂)_z8') -, preferably-phenylene- (CH ₂)_z8' -).

In another preferred embodiment, Z ^3' is C _1－3 alkylene. In one embodiment, Z ^3' may be-CH ₂CH₂CH₂ -. In another embodiment, Z ^3' may be-CH ₂CH₂ -.

R ^d3' as described above is, independently at each occurrence, -Z ² -Y-A.

R ^d4' is independently a hydrogen atom, a hydroxyl group or a 1-valent organic group at each occurrence. The 1-valent organic group is a 1-valent organic group other than the above-mentioned-Z ² -Y-A.

In the above R ^d4', the 1-valent organic group is preferably a C _1－20 alkyl group, more preferably a C _1－6 alkyl group, and still more preferably a methyl group.

In another embodiment, R ^d4' is a1 valent organic group, preferably C _1－20 alkyl, more preferably C _1－6 alkyl.

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. Wherein the sum of q2 'and r2' is 3 in the (CR ^d3' _q2'R^d4' _r2') unit.

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

R ^d3 is independently at each occurrence-Z ² -Y-A.

R ^d4 is independently a hydrogen atom, a hydroxyl group or a 1-valent organic group at each occurrence. The 1-valent organic group is a 1-valent organic group other than the above-mentioned-Z ² -Y-A.

In the above R ^d4, the 1-valent organic group is preferably a C _1－20 alkyl group, more preferably a C _1－6 alkyl group, and still more preferably a methyl group.

In another embodiment, R ^d4 is a 1 valent organic group, preferably C _1－20 alkyl, more preferably C _1－6 alkyl.

P2 is an integer of 0 to 3 independently at each occurrence, q2 is an integer of 0 to 3 independently at each occurrence, and r2 is an integer of 0 to 3 independently at each occurrence. In addition, the sum of p2, q2, and r2 is 3 in the (CR ^d2 _p2R^d3 _q2R^d4 _r2) unit.

In one embodiment, p2 is independently an integer from 1 to 3, preferably 2 or 3, more preferably 3, at each occurrence.

In another embodiment, q2 is independently an integer from 1 to 3, preferably 2 or 3, more preferably 3, at each occurrence.

In a preferred embodiment, r2 is independently an integer from 0 to 2, preferably 0 or 1, more preferably 0, at each occurrence.

In one embodiment, p2 is 3.

In another embodiment, q2 is 3.

R ^e1 as described above is, independently at each occurrence, -Z ² -Y-A.

R ^f1 is independently a hydrogen atom, a hydroxyl group or a 1-valent organic group at each occurrence. The 1-valent organic group is a 1-valent organic group other than the above-described hydrolyzable groups.

In the above R ^f1, the 1-valent organic group is preferably a C _1－20 alkyl group, more preferably a C _1－6 alkyl group, and still more preferably a methyl group.

In another embodiment, R ^f1 is a 1 valent organic group, preferably C _1－20 alkyl, more preferably C _1－6 alkyl.

Where k2 is an integer of 0 to 3 independently at each occurrence, l2 is an integer of 0 to 3 independently at each occurrence, and m2 is an integer of 0 to 3 independently at each occurrence. In addition, the sum of k2, l2 and m2 is 3 in the (CR ^d1 _k2R^e1 _l2R^f1 _m2) unit.

In one embodiment, k2 is independently an integer from 1 to 3, preferably 2 or 3, more preferably 3, at each occurrence.

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

In a preferred embodiment, m2 is independently an integer from 0 to 2, preferably 0 or 1, more preferably 0, at each occurrence.

In one embodiment, k2 is 3.

In another embodiment, l2 is 3.

Wherein in formula (D4), at least 1-Y-A is present.

R ^g1 and R ^h1 are each independently-Z ⁴－Y－A、－Z⁴－SiR^a1 _k1R^b1 _l1R^c1 _m1 or-Z ⁴－CR^d1 _k2R^e1 _l2R^f1 _m2.

Z ⁴ is independently a single bond, an oxygen atom, or a 2-valent organic group at each occurrence. The right side of the structure denoted as Z ⁴ below is bonded to (-Y-A group, etc.).

Wherein in formula (D5), at least 1-Y-A is present.

In one embodiment, Z ⁴ is an oxygen atom.

In one embodiment, Z ⁴ is a 2-valent organic group.

The above-mentioned Z ⁴ is preferably C _1－6 alkylene, - (CH ₂)_z5"－O－(CH₂)_z6" - (wherein, Z5 "is an integer of 0 to 6, for example an integer of 1 to 6), 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). The C _1－6 alkylene group may be straight or branched, preferably straight, and these groups may be substituted with 1 or more substituents selected from the group consisting of fluorine atom, C _1－6 alkyl group, C _2－6 alkenyl group and C _2－6 alkynyl group, preferably unsubstituted.

In a preferred embodiment, Z ⁴ is C _1－6 alkylene or- (CH ₂)_z7" -phenylene- (CH ₂)_z8") -, preferably-phenylene- (CH ₂)_z8"－.Z³) is a group which can further improve the light resistance, particularly the ultraviolet resistance.

In another preferred embodiment, Z ⁴ is C _1－3 alkylene. In one embodiment, Z ⁴ may be-CH ₂CH₂CH₂ -. In another embodiment, Z ⁴ may be-CH ₂CH₂ -.

In one embodiment, R ^D is a group of formula (D1).

In one embodiment, R ^D is a group of formula (D2).

In one embodiment, R ^D is a group of formula (D3).

In one embodiment, R ^D is a group of formula (D4).

In one embodiment, R ^D is a group of formula (D5).

The number average molecular weight of the fluorinated polyether group-containing unsaturated compound of the present invention is preferably 1,000 or more, more preferably 1,500 or more, and may be, for example, 2,000 or more, 4,000 or more, or 5,000 or more. The number average molecular weight of the fluorinated polyether group-containing unsaturated compound of the present invention is preferably 100,000 or less, more preferably 50,000 or less, still more preferably 30,000 or less, still more preferably 10,000 or less, and may be, for example, 8,000 or less, 6,000 or less, or 5,000 or less. In the present specification, the number average molecular weight of the unsaturated compound containing a fluoropolyether group is a value measured by ¹⁹ F-NMR.

In one embodiment, the number average molecular weight of the unsaturated compound containing a fluoropolyether group is 1,000 ～ 100,000, preferably 2,000 to 30,000, more preferably 2,000 to 10,000.

The mass ratio of the fluoropolyether group-containing thiol compound of the present invention to the fluoropolyether group-containing unsaturated compound is preferably 0.1:100 to 100:0.1, more preferably 5:100 to 100:5, and still more preferably 10:100 to 100:10.

