TW202346474A - Thiol compound containing fluoropolyether group - Google Patents

Abstract

The present invention provides a thiol compound containing a fluoropolyether group, which contains two or more thiol groups selected from secondary thiol groups and tertiary thiol groups.

Description

Thiol compounds containing fluoropolyether groups

The present disclosure relates to thiol compounds containing fluoropolyether groups.

As a fluoropolyether group-containing thiol compound, a compound having a fluoropolyether group and a primary thiol group is known (Patent Document 1).

[Prior technical literature]

[Patent Document]

Patent document 1: Japanese Patent Application Publication No. 2006-291206.

The purpose of this disclosure is to provide a fluoropolyether group-containing thiol compound with excellent stability.

This disclosure includes the following aspects.

[1] A fluoropolyether group-containing thiol compound containing two or more thiol groups selected from the group consisting of secondary thiol groups and tertiary thiol groups.

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

[3] The fluoropolyether group-containing thiol compound as described in [1] or [2] above, which contains 2 to 6 of the aforementioned thiol groups.

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

[5] The fluoropolyether group-containing thiol compound according to any one of [1] to [4] above, wherein the thiol group is present on both ends of the fluoropolyether group.

[6] The fluoropolyether group-containing thiol compound as described in any one of the above [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)

[In the formula:

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 by more than 1 fluorine atom,

Rf ² is a C _1-6 alkylene group which may be substituted by more than one fluorine atom,

R ^F are each independently a divalent fluoropolyether group,

p is 0 or 1,

q is each independently 0 or 1,

X ^A is each independently a single bond or an organic group with 2 to 10 valences,

R ^S is each independently a monovalent group containing a group represented by -CR ¹ R ² -SH,

R ¹ is a hydrocarbon group,

R ² is a hydrogen atom or a hydrocarbon group,

In formulas (1) and (2), there are at least 2 groups represented by -CR ¹ R ² -SH.

α1 is an integer from 1 to 9,

α2 is an integer from 1 to 9,

β is each independently an integer from 1 to 9].

[7] The fluoropolyether group-containing thiol compound as described in the above [6], wherein Rf ¹ is each independently a C _1-16 perfluoroalkyl group,

Rf ² is each independently a C _1-6 perfluoroalkylene group.

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

-(OC ₆ F ₁₂ ) _a -(OC ₅ F ₁₀ ) _b -(OC ₄ F ₈ ) _c -(OC ₃ R ^Fa ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f -

[In the formula, R ^Fa 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 from 0 to 200. The sum of a, b, c, d, e and f is 1 or more. The sum of a, b, c, d, e or f The order in which the repeating units enclosed in parentheses are present in the formula is arbitrary, but when all R ^Fa are hydrogen atoms or chlorine atoms, at least one of a, b, c, e and f is 1 or more].

[9] The fluoropolyether group-containing thiol compound as described in the above [8], wherein R ^Fa is a fluorine atom.

[10] The fluoropolyether group-containing thiol compound as described in any one of the above [6] to [9], wherein R ^F is each independently the following formula (f1), (f2), (f3) , (f4), (f5), or the basis shown in (f6),

-(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e - (f1)

[In the formula, d is an integer from 1 to 200, and e is 0 or 1];

-(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f2)

[In the formula, c and d are each independently an integer from 0 to 30,

e and f are each independently an integer from 1 to 200,

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

The order of existence of each repeating unit enclosed by parentheses of subscript c, d, e or f is arbitrary in the formula];

-(R ⁶ -R ⁷ ) _g - (f3)

[In the formula, R ⁶ is OCF ₂ or OC ₂ F ₄ ,

R ⁷ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or a combination of 2 or 3 groups selected from these groups,

g is an integer from 2 to 100];

-(R ⁶ -R ⁷ ) _g -R ^r -(R ^7' -R ^6' ) _g' - (f4)

[In the formula, R ⁶ is OCF ₂ or OC ₂ F ₄ ,

R ⁷ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or a combination of 2 or 3 groups independently selected from these groups,

R ^6' is OCF ₂ or OC ₂ F ₄ ,

R ^7' is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or a combination of 2 or 3 groups independently selected from these groups,

g is an integer from 2 to 100,

g’ is an integer from 2 to 100,

R ^r is

(In the formula, * represents the bonding position)];

-(OC ₆ F ₁₂ ) _a -(OC ₅ F ₁₀ ) _b -(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f5)

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

-(OC ₆ F ₁₂ ) _a -(OC ₅ F ₁₀ ) _b -(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f6)

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

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

-R ^Sa (S1)

-NR ^Sa _n1 R ³ _2-n1 (S2)

-CR ^Sa _n2 R ³ _3-n2 (S3)

[In the formula:

R ^Sa is -Z-CR ¹ R ² -SH,

Z is a single bond or a 2-valent base,

R ¹ is a hydrocarbon group,

R ² is a hydrogen atom or a hydrocarbon group,

R ³ is a hydrogen atom or a hydrocarbon group,

n1 is 1 or 2,

n2 is 1, 2 or 3].

[12] The fluoropolyether group-containing thiol compound as described in [11] above, wherein Z is -R ¹¹ -R ¹² -,

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

R ¹² is -OCO-(CH ₂ ) _m -,

m is an integer from 0 to 6.

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

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

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

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

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

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

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

-(R ²¹ ) _m1 -(R ²² ) _m2 -

[In the formula:

R ²¹ is C _1-6 alkylene group,

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

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

m1 is an integer from 0 to 10,

m2 is an integer from 0 to 10,

The total of m1 and m2 is more than 1,

The order of existence 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] above, which has a number average molecular weight of 1,000 to 100,000.

[21] The fluoropolyether group-containing thiol compound as described in any one of [1] to [20] above, which has a viscosity of 100 to 10,000 cP.

[22] A curable composition containing the fluoropolyether group-containing thiol compound as described in any one of [1] to [21] above.

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

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

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

[26] The curable composition according to any one of [23] to [25] above, 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] above, wherein the group having a carbon-carbon double bond is present on both ends of the fluoropolyether group.

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

R ^D _δ -X ^B -R ^F2 -X ^B -R ^D _δ (4)

[In the formula:

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 by more than 1 fluorine atom,

Rf ² is a C _1-6 alkylene group which may be substituted by more than one fluorine atom,

R ^F are each independently a divalent fluoropolyether group,

p is 0 or 1,

q is each independently 0 or 1,

X ^B is each independently a single bond or an organic group with 2 to 10 valences,

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

γ1 is an integer from 1 to 9,

γ2 is an integer from 1 to 9,

δ is each independently an integer from 1 to 9].

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

-Y-A

[In the formula:

Y is a single bond, oxygen atom or divalent organic group,

A is -CR ⁴¹ =CH ₂ ,

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

[30] The curable composition as described in the above [28] or [29], wherein 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 the above [28] to [30], wherein R ^D is the following formula (D1), (D2), (D3), (D4) or (D5) The basis shown is,

-Y-A (D1)

-SiR ^a1 _k1 R ^b1 _l1 R ^c1 _m1 (D3)

-CR ^d1 _k2 R ^e1 _l2 R ^f1 _m2 (D4)

-NR ^g1 R ^h1 (D5)

[In the formula,

Y is a single bond, oxygen atom or divalent organic group,

A is -CR ⁴¹ =CH ₂ ,

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

Each time X ¹⁰ appears, it is independently a single bond or a divalent organic radical.

R ¹³ is independently a hydrogen atom or a monovalent organic group each time it appears,

Each occurrence of t is independently an integer above 2,

Each occurrence of R ¹⁴ is independently a hydrogen atom or a halogen atom,

R ^a1 is independently -Z ¹ -SiR ^a2 _p1 R ^a3 _q1 R ^a4 _r1 on each occurrence,

Z ¹ is independently a single bond, an oxygen atom or a divalent organic group each time it appears,

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

Z ^1' is independently a single bond, an oxygen atom or a divalent organic group each time it appears,

R ^a3' is independently -Z ² -YA on each occurrence,

Each occurrence of R ^a4' is independently a hydrogen atom, a hydroxyl group or a monovalent organic group,

Each time Z ² appears, it is independently a single bond, an oxygen atom or a divalent organic group,

q1’ is independently an integer from 0 to 3 each time it appears,

r1’ is independently an integer from 0 to 3 on each occurrence,

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

R ^a3 is independently -Z ² -YA on each occurrence,

Each occurrence of R ^a4 is independently a hydrogen atom, a hydroxyl group or a monovalent organic group,

p1 is independently an integer from 0 to 3 on each occurrence,

q1 is independently an integer from 0 to 3 on each occurrence,

r1 is independently an integer from 0 to 3 on each occurrence,

Here, the total of p1, q1 and r1 is 3 in the (SiR ^a2 _p1 R ^a3 _q1 R ^a4 _r1 ) unit,

R ^b1 is independently -Z ² -YA on each occurrence,

Each time R ^c1 appears, it is independently a hydrogen atom, a hydroxyl group or a monovalent organic group,

k1 is independently an integer from 0 to 3 on each occurrence,

l1 is independently an integer from 0 to 3 each time it appears,

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

Here, the total of k1, l1, and m1 is 3 in the (SiR ^a1 _k1 R ^b1 _l1 R ^c1 _m1 ) unit,

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

R ^d1 is independently -Z ³ -CR ^d2 _p2 R ^d3 _q2 R ^d4 _r2 on each occurrence,

Each time Z ³ appears, it is independently a single bond, an oxygen atom or a divalent organic group,

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

Z ^3' is independently an oxygen atom or a divalent organic group each time it appears,

R ^d3' is independently -Z ² -YA on each occurrence,

Each time R ^d4' appears, it is independently a hydrogen atom, a hydroxyl group or a monovalent organic group,

q2’ is independently an integer from 0 to 3 each time it appears,

r2’ is independently an integer from 0 to 3 on each occurrence,

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

R ^d3 is independently -Z ² -YA on each occurrence;

R ^d4 is independently a hydrogen atom, a hydroxyl group or a monovalent organic group each time it appears;

p2 is independently an integer from 0 to 3 each time it appears;

q2 is independently an integer from 0 to 3 each time it appears;

r2 is independently an integer from 0 to 3 on each occurrence;

Here, the total of p2, q2 and r2 in the (CR ^d2 _p2 R ^d3 _q2 R ^d4 _r2 ) unit is 3,

R ^e1 is independently -Z ² -YA on each occurrence,

Each occurrence of R ^f1 is independently a hydrogen atom, a hydroxyl group or a monovalent organic group,

k2 is independently an integer from 0 to 3 on each occurrence,

l2 is independently an integer from 0 to 3 each time it appears,

m2 is independently an integer from 0 to 3 on each occurrence,

Here, the total of k2, l2, and m2 is 3 in the (CR ^d1 _k2 R ^e1 _l2 R ^f1 _m2 ) unit,

In formula (D4), there is at least 1 A,

Each occurrence of R ^g1 and R ^h1 is independently -Z ⁴ -YA, -Z ⁴ -SiR ^a1 _k1 R ^b1 _l1 R ^c1 _m1 , or -Z ⁴ -CR ^d1 _k2 R ^e1 _l2 R ^f1 _m2 ,

Z ⁴ is independently a single bond, an oxygen atom or a divalent organic radical each time it appears.

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

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

-{(R ³¹ ) _p' -(X ^a ) _q' }-R ³² -

[In the formula:

R ³¹ is a single bond, -(CH ₂ ) _s' -or ortho-, meta- or p-phenylene group,

R ³² is a single bond, -(CH ₂ ) _t' -or ortho-, meta- or p-phenylene group,

s’ is an integer from 1 to 20,

t’ is an integer from 1 to 20,

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

_Each occurrence ^of o-, m- or p-phenylene, -C(O)O-, -CONR ³⁴ -, -O-CONR ³⁴ -, -NR ³⁴ -, -Si(R ³³ ) ₂ -, -(Si (R ³³ ) ₂ O) _m' -Si(R ³³ ) ₂ -, and -(CH ₂ ) _n' -,

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

Each occurrence of R ³⁴ is independently a hydrogen atom, a phenyl group or a C _1-6 alkyl group,

Each occurrence of m’ is independently an integer from 1 to 100,

n’ is independently an integer from 1 to 20 on each occurrence,

r’ is an integer from 1 to 10,

p’ is 0 or 1,

q’ is 0 or 1,

Here, at least one of p' and q' is 1, and the order in which the repeating units enclosed in parentheses of p' or q' exists is arbitrary].

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

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

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

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

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

[38] The curable composition according to any one of [22] to [37] above, further containing 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),

Rf ⁵ -(OC ₄ F ₈ ) _a' -(OC ₃ F ₆ ) _b' -(OC ₂ F ₄ ) _c' -(OCF ₂ ) _d' -Rf ⁶ ...(5)

[In the formula:

Rf ⁵ is a C _1-16 alkyl group which may be substituted by more than one fluorine atom,

Rf ⁶ is a C _1-16 alkyl group, a fluorine atom or a hydrogen atom that may be substituted by more than one fluorine atom,

a’, b’, c’ and d’ are each independently an integer between 0 and 300,

The order of existence of each repeating unit enclosed in parentheses of the subscript a', b', c' or d' is arbitrary in the formula].

[40] The curable composition according to any one of the above [22] to [39], which is solvent-free.

[41] The curable composition according to any one of [22] to [40] above, which has a viscosity of 100 to 10,000 cP.

[42] A hardened material obtained by hardening the curable composition according to any one of the above [22] to [41].

[43] The hardened material according to the above [42], which has a tensile elastic modulus of 0.5 to 500 MPa.

[44] The hardened material according to the above [42], which is a sealing material.

[45] The hardened material according to the above [42], which is a sealing material for electronic equipment.

[46] An article including a base material and a layer on the base material hardened with the curable composition according to any one of [22] to [41] above.

[47] A compound represented by formula (c1),

(OH-X ¹² ) ₂ NCO-X ¹¹ -R ^F2 -X ¹¹ -CON(X ¹² -OH) ₂ (c1)

[In the formula:

R ^F2 is -Rf ² _p -R ^F -O _q -,

Rf ² is a C _1-6 alkylene group which may be substituted by more than one fluorine atom,

R ^F are each independently a divalent fluoropolyether group,

p is 0 or 1,

q is each independently 0 or 1,

X ¹¹ is a single bond or a divalent hydrocarbon group,

X ¹² is a divalent hydrocarbon group].

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

When used in this specification, "monovalent organic group" means a monovalent group containing carbon. The monovalent organic group is not particularly limited and may be a hydrocarbon group or a derivative thereof. Derivatives of hydrocarbon groups refer to the terminal or A group having at least one N, O, S, Si, amide group, sulfonyl group, siloxane, carbonyl group, carbonyl oxygen, etc. group in the molecular chain. In addition, when expressed only as "organic group", it is a monovalent organic group. In addition, the "divalent organic group" means a divalent group containing carbon. The divalent organic group is not particularly limited, and examples include a divalent group in which one hydrogen atom is detached from the organic group. Similarly, "2 to 10 valent organic groups" refers to 2 to 10 valent groups containing carbon. The 2 to 10 valent organic groups are not particularly limited. Examples include: further detaching 1 to 9 hydrogen atoms from the organic group. The resulting price base is 2 to 10.

When used in this specification, a "hydrocarbon group" refers to a group containing carbon and hydrogen and detaching one hydrogen atom from a hydrocarbon. The hydrocarbon group is not particularly limited, and examples thereof include C _1-20 hydrocarbon groups that may be substituted by one or more substituents, such as aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and the like. The above-mentioned "aliphatic hydrocarbon group" may be linear, branched, or cyclic, and may be saturated or unsaturated. In addition, the hydrocarbon group may contain one or more ring structures.

When used in this specification, the substituent of "hydrocarbyl" is not particularly limited, and examples thereof include: C _1-6 alkyl and C _2-6 alkenyl selected from halogen atoms, which may be substituted by one or more halogen atoms. , C _2-6 alkynyl group, C _3-10 cycloalkyl group, C _3-10 unsaturated cycloalkyl group, 5 to 10 membered heterocyclic group, 5 to 10 membered unsaturated heterocyclic group, C ₆ -10 One or more radicals of an aryl group and a heteroaryl group of 5 to 10 members.

As used in this specification, "hydrolyzable group" refers to a group that can undergo a hydrolysis reaction, that is, a group that can be separated from the main skeleton of the compound through a hydrolysis reaction. Examples of hydrolyzable groups include: -OR ^j , -OCOR ^j , -ON=CR ^j ₂ , -NR ^j ₂ , -NHR ^j , -NCO, halogen (in this equation, R ^j represents substituted or unsubstituted C _{1 -4} alkyl) etc.

(thiol compound containing fluoropolyether group)

The present disclosure provides fluoropolyether group-containing thiol compounds containing two or more thiol groups selected from secondary thiol groups and tertiary thiol groups.

The thiol group in the fluoropolyether group-containing thiol compound disclosed in the present disclosure is a secondary thiol group and a tertiary thiol group, so it has excellent storage stability.

The above-mentioned secondary thiol refers to a compound in which the carbon atom to which the thiol group (SH) is bonded has a hydrocarbon group as a substituent, such as a group represented by -CHR-SH (in the formula, R is a hydrocarbon group).

The above-mentioned tertiary thiol refers to a compound in which the carbon atom to which the thiol group (SH) is bonded has two hydrocarbon groups as substituents, such as -CR ₂ -SH (in the formula, each R is independently a hydrocarbon group). .

The number of thiol groups contained in the fluoropolyether group-containing thiol compound of the present disclosure is preferably 2 or more, more preferably 3 or more, and still more preferably 4 or more. Furthermore, the number of thiol groups contained in the fluoropolyether group-containing thiol compound of the present disclosure is preferably 6 or less, such as 5 or less or 4 or less.

In one aspect, the number of thiol groups contained in the fluoropolyether group-containing thiol compound of the present disclosure is preferably 2 to 6, and more preferably 2 to 4. In one aspect, the number of thiol groups contained in the fluoropolyether group-containing thiol compound of the present disclosure is 2. In other aspects, the number of thiol groups contained in the fluoropolyether group-containing thiol compound of the present disclosure is 4. Since the fluoropolyether group-containing thiol compound has multiple thiol groups, the curability can be improved.

In a preferred embodiment, the above-mentioned thiol groups are present on both ends of the fluoropolyether group.

In a preferred aspect, in the thiol compound containing a fluoropolyether group of the present disclosure, the number of the above-mentioned thiol groups present on both ends of the fluoropolyether group is the same. For example, there is one thiol group on each end side of the fluoropolyether group, or there are two thiol groups on each end side of the fluoropolyether group. Thiol compounds containing fluoropolyether groups have a plurality of thiol groups on both ends of the fluoropolyether group, thereby further improving the curability. For example, they can be cured even with ultraviolet irradiation of 2000mJ/ ^cm3 or less. Even the exposure dose is below 1000mJ/ ^cm3 .

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

In other aspects, the thiol group is a tertiary thiol group.

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

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

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

The above SP value can be obtained by Fedors' calculation method.

The viscosity of the fluoropolyether group-containing thiol compound disclosed in the present disclosure is preferably 100 cP or more, more preferably 300 cP or more, and even more preferably 500 cP or more. In addition, the viscosity of the fluoropolyether group-containing thiol compound of the present disclosure is preferably 10,000 cP or less, more preferably 7,000 cP or less, and still more preferably 5,000 cP or less.

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

The above viscosity can be measured with a TV-10 viscometer manufactured by Toki Industrial Co., Ltd. (Rotor No. THM1, rotation speed 1.0 rpm, measurement temperature 25°C).

In a preferred aspect, the fluoropolyether group-containing thiol compound of the present disclosure is 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 formula:

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 by more than 1 fluorine atom,

Rf ² is a C _1-6 alkylene group which may be substituted by more than one fluorine atom,

R ^F are each independently a divalent fluoropolyether group,

p is 0 or 1,

q is each independently 0 or 1,

X ^A is each independently a single bond or an organic group with 2 to 10 valences,

R ^S is each independently a monovalent group containing a group represented by -CR ¹ R ² -SH,

R ¹ is a hydrocarbon group,

R ² is a hydrogen atom or a hydrocarbon group,

In formulas (1) and (2), there are at least 2 groups represented by -CR ¹ R ² -SH.

α1 is an integer from 1 to 9,

α2 is an integer from 1 to 9,

β is each independently an integer from 1 to 9].

In the above formula (1), R ^F1 is Rf ^{1 -RF} -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 by one or more fluorine atoms.

The "C _1-16 alkyl group" in the above-mentioned C _1-16 alkyl group that can be substituted by more than one fluorine atom can be a straight chain or branched chain, preferably a straight chain or branched chain C _1-6 alkyl group. , especially C _1-3 alkyl, more preferably straight-chain C _1-6 alkyl, especially C _1-3 alkyl.

The above-mentioned Rf ¹ is preferably a C _1-16 alkyl group substituted by one or more fluorine atoms, more preferably a CF ₂ HC _1-15 perfluoroalkyl group, and still more preferably a C _1-16 perfluoroalkyl group.

The above-mentioned C _1-16 perfluoroalkyl group can be a straight chain or a branched chain, preferably a straight chain or branched chain C _1-6 perfluoroalkyl group, especially a C _1-3 perfluoroalkyl group, and more preferably a straight chain or branched chain C 1-6 perfluoroalkyl group. The C _1-6 perfluoroalkyl group in the chain, especially the C _1-3 perfluoroalkyl group, is specifically -CF ₃ , -CF ₂ CF ₃ , or -CF ₂ CF ₂ CF ₃ .

In the above formula, Rf ² is a C _1-6 alkylene group which may be substituted by one or more fluorine atoms.

The "C _1-6 alkylene group" in the above-mentioned C _1-6 alkylene group which may be substituted by more than one fluorine atom can be a straight chain or a branched chain, preferably a straight chain or branched chain C _1-3 Alkylene group is more preferably a straight-chain C _1-3 alkylene group.

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

The above-mentioned C _1-6 perfluoroalkylene group can be a straight chain or a branched chain, preferably a straight chain or branched chain C _1-3 perfluoroalkylene group, and more preferably a straight chain C _1-3 perfluoroalkylene group. The alkyl group is specifically -CF ₂ -, -CF ₂ CF ₂ -, or -CF ₂ CF ₂ CF ₂ -.

In the above formula, p is 0 or 1. In one state, p is 0. p is 1 in other configurations.

In the above formula, q is each independently 0 or 1. In one state, q is 0. In other configurations, q is 1.

In the above formulas (1) and (2), R ^F is independently a divalent fluoropolyether group each time it appears.

^RF preferably contains a group represented by the following formula.

-(OC _h1 R ^Fa _2h1 ) _h3 -(OC _h2 R ^Fa _2h2-2 ) _h4 -

[In the formula:

Each occurrence of R ^Fa is independently a hydrogen atom, a fluorine atom, or a chlorine atom,

h1 is an integer from 1 to 6,

h2 is an integer from 4 to 8,

h3 is an integer above 0,

h4 is an integer above 0,

However, the total of h3 and h4 is 1 or more, preferably 2 or more, more preferably 5 or more, and the order in which the repeating units enclosed in parentheses of h3 and h4 exist in the formula is arbitrary].

In one aspect, ^RF may be linear or branched. R ^F is preferably a base represented by the following formula

-(OC ₆ F ₁₂ ) _a -(OC ₅ F ₁₀ ) _b -(OC ₄ F ₈ ) _c -(OC ₃ R ^Fa ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f -

[In the formula:

Each occurrence of R ^Fa is independently a hydrogen atom, a fluorine atom, or a chlorine atom,

a, b, c, d, e and f are each independently an integer from 0 to 200, and the sum of a, b, c, d, e and f is 1 or more. The order in which the repeating units enclosed in parentheses of a, b, c, d, e or f are present is arbitrary in the formula. However, when 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, when all R ^Fa are hydrogen atoms or chlorine atoms, at least 1 of a, b, c, e and f must be 1 or more.

Preferably, a, b, c, d, e and f are each independently an integer from 0 to 100.

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

The repeating units may be linear or branched. For example -(OC ₆ F ₁₂ )- can be -(OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ CF ₂ CF ₂ CF ₂ )-, -(OCF ₂ CF(CF ₃ )CF ₂ CF ₂ CF ₂ )-, -(OCF ₂ CF ₂ CF(CF ₃ )CF ₂ CF ₂ )-, - (OCF ₂ CF ₂ CF ₂ CF(CF ₃ )CF ₂ )-, -(OCF ₂ CF ₂ CF ₂ CF ₂ CF(CF ₃ ))-etc. -(OC ₅ F ₁₀ )- can be -(OCF ₂ CF ₂ CF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ CF ₂ CF ₂ )-, -(OCF ₂ CF(CF ₃ ) CF ₂ CF ₂ )-, -(OCF ₂ CF ₂ CF(CF ₃ )CF ₂ )-, -(OCF ₂ CF ₂ CF ₂ CF(CF ₃ ))-, etc. -(OC ₄ F ₈ )- can be -(OCF ₂ CF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ CF ₂ )-, -(OCF ₂ CF(CF ₃ )CF ₂ )- ,-(OCF ₂ CF ₂ CF(CF ₃ ))-,-(OC(CF ₃ ) ₂ CF ₂ )-,-(OCF ₂ C(CF ₃ ) ₂ )-,-(OCF(CF ₃ )CF( Any one of CF ₃ ))-, -(OCF(C ₂ F ₅ )CF ₂ )- and -(OCF ₂ CF(C ₂ F ₅ ))-. -(OC ₃ F ₆ )- (that is, in the above formula, R ^Fa is a fluorine atom) can be -(OCF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ )- and -(OCF ₂ CF (CF ₃ )) - any of them. -(OC ₂ F ₄ )- can be any one of -(OCF ₂ CF ₂ )- and -(OCF(CF ₃ ))-.

In one aspect, the repeating units are linear. By making the repeating units linear, the surface smoothness, abrasion resistance, etc. of the surface treatment layer can be improved.

In one aspect, the repeating units are branched. By making the above-mentioned repeating units branched, the dynamic friction coefficient of the surface treatment layer can be increased.

In one aspect, R ^F may contain a ring structure.

The above ring structure may be a three-member ring, a four-member ring, a five-member ring, or a six-member ring as described below.

[In the formula, * represents the bonding position]

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

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

[In the formula, * represents the bonding position]

In one aspect, each occurrence of R ^F is independently a basis represented by any one of the following formulas (f1) to (f6).