The curable composition of the present invention may further contain a fluorine-containing oil.

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

[ Formula:

A ', b', c 'and d' are each independently integers of 0 to 300,

The sum of a ', b', c 'and d' being at least 1,

The order of the presence of the repeating units indicated by the subscripts a ', b', c 'or d' and bracketed is arbitrary in the formula. ]

Rf ⁵ is a C1-16 alkyl group which may be substituted with 1 or more fluorine atoms, preferably a perfluoroalkyl group of C _1―16.

Rf ⁶ is a C1-16 alkyl group which may be substituted with 1 or more fluorine atoms, a fluorine atom or a hydrogen atom, preferably a C _1－16 perfluoroalkyl group.

In a preferred embodiment, rf ⁵ and Rf ⁶ are each independently a perfluoroalkyl group of C _1―16, more preferably a C _1－3 perfluoroalkyl group.

The sum of a ', b', c 'and d' is at least 1, preferably 1 to 300, more preferably 20 to 300.

Among the repeating units of the above fluorine-containing oil, - (OC ₄F₈) -may be any of －(OCF₂CF₂CF₂CF₂)－、－(OCF(CF₃)CF₂CF₂)－、－(OCF₂CF(CF₃)CF₂)－、－(OCF₂CF₂CF(CF₃))－、－(OC(CF₃)₂CF₂)－、－(OCF₂C(CF₃)₂)－、－(OCF(CF₃)CF(CF₃))－、－(OCF(C₂F₅)CF₂)－ and (OCF ₂CF(C₂F₅)) -, preferably- (OCF ₂CF₂CF₂CF₂)－.－(OC₃F₆) -may be any of- (OCF ₂CF₂CF₂)－、－(OCF(CF₃)CF₂) -and (OCF ₂CF(CF₃)) -, preferably- (OCF ₂CF₂CF₂)－.－(OC₂F₄) -may be any of- (OCF ₂CF₂) -and (OCF (CF ₃)) -, preferably- (OCF ₂CF₂) -.

Examples of the perfluoro (poly) ether compound represented by the above general formula (5) include compounds represented by any one of the following general formulae (5 a) and (5 b) (which may be a mixture of 1 or 2 or more).

Rf⁵－(OCF₂CF₂CF₂)_b"－Rf⁶…(5a)

Rf⁵－(OCF₂CF₂CF₂CF₂)_a"－(OCF₂CF₂CF₂)_b"－(OCF₂CF₂)_c"－(OCF₂)_d"－Rf⁶…(5b)

In these formulae, rf ⁵ and Rf ⁶ are as described above; in the formula (5 a), b' is an integer of 1 to 100 inclusive; in the formula (5 b), a "and b" are each independently an integer of 0 to 30, and c "and d" are each independently an integer of 1 to 300. The order of the presence of the repeating units denoted by the subscripts a ", b", c ", d" and bracketed is arbitrary in the formula.

From another viewpoint, the fluorine-containing oil may be a compound represented by the general formula Rf ³ -F (wherein Rf ³ is a C _5－16 perfluoroalkyl group). In addition, chlorotrifluoroethylene oligomer may be used.

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.

The fluorine-containing oil may be contained in an amount of, for example, 0.01 to 50% by mass, preferably 0.1 to 30% by mass, and for example, 1 to 15% by mass, relative to the curable composition of the present invention.

In one embodiment, the curable composition of the present invention contains substantially no fluorine-containing oil. Substantially free of fluorine-containing oil means that the oil is completely free of fluorine-containing oil or may contain a very small amount of fluorine-containing oil.

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

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

The polymerization initiator is preferably a radical polymerization initiator.

The radical polymerization initiator is a compound that generates a radical 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 preferable.

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

Examples of the radical photopolymerization initiator include: diketones such as benzil and diacetyl; benzoin and other acyloins; benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and the like; thioxanthones such as thioxanthone, 2, 4-diethylthioxanthone, thioxanthone-4-sulfonic acid, and the like; benzophenone compounds such as benzophenone, 4 '-bis (dimethylamino) benzophenone, and 4,4' -bis (diethylamino) benzophenone; acetophenones such as acetophenone, 2- (4-toluenesulfonyloxy) -2-phenylacetophenone, p-dimethylaminoacetophenone, 2' -dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl [4- (methylthio) phenyl ] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; quinones such as anthraquinone and 1, 4-naphthoquinone; aminobenzoates such as ethyl 2-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate (n-butoxy) ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-ethylhexyl 4-dimethylaminobenzoate; halides such as benzoyl methyl chloride and trihalomethylphenyl sulfone; acyl phosphine oxides; and peroxides such as di-t-butyl peroxide.

The following commercial products can be exemplified as the above-mentioned radical photopolymerization initiator.

IRGACURE 651:2, 2-dimethoxy-1, 2-diphenylethan-1-one,

IRGACURE 184: 1-hydroxy-cyclohexyl-phenyl-ketone,

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

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

IRGACURE 907: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one,

IRGACURE 369: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,

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

IRGACURE 819: bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide,

IRGACURE 784: bis (. Eta.5-2, 4-cyclopentadienyl-1-yl) -bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) -titanium,

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

IRGACURE oxide 02: ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (0-acetyl oxime),

IRGACURE261、IRGACURE369、IRGACURE500、

DAROCUR 1173: 2-hydroxy-2-methyl-1-phenyl-propan-1-one,

DAROCUR TPO:2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide,

DAROCUR1116、DAROCUR2959、DAROCUR1664、DAROCUR4043、

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

IRGACURE 500: mixtures of IRGACURE 184 and benzophenone (1:1),

IRGACURE 1300: a mixture of IRGACURE 369 and IRGACURE 651 (3:7),

IRGACURE 1800: a mixture of CGI 403 and IRGACURE 184 (1:3),

IRGACURE 1870: a mixture of CGI 403 and IRGACURE 184 (7:3),

DAROCUR 4265: DAROCUR TPO and DAROCUR 1173 (1:1).

Wherein IRGACURE is BASF corporation and DAROCUR is Merck Japan corporation.

The curable composition of the present invention may further contain 1 or more other components selected from the group consisting of organic solvents, water and catalysts.