-(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e - (f1)

[In the formula, d is an integer from 1 to 200, and e is 0 or 1];

-(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f2)

[In the formula, c and d are each independently an integer from 0 to 30, e and f are each independently an integer from 1 to 200,

The sum of c, d, e and f is 2 or more,

The order of existence of each repeating unit enclosed by parentheses of subscript c, d, e or f is arbitrary in the formula];

-(R ⁶ -R ⁷ ) _g - (f3)

[In the formula, R ⁶ is OCF ₂ or OC ₂ F ₄ ,

R ⁷ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or a combination of 2 or 3 groups independently selected from these groups,

g is an integer from 2 to 100];

-(R ⁶ -R ⁷ ) _g -R ^r -(R ^7' -R ^6' ) _g' - (f4)

[In the formula, R ⁶ is OCF ₂ or OC ₂ F ₄ ,

R ⁷ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or a combination of 2 or 3 groups independently selected from these groups,

R ^6' is OCF ₂ or OC ₂ F ₄ ,

R ^7' is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or a combination of 2 or 3 groups independently selected from these groups,

g is an integer from 2 to 100,

g’ is an integer from 2 to 100,

R ^r is

(In the formula, * represents the bonding position)];

-(OC ₆ F ₁₂ ) _a -(OC ₅ F ₁₀ ) _b -(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f5)

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

-(OC ₆ F ₁₂ ) _a -(OC ₅ F ₁₀ ) _b -(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f6)

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

In the above formula (f1), d is preferably an integer of 5 to 200, more preferably 10 to 100, still more preferably 15 to 50, for example, 25 to 35. In one aspect, e is 1. In other aspects, e is 0. In the above formula (f1), OC ₃ F ₆ is preferably OCF ₂ CF ₂ CF ₂ , OCF ₂ CF (CF ₃ ), or OCF (CF ₃ )CF ₂ , and more preferably OCF ₂ CF ₂ CF ₂ . OC ₂ F ₄ is OCF ₂ CF ₂ or OCF (CF ₃ ), preferably OCF ₂ CF ₂ .

In the above formula (f2), e and f are each independently preferably an integer from 5 to 200, more preferably an integer from 10 to 200. Moreover, the sum of c, d, e and f is preferably 5 or more, more preferably 10 or more, for example, 15 or more or 20 or more. In one aspect, the above formula (f2) is preferably -(OCF ₂ CF ₂ CF ₂ CF ₂ ) _c -(OCF ₂ CF ₂ CF ₂ ) _d -(OCF ₂ CF ₂ ) _e -(OCF ₂ ) _f - The basis shown. In other aspects, formula (f2) is a base represented by -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f -.

In the above formula (f3), R ⁶ is preferably OC ₂ F ₄ . In the above (f3), R ⁷ is preferably a group selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ , or a combination of 2 or 3 groups independently selected from these groups, more preferably A group selected from OC ₃ F ₆ and OC ₄ F ₈ . The combination of 2 or 3 groups independently selected from OC ₂ F ₄ , OC ₃ F ₆ and OC ₄ F ₈ is not particularly limited. Examples include: -OC ₂ F ₄ OC ₃ F ₆ -, -OC ₂ F ₄ OC ₄ F ₈ -, -OC ₃ F ₆ OC ₂ F ₄ -, -OC ₃ F ₆ OC ₃ F ₆ -, -OC ₃ F ₆ OC ₄ F ₈ -, -OC ₄ F ₈ OC ₄ F ₈ - , -OC ₄ F ₈ OC ₃ F ₆ -, -OC ₄ F ₈ OC ₂ F ₄ -, -OC ₂ F ₄ OC 2 F ₄ OC ₃ F ₆ -, -OC ₂ F ₄ OC ₂ F _{4 OC 4 F 8} -, -OC ₂ F ₄ OC ₃ F ₆ OC ₂ F ₄ -, -OC ₂ F ₄ OC ₃ F ₆ OC ₃ F ₆ -, -OC ₂ F ₄ OC ₄ F ₈ OC ₂ F ₄ -, -OC ₃ F ₆ OC ₂ F ₄ OC ₂ F ₄ -, -OC ₃ F ₆ OC ₂ F ₄ OC ₃ F ₆ -, -OC ₃ F ₆ OC ₃ F ₆ OC ₂ F ₄ -, and -OC ₄ F ₈ OC ₂ F ₄ OC ₂ F ₄ -etc. In the above formula (f3), g is preferably an integer of 3 or more, more preferably 5 or more. The above g is preferably an integer of 50 or less. In the above formula (f3), OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ may be either linear or branched chains, and linear chains are preferred. In this aspect, the above formula (f3) is preferably -(OC ₂ F ₄ -OC ₃ F ₆ ) _g - or -(OC ₂ F ₄ -OC ₄ F ₈ ) _g -.

In the above-mentioned formula (f4), R ⁶ , R ⁷ and g are synonymous with the description of the above-mentioned formula (f3) and have the same aspect. R ^6' , R ^7' and g' are respectively synonymous and have the same aspect as R ⁶ , R ⁷ and g described in the above formula (f3). R ^r is preferably

[In the formula, * represents the bonding position];

R ^r is better;

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

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

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

In one aspect, the above-mentioned R ^F is a base represented by the above-mentioned formula (f1).

In one aspect, the above-mentioned R ^F is a base represented by the above-mentioned formula (f2).

In one aspect, the above-mentioned R ^F is a base represented by the above-mentioned formula (f3).

In one aspect, the above-mentioned R ^F is a base represented by the above-mentioned formula (f4).

In one aspect, the above-mentioned R ^F is a base represented by the above-mentioned formula (f5).

In one aspect, R ^F is the base represented by the above formula (f6).

In the above 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 more preferably The optimal range is 0.2 to 0.85. By setting the e/f ratio to 10 or less, the smoothness, abrasion resistance, and chemical resistance (for example, durability against artificial sweat) of the surface treatment layer obtained from the compound can be further improved. The smaller the e/f ratio is, the more smoothness and wear resistance of the surface treatment layer can be 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 larger the e/f ratio is, the more the stability of the compound can be improved.

In one aspect, the above-mentioned e/f ratio is preferably 0.2 to 0.95, more preferably 0.2 to 0.9.

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

In the above-mentioned fluoropolyether group-containing thiol compound, the number average molecular weight of the ^RF1 and ^RF2 parts is not particularly limited, but is, for example, 500 to 30,000, preferably 1,500 to 30,000, and more preferably 2,000 to 10,000. In this specification, the number average molecular weight of ^RF1 and ^RF2 is a value measured by ¹⁹ F-NMR.

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

-R ^Sa (S1)

-NR ^Sa _n1 R ³ _2-n1 (S2)

-CR ^Sa _n2 R ³ _3-n2 (S3)

[In the formula:

R ^Sa is -Z-CR ¹ R ² -SH,

Z is a single bond or a 2-valent base,

R ¹ is a hydrocarbon group,

R ² is a hydrogen atom or a hydrocarbon group,

R ³ is a hydrogen atom or a hydrocarbon group,

n1 is 1 or 2,

n2 is 1, 2 or 3].

R ^Sa is -Z-CR ¹ R ² -SH.

Z is a single bond or a divalent base. In one form, Z is a single bond. In other aspects, Z is a divalent organic group.

Z is preferably -R ¹¹ -R ¹² -. In the formula, R ¹¹ is a single bond or a C _1-6 alkylene group, and R ¹² is -OC(O)-(CH ₂ ) _m - (m is an integer from 0 to 6). Here, in -OC(O)-(CH ₂ ) _m -, the right side is bonded to CR ¹ R ² -SH.

The C _1-6 alkylene group in R ¹¹ may be a straight chain or a branched chain. In one aspect, the C _1-6 alkylene group is a straight chain. In other aspects, the C _1-6 alkylene group is a branched chain.

The C _1-6 alkylene group in R ¹¹ is preferably a C _1-4 alkylene group.

m is preferably an integer from 0 to 4, more preferably an integer from 0 to 3.

In one aspect, m is 0.

In other aspects, m is an integer from 1 to 6, preferably an integer from 1 to 4, and more preferably an integer from 1 to 3.

R ¹ is a hydrocarbon group.

R ² is a hydrogen atom or a hydrocarbon group.

In one aspect, R ² is a hydrogen atom.

In other aspects, R ² is a hydrocarbyl group.

The hydrocarbon 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, still more preferably a methyl group.

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

In a preferred embodiment, R ¹ is a C _1-6 alkyl group, and R ² is a hydrogen atom or a C _1-6 alkyl group. In one aspect, R ¹ is a C _1-6 alkyl group, and R ² is a hydrogen atom. In other aspects, 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 aspect, R ³ is a hydrogen atom.

In other aspects, R ³ is a hydrocarbyl group.

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 or ethyl group, still more preferably a methyl group.

The C _1-6 alkyl group in R ³ may be a straight chain or a branched chain. In one aspect, the C _1-6 alkyl group is straight chain. In other aspects, the C _1-6 alkyl group is branched.

n1 is 1 or 2. In one aspect, n1 is 1. In other configurations, n1 is 2.

n2 is 1, 2 or 3. In one aspect, n2 is 1. In other configurations, n2 is 2. In other configurations, n2 is 3.

In a preferred embodiment, R ^S is a base represented by formula (S2) or (S3).

In one aspect, R ^S is the base represented by formula (S2).

In one aspect, R ^S is the base represented by formula (S3).

^In the above ^formulas (1) and ( ^{2 )} , Linker. Therefore, X ^A may be a single bond or an arbitrary group as long as the compound represented by formulas (1) and (2) can exist stably.

In the above formula (1), α1 is an integer from 1 to 9, and α2 is an integer from 1 to 9. These α1 and α2 can respond to changes in the valence of X ^A. The sum of α1 and α2 is the same as the valence of X ^A. For example, when X ^A is a 10-valent organic group, the sum of α1 and α2 is 10, for example, α1 is 9 and α2 is 1, α1 is 5 and α2 is 5, or α1 is 1 and α2 is 9. Moreover, when X ^A is a divalent organic group, α1 and α2 are 1.

In the above formula (2), β is each independently an integer from 1 to 9. β can respond to changes in the valence of X ^A. That is, β is the value minus 1 from the valence of X ^A.

X ^A is each independently a single bond or an organic group with 2 to 10 valences.

The 2- to 10-valent organic groups in the above-mentioned X ^A are preferably 2 to 8-valent organic groups. In one aspect, the 2- to 10-valent organic group is preferably a 2- to 4-valent organic group, and more preferably a 2-valent organic group. In other aspects, the 2- to 10-valent organic group is preferably a 3- to 8-valent organic group, more preferably a 3 to 6-valent organic group.

In one aspect, X ^A is a single bond or a divalent organic group, α is 1, and α2 is 1.

In one aspect, X ^A is a single bond or a divalent organic group, and β is 1.

In one aspect, X ^A is an organic group with 3 to 6 valences, α1 is 1, and α2 is 2 to 5.

In one aspect, X ^A is an organic group with 3 to 6 valence, and β is 2 to 5.

In one aspect, X ^A is a trivalent organic group, α1 is 1, and α2 is 2.

In one aspect, X ^A is a trivalent organic group, and β is 2.

In one aspect, X ^A is a single bond or a divalent organic group, and α1, α2, and β are 1.

In a preferred embodiment, X ^A is a base represented by the following formula.

-(R ²¹ ) _m1 -(R ²² ) _m2 -

[In the formula:

R ²¹ is C _1-6 alkylene group,

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

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

m1 is an integer from 0 to 10,

m2 is an integer from 0 to 10,

The total of m1 and m2 is more than 1,

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

Here, X ^A (typically the hydrogen atom of X ^A ) may be substituted with one or more substituents selected from a fluorine atom, a C _1-3 alkyl group and a C _1-3 fluoroalkyl group. In a preferred embodiment, X ^A is unsubstituted by these groups.

In one aspect, X ^A is each independently -(R ²¹ ) _m1-1 -(R ²² ) _m2 -R ²⁴ -. R ²¹ , R ²² , m1 and m2 are synonymous with the above. The order in which R ²¹ and R ²² exist is arbitrary in the formula. R ²⁴ represents a single bond, -(CH ₂ ) _t5 - or o-, m- or p-phenylene group, preferably -(CH ₂ ) _t5 -. t5 is an integer from 1 to 20, preferably an integer from 2 to 6, and more preferably an integer from 2 to 3. Here, R ²⁴ (typically the hydrogen atom of R ²⁴ ) may be substituted with one or more substituents selected from a fluorine atom, a C _1-3 alkyl group and a C _1-3 fluoroalkyl group. In a preferred embodiment, R ²⁴ is unsubstituted by these groups.

The C _1-6 alkylene group in R ²¹ may be a straight chain or a branched chain. In one aspect, the C _1-6 alkylene group is a straight chain. In other aspects, the C _1-6 alkylene group is a branched chain.

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 -, -CONR ²³ -, 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 aspect, R ²³ is a hydrogen atom.

In other aspects, R ²³ is C _1-6 alkyl.

The C _1-6 alkyl group in R ²³ may be a straight chain or a branched chain. In one aspect, the C _1-6 alkyl group is straight chain. In other aspects, the C _1-6 alkyl group 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 from 0 to 10, preferably an integer from 0 to 4, more preferably an integer from 0 to 2.

m2 is an integer from 0 to 10, preferably an integer from 0 to 2, more preferably 0 or 1.

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

In one aspect, (m1,m2) is (0,1), (1,1), (2,1), or (1,0).

In a preferred form, X ^A is each independently:

single key;

-R ²¹ -R ²² -R ²⁴ -;

-R ²¹ -R ²² -;

-R ²² -R ²⁴ -; or

-R ²² -;

(In the formula:

R ²¹ is C _1-6 alkylene group,

R ²² is -O-, or -CO-,

R ²⁴ is C _1-6 alkylene group).

The number average molecular weight of the fluoropolyether group-containing thiol compound of the present disclosure is preferably more than 1,000, more preferably more than 1,500, for example, it can be more than 2,000, more than 4,000, or more than 5,000. In addition, the number average molecular weight of the fluoropolyether group-containing thiol compound of the present disclosure 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, for example, it can be 8,000 or less, Below 6,000, or below 5,000. In this specification, the number average molecular weight of the thiol compound containing a fluoropolyether group is a value measured by ¹⁹ F-NMR.