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

Examples of the fluorinated organic solvent include perfluorohexane, perfluorooctane, perfluorodimethylcyclohexane, perfluorodecalin, perfluoroalkyl ethanol, perfluorobenzene, perfluorotoluene, perfluoroalkyl amine (trade name), perfluoroalkyl ether, perfluorobutyl tetrahydrofuran, polyfluoroaliphatic hydrocarbon (ASAHIKLIN AC trade name), hydrochlorofluorocarbon (ASAHIKLIN AK-225 trade name), hydrofluoroether (NOVEC (trade name), HFE-7100 (trade name), HFE-7300 (trade name), 1,2, 3, 4-heptafluorocyclopentane, fluoroalkyl alcohol, perfluoroalkyl bromide, perfluoroalkyl iodide, perfluoropolyether (Krytox (trade name), demum (trade name), fomblin (trade name), 1, 3-bistrifluoromethyl benzene, 2- (perfluoroalkyl) ethyl methacrylate, 2- (perfluoroalkyl) ethyl acrylate, perfluoroalkyl vinyl fluoride, fluorocarbon 134a, and oligomer.

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

Among them, methyl isobutyl ketone, propylene glycol monomethyl ether, hexadecane, butyl acetate, acetone, 2-butanone, cyclohexanone, ethyl acetate, diacetone alcohol, ethanol or 2-propanol is preferable as the organic solvent.

The organic solvents may be used alone or in combination of at least 2 kinds.

In the curable composition, the organic solvent is used preferably in a range of 10 to 99% by mass, more preferably 30 to 95% by mass, still more preferably 50 to 95% by mass.

In one embodiment, the curable composition of the present invention is free of a solvent, i.e., substantially free of a solvent. The term "substantially free of solvent" means that a solvent is not intentionally added, and a trace amount of the solvent inevitably contained, for example, a trace amount of water or the like may be present. 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.

Examples of the catalyst include acids (e.g., hydrochloric acid, acetic acid, and trifluoroacetic acid), bases (e.g., ammonia, triethylamine, and diethylamine), and transition metals (e.g., ti, ni, and Sn).

The viscosity of the curable composition of the present invention is preferably 100cP or more, more preferably 300cP or more, and still more preferably 500cP or more. The viscosity of the fluoropolyether group-containing thiol compound of the present invention is preferably 10000cP or less, more preferably 7000cP or less, and still more preferably 5000cP or less.

In one embodiment, the curable composition of the present invention has a viscosity of 100 to 10000cP, preferably 300 to 7000cP, and more preferably 500 to 5000cP.

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

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

The tensile elastic modulus of the cured product of the present invention is preferably 0.5 to 500MPa, more preferably 0.6 to 300MPa, and still more preferably 0.7 to 100MPa.

The tensile elastic modulus was measured by using an Autograph (AGS-J manufactured by Shimadzu corporation, load cell: 50N, distance between clamps at room temperature: 40mm, test speed: 5.0mm/min, test piece: width 1cm, height 6cm, film thickness 130 μm).

The cured product of the present invention is preferably a sealing material.

The sealing material is preferably a sealing material for electronic devices.

The invention comprises: a substrate; and a layer (hereinafter also referred to as "surface-treated layer") formed by curing the curable composition of the present invention on the substrate.

The substrate that can be used in the present invention may be composed of, for example, glass, resin (natural or synthetic resin, for example, a conventional plastic material), OCA (Optical CLEAR ADHESIVE, optical adhesive), polarizing plate metal, ceramic, semiconductor (silicon, germanium, etc.), electronic equipment, fiber (fabric, nonwoven fabric, etc.), fur, leather, wood, tao Ciqi, stone, etc., building elements, etc., sanitary articles, any appropriate material.

In a preferred embodiment, the substrate is glass, resin, polarizing plate, OCA (Optical CLEAR ADHESIVE, optical adhesive) or metal, preferably glass, resin, polarizing plate or OCA (Optical CLEAR ADHESIVE, optical adhesive).

The glass is preferably a sapphire glass, a soda lime glass, an alkali aluminosilicate glass, a borosilicate glass, an alkali-free glass, a crystal glass, or a quartz glass, and particularly preferably a chemically strengthened soda lime glass, a chemically strengthened alkali aluminosilicate glass, or a chemically bonded borosilicate glass.

For example, when the article to be manufactured is an optical member, the material constituting the surface of the base material may be a material for an optical member, such as glass or transparent plastic. In addition, when the article to be manufactured is an optical member, some layers (or films) such as a hard coat layer or an antireflection layer may be formed on the surface (outermost layer) of the substrate. In the antireflection layer, any of a single antireflection layer and a multilayer antireflection layer may be used. Examples of the inorganic substance that can be used for the antireflection layer include SiO₂、SiO、ZrO₂、TiO₂、TiO、Ti₂O₃、Ti₂O₅、Al₂O₃、Ta₂O₅、Ta₃O₅、Nb₂O₅、HfO₂、Si₃N₄、CeO₂、MgO、Y₂O₃、SnO₂、MgF₂、WO₃. These inorganic substances may be used alone or in combination (for example, as a mixture) of 2 or more of these. In the case of forming a multilayer antireflective layer, siO ₂ and/or SiO is preferably used as the outermost layer. In the case where the object to be manufactured is an optical glass member for a touch panel, a transparent electrode, for example, a thin film made of Indium Tin Oxide (ITO) or indium zinc oxide may be provided on a part of the surface of the substrate (glass). The substrate may further include an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomized film layer, a hard coat film layer, a polarizing film, a retardation film, a liquid crystal display device, and the like, according to specific specifications thereof, and the like.

The shape of the substrate is not particularly limited, and may be, for example, a plate, a film, or other forms. The surface area of the substrate of the surface treatment layer to be formed may be at least a part of the surface of the substrate, and may be appropriately determined according to the purpose of the article to be manufactured, the specific specification, and the like.

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 from the composition of the present invention.

The layer formation of the composition of the present invention can be performed by applying the above composition so as to cover the surface of the substrate. The covering method is not particularly limited. For example, a wet coverage method and a dry coverage method can be used.

Examples of the wet coating method include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating, and the like.

Examples of the dry coating method include vapor deposition (usually vacuum vapor deposition), sputtering, CVD, and the like. Specific examples of the vapor deposition method (typically, vacuum vapor deposition method) include resistance heating, high-frequency heating using an electron beam, microwave, or the like, ion beam, and the like. Specific examples of the CVD method include plasma CVD, optical CVD, thermal CVD, and the like.

The coating may be performed by an atmospheric pressure plasma method.

When the dry coating method is used, the curable composition of the present invention can be used as it is in the dry coating method or diluted with the above-mentioned organic solvent and used in the dry coating method.

The layer formation of the curable composition of the present invention is preferably carried out in such a manner that the curable composition of the present invention is present in the layer together with a catalyst for hydrolysis and dehydration condensation. In short, in the case of using the wet coverage method, the curable composition of the present invention is diluted with a solvent, and then a catalyst is added to the diluted solution of the curable composition of the present invention immediately before application to the surface of a substrate. When the method is carried out by the dry coating method, the curable composition of the present invention to which a catalyst is added may be directly subjected to vapor deposition (usually vacuum vapor deposition), or may be subjected to vapor deposition (usually vacuum vapor deposition) using a particulate material in which a metal porous body such as iron or copper is impregnated with the curable composition of the present invention to which a catalyst is added.

Any suitable acid or base may be used as the catalyst. As the acid catalyst, hydrochloric acid, acetic acid, formic acid, trifluoroacetic acid, and the like can be used, for example. As the base catalyst, ammonia, organic amines, and the like can be used, for example.

The surface treatment layer included in the article of the present invention has a liquid-repellent property. The surface-treated layer may have, in addition to high slipperiness, antibacterial properties, water repellency, oil repellency, stain repellency (for example, prevention of adhesion of dirt such as fingerprints), water repellency (prevention of penetration of water into electronic parts, etc.), surface slipperiness (or lubricity, wiping property of dirt such as fingerprints, excellent touch feeling to fingers, etc.), and the like, depending on the composition of the composition used, and may be suitably used as a functional film.

In a preferred embodiment, the article of the present invention is useful for glass for vehicles, ships, or aircraft, mirror glass (mirror glass), glass for automobiles, door mirrors for automobiles, wing mirrors for automobiles, or the like, or glass for in-vehicle cameras, for example. Further, the present invention is useful for a substrate for outdoor use such as glass or curved mirror of a monitoring camera.

The present invention therefore also relates to an optical material having the above surface-treated layer in the outermost layer.

As the optical material, in addition to the optical materials related to a display or the like, which will be described later, various optical materials are preferably listed: such as cathode ray tubes (CRTs; e.g., computer displays), liquid crystal displays, plasma displays, organic EL displays, inorganic thin film EL dot matrix displays, rear projection displays, fluorescent display tubes (VFDs), field emission displays (FEDs; field Emission Display), and the like, or protective plates for these displays, or materials having been subjected to antireflection film treatment on the surfaces thereof.

The article of the present invention is not particularly limited, and may be an optical member. Examples of the optical member may be listed as follows: lenses such as spectacles; front protection plates, antireflection plates, polarizing plates, antiglare plates, and the like for displays such as PDP, LCD, and the like; touch panel pieces of devices such as mobile phones and portable information terminals; disc surfaces of optical discs such as Blu-ray discs, DVD discs, CD-R, MO, etc.; an optical fiber; a display surface of a timepiece, and the like.

In addition, the article of the present invention may be a medical device or a medical material.

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

The thiol compound having a fluoropolyether group, the curable composition, the cured product, and the like of the present invention are described in detail above. The present invention is not limited to the above examples.

Examples

The thiol compound having a fluoropolyether 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 presence of the repeating units constituting the fluoropolyether is arbitrary, and the chemical formula shown below represents the average composition.

(Measurement of viscosity)

The compositions shown in Table 2, in which the unsaturated compound containing a fluoropolyether group, the thiol compound containing a fluoropolyether group and the photopolymerization initiator were mixed, were measured for viscosity at a measurement temperature of 25℃at a rotation speed of 1.0rpm using a TV-10 viscometer (spindle No. THM1) manufactured by Tokyo industries, ltd.

(Determination of tensile elastic modulus)

A cured coating film (film thickness: 130 μm) was prepared from the curable composition shown in Table 2, a test piece having a width of 1cm and a length of 6cm was cut from the cured coating film, and the tensile elastic modulus was measured at room temperature at a distance of 40mm between clamps and a tensile speed of 5.0mm/min using an Autograph (AGS-J, load cell: 50N, manufactured by Shimadzu corporation).

1. Synthesis of unsaturated Compound containing fluoropolyether group

Synthesis example 1 Synthesis of Compound (A-1)

74G of perfluoropolyether dicarboxylic acid (average composition: m=15, n=12) represented by the following formula (1), 33.5mL of 1, 3-bis (trifluoromethyl) benzene, 1.48g of DMF and 13.5g of thionyl chloride were added to the flask and stirred, and reacted at 80℃for 3 hours. After the solvent was distilled off, the resultant was ice-cooled, 11.1g of diallylamine was added dropwise, and the mixture was stirred at room temperature overnight. The reaction solution was separated, washed, and then the solvent was distilled off to obtain 65g of a perfluoropolyether compound having an allyl group represented by the following formula (A-1). The number average molecular weight of this compound was 2700 as determined by ¹⁹ F-NMR, and the viscosity of this compound was 300cP.

Compound (1)

Compound (A-1)

Synthesis example 2 Synthesis of Compound (A-2)

20G of a perfluoropolyether diester represented by the formula (2) (average composition: m=15, n=12) and 2.64g of 2, 2-diallylpent-4-en-1-amine were charged into a flask, and stirred at room temperature under reduced pressure to obtain 20.5g of a perfluoropolyether compound having an allyl group represented by the following formula (a-2). The number average molecular weight of this compound was 2700 as determined by ¹⁹ F-NMR, and the viscosity of this compound was 400cP.

Compound (2)

Compound (A-2)

Synthesis example 3 Synthesis of Compound (A-3)

By the method described in example 6 of Japanese patent application laid-open No. 2016-204656, from 10g of a perfluoropolyether diester (average composition: m=15, n=12) represented by the formula (2), 8.52g of a perfluoropolyether compound having an allyl group represented by the following formula (A-3) was obtained. The number average molecular weight of this compound was 2600 as determined by ¹⁹ F-NMR, and the viscosity of this compound was 300cP.

Compound (A-3)

2. Synthesis of thiol Compound containing fluoropolyether group

Synthesis example 4 Synthesis of Compound (B-1)

(Example 4-1) Synthesis of Compound (X-1)

100G of a perfluoropolyether diester represented by the formula (2) (average composition: m=15, n=12) and 8.4g of diethanolamine were charged into a flask, and stirring was carried out at 70 ℃ under reduced pressure for one time to obtain 104.8g of a perfluoropolyether compound having a hydroxyl group represented by the formula (X-1).

Compound (X-1)

(Example 4-2) Synthesis of Compound (X-2)

104.8G of the compound represented by the formula (X-1) obtained in example 4-1, 300mL of 1, 3-bis (trifluoromethyl) benzene and 20g of triethylamine were charged into a flask, and 41.5g of 2-bromopropionyl bromide was added dropwise to the flask in an ice bath, followed by a reaction overnight. After washing the reaction solution, the solvent was distilled off to obtain 108g of a perfluoropolyether compound having a bromo group represented by the formula (X-2).