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

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

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

R ⁵¹ OCO-X ¹ -PFPE-X ¹ -COOR ⁵¹ (a)

[In the formula:

PFPE is fluoropolyether-based,

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 divalent organic group].

HN(X ² -OH) ₂ (b)

[In the formula, X ² is each independently a divalent organic group].

(OH-X ² ) ₂ NCO-X ¹ -PFPE-X ¹ -CON(X ² -OH) ₂ (c)

[In the formula, PFPE, X ¹ and X ² are synonymous with the above].

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

Next, the compound represented by formula (c) and the compound represented by formula (d) are reacted to obtain the compound represented by formula (e).

[In the formula:

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

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

R ⁵² is hydrocarbyl].

[In the formula, PFPE, X ¹ , X ² , R ⁵² , and Hal ² are synonymous with the above].

In addition, R ⁵² corresponds to R ¹ in the formula (2), and the -X ² -O-CO- part corresponds to Z in the formula (S2).

Next, the compound represented by formula (e) and the compound represented by formula (f) are reacted to obtain the compound represented by formula (g).

[In the formula, R ⁵³ is C _1-6 alkyl, preferably methyl or ethyl, especially ethyl].

[In the formula, PFPE, X ¹ , X ² , R ⁵² , and R ⁵³ are synonymous with the above].

Next, by treating the compound represented by formula (g) with an alkyl amine, preferably n-butylamine, the fluoropolyether group-containing thiol compound represented by formula (h) of the present disclosure is obtained.

[In the formula, PFPE, X ¹ , X ² , and R ⁵² are synonymous with the above].

The compound represented by the above formula (c) is a practical intermediate for the production of the fluoropolyether group-containing thiol compound of the present disclosure. Therefore, the present disclosure provides compounds represented by the following formula (c1).

(OH-X ¹² ) ₂ NCO-X ¹¹ -R ^F2 -X ¹¹ -CON(X ¹² -OH) ₂ (c1)

[In the formula:

R ^F2 is -Rf ² _p -R ^F -O _q -,

Rf ² is a C _1-6 alkylene group which may be substituted by more than one fluorine atom,

R ^F are each independently a divalent fluoropolyether group,

p is 0 or 1,

q is each independently 0 or 1,

X ¹¹ is a single bond or a divalent hydrocarbon group,

X ¹² is a divalent hydrocarbon group].

R ^F2 is synonymous with R ^F2 in the above formulas (1) and (2).

The above divalent hydrocarbon group is preferably:

R ⁶¹ -R ⁶² -R ⁶³

[In the formula:

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

R ⁶² is a single bond or phenylene group,

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

But exclude the case where they are all single keys].

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

X ¹¹ is preferably a single key.

X ¹² is preferably C _1-6 alkylene group.

Other methods include the following methods.

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

HO-X ¹ -PFPE-X ¹ -OH (i)

[In the formula, X ¹ has the same meaning as above].

[In the formula, R ⁵² has the same meaning as above].

[In the formula, PFPE, X ¹ , and R ⁵² are synonymous with the above].

Still another method can be listed as the following method.

The compound represented by formula (m) can be reacted with the compound represented by formula (n) to obtain the compound represented by formula (o).

Hal ³ -X ³ -CH=CH ₂ (m)

[In the formula:

Hal ³ is a halogen atom, preferably bromine,

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

CH ₂ =CH-X ³ -OX ¹ -PFPE-X ¹ -OX ³ -CH=CH ₂ (n)

[In the formula, PFPE, X ¹ , and X ³ are synonymous with the above].

[In the formula, PFPE, X ¹ , and X ³ are synonymous with the above].

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

[In the formula, PFPE, X ¹ , and X ³ are synonymous with the above].

Next, the compound represented by formula (p) and the compound represented by formula (j) are reacted to obtain the compound represented by formula (q).

[In the formula, R ⁵² has the same meaning as above].

[In the formula, PFPE, X ¹ , X ³ , and R ⁵² are synonymous with the above].

(hardening composition)

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

The curable composition of the present disclosure may further comprise an unsaturated compound containing a fluoropolyether group containing a group having a carbon-carbon double bond.

(Unsaturated compound containing fluoropolyether group)

The above-mentioned group containing a carbon-carbon double bond is not particularly limited as long as it is a group containing a carbon-carbon double bond. Typically, base systems containing carbon-carbon double bonds have carbon-carbon double bonds at the termini.

The above-mentioned group having a carbon-carbon double bond is preferably allyl, vinyl, or (meth)acrylyl, more preferably allyl.

In one aspect, the number of groups with carbon-carbon double bonds in the unsaturated compound containing a fluoropolyether group is preferably 2 to 8, more preferably 2 to 6, and still more preferably 2 to 4. .

In a preferred embodiment, the above-mentioned groups having carbon-carbon double bonds are present at both ends of the unsaturated compound containing the fluoropolyether group.

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

In a preferred embodiment, the above-mentioned 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 _δ (4)

[In the formula:

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 by more than 1 fluorine atom,

Rf ² is a C _1-6 alkylene group which may be substituted by more than one fluorine atom,

R ^F are each independently a divalent fluoropolyether group,

p is 0 or 1,

q is each independently 0 or 1,

X ^B is each independently a single bond or an organic group with 2 to 10 valences,

R ^D are each independently a radical containing a carbon-carbon double bond,

γ1 is an integer from 1 to 9,

γ2 is an integer from 1 to 9,

δ is each independently an integer from 1 to 9].

In the above formula, ^RF1 and ^RF2 are synonymous with ^RF1 and ^RF2 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 with 2 to 10 valence. This X ^B can be interpreted as a linker connecting ^RD and ^RF1 or ^RF2 . Therefore, X ^B may be any organic group as long as it can stabilize the existence of the compounds represented by formulas (3) and (4).

In the above formula, γ1 is an integer from 1 to 9, γ2 is an integer from 1 to 9, and δ is an integer from 1 to 9. These γ1, γ2 and δ are determined according to the valence of X ^B. In formula (3), the sum of γ1 and γ2 is the value of the valence of X ^B. For example, when X ^B is a 10-valent organic group, the sum of γ1 and γ2 is 10. For example, γ1 is 9 and γ2 is 1, γ1 is 5 and γ2 is 5, or γ1 is 1 and γ2 is 9. Moreover, when X ^B is a divalent 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 valent of 2 to 7, more preferably a valent of 2 to 4, and more preferably a divalent organic base. γ1, γ2 and δ can be an integer from 1 to 6, an integer from 1 to 3, or 1, etc. according to X ^B.

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

-(R ³¹ ) _p' -(X ^a ) _q' -R ³² -

[In the formula:

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

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

s’ is an integer from 1 to 20, preferably an integer from 1 to 6, more preferably an integer from 1 to 3, and more preferably 1 or 2,

t’ is an integer from 1 to 20, preferably an integer from 2 to 6, more preferably an integer from 2 to 3,

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

_Each occurrence ^of o-, m- or p-phenylene, -C(O)O-, -CONR ³⁴ -, -O-CONR ³⁴ -, -NR ³⁴ -, -Si(R ³³ ) ₂ -, -(Si (R ³³ ) ₂ O) _m' -Si(R ³³ ) ₂ -, and -(CH ₂ ) _n' -,

The above substituents are synonymous with the substituents of the above hydrocarbon groups,

R ³³ independently represents phenyl, C _1-6 alkyl or C _1-6 alkoxy each time it appears, preferably C _1-6 alkyl, more preferably methyl,

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

Each occurrence of m' is independently an integer from 1 to 100, preferably an integer from 1 to 20,

Each time n' appears, it is independently an integer from 1 to 20, preferably an integer from 1 to 6, and more preferably an integer from 1 to 3,

r’ is an integer from 1 to 10, preferably an integer from 1 to 5, more preferably an integer from 1 to 3,

p’ is 0 or 1,

q’ is 0 or 1,

Here, at least one of p' and q' is 1, and the order in which the repeating units enclosed in parentheses of p' or q' exists is arbitrary].

Each occurrence of R ^D is independently a radical having a carbon-carbon double bond.

The group containing a carbon-carbon double bond in the above R ^D is a group represented by -YA (in the formula, Y represents a single bond, an oxygen atom or a divalent organic group, A is -CR ⁴¹ =CH ₂ , and R ⁴¹ are each independent Ground is a hydrogen atom or a C _1-3 alkyl group (preferably methyl)).

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

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

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

-Y-A (D1)

-SiR ^a1 _k1 R ^b1 _l1 R ^c1 _m1 (D3)

-CR ^d1 _k2 R ^e1 _l2 R ^f1 _m2 (D4)

-NR ^g1 R ^h1 (D5)

[In the formula,

Y is a single bond, oxygen atom or divalent organic group,

A is -CR ⁴¹ =CH ₂ ,

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

Each time X ¹⁰ appears, it is independently a single bond or a divalent organic radical.

R ¹³ is independently a hydrogen atom or a monovalent organic group each time it appears,

Each occurrence of t is independently an integer above 2,

Each occurrence of R ¹⁴ is independently a hydrogen atom or a halogen atom,

R ^a1 is independently -Z ¹ -SiR ^a2 _p1 R ^a3 _q1 R ^a4 _r1 on each occurrence,

Z ¹ is independently a single bond, an oxygen atom or a divalent organic group each time it appears,

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

Z ^1' is independently a single bond, an oxygen atom or a divalent organic group each time it appears,

R ^a3' is independently -Z ² -YA on each occurrence,

Each occurrence of R ^a4' is independently a hydrogen atom, a hydroxyl group or a monovalent organic group,

Each time Z ² appears, it is independently a single bond, an oxygen atom or a divalent organic group,

q1’ is independently an integer from 0 to 3 each time it appears,

r1’ is independently an integer from 0 to 3 on each occurrence,

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

R ^a3 is independently -Z ² -YA on each occurrence,

Each occurrence of R ^a4 is independently a hydrogen atom, a hydroxyl group or a monovalent organic group,

p1 is independently an integer from 0 to 3 on each occurrence,

q1 is independently an integer from 0 to 3 on each occurrence,

r1 is independently an integer from 0 to 3 on each occurrence,

Here, the total of p1, q1 and r1 is 3 in the (SiR ^a2 _p1 R ^a3 _q1 R ^a4 _r1 ) unit,

R ^b1 is independently -Z ² -YA on each occurrence,

Each time R ^c1 appears, it is independently a hydrogen atom, a hydroxyl group or a monovalent organic group,

k1 is independently an integer from 0 to 3 on each occurrence,

l1 is independently an integer from 0 to 3 each time it appears,

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

Here, the total of k1, l1, and m1 is 3 in the (SiR ^a1 _k1 R ^b1 _l1 R ^c1 _m1 ) unit,

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

R ^d1 is independently -Z ³ -CR ^d2 _p2 R ^d3 _q2 R ^d4 _r2 on each occurrence,

Each time Z ³ appears, it is independently a single bond, an oxygen atom or a divalent organic group,

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

Z ^3' is independently an oxygen atom or a divalent organic group each time it appears,

R ^d3' is independently -Z ² -YA on each occurrence,

Each time R ^d4' appears, it is independently a hydrogen atom, a hydroxyl group or a monovalent organic group,

q2’ is independently an integer from 0 to 3 each time it appears,

r2’ is independently an integer from 0 to 3 on each occurrence,

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

R ^d3 is independently -Z ² -YA on each occurrence;

R ^d4 is independently a hydrogen atom, a hydroxyl group or a monovalent organic group each time it appears;

p2 is independently an integer from 0 to 3 each time it appears;

q2 is independently an integer from 0 to 3 each time it appears;

r2 is independently an integer from 0 to 3 on each occurrence;

Here, the total of p2, q2 and r2 in the (CR ^d2 _p2 R ^d3 _q2 R ^d4 _r2 ) unit is 3,

R ^e1 is independently -Z ² -YA on each occurrence,

Each occurrence of R ^f1 is independently a hydrogen atom, a hydroxyl group or a monovalent organic group,

k2 is independently an integer from 0 to 3 on each occurrence,

l2 is independently an integer from 0 to 3 each time it appears,

m2 is independently an integer from 0 to 3 on each occurrence,

Here, the total of k2, l2, and m2 is 3 in the (CR ^d1 _k2 R ^e1 _l2 R ^f1 _m2 ) unit,

In formula (D4), there is at least 1 A,

Each occurrence of R ^g1 and R ^h1 is independently -Z ⁴ -YA, -Z ⁴ -SiR ^a1 _k1 R ^b1 _l1 R ^c1 _m1 , or -Z ⁴ -CR ^d1 _k2 R ^e1 _l2 R ^f1 _m2 ,

Z ⁴ is independently a single bond, an oxygen atom or a divalent organic radical each time it appears.

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

In the above formula, X ¹⁰ is independently a single bond or a divalent organic group each time it appears. The divalent organic group is preferably -R ²⁸ -O _x -R ²⁹ - (in the formula, R ²⁸ and R ²⁹ are each independently a single bond or a C _1-20 alkylene group each time they appear, and x is 0 or 1). The C _1-20 alkylene group can be a straight chain or a branched chain, preferably a straight chain. The C _1-20 alkylene group is preferably a C _1-10 alkylene group, more preferably a C _1-6 alkylene group, and still more preferably a C _1-3 alkylene group.

In one aspect, each occurrence of X ¹⁰ is independently -C _1-6 alkylene-OC _1-6 alkylene- or -OC _1-6 alkylene-.

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

In the above formula, R ¹³ is independently a hydrogen atom or a monovalent organic group each time it appears.

The monovalent organic group is preferably a C _1-20 alkyl group. The C _1-20 alkyl group can be a straight chain or a branched chain, preferably a straight chain.

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

In the above formula, t is independently an integer above 2 each time it appears.

In a preferred embodiment, t is independently an integer between 2 and 10 each time it appears, preferably an integer between 2 and 6.

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

In the above formula, R ^a1 is independently -Z ¹ -SiR ^a2 _p1 R ^a3 _q1 R ^a4 _r1 each time it appears.

The above-mentioned Z ¹ is independently a single bond, an oxygen atom or a divalent organic group each time it appears. In addition, the following describes the structure of Z ¹ in which the right side is bonded to (SiR ^a2 _p1 R ^a3 _q1 R ^a4 _r1 ).

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

The above Z ¹ is preferably a C _1-6 alkylene group, -(CH ₂ ) _z1 -O-(CH ₂ ) _z2 -(in the formula, z1 is an integer from 0 to 6, for example, an integer from 1 to 6, z2 is an integer from 0 to 6, such as an integer from 1 to 6), -(CH ₂ ) _z3 -phenylene-(CH ₂ ) _z4 -(where z3 is an integer from 0 to 6, such as an integer from 1 to 6, z4 is an integer from 0 to 6, such as an integer from 1 to 6), or -(CH ₂ ) _z5 -C _3-10 cycloalkyl-(CH ₂ ) _z6 -(where z5 is an integer from 0 to 6) , such as an integer from 1 to 6, z6 is an integer from 0 to 6, such as an integer from 1 to 6). The C _1-6 alkylene group can be a straight chain or a branched chain, preferably a straight chain. These groups may be substituted by, for example, one 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, and are preferably unsubstituted.

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

In other preferred embodiments, the above-mentioned Z ¹ is a C _1-3 alkylene group. In one aspect, Z ¹ can be -CH ₂ CH ₂ CH ₂ -. In other aspects, Z ¹ can be -CH ₂ CH ₂ -.

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

The above-mentioned Z ^1' is independently a single bond, an oxygen atom or a divalent organic group each time it appears. In addition, the structure described below is Z ^1' , in which the right side is bonded to (SiR ^a3' _q1' R ^a4' _r1' ).

In a preferred embodiment, Z ^1' is a divalent organic group.

The above Z ^1' is preferably a C _1-6 alkylene group, -(CH ₂ ) _z1' -O-(CH ₂ ) _z2' -(in the formula, z1' is an integer from 0 to 6, for example, from 1 to 6 Integer, z2' is an integer from 0 to 6, such as an integer from 1 to 6), or -(CH ₂ ) _z3' -phenyl-(CH ₂ ) _z4' -(in the formula, z3' is an integer from 0 to 6 An integer, such as an integer from 1 to 6, z4' is an integer from 0 to 6, such as an integer from 1 to 6). The C _1-6 alkylene group can be a straight chain or a branched chain, preferably a straight chain. These groups may be substituted by, for example, one 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, and 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' -. When Z ^1' is the base, the light resistance, especially the ultraviolet resistance, can be improved.

In other preferred embodiments, the above-mentioned Z ^1' is a C _1-3 alkylene group. In one aspect, Z ^1' can be -CH ₂ CH ₂ CH ₂ -. In other aspects, Z ^1' can be -CH ₂ CH ₂ -.

Each occurrence of R ^a3' is independently -Z ² -YA.

Each occurrence of Z ² is independently a single bond, an oxygen atom or a divalent organic radical. Furthermore, the following describes the structure of Z ² in which the right side is bonded to (YA).

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

Z ² is preferably C _1-6 alkylene, -(CH ₂ ) _z11 -O-(CH ₂ ) _z12 -(in the formula, z11 is an integer from 0 to 6, for example, an integer from 1 to 6, z12 is 0 to an integer of 0 to 6, such as an integer of 1 to 6), -(CH ₂ ) _z13 -phenylene-(CH ₂ ) _z14 -(where z13 is an integer of 0 to 6, such as an integer of 1 to 6, z14 is an integer from 0 to 6, such as an integer from 1 to 6), or -(CH ₂ ) _z15 -C _3-10 cycloalkyl-(CH ₂ ) _z16 -(where z15 is an integer from 0 to 6, For example, an integer from 1 to 6, z16 is an integer from 0 to 6, such as an integer from 1 to 6). The C _1-6 alkylene group can be a straight chain or a branched chain, preferably a straight chain. These groups may be substituted by, for example, one 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, and are preferably unsubstituted.

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

In other preferred embodiments, Z ² is C _1-3 alkylene group. In one aspect, Z ² can be -CH ₂ CH ₂ CH ₂ -. In other aspects, Z ² can be -CH ₂ CH ₂ -.

Each occurrence of R ^a4' is independently a hydrogen atom, a hydroxyl group or a monovalent organic group. This monovalent organic group is a monovalent organic group other than the above-mentioned hydrolyzable group. The monovalent organic group is a monovalent organic group other than -Z ² -YA mentioned above.

In R ^a4' , the monovalent 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 in each occurrence, and r1' is an integer from 0 to 3 in each occurrence independently. Here, the total of q1' and r1' is 3 in the (SiR ^a3' _q1' R ^a4' _r1' ) unit.

In a preferred aspect, q1' is independently an integer from 1 to 3 each time it appears, preferably 2 or 3, and more preferably 3. At this time, r1' is independently an integer from 0 to 2 each time it appears, preferably 0 or 1, and more preferably 0.

Each occurrence of R ^a3 is independently -Z ² -YA.

Each occurrence of R ^a4 is independently a hydrogen atom, a hydroxyl group or a monovalent organic group. This monovalent organic group is a monovalent organic group other than the above-mentioned hydrolyzable group. The monovalent organic group is a monovalent organic group other than -Z ² -YA mentioned above.

In R ^a4 , the monovalent 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 independently an integer from 0 to 3 in each occurrence, q1 is an integer from 0 to 3 in each occurrence independently, and r1 is an integer from 0 to 3 in each occurrence independently. Here, the total of p1, q1, and r1 is 3 in the unit (SiR ^a2 _p1 R ^a3 _q1 R ^a4 _r1 ).

In one aspect, p1 is independently an integer from 1 to 3 each time it appears, preferably 2 or 3, and more preferably 3.

In other aspects, q1 is independently an integer from 1 to 3 each time it appears, preferably 2 or 3, and more preferably 3.

In a preferred embodiment, r1 is independently an integer from 0 to 2 each time it appears, preferably 0 or 1, and more preferably 0.

In one aspect, p1 is 3.

In other configurations, q1 is 3.

In the above formula, R ^b1 is independently -Z ² -YA each time it appears.

In the above formula, R ^c1 is independently a hydrogen atom, a hydroxyl group or a monovalent organic group each time it appears. The monovalent organic group is a monovalent organic group other than -Z ² -YA mentioned above.

In R ^c1 , the monovalent 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 from 0 to 3 each time it appears, l1 is an integer from 0 to 3 each time it appears, and m1 is an integer from 0 to 3 each time it appears. Here, the total of k1, l1, and m1 is 3 in the (SiR ^a1 _k1 R ^b1 _l1 R ^c1 _m1 ) unit.

In one aspect, k1 is independently an integer from 1 to 3 each time it appears, preferably 2 or 3, and more preferably 3.

In other aspects, l1 is independently an integer from 1 to 3 each time it appears, preferably 2 or 3, and more preferably 3.

In a preferred aspect, m1 is independently an integer from 0 to 2 each time it appears, preferably 0 or 1, and more preferably 0.

In one form, k1 is 3.

In other aspects, l1 is 3.

Here, in formula (D3), there is at least one -Y-A.

Each occurrence of R ^d1 is independently -Z ³ -CR ^d2 _p2 R ^d3 _q2 R ^d4 _r2 .

Each occurrence of Z ³ is independently a single bond, an oxygen atom or a divalent organic group. In addition, the following describes the structure of Z ³ in which the right side is bonded to (CR ^d2 _p2 R ^d3 _q2 R ^d4 _r2 ).

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

The above Z ³ is preferably a C _1-6 alkylene group, -(CH ₂ ) _z5 -O-(CH ₂ ) _z6 -(in the formula, z5 is an integer from 0 to 6, for example, an integer from 1 to 6, z6 is an integer from 0 to 6, such as an integer from 1 to 6), -(CH ₂ ) _z7 -phenylene-(CH ₂ ) _z8 -(where z7 is an integer from 0 to 6, such as an integer from 1 to 6, z8 is an integer from 0 to 6, such as an integer from 1 to 6), or -(CH ₂ ) _z9 -C _3-10 cycloalkyl-(CH ₂ ) _z10 -(where z9 is an integer from 0 to 6) , such as an integer from 1 to 6, z10 is an integer from 0 to 6, such as an integer from 1 to 6). The C _1-6 alkylene group can be a straight chain or a branched chain, preferably a straight chain. These groups may be substituted by, for example, one 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, and are preferably unsubstituted.

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

In other preferred embodiments, the above-mentioned Z ³ is a C _1-3 alkylene group. In one aspect, Z ³ can be -CH ₂ CH ₂ CH ₂ -. In other aspects, Z ³ can be -CH ₂ CH ₂ -.

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

Each occurrence of Z ^3' is independently a single bond, an oxygen atom or a divalent organic group. Furthermore, the structure described below is Z ^3' , the right side of which is bonded to (CR ^d3' _q2' R ^d4' _r2' ).

The above Z ^3' is preferably a C _1-6 alkylene group, -(CH ₂ ) _z5' -O-(CH ₂ ) _z6' -(in the formula, z5' is an integer from 0 to 6, such as 1 to 6 Integer, z6' is an integer from 0 to 6, such as an integer from 1 to 6), -(CH ₂ ) _z7' -phenylene-(CH ₂ ) _z8' -(where z7' is an integer from 0 to 6 , such as an integer from 1 to 6, z8' is an integer from 0 to 6, such as an integer from 1 to 6), or -(CH ₂ ) _z9' -C _3-10 cycloalkyl-(CH ₂ ) _z10' - (In the formula, z9' is an integer from 0 to 6, such as an integer from 1 to 6, and z10' is an integer from 0 to 6, such as an integer from 1 to 6). The C _1-6 alkylene group can be a straight chain or a branched chain, preferably a straight chain. These groups may be substituted by, for example, one 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, and are preferably 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 other preferred embodiments, the above-mentioned Z ^3' is a C _1-3 alkylene group. In one aspect, Z ^3' can be -CH ₂ CH ₂ CH ₂ -. In other aspects, Z ^3' can be -CH ₂ CH ₂ -.

The above R ^d3' is independently -Z ² -YA on each occurrence.

The above-mentioned R ^d4' is independently a hydrogen atom, a hydroxyl group or a monovalent organic group each time it appears. The monovalent organic group is a monovalent organic group other than -Z ² -YA mentioned above.

Among the above-mentioned R ^d4' , the monovalent 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 other aspects, the monovalent organic group of R ^d4' is preferably a C _1-20 alkyl group, more preferably a C _1-6 alkyl group.

q2' is independently an integer from 0 to 3 in each occurrence, and r2' is an integer from 0 to 3 in each occurrence independently. Here, the total of q2' and r2' is 3 in the unit (CR ^d3' _q2' R ^d4' _r2' ).

In a preferred embodiment, q2' is independently an integer from 1 to 3 each time it appears, preferably 2 or 3, and more preferably 3. At this time, r2' is independently an integer from 0 to 2 each time it appears, preferably 0 or 1, and more preferably 0.

R ^d3 is independently -Z ² -YA on each occurrence.

The above-mentioned R ^d4 is independently a hydrogen atom, a hydroxyl group or a monovalent organic group each time it appears. The monovalent organic group is a monovalent organic group other than -Z ² -YA mentioned above.

In the above-mentioned R ^d4 , the monovalent 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 other aspects, the monovalent organic group of R ^d4 is preferably a C _1-20 alkyl group, more preferably a C _1-6 alkyl group.

The above p2 is an integer from 0 to 3 independently every time it appears, q2 is an integer from 0 to 3 independently every time it appears, and r2 is an integer from 0 to 3 independently every time it appears. Furthermore, the total of p2, q2, and r2 is 3 in the unit (CR ^d2 _p2 R ^d3 _q2 R ^d4 _r2 ).

In one aspect, p2 is independently an integer from 1 to 3 each time it appears, preferably 2 or 3, and more preferably 3.

In other aspects, q2 is independently an integer from 1 to 3 each time it appears, preferably 2 or 3, and more preferably 3.

In a preferred embodiment, r2 is independently an integer from 0 to 2 each time it appears, preferably 0 or 1, and more preferably 0.

In one aspect, p2 is 3.

In other configurations, q2 is 3.

The above R ^e1 is independently -Z ² -YA on each occurrence.

The above-mentioned R ^f1 is independently a hydrogen atom, a hydroxyl group or a monovalent organic group each time it appears. This monovalent organic group is a monovalent organic group other than the above-mentioned hydrolyzable group.

In the above-mentioned R ^f1 , the monovalent 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 other aspects, the monovalent organic group of R ^f1 is preferably a C _1-20 alkyl group, more preferably a C _1-6 alkyl group.

The above k2 is an integer from 0 to 3 independently every time it appears, l2 is an integer from 0 to 3 independently every time it appears, and m2 is an integer from 0 to 3 independently every time it appears. Furthermore, the total of k2, l2, and m2 is 3 in the unit (CR ^d1 _k2 R ^e1 _l2 R ^f1 _m2 ).

In one aspect, k2 is independently an integer from 1 to 3 each time it appears, preferably 2 or 3, and more preferably 3.

In other aspects, l2 is independently an integer from 1 to 3 each time it appears, preferably 2 or 3, and more preferably 3.