Compound (X-2)

(Example 4-3) Synthesis of Compound (X-3)

108G of the compound represented by the formula (X-2) obtained in example 4-2, 27.4g of potassium O-ethylxanthate, 540mL of 1, 3-bis (trifluoromethyl) benzene and 54mL of pyridine were charged into a flask, and reacted overnight at room temperature. After washing the reaction solution with water, the solvent was distilled off to obtain 111.7g of a perfluoropolyether compound having a xanthate group represented by the formula (X-3).

Compound (X-3)

(Example 4-4) Synthesis of Compound (B-1)

110G of the compound represented by the formula (X-3) obtained in example 4-3, 550mL of 1, 3-bis (trifluoromethyl) benzene and 17.1mL of n-butylamine were charged into a flask and reacted in an ice bath for 4 hours. After washing the reaction solution, the washed solution was added dropwise to hexane to obtain 67.2g of a perfluoropolyether compound having a thiol group represented by the formula (B-1). The number average molecular weight of this compound was 3100 and the viscosity of this compound was 2200cP as determined by ¹⁹ F-NMR.

Compound (B-1)

Synthesis example 5 Synthesis of Compound (B-2)

(Example 5-1) Synthesis of Compound (Y-1)

The perfluoropolyether diol of formula (3) (average composition: m=10, n=10) 15g, allyl bromide 18g, tetrabutylammonium bromide 0.48g and sodium hydroxide 0.69g were added to the flask and stirred at 70 ℃. The reaction solution was separated, washed, and then the solvent was distilled off to obtain 13.9g of a perfluoropolyether compound having an allyl group represented by the formula (Y-1).

Compound (3)

Compound (Y-1)

(Example 5-2) Synthesis of Compound (Y-2)

12G of the compound represented by the formula (Y-1), 13mL of 1, 3-bis (trifluoromethyl) benzene and 4.5mL of methylene chloride were added to the flask and dissolved, and after adding 3.42g of p-chloroperbenzoic acid, the mixture was reacted at 40 ℃. After washing the reaction solution, the solvent was distilled off to obtain 9.70g of the perfluoropolyether compound having an epoxy group represented by the formula (Y-2).

Compound (Y-2)

(Example 5-3) Synthesis of Compound (Y-3)

7.23G of the compound represented by the compound (Y-2), 90mL of acetone and 35mL of 1M hydrochloric acid were charged into the flask, and the mixture was stirred at room temperature. After the stirring was stopped, the separated upper layer was removed to obtain 6.87g of the perfluoropolyether compound represented by the formula (Y-3).

Compound (Y-3)

(Example 5-4) Synthesis of Compound (B-2)

4.70G of the compound represented by the compound (Y-3), 0.167g of p-toluenesulfonic acid monohydrate, 0.935g of thiolactic acid and 20mL of 1, 3-bis (trifluoromethyl) benzene were charged into a flask and reacted at reflux temperature overnight. After washing the reaction liquid, the solvent was distilled off to obtain a perfluoropolyether compound having a thiol group represented by the formula (B-2). The number average molecular weight of this compound was 2500, and the viscosity of this compound was 1100cP as determined by ¹⁹ F-NMR.

Compound (B-2)

Synthesis example 6 Synthesis of Compound (B-3)

10G of a perfluoropolyether diol of the formula (3) (average composition: m=10, n=10), 20mL of 1, 3-bis (trifluoromethyl) benzene, 2.1g of thiolactic acid and 0.38g of p-toluenesulfone monohydrate were added to the flask and reacted at reflux temperature overnight. After washing the reaction solution with water, the solvent was distilled off to obtain 9.54g of a perfluoropolyether compound having a thiol group represented by the formula (B-3). The number average molecular weight of this compound was 2200, and the viscosity of this compound was 300cP, as determined by ¹⁹ F-NMR.

Compound (B-3)

Synthesis example 7 Synthesis of Compound (B-4)

10G of the perfluoropolyether alcohol of the formula (4) (m=15), 30mL of 1, 3-bis (trifluoromethyl) benzene, and 0.51g of thiolactic acid, 95mg of p-toluenesulfonic acid monohydrate were charged into the flask and reacted at reflux temperature overnight. After washing the reaction solution with water, the solvent was distilled off to obtain 9.33g of a perfluoropolyether compound having a thiol group represented by the formula (B-4). The number average molecular weight of this compound was 2600 as determined by ¹⁹ F-NMR, and the viscosity of this compound was 200cP.

Compound (4)

CF₃CF₂CF₂O(CF₂CF₂CF₂O)_mCF₂CF₂CH₂OH

Compound (B-4)

Synthesis example 8 Synthesis of Compound (B-5)

(Example 8-1) Synthesis of Compound (Z-1)

10.0G of a perfluoropolyether compound having an allyl group represented by the formula (A-1), 30mL of 1, 3-bis (trifluoromethyl) benzene, 2.44g of thioacetic acid and 0.263g of AIBN (azobisisobutyronitrile) were charged into a flask, and the reaction was carried out at 80 ℃. The reaction solution was washed with water to obtain 8.97g of a perfluoropolyether compound represented by the formula (Z-1).

Compound (Z-1)

(Example 8-2) Synthesis of Compound (B-5)

A compound of formula (Z-1) 8.97g, novec7200 (manufactured by 3M Co., ltd.) 50mL and methanol 5mL were added to the flask, and stirred. Sodium 0.41g was added to give sodium methoxide, and the deprotection reaction of acetyl group was performed at room temperature for 1 hour. The reaction solution was washed with hydrochloric acid, and then the solvent was distilled off, whereby 7.53g of a perfluoropolyether compound having a thiol group represented by the formula (B-5) was obtained. The number average molecular weight of this compound was 2800 as determined by ¹⁹ F-NMR, and the viscosity of this compound was 1500cP.

Compound (B-5)

Synthesis example 9 Synthesis of Compound (A-4)

(Example 9-1) Synthesis of Compound (R-1)

2.32G of the compound represented by the compound (Y-1), 7.2mL of 1, 3-bis (trifluoromethyl) benzene, 0.030g of triacetoxymethylsilane and 0.686g of trichlorosilane were charged, and stirred at 5℃for 30 minutes. After 0.050mL of a 2% xylene solution of Pt complex of 1, 3-divinyl-1, 3-tetramethyldisiloxane was added, the mixture was stirred at 60℃for 5 hours. Thereafter, volatile components were removed by distillation to obtain 1.97g of a perfluoropolyether compound having a trichlorosilane group represented by the formula (R-1).