In a preferred embodiment, m2 is independently an integer from 0 to 2 each time it appears, preferably 0 or 1, and more preferably 0.

In one form, k2 is 3.

In other configurations, l2 is 3.

Here, in formula (D4), at least one -Y-A exists.

Each occurrence of R ^g1 and R ^h1 is independently -Z ⁴ -YA, -Z ⁴ -SiR ^a1 _k1 R ^b1 _l1 R ^c1 _m1 , or -Z ⁴ -CR ^d1 _k2 R ^e1 _l2 R ^f1 _m2 .

Each occurrence of Z ⁴ is independently a single bond, an oxygen atom or a divalent organic group. In addition, the following describes the structure of Z ⁴ in which the right side is bonded to (-YA group, etc.).

Here, in formula (D5), at least one -Y-A exists.

In one form, Z ⁴ is an oxygen atom.

In one aspect, Z ⁴ is a divalent organic group.

The above Z ⁴ is preferably a C _1-6 alkylene group, -(CH ₂ ) _z5” -O-(CH ₂ ) _z6” -(in the formula, z5” is an integer from 0 to 6, such as an integer from 1 to 6 , z6″ is an integer from 0 to 6, such as an integer from 1 to 6), or -(CH ₂ ) _z7″ -phenylene-(CH ₂ ) _z8″ -(where z7″ is an integer from 0 to 6) , such as an integer from 1 to 6, z8″ is an integer from 0 to 6, such as an integer from 1 to 6). The C _1-6 alkylene group can be a straight chain or a branched chain, preferably a straight chain. These groups may be substituted by, for example, one 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, and are preferably unsubstituted.

In a preferred embodiment, Z ⁴ is C _1-6 alkylene group or -(CH ₂ ) _z7” -phenylene group -(CH ₂ ) _z8” -, preferably -phenylene group -(CH ₂ ) _{z8 ”} -. When Z ³ is used as the base, the light resistance, especially the UV resistance, can be improved.

In other preferred embodiments, the above-mentioned Z ⁴ is a C _1-3 alkylene group. In one aspect, Z ⁴ can be -CH ₂ CH ₂ CH ₂ -. In other aspects, Z ⁴ can be -CH ₂ CH ₂ -.

In one aspect, R ^D is the base represented by formula (D1).

In one aspect, R ^D is the base represented by formula (D2).

In one aspect, R ^D is the base represented by formula (D3).

In one aspect, R ^D is the base represented by formula (D4).

In one aspect, R ^D is the base represented by formula (D5).

The number average molecular weight of the unsaturated compound containing a fluoropolyether group of the present disclosure is preferably more than 1,000, more preferably more than 1,500, for example, it can be more than 2,000, more than 4,000, or more than 5,000. In addition, the number average molecular weight of the unsaturated compound containing a fluoropolyether group of the present disclosure 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, for example, it can be 8,000 or less, Below 6,000, or below 5,000. In this specification, the number average molecular weight of the unsaturated compound containing a fluoropolyether group is a value measured by ¹⁹ F-NMR.

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

The mass ratio of the thiol compound containing a fluoropolyether group and the unsaturated compound containing a fluoropolyether group of the present disclosure is preferably 0.1:100 to 100:0.1, more preferably 5:100 to 100:5, and more preferably The best range is 10:100 to 100:10.

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

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

Rf ⁵ -(OC ₄ F ₈ ) _a' -(OC ₃ F ₆ ) _b' -(OC ₂ F ₄ ) _c' -(OCF ₂ ) _d' -Rf ⁶ ...(5)

[In the formula:

Rf ⁵ is a C _1-16 alkyl group which may be substituted by more than one fluorine atom,

Rf ⁶ is a C _1-16 alkyl group, a fluorine atom or a hydrogen atom that may be substituted by more than one fluorine atom,

a’, b’, c’ and d’ are each independently an integer between 0 and 300,

The sum of a’, b’, c’ and d’ is at least 1,

The order of existence of each repeating unit enclosed in parentheses of the subscript a', b', c' or d' is arbitrary in the formula].

Rf ⁵ is an alkyl group having 1 to 16 carbon atoms which may be substituted by one or more fluorine atoms, preferably a perfluoroalkyl group having 1 to ₁₆ carbon atoms.

Rf ⁶ is an alkyl group having 1 to 16 carbon atoms, which may be substituted by one 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 C _1-16 perfluoroalkyl group, 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-mentioned fluorine-containing oil, -(OC ₄ F ₈ )- can be -(OCF ₂ CF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ CF ₂ )-, -(OCF ₂ CF(CF ₃ )CF ₂ )-, -(OCF ₂ CF ₂ CF(CF ₃ ))-, -(OC(CF ₃ ) ₂ CF ₂ )-, -(OCF ₂ C(CF ₃ ) ₂ )-, Any one of -(OCF(CF ₃ )CF(CF ₃ ))-, -(OCF(C ₂ F ₅ )CF ₂ )- and (OCF ₂ CF(C ₂ F ₅ ))-, preferably - (OCF ₂ CF ₂ CF ₂ CF ₂ )-. -(OC ₃ F ₆ )- can be any one of -(OCF ₂ CF ₂ CF ₂ )-, -(OCF(CF ₃ )CF ₂ )- and (OCF ₂ CF(CF ₃ ))-, preferably is -(OCF ₂ CF ₂ CF ₂ )-. -(OC ₂ F ₄ )- can be any one of -(OCF ₂ CF ₂ )- and (OCF(CF ₃ ))-, and is preferably -(OCF ₂ CF ₂ )-.

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

Rf ⁵ -(OCF ₂ CF ₂ CF ₂ ) _b” -Rf ⁶ ...(5a)

Rf ⁵ -(OCF ₂ CF ₂ CF ₂ CF ₂ ) _a” -(OCF ₂ CF ₂ CF ₂ ) _b” -(OCF ₂ CF ₂ )c”-(OCF ₂ )d”-Rf ⁶ ． ． ． (5b)

In this equation, Rf ⁵ and Rf ⁶ are as above; in formula (5a), b” is an integer from 1 to 100; in formula (5b), a” and b” are each independently from 0 to 30 is an integer, c" and d" are each independently an integer from 1 to 300. The order of existence of the repeating units enclosed by the parentheses of the subscripts a", b", c" and d" is arbitrary in the formula.

Furthermore, from another viewpoint, the fluorinated oil may be a compound represented by the general formula Rf ³ -F (in the formula, Rf ³ is a C _5-16 perfluoroalkyl group). Alternatively, it may be a chlorotrifluoroethylene oligomer.

The above-mentioned fluorine-containing oil may have an average molecular weight of 500 to 10,000. The molecular weight of fluorinated oil can be determined using GPC.

Relative to the curable composition of the present disclosure, the fluorine-containing oil may contain, for example, 0.01 to 50 mass%, preferably 0.1 to 30 mass%, such as 1 to 15 mass%.

In one aspect, the curable composition of the present disclosure contains substantially no fluorine-containing oil. Substantially does not contain fluorinated oil means that it does not contain fluorinated oil at all or may contain a very small amount of fluorinated oil.

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

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

The above-mentioned polymerization initiator is preferably a radical polymerization initiator.

The above-mentioned free radical polymerization initiator is a compound that generates free radicals by heat or light, and examples thereof include: free radical thermal polymerization initiator and free radical photopolymerization initiator. In the present invention, the above-mentioned radical photopolymerization initiator is preferred.

Examples of the radical thermal polymerization initiator include benzyl peroxide, dihydroxyperoxides such as lauryl peroxide, and dioxanes such as dicumyl peroxide and tert-butyl diperoxide. basic fault Oxides, peroxycarbonates such as diisopropyl peroxydicarbonate, bis(4-tert-butylcyclohexyl)peroxydicarbonate, tert-butyl peroxyoctanoate, tert-butyl peroxybenzoate Peroxide compounds such as alkyl peroxyesters such as butyl ester, and free radical-generating azo compounds such as azobisisobutyronitrile.

啉基-1-丙酮、2-苄基-2-二甲胺基-1-(4-

啉基苯基)-丁烷-1-酮等苯乙酮類、蒽醌、1,4-萘醌等醌類、2-二甲胺基苯甲酸乙酯、4-二甲胺基苯甲酸乙酯、4-二甲胺基苯甲酸(正丁氧基)乙酯、4-二甲胺基苯甲酸異戊酯、4-二甲胺基苯甲酸2-乙基己酯等胺基苯甲酸類、2-氯苯乙酮、三鹵甲基苯基碸等鹵化合物、醯基膦氧化物類、二第三丁基過氧化物等過氧化物等。 Examples of the above-mentioned radical photopolymerization initiator include benzoethylene glycol, diketones such as diacetyl, alcohols and ketones such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzene, etc. Azoin ethers such as azoin isopropyl ether, thioxanthone such as thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-sulfonic acid, diphenyl ketone, 4,4 Diphenyl ketones such as '-bis(dimethylamino)diphenylketone, 4,4'-bis(diethylamino)diphenylketone, acetophenone, 2-(4-toluenesulfonyl ketone) Oxy)-2-phenylacetophenone, p-dimethylaminoacetophenone, 2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl Base[4-(methylthio)phenyl]-2-N-

Phino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-

Acetophenones such as linylphenyl)-butan-1-one, anthraquinones, quinones such as 1,4-naphthoquinone, ethyl 2-dimethylaminobenzoate, 4-dimethylaminobenzoic acid Ethyl ester, ethyl 4-dimethylaminobenzoate (n-butoxy), isopentyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate and other aminobenzenes Formic acid, 2-chloroacetophenone, halogen compounds such as trihalomethylphenyltrilane, acylphosphine oxides, peroxides such as di-tert-butyl peroxide, etc.

Examples of commercially available types of the above-mentioned radical photopolymerization initiator are as follows.

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-propanyl)-benzyl]phenyl}-2-methyl-propan-1-one;

啉基丙烷-1-酮； IRGACURE 907: 2-methyl-1-(4-methylthiophenyl)-2-N-

linylpropan-1-one;

啉基苯基)-丁酮-1； IRGACURE 369: 2-benzyl-2-dimethylamino-1-(4-

linylphenyl)-butanone-1;

啉基)苯基]-1-丁酮； IRGACURE 379: 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-

Phylyl)phenyl]-1-butanone;

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

IRGACURE 784: Bis(eta5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium;

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

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

IRGACURE 261, IRGACURE 369, IRGACURE 500;

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

DAROCUR TPO: 2,4,6-Trimethylbenzyl-diphenyl-phosphine oxide;

DAROCUR 1116, DAROCUR 2959, DAROCUR 1664, DAROCUR 4043;

IRGACURE 754 Oxyphenylacetic acid: a mixture of 2-[2-side oxy-2-phenyl acetyloxyethoxy]ethyl ester, oxyphenylacetic acid and 2-(2-hydroxyethoxy)ethyl ester;

IRGACURE 500: a mixture of IRGACURE 184 and benzophenone (1:1);

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

IRGACURE 1800: a mixture of CGI403 and IRGACURE 184 (1:3);

IRGACURE 1870: a mixture of CGI403 and IRGACURE 184 (7:3);

DAROCUR 4265: A mixture (1:1) of DAROCUR TPO and DAROCUR 1173.

In addition, IRGACURE is manufactured by BASF, and DAROCUR is manufactured by Merck JAPAN.

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

Examples of the organic solvent include fluorine-containing organic solvents and fluorine-free organic solvents.

Examples of the above-mentioned fluorine-containing organic solvent include: perfluorohexane, perfluorooctane, perfluorodimethylcyclohexane, perfluorodecalin, perfluoroalkylethanol, perfluorobenzene, perfluorotoluene, perfluoro Alkyl amines (Fluorinert (trade name), etc.), perfluoroalkyl ethers, perfluorobutyltetrahydrofuran, polyfluoroaliphatic hydrocarbons (Asahiklin AC6000 (trade name)), chlorofluorocarbons (Asahiklin AK-225 (trade name) etc.), hydrofluoroethers (Novec (trade name), HFE-7100 (trade name), HFE-7300 (trade name), etc.), 1,1,2,2,3,3,4-heptafluorocyclopentane , fluorinated alcohols, perfluoroalkyl bromides, perfluoroalkyl iodides, perfluoropolyethers (Krytox (trade name), DEMNUM (trade name), Fomblin (trade name), etc.), 1,3-bistri Fluoromethylbenzene, 2-(perfluoroalkyl)ethyl methacrylate, 2-(perfluoroalkyl)ethyl acrylate, perfluoroalkylethylene, chlorofluorocarbon (Freon) 134a, and hexafluoropropylene oligo Polymer.

Examples of the above-mentioned fluorine-free organic solvents include acetone, methyl isobutyl ketone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, and propylene glycol. Monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether pentane, hexane, heptane, octane, dichloromethane, chloroform, carbon tetrachloride, dichloroethane , carbon disulfide, benzene, toluene, xylene, nitrobenzene, diethyl ether, dimethoxyethane, diethylene glycol dimethyl ether, triglyceryl dimethyl ether, ethyl acetate, butyl acetate, dimethyl Methanamide, dimethylstyrene, 2-butanone, acetonitrile, benzonitrile, butanol, 1-propanol, 2-propanol, ethanol, methanol, and diacetone alcohol.

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

The above-mentioned organic solvent may be used individually by 1 type, and may be used in combination of 2 or more types.

The above-mentioned organic solvent is preferably used in the curable composition in the range of 10 to 99 mass%, more preferably 30 to 95 mass%, and still more preferably 50 to 95 mass%.

In one aspect, the curable composition of the present disclosure is solvent-free, that is, it contains substantially no solvent. "Substantially does not contain solvent" means that in a state where no solvent is intentionally added, trace amounts of unavoidable solvents, such as water, may be present. For example, the solvent content in the curable composition of the present disclosure 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 (such as hydrochloric acid, acetic acid, trifluoroacetic acid, etc.), bases (such as ammonia, triethylamine, diethylamine, etc.), transition metals (such as Ti, Ni, Sn, etc.).

The viscosity of the curable composition of the present disclosure is preferably 100 cP or more, more preferably 300 cP or more, and still more preferably 500 cP or more. In addition, the viscosity of the fluoropolyether group-containing thiol compound of the present disclosure is preferably 10,000 cP or less, more preferably 7,000 cP or less, and still more preferably 5,000 cP or less.

In one aspect, the viscosity of the curable composition of the present disclosure is 100 to 10,000 cP, preferably 300 to 7,000 cP, and more preferably 500 to 5,000 cP.

In one aspect, the curable composition of the present disclosure is a surface treatment agent.

The present disclosure provides a hardened product obtained by hardening the curable composition of the present disclosure.

The tensile elastic modulus of the hardened material of the present disclosure is preferably 0.5 to 500MPa, more preferably 0.6 to 300MPa, and even more preferably 0.7 to 100MPa.

The above tensile elastic modulus can be determined using Autograph (AGS-J manufactured by Shimadzu Corporation, dynamometer: 50N, at room temperature, distance between chucks: 40mm, test speed: 5.0mm/min, test piece: width 1cm, height 6cm , film thickness 130μm) measured.

The hardened material of the present disclosure is preferably a sealing material.

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

The present disclosure includes a base material and a layer (hereinafter referred to as "surface treatment layer") formed by hardening the curable composition of the present disclosure on the base material.

Substrates that can be used in the present disclosure include glass, resin (natural or synthetic resin, such as general plastic materials), OCA (Optical Clear Adhesive), polarizing plate metal, ceramics, semiconductors (silicon, germanium, etc.) , electronic equipment, fibers (fabrics, non-woven fabrics, etc.), fur, leather, wood, ceramics, stone and other building components, sanitary products, and any appropriate materials.

In a preferred aspect, the above-mentioned substrate is glass, resin, polarizing plate, OCA (Optical Clear Adhesive: optical glue) or metal, preferably glass, resin, polarizing plate or OCA (Optical Clear Adhesive: optical glue).

The above-mentioned glass is preferably sapphire glass, soda-lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass, quartz glass, and particularly preferably chemically strengthened soda-lime glass, chemically strengthened alkali aluminosilicate Glass, and chemically bonded borosilicate glass.

For example, when the article to be manufactured is an optical component, the material constituting the surface of the base material can be a material for optical components, such as glass or transparent plastic. In addition, when the article to be manufactured is an optical component, any layer (or film), such as a hard coating layer or an anti-reflective layer, can be formed on the surface of the base material (outermost layer). As the anti-reflection layer, either a single-layer anti-reflection layer or a multi-layer anti-reflection layer can be used. Examples of inorganic substances that can be used in the anti-reflective layer include: SiO ₂ , SiO, ZrO ₂ , TiO ₂ , TiO, Ti ₂ O ₃ , Ti ₂ O ₅ , Al ₂ O ₃ , Ta ₂ O ₅ , Ta ₃ O ₅ , Nb ₂ O ₅ , HfO ₂ , Si ₃ N ₄ , CeO ₂ , MgO, Y ₂ O ₃ , SnO ₂ , MgF ₂ , WO ₃ , etc. These inorganic substances can be used alone or in combination of two or more of them (for example, a mixture). When forming a multi-layer anti-reflection layer, the outermost layer is preferably made of SiO ₂ and/or SiO. When the article to be manufactured is an optical glass part for a touch panel, a transparent electrode may be provided on a part of the surface of the base material (glass), for example, a thin film of indium tin oxide (ITO) or indium zinc oxide may be used. In addition, the base material can have an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomized film layer, a hard coating layer, a polarizing film, a phase difference film, and a liquid crystal display according to its specific specifications. Modules etc.

The shape of the above-mentioned base material is not particularly limited, and may be, for example, plate-shaped, film-shaped, or other forms. In addition, the surface area of the base material to be formed with the surface treatment layer only needs to be at least a part of the surface of the base material, and can be appropriately determined according to the use and specific specifications of the article to be produced.

The article of the present disclosure can be manufactured by forming a layer of the composition of the present disclosure on the surface of the above-mentioned substrate, and optionally post-processing the layer, thereby forming a layer of the composition of the present disclosure.

The layer formation of the composition of the present disclosure can be implemented by applying the above composition to the surface of the substrate to cover the surface. The covering method is not particularly limited. For example, a wet coating method and a dry coating method can be used.

Examples of wet coating methods include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating, and similar methods.

Examples of dry coating methods include evaporation (usually vacuum evaporation), sputtering, CVD and similar methods. Specific examples of the evaporation method (generally vacuum evaporation method) include resistance heating, high-frequency heating using electron beams, microwaves, etc., ion beams, and similar methods. Specific examples of the CVD method include plasma-CVD, optical CVD, thermal CVD and similar methods.

In addition, it can be coated by normal pressure plasma method.

When using the dry coating method, the curable composition of the present disclosure can be directly subjected to the dry coating method, or can be diluted with the above-mentioned organic solvent and then subjected to the dry coating method.

The formation of the layer of the curable composition of the present disclosure is preferably carried out in such a manner that the curable composition of the present disclosure is present together with a catalyst for hydrolysis and dehydration condensation in the layer. For convenience, when implementing the wet coating method, after diluting the curable composition of the present disclosure with a solvent, a catalyst can be added to the diluted solution of the curable composition of the present disclosure before applying to the surface of the substrate. When implemented by the dry coating method, the curable composition of the present disclosure with the addition of a catalyst can be directly subjected to evaporation (usually vacuum evaporation), or it can be used A porous metal such as iron or copper is impregnated with a curable composition disclosed in this disclosure and a catalyst is added thereto, and an ingot-shaped substance is evaporated (usually vacuum evaporated).

Any suitable acid or alkali can be used as the catalyst. As the acid catalyst, for example, hydrochloric acid, acetic acid, formic acid, trifluoroacetic acid, etc. can be used. Moreover, as an alkali catalyst, ammonia, organic amines, etc. can be used, for example.

The surface treatment layer included in the articles of the present disclosure has synovial properties. In addition, in addition to having high synoviality, the above-mentioned surface treatment layer can also have antibacterial properties, water repellency, oil repellency, antifouling properties (for example, preventing the adhesion of dirt such as fingerprints), and waterproof properties (for example, depending on the composition of the composition used). Preventing water from intruding into electronic parts, etc.), surface smoothness (or lubricity, wiping off dirt such as fingerprints, or excellent touch with fingers), etc., can be suitably used as a functional film.

In a preferred aspect, the article disclosed herein can be used in vehicle, ship or aircraft glass or mirror glass, such as automotive glass, automotive side mirrors or automotive fender rearview mirrors, etc., or for automotive cameras. Use glass, etc. In addition, it can be used as a base material for outdoor use such as glass used in anti-theft cameras or corner mirrors.

Therefore, the present disclosure further relates to optical materials having the above-mentioned surface treatment layer on the outermost layer.

Optical materials include, in addition to optical materials related to displays and the like exemplified below, various optical materials such as cathode ray tubes (CRT; for example, computer screens), liquid crystal displays, plasma displays, and organic EL. Displays, inorganic thin film EL dot matrix displays, rear projection displays, fluorescent display tubes (VFD), field emission displays (FED; Field Emission Display) and other displays or protective boards of these displays, or anti-reflective coatings implemented on these surfaces Reflective film processor.

The object of the present disclosure is not particularly limited and may be an optical component. Examples of optical components include: lenses for glasses, etc.; front protection plates, anti-reflection plates, polarizing plates, etc. for monitors such as PDP and LCD. Anti-glare boards; touch panels for mobile phones, mobile information terminals and other machines; disc surfaces for Blu-ray (registered trademark) discs, DVD discs, CD-R, MO and other discs; optical fibers; display surfaces for watches and clocks wait.

In addition, the articles disclosed herein may be medical machines or medical materials.

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

The above describes in detail the fluoropolyether group-containing thiol compound, curable composition, cured product, etc. of the present disclosure. In addition, the fluoropolyether group-containing thiol compound, curable composition, cured product, etc. of the present disclosure are not limited to those illustrated above.

(Example)

The fluoropolyether group-containing thiol compound and curable composition of the present disclosure will be more specifically explained through the following examples, but the present disclosure is not limited to these examples. In addition, in this example, the order in which the repeating units constituting the fluoropolyether exists is arbitrary, and the chemical formula shown below represents the average composition.

(Measurement of viscosity)

For the composition shown in Table 2, which is a mixture of an unsaturated compound containing a fluoropolyether group, a thiol compound containing a fluoropolyether group, and a photopolymerization initiator, type TV-10 manufactured by Toki Sangyo Co., Ltd. The viscometer (spindle No. THM1) measures the viscosity at a rotation speed of 1.0 rpm and a measurement temperature of 25°C.

(Measurement of tensile elastic modulus)

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

1. Synthesis of unsaturated compounds containing fluoropolyether groups

Synthesis Example 1 Synthesis of Compound (A-1)

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

Compound(1)

Compound (A-1)

Synthesis Example 2 Synthesis of Compound (A-2)

Add 20g of perfluoropolyether diester shown in formula (2) (average composition: m=15, n=12) and 2.64g of 2,2-diallylpent-4-en-1-amine into the flask and place in the flask. By stirring at room temperature under reduced pressure, 20.5 g of a perfluoropolyether compound having an allyl group represented by the following formula (A-2) was obtained. The number average molecular weight of the compound measured by ¹⁹ F-NMR was 2700, and the viscosity of the compound was 400 cP.

Compound(2)

Compound (A-2)

Synthesis Example 3 Synthesis of Compound (A-3)

According to the method described in Example 6 of Japanese Patent Application Laid-Open No. 2016-204656, 10 g of perfluoropolyether diester (average composition: m=15, n=12) represented by formula (2) was used as a raw material to obtain the following formula 8.52 g of the perfluoropolyether compound having an allyl group shown in (A-3). The number average molecular weight of the compound measured by ¹⁹ F-NMR was 2600, and the viscosity of the compound was 300 cP.

Compound (A-3)

2. Synthesis of thiol compounds containing fluoropolyether groups

Synthesis Example 4 Synthesis of Compound (B-1)

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

Add 100g of the perfluoropolyether diester shown in formula (2) (average composition: m=15, n=12) and 8.4g of diethanolamine into the flask and stir at 70°C under reduced pressure overnight to obtain the formula ( 104.8 g of the perfluoropolyether compound having a hydroxyl group represented by X-1).

Compound (X-1)

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

Add 104.8 g of the compound represented by formula (X-1) obtained in Example 4-1, 300 mL of 1,3-bis(trifluoromethyl)benzene, and 20 g of triethylamine into the flask, and add 2-bromine dropwise in an ice bath. 41.5g of propyl bromide, react overnight. After washing the reaction liquid, the solvent was distilled off, thereby obtaining 108 g of a perfluoropolyether compound having a bromine group represented by formula (X-2).

Compound (X-2)

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

Add 108g of the compound represented by 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 into the flask. React at room temperature overnight. After washing the reaction liquid with water, the solvent was distilled off, thereby obtaining 111.7 g of a perfluoropolyether compound having a xanthate group represented by formula (X-3).

Compound (X-3)

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

110 g of the compound represented by formula (X-3) obtained in Example 4-3, 550 mL of 1,3-bis(trifluoromethyl)benzene, and 17.1 mL of n-butylamine were added to the flask, and the reaction was carried out in an ice bath for 4 hours. After washing the reaction liquid, hexane was added dropwise, thereby obtaining 67.2 g of a perfluoropolyether compound having a thiol group represented by formula (B-1). The number average molecular weight of the compound measured by ¹⁹ F-NMR was 3100, and the viscosity of the compound was 2200 cP.

Compound (B-1)

Synthesis Example 5 Synthesis of Compound (B-2)

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

Add 15g of perfluoropolyether glycol of formula (3) (average composition: m=10, n=10), 18g of propylene bromide, 0.48g of tetrabutylammonium bromide, and 0.69g of sodium hydroxide into the flask, and place at 70 °C and stir overnight. The reaction liquid was separated, washed, and the solvent was distilled off to obtain 13.9 g of a perfluoropolyether compound having an allyl group represented by formula (Y-1).

Compound(3)

Compound (Y-1)

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

Add 12 g of the compound represented by formula (Y-1), 13 mL of 1,3-bis(trifluoromethyl)benzene, and 4.5 mL of methylene chloride into the flask and dissolve them. After adding 3.42 g of p-chloroperoxybenzoic acid, React overnight at 40°C. The reaction liquid was washed, and the solvent was distilled off to obtain 9.70 g of a perfluoropolyether compound having an epoxy group represented by formula (Y-2).

Compound(Y-2)

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

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

Compound (Y-3)

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

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

Compound (B-2)

Synthesis Example 6 Synthesis of Compound (B-3)

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

Compound (B-3)

Synthesis Example 7 Synthesis of Compound (B-4)

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

Compound(4)

CF ₃ CF ₂ CF ₂ O(CF ₂ CF ₂ CF ₂ O) _m CF ₂ CF ₂ CH ₂ OH

Compound (B-4)

Synthesis Example 8 Synthesis of Compound (B-5)

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

10.0 g of the perfluoropolyether compound having an allyl group represented by formula (A-1), 30 mL of 1,3-bis(trifluoromethyl)benzene, 2.44 g of thioacetic acid, and AIBN (azobisisobutyl Nitrile) 0.263g was added to the flask and reacted at 80°C. The reaction liquid was washed with water to obtain 8.97g of the perfluoropolyether compound represented by formula (Z-1).