Compound (R-1)

(Example 9-2) Synthesis of Compound (A-4)

1.15G of the compound represented by the formula (R-1) and 3.6mL of 1, 3-bis (trifluoromethyl) benzene were charged, and stirred at 5℃for 30 minutes. After that, 6.22ml of a 0.9M diethyl ether solution of allylmagnesium bromide was added thereto, and the mixture was stirred at room temperature for 10 hours. Thereafter, the mixture was cooled to 5℃and 1.78mL of methanol was added thereto, followed by filtration of the insoluble matter. Then, volatile components were distilled off, and then, the nonvolatile components were diluted with perfluorohexane, washed with methanol, and then, the solvent was distilled off to obtain 1.12g of the perfluoropolyether compound having an allyl group represented by the formula (A-4). The number average molecular weight of this compound was 2400 as determined by ¹⁹ F-NMR, and the viscosity of this compound was 400cP.

Compound (A-4)

Synthesis example 10 Synthesis of Compound (B-6)

(Example 10-1) Synthesis of Compound (S-1)

15.2G of a perfluoropolyether compound having an allyl group represented by the formula (S-1) was obtained in the same manner as in (example 5-1) except that 17g of the perfluoropolyether diol (m=12) of the formula (5) was used instead of the perfluoropolyether of the formula (3).

Compound (5)

HOCH₂CF₂CF₂O(CF₂CF₂CF₂O)_nCF₂CF₂CH₂OH

Compound (S-1)

(Example 10-2) Synthesis of Compound (S-2)

11.2G of a perfluoropolyether compound having an epoxy group represented by the formula (S-2) was obtained in the same manner as in (example 5-2) except that 14g of the compound represented by the formula (S-1) was used instead of the compound represented by the formula (Y-1).

Compound (S-2)

(Example 10-3) Synthesis of Compound (S-3)

A perfluoropolyether compound represented by the formula (S-3) was obtained in the same manner as in (example 5-3) except that 8.1g of the compound represented by the formula (S-2) was used instead of the compound represented by the formula (Y-2).

Compound (S-3)

(Example 10-4) Synthesis of Compound (B-6)

A perfluoropolyether compound having a thiol group represented by the formula (B-6) was obtained in the same manner as in (example 5-4) except that 5.3g of the compound represented by the formula (S-3) was used instead of the compound represented by the formula (Y-3). The number average molecular weight of this compound was 2750, and the viscosity of this compound was 1400cP as determined by ¹⁹ F-NMR.

Compound (B-6)

Examples

1. Storage stability of thiol Compound containing fluoropolyether group

Thiol compounds (B-1) to (B-6) containing a fluoropolyether group obtained in Synthesis examples 4 to 8 were each placed in a screw tube (No. 3) in an amount of 1mL, and left to stand in air at room temperature for 2 weeks. A horizontal line was drawn at a position 3cm from the bottom of the screw tube, and the time for which the liquid end flowed through the horizontal line when the screw tube was laid flat was compared with the initial sample and the sample after 2 weeks. The evaluation criteria are shown in Table 1 below.

G: the sample measurement time after 2 weeks was 2 times lower than that of the initial sample.

NG: the measurement time of the sample after 2 weeks is more than 2 times of that of the initial sample.

TABLE 1

Compounds of formula (I)	Stability of
		B-1	G
B-2	G
		B-3	G
B-4	G
		B-5	NG
B-6	G

Examples 1 to 8 and comparative examples 1 to 2

2. Preparation and viscosity measurement of curable composition

The unsaturated compounds containing a fluoropolyether group obtained in Synthesis examples 1 to 3 and 9 and the thiol compounds containing a fluoropolyether group obtained in Synthesis examples 4 to 8 and 10 were mixed so that the equivalent weight of allyl group and thiol group became the same, and 2 parts by mass of Omnirad184 (IGM RESINS B.V. Co.) as a photopolymerization initiator (C) was further mixed to obtain curable compositions 1 to 10. The composition is shown in Table 2. Curable compositions 1 to 6, 9 and 10 are examples, and curable compositions 7 to 8 are comparative examples. Further, viscosity measurement was performed on these curable compositions at 25 ℃.

3. Curing test

The curable compositions 1 to 10 of examples 1 to 8 and comparative examples 1 to 2 were applied to a glass plate as a substrate by an applicator so that the film thickness became 100. Mu.m, and irradiated with ultraviolet light (wavelength: 365 nm), and whether or not a cured film could be produced was examined. The irradiation amount was set at 1000mJ/cm ². The evaluation criteria are as follows. The results are shown in Table 2.

VG: the cured coating film was obtained, and the surface was tack-free.

G: curing takes place and no longer flows.

NG: failing to cure, the resin was in a liquid state.

TABLE 2

The tensile elastic modulus of the cured film produced from the curable composition 1 was 0.95MPa.

As is clear from the results in Table 1, the adhesion of the fluoropolyether group-containing thiol compounds (B-1) to (B-4) and (B-6) having a secondary thiol group was suppressed as compared with the fluoropolyether group-containing thiol compound (B-5) having a primary thiol group, and excellent stability under air was confirmed.

As is clear from the results in Table 2, examples 1 to 8, which contain compositions containing fluoropolyether group-containing thiol compounds (B-1) to (B-3) and (B-6) having a plurality of secondary thiol groups at the terminal, are more excellent in curability by ultraviolet rays, as compared with comparative example 1, which contains composition containing fluoropolyether group-containing thiol compound (B-4) having only 1 secondary thiol group, and comparative example 2, which contains composition containing fluoropolyether group-containing thiol compound (B-5) having a plurality of primary thiol groups.

Industrial applicability

The fluoropolyether group-containing thiol compound of the present invention can be suitably used for various purposes, for example, for coating agents.

Claims

1. A thiol compound having a fluoropolyether group, characterized in that,

Contains more than 2 thiol groups selected from secondary or tertiary thiol groups.

2. A fluoropolyether group-containing thiol compound according to claim 1,

The fluorine content is 30 mass% or more.

3. A fluoropolyether group-containing thiol compound according to claim 1 or 2,

Contains 2 to 6 of the thiol groups.

4. A fluoropolyether group-containing thiol compound according to claim 1 to 3,

The thiol group is a secondary thiol group.

5. A thiol compound having a fluoropolyether group according to claim 1 to 4,

The thiol groups are present on both end sides of the fluoropolyether group.

6. A thiol compound having a fluoropolyether group according to claim 1 to 5,

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)

wherein:

R ^F1 are each independently Rf ¹－R^F－O_q -,

R ^F2 is-Rf ² _p－R^F－O_q -,

R ^F is independently a 2-valent fluoropolyether group,

P is either 0 or 1 and,

Q is each independently 0 or 1,

R ¹ is a hydrocarbon group, and the hydrocarbon group,

R ² is a hydrogen atom or a hydrocarbon group,

Alpha 1 is an integer of 1 to 9,

Alpha 2 is an integer of 1 to 9,

Beta is an integer of 1 to 9.

7. A fluoropolyether group-containing thiol compound according to claim 6,

Rf ¹ is each independently C _1－16 perfluoroalkyl,

Rf ² is each independently C _1－6 perfluoroalkylene.

8. A fluoropolyether group-containing thiol compound according to claim 6 or 7,

R ^F are each independently a group of the formula:

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, and the order in which the repeating units are each represented by a, b, c, d, e or f and bracketed is arbitrary in the formula, but in the case where all R ^Fa are hydrogen atoms or chlorine atoms, at least 1 of a, b, c, e and f is 1 or more.

9. A fluoropolyether group-containing thiol compound according to claim 8,

R ^Fa is a fluorine atom.

10. A thiol compound having a fluoropolyether group according to claim 6 to 9,

R ^F is each independently a group represented by the following formula (f 1), (f 2), (f 3), (f 4), (f 5) or (f 6),

－(OC₃F₆)_d－(OC₂F₄)_e－ (f1)

In the formula (f 1), d is an integer of 1 to 200, e is 0 or 1,

－(OC₄F₈)_c－(OC₃F₆)_d－(OC₂F₄)_e－(OCF₂)_f－ (f2)

In the formula (f 2), c and d are each independently an integer of 0 to 30,

E and f are each independently integers of 1 to 200,

C. d, e and f are integers from 10 to 200,

－(R⁶－R⁷)_g－ (f3)

In the formula (f 3), R ⁶ is OCF ₂ or OC ₂F₄,

G is an integer of 2 to 100,

－(R⁶－R⁷)_g－R^r－(R^7'－R^6')_g'－ (f4)

In the formula (f 4), R ⁶ is OCF ₂ or OC ₂F₄,

R ^6' is OCF ₂ or OC ₂F₄,

G is an integer of 2 to 100,

G' is an integer of 2 to 100,

R ^r is

Wherein, represents a bonding position;

－(OC₆F₁₂)_a－(OC₅F₁₀)_b－(OC₄F₈)_c－(OC₃F₆)_d－(OC₂F₄)_e－(OCF₂)_f－ (f5)

－(OC₆F₁₂)_a－(OC₅F₁₀)_b－(OC₄F₈)_c－(OC₃F₆)_d－(OC₂F₄)_e－(OCF₂)_f－ (f6)

11. A thiol compound having a fluoropolyether group according to claim 6 to 10,

R ^S is a group represented by the following formula (S1), (S2) or (S3):

-R^Sa (S1)

-NR^Sa _n1R³ _2-n1 (S2)

-CR^Sa _n2R³ _3-n2 (S3)

in the formulas (S1), (S2) and (S3):

R ^Sa is-Z-CR ¹R² -SH,

Z is a single bond or a group of valence 2,

R ¹ is a hydrocarbon group, and the hydrocarbon group,

R ² is a hydrogen atom or a hydrocarbon group,

R ³ is a hydrogen atom or a hydrocarbon group,

N1 is 1 or 2, and the number of the N-type compounds is 1 or 2,

N2 is 1, 2 or 3.

12. A fluoropolyether group-containing thiol compound according to claim 11,

Z is-R ¹¹-R¹² -,

R ¹¹ is a single bond or C _1-6 alkylene,

R ¹² is-OCO- (CH ₂)_m -,

M is an integer of 0 to 6.

13. A thiol compound having a fluoropolyether group according to claim 6 to 12,

R ¹ is C _1-6 alkyl, R ² is hydrogen atom or C _1-6 alkyl.

14. A thiol compound having a fluoropolyether group according to claim 11 to 13,

R ³ is a hydrogen atom or a C _1-6 alkyl group.

15. A thiol compound having a fluoropolyether group according to claim 11 to 14,

R ^S is a group represented by the formula (S2) or (S3).

16. A thiol compound having a fluoropolyether group according to claim 11 to 15,

R ^S is a group represented by formula (S2).

17. A thiol compound having a fluoropolyether group according to claim 11 to 15,

R ^S is a group represented by formula (S3).

18. A thiol compound having a fluoropolyether group according to claim 6 to 17,

Α1, α2, and β are 1.

19. A thiol compound having a fluoropolyether group according to claim 6 to 18,

X ^A is a group of the formula:

－(R²¹)_m1－(R²²)_m2－

wherein:

r ²¹ is a C _1－6 alkylene group,

R ²² is-O- -CO-, -OCO-, -COO-, -NR ²³－、－CONR²³ -or-NR ²³ CO-,

R ²³ is a hydrogen atom or a C _1－6 alkyl group,

M1 is an integer of 0 to 10,

M2 is an integer of 0 to 10,

The sum of m1 and m2 is 1 or more,

The order of presence of R ²¹ and R ²² is arbitrary in the formula.

20. A thiol compound having a fluoropolyether group according to claim 1 to 18,

The number average molecular weight was 1,000 ～ 100,000.

21. The fluoropolyether group-containing thiol compound according to claim 1 to 20,

The viscosity is 100-10000 _c P.

22. A curable composition characterized by comprising:

The fluoropolyether group-containing thiol compound according to any one of claims 1 to 21.

23. The curable composition according to claim 22, it is characterized in that the method comprises the steps of,

Also included are unsaturated compounds containing a fluoropolyether group that contain a group having a carbon-carbon double bond.

24. The curable composition according to claim 23,

The number of the groups having carbon-carbon double bonds is 2 to 8.

25. The curable composition according to claim 23 or 24,

The group having a carbon-carbon double bond is an allyl group, a vinyl group or a (meth) acrylic group.

26. The curable composition according to any one of claim 23 to 25,

The group having a carbon-carbon double bond is an allyl group.

27. The curable composition according to any one of claims 23 to 26, wherein:

the group having a carbon-carbon double bond is present at both end sides of the fluoropolyether group.

28. The curable composition according to any one of claim 23 to 27,

The unsaturated compound containing a fluoropolyether 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 ₈(4)

in the formulas (3) and (4):

R ^F1 are each independently Rf ¹－R^F－O_q -,

R ^F2 is-Rf ² _p－R^F－O_q -,

R ^F is independently a 2-valent fluoropolyether group,

P is either 0 or 1 and,

Q is each independently 0 or 1,

R ^D are each independently a group comprising a carbon-carbon double bond,

Gamma 1 is an integer of 1 to 9,

Gamma 2 is an integer of 1 to 9,

Delta is an integer of 1 to 9.

29. The curable composition according to claim 28, it is characterized in that the method comprises the steps of,

The group containing a carbon-carbon double bond is a group represented by the following formula:

－Y－A

wherein:

y is a single bond, an oxygen atom or a 2-valent organic group,

A is-CR ⁴¹＝CH₂, and the total number of the components is,

R ⁴¹ is each independently a hydrogen atom or a C _1－3 alkyl group.

30. The curable composition according to claim 28 or 29,

Y is-CR ⁴² ₂ -or-CO-,

R ⁴² is each independently a hydrogen atom or a C _1－6 alkyl group.

31. The curable composition according to any one of claim 28 to 30,

R ^D is a group represented by the following formula (D1), (D2), (D3), (D4) or (D5):

-Y-A (D1)

-SiR^a1 _k1R^b1 ₁₁R^c1 _m1 (D3)

-CR^d1 _k2R^e1R^f1 _m2 (D4)

-NR^g1R^h1 (D5)

In the formulas (D1), (D2), (D3), (D4) and (D5),

Y is a single bond, an oxygen atom or a 2-valent organic group,

A is-CR ⁴¹＝CH₂, and the total number of the components is,

R ⁴¹ is each independently a hydrogen atom or a C _1－3 alkyl group,

T is an integer of2 or more independently at each occurrence,

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

R ^a1 is independently at each occurrence-Z ¹－SiR^a2 _p1R^a3 _q1R^a4 _r1,

R ^a2 is independently at each occurrence-Z ^1'－SiR^a3' _q1'R^a4' _r1',

R ^a3' is independently at each occurrence-Z ² -Y-A,

Q1' is independently an integer from 0 to 3 at each occurrence,

R1' is independently an integer from 0 to 3 at each occurrence,

Here, the sum of q1 'and r1' is 3 in the (SiR ^a3' _q1'R^a4' _r1') unit,

R ^a3 is independently at each occurrence-Z ² -Y-A,

P1 is independently an integer from 0 to 3 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,

Here, the sum of p1, q1 and r1 is 3 in the (SiR ^a2 _p1R^a3 _q1R^a4 _r1) unit,

R ^b1 is independently at each occurrence-Z ² -Y-A,

K1 is independently an integer of 0 to 3 at each occurrence,

L1 is independently an integer from 0 to 3 at each occurrence,

M1 is independently an integer of 0 to 3 at each occurrence,

Here, the sum of k1, l1 and m1 is 3 in the (SiR ^a1 _k1R^b1 _l1R^c1 _m1) unit,

In formula (D3), at least 1-Y-A is present,

R ^d1 is independently at each occurrence-Z ³－CR^d2 _p2R^d3 _q2R^d4 _r2,

R ^d2 is independently at each occurrence-Z ^3'－CR^d3' _q2'R^d4' _r2',

R ^d3' is independently at each occurrence-Z ² -Y-A,

Q2' is independently an integer from 0 to 3 at each occurrence,

R2' is independently an integer from 0 to 3 at each occurrence,

Here, the sum of q2 'and r2' is 3 in the (CR ^d3' _q2'R^d4' _r2') unit,

R ^d3 is independently at each occurrence-Z ² -Y-A;

p2 is independently an integer from 0 to 3 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;

Here, the sum of p2, q2 and r2 is 3 in the (CR ^d2 _p2R^d3 _q2R^d4 _r2) unit,

R ^e1 is independently at each occurrence-Z ² -Y-A,

K2 is independently an integer from 0 to 3 at each occurrence,

L2 is independently an integer from 0 to 3 at each occurrence,

M2 is independently an integer from 0 to 3 at each occurrence,

Here, the sum of k2, l2 and m2 is 3 in the (CR ^d1 _k2R^e1 _l2R^f1 _m2) unit,

In the formula (D4), at least 1A is present,

In formula (D5), at least 1A is present.

32. The curable composition according to any one of claim 28 to 31,

Each X ^B is independently a 2-valent group represented by the following formula:

－{(R³¹)_p'－(X^a)_q'}－R³²－

[ formula:

r ³¹ is a single bond, - (CH ₂)_s' -or o-, m-or p-phenylene,

R ³² is a single bond, - (CH ₂)_t' -or o-, m-or p-phenylene,

S' is an integer of 1 to 20,

T' is an integer of 1 to 20,

X ^a represents- (X ^b)_r' -,

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 of 1 to 10,

P' is either 0 or 1 and,

Q' is 0 or 1,

33. The curable composition according to any one of claim 23 to 32,

The mass ratio of the thiol compound containing a fluoropolyether group to the unsaturated compound containing a fluoropolyether group is 0.1:100 to 100:0.1.

34. The curable composition according to any one of claim 22 to 33,

And a polymerization initiator.

35. The curable composition according to claim 34, it is characterized in that the method comprises the steps of,

The polymerization initiator is a radical polymerization initiator.

36. The curable composition according to claim 34, it is characterized in that the method comprises the steps of,

The polymerization initiator is a radical photopolymerization initiator.

37. The curable composition according to claim 34, it is characterized in that the method comprises the steps of,

The polymerization initiator has 1 to 3 aromatic ring structures.

38. The curable composition according to any one of claim 22 to 37,

And also contains fluorine-containing oil.

39. The curable composition of claim 38, wherein the curable composition,

The fluorine-containing oil is a compound represented by the following formula (5):

in formula (5):

A ', b', c 'and d' are each independently integers of 0 to 300,

40. The curable composition according to claim 22 to 39, it is characterized in that the method comprises the steps of,

The composition is solvent-free.

41. The curable composition according to claim 22 to 39, it is characterized in that the method comprises the steps of,

The viscosity is 100-10000 _c P.

42. A cured product of the curable composition according to any one of claims 22 to 41.

43. The cured product of claim 42,

The tensile elastic modulus is 0.5-500 MP _a.

44. The cured product of claim 42,

Which is a sealing material.

45. The cured product of claim 42,

Which is a sealing material for electronic devices.

46. An article comprising a substrate and a layer formed on the substrate by curing the curable composition of any one of claims 22 to 41.

47. A compound represented by the formula (c 1),

(OH-X¹²)₂NCO-X¹¹-R^F2-X¹¹-CON(X¹²-OH)₂ (c1)

In formula (c 1):

R ^F2 is-Rf ² _p-R^F-O_q -,

Rf ² is a C _1-6 alkylene group which may be substituted with 1 or more fluorine atoms,

R ^F is independently a 2-valent fluoropolyether group,

P is either 0 or 1 and,

Q is each independently 0 or 1,

X ¹¹ is a single bond or a 2-valent hydrocarbon group,

X ¹² is a hydrocarbon group of valence 2.