Compound (Z-1)

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

8.97 g of the compound represented by formula (Z-1), 50 mL of Novec7200 (manufactured by 3M Company), and 5 mL of methanol were added to the flask and stirred. 0.41g of sodium was added to generate sodium methoxide, and the acetyl group was deprotected at room temperature for 1 hour. The reaction liquid was washed with hydrochloric acid, and the solvent was distilled off to obtain 7.53 g of a perfluoropolyether compound having a thiol group represented by formula (B-5). The number average molecular weight of the compound measured by ¹⁹ F-NMR was 2800, and the viscosity of the compound was 1500 cP.

Compound (B-5)

Synthesis Example 9 Synthesis of Compound (A-4)

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

Add 2.32g of the compound represented by compound (Y-1), 7.2mL of 1,3-bis(trifluoromethyl)benzene, 0.030g of triacetyloxymethylsilane and 0.686g of trichlorosilane, and stir at 5°C. 30 minutes. After adding 0.050 mL of a 2% xylene solution of the Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, the mixture was stirred at 60°C for 5 hours. Thereafter, volatile components were distilled off, thereby obtaining 1.97 g of a perfluoropolyether compound having a trichlorosilyl group represented by formula (R-1).

Compound (R-1)

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

1.15 g of the compound represented by formula (R-1) and 3.6 mL of 1,3-bis(trifluoromethyl)benzene were added, and stirred at 5°C for 30 minutes. Next, 6.22 ml of a 0.9 M diethyl ether solution of allyl magnesium bromide was added, followed by stirring at room temperature for 10 hours. Thereafter, the mixture was cooled to 5°C, 1.78 mL of methanol was added, and the insoluble matter was filtered. Next, after the volatile components were distilled off, the non-volatile components were diluted with perfluorohexane, washed with methanol, and the solvent was distilled off, thereby obtaining 1.12 g of a perfluoropolyether compound having an allyl group represented by formula (A-4). The number average molecular weight of the compound measured by ¹⁹ F-NMR was 2400, and the viscosity of the compound was 400 cP.

Compound (A-4)

Synthesis Example 10 Synthesis of Compound (B-6)

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

Except using 17 g of perfluoropolyether diol (m=12) of formula (5) to replace the perfluoropolyether of formula (3), obtain formula (S-1) in the same manner as (Example 5-1). Indicates 15.2 g of a perfluoropolyether compound having an allyl group.

Compound(5)

HOCH ₂ CF ₂ CF ₂ O(CF ₂ CF ₂ CF ₂ O) _n CF ₂ CF ₂ CH ₂ OH

Compound (S-1)

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

Except using 14 g of the compound represented by the formula (S-1) instead of the compound represented by the formula (Y-1), the formula (S-2) having an epoxy group was obtained in the same manner as in (Example 5-2). 11.2g of perfluoropolyether compound.

Compound (S-2)

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

Except using 8.1 g of the compound represented by formula (S-2) instead of the compound represented by formula (Y-2), the perfluorinated compound represented by formula (S-3) was obtained in the same manner as (Example 5-3). Polyether compound.

Compound (S-3)

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

Except using 5.3g of the compound represented by the formula (S-3) instead of the compound represented by the formula (Y-3), in the same manner as (Example 5-4), a thiol represented by the formula (B-6) was obtained Based on perfluoropolyether compounds. The number average molecular weight of the compound measured by ¹⁹ F-NMR was 2750, and the viscosity of the compound was 1400 cP.

Compound (B-6)

Example

1. Storage stability of thiol compounds containing fluoropolyether groups

Take 1 mL of the fluoropolyether group-containing thiol compounds (B-1) to (B-6) obtained in Synthesis Examples 4 to 8, respectively, and put them into a screw-top bottle (No. 3), and leave them at room temperature and in the air for 2 weeks. Draw a horizontal line 3cm from the bottom of the screw-top bottle, tilt the screw-top bottle sideways and measure the time for the liquid end to pass the horizontal line. Compare the above measurement time of the initial sample and the sample after 2 weeks. The evaluation criteria are as follows, and the results are shown in Table 1.

G: The measurement time of the sample after 2 weeks was less than twice that of the initial sample.

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

[Table 1]

Examples 1 to 8 and Comparative Examples 1 to 2

2. Preparation and viscosity measurement of hardening composition

The fluoropolyether group-containing unsaturated compounds obtained in Synthesis Examples 1 to 3 and 9 and the fluoropolyether group-containing thiol compounds obtained in Synthesis Examples 4 to 8 and 10 were mixed so that the equivalents of allyl groups and thiol groups were the same. and further mixed 2 parts by mass of Omnirad 184 (manufactured by IGMResins B.V.) as the photopolymerization initiator (C) to obtain curable compositions 1 to 10. The composition is presented in Table 2. In addition, curable compositions 1 to 6, 9 and 10 are examples, and curable compositions 7 to 8 are comparative examples. Moreover, the viscosity of these curable compositions was measured at 25°C.

3. Hardening test

The curable compositions 1 to 10 of Examples 1 to 8 and Comparative Examples 1 to 2 were applied to the glass plate of the base material with an applicator so that the film thickness became 100 μm, and the feasibility of irradiation with ultraviolet rays (wavelength: 365 nm) was investigated to produce Hardened coating. The irradiation dose is 1000mJ/cm ² . The evaluation criteria are as follows. The results are presented in Table 2.

VG: A hardened coating film is obtained and the surface is non-sticky.

G: Hardened and unable to flow.

NG: Cannot be hardened and is liquid.

[Table 2]

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

From the results in Table 1, it can be confirmed that compared with the fluoropolyether group-containing thiol compound (B-5) having a primary thiol group, the fluoropolyether group-containing thiol compound (B-5) having a secondary thiol group is -1) to (B-4), and (B-6) can suppress viscosity increase and have excellent stability in air.

It can be confirmed from the results in Table 2 that compared to Comparative Example 1 including the fluoropolyether group-containing thiol compound (B-4) having only one secondary thiol group, and the composition including a plurality of primary Comparative Example 2 of a composition of a thiol group-containing fluoropolyether group-containing thiol compound (B-5), including a fluoropolyether group-containing thiol compound (B-1) having a plurality of secondary thiol groups at the terminal ) to (B-3) and (B-6), the ultraviolet curing properties of Examples 1 to 8 are more excellent.

(industrial applicability)

The fluoropolyether group-containing thiol compound of the present disclosure can be used in various applications, such as being suitable as a coating agent.

Claims (47)

A fluoropolyether group-containing thiol compound contains two or more thiol groups selected from secondary thiol groups and tertiary thiol groups. The thiol compound containing a fluoropolyether group as described in claim 1, wherein the fluorine content is 30% by mass or more. The fluoropolyether group-containing thiol compound as described in claim 1 or 2, which contains 2 to 6 aforementioned thiol groups. The fluoropolyether group-containing thiol compound as described in any one of claims 1 to 3, wherein the aforementioned thiol group is a secondary thiol group. The thiol compound containing a fluoropolyether group according to any one of claims 1 to 4, wherein the thiol group is present on both ends of the fluoropolyether group. The fluoropolyether group-containing thiol compound according to any one of claims 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) [In the formula: 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 by more than 1 fluorine atom, Rf ² is a C _1-6 alkylene group which may be substituted by more than one fluorine atom, R ^F are each independently a divalent fluoropolyether group, p is 0 or 1, q is each independently 0 or 1, X ^A is each independently a single bond or an organic group with 2 to 10 valences, R ^S is each independently a monovalent group containing a group represented by -CR ¹ R ² -SH, R ¹ is a hydrocarbon group, R ² is a hydrogen atom or a hydrocarbon group, In formulas (1) and (2), there are at least 2 groups represented by -CR ¹ R ² -SH. α1 is an integer from 1 to 9, α2 is an integer from 1 to 9, β is each independently an integer from 1 to 9]. The fluoropolyether group-containing thiol compound as described in claim 6, wherein Rf ¹ is each independently a C _1-16 perfluoroalkyl group, Rf ² is each independently a C _1-6 perfluoroalkylene group. The thiol compound containing a fluoropolyether group as described in claim 6 or 7, wherein R ^F is each independently a group represented by the following formula: -(OC ₆ F ₁₂ ) _a -(OC ₅ F ₁₀ ) _b -(OC ₄ F ₈ ) _c -(OC ₃ R ^Fa ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - [In the formula, R ^Fa 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 from 0 to 200. The sum of a, b, c, d, e and f is 1 or more. The sum of a, b, c, d, e or f The order in which the repeating units enclosed in parentheses are present in the formula is arbitrary, but when all R ^Fa are hydrogen atoms or chlorine atoms, at least one of a, b, c, e and f is 1 or more]. The thiol compound containing a fluoropolyether group as described in claim 8, wherein R ^Fa is a fluorine atom. The fluoropolyether group-containing thiol compound as described in any one of claims 6 to 9, wherein R ^F is each independently the following formula (f1), (f2), (f3), (f4), ( f5), or the basis shown in (f6), -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e - (f1) [In the formula, d is an integer from 1 to 200, and e is 0 or 1]; -(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f2) [In the formula, c and d are each independently an integer from 0 to 30, e and f are each independently an integer from 1 to 200, The sum of c, d, e and f is an integer from 10 to 200, The order of existence of each repeating unit enclosed by parentheses of subscript c, d, e or f is arbitrary in the formula]; -(R ⁶ -R ⁷ ) _g - (f3) [In the formula, R ⁶ is OCF ₂ or OC ₂ F ₄ , R ⁷ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or a combination of 2 or 3 groups selected from these groups, g is an integer from 2 to 100]; -(R ⁶ -R ⁷ ) _g -R ^r -(R ^7' -R ^6' ) _g' - (f4) [In the formula, R ⁶ is OCF ₂ or OC ₂ F ₄ , R ⁷ is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or a combination of 2 or 3 groups independently selected from these groups, R ^6' is OCF ₂ or OC ₂ F ₄ , R ^7' is a group selected from OC ₂ F ₄ , OC ₃ F ₆ , OC ₄ F ₈ , OC ₅ F ₁₀ and OC ₆ F ₁₂ , or a combination of 2 or 3 groups independently selected from these groups, g is an integer from 2 to 100, g’ is an integer from 2 to 100, R ^r is

(In the formula, * represents the bonding position)]; -(OC ₆ F ₁₂ ) _a -(OC ₅ F ₁₀ ) _b -(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f5) [In the formula, e is an integer from 1 to 200, a, b, c, d and f are each independently an integer from 0 to 200, and a, b, c, d, e or f are enclosed in parentheses The order of existence of each repeating unit in the formula is arbitrary]; -(OC ₆ F ₁₂ ) _a -(OC ₅ F ₁₀ ) _b -(OC ₄ F ₈ ) _c -(OC ₃ F ₆ ) _d -(OC ₂ F ₄ ) _e -(OCF ₂ ) _f - (f6) [In the formula, f is an integer from 1 to 200, a, b, c, d and e are each independently an integer from 0 to 200, and a, b, c, d, e or f are enclosed in parentheses The order of existence of each repeating unit in the formula is arbitrary]. The fluoropolyether group-containing thiol compound as described in any one of claims 6 to 10, wherein R ^S is a group represented by the following formula (S1), (S2), or (S3), -R ^Sa (S1) -NR ^Sa _n1 R ³ _2-n1 (S2) -CR ^Sa _n2 R ³ _3-n2 (S3) [In the formula: R ^Sa is -Z-CR ¹ R ² -SH, Z is a single bond or a 2-valent base, R ¹ is a hydrocarbon group, R ² is a hydrogen atom or a hydrocarbon group, R ³ is a hydrogen atom or a hydrocarbon group, n1 is 1 or 2, n2 is 1, 2 or 3]. The fluoropolyether group-containing thiol compound as described in claim 11, wherein Z is -R ¹¹ -R ¹² -, R ¹¹ is a single bond or C _1-6 alkylene group, R ¹² is -OCO-(CH ₂ ) _m -, m is an integer from 0 to 6. The fluoropolyether group-containing thiol compound as described in any one of claims 6 to 12, wherein R ¹ is a C _1-6 alkyl group, and R ² is a hydrogen atom or a C _1-6 alkyl group. The fluoropolyether group-containing thiol compound as described in any one of claims 11 to 13, wherein R ³ is a hydrogen atom or a C _1-6 alkyl group. The thiol compound containing a fluoropolyether group as described in any one of claims 11 to 14, wherein R ^S is a group represented by formula (S2) or (S3). The thiol compound containing a fluoropolyether group as described in any one of claims 11 to 15, wherein R ^S is a group represented by formula (S2). The thiol compound containing a fluoropolyether group as described in any one of claims 11 to 15, wherein R ^S is a group represented by formula (S3). The fluoropolyether group-containing thiol compound as described in any one of claims 6 to 17, wherein α1, α2, and β are 1. The thiol compound containing a fluoropolyether group as described in any one of claims 6 to 18, wherein X ^A is a group represented by the following formula, -(R ²¹ ) _m1 -(R ²² ) _m2 - [In the formula: R ²¹ is C _1-6 alkylene group, R ²² is -O-, -CO-, -OCO-, -COO-, -NR ²³ -, -CONR ²³ -, or -NR ²³ CO-, R ²³ is a hydrogen atom or C _1-6 alkyl group, m1 is an integer from 0 to 10, m2 is an integer from 0 to 10, The total of m1 and m2 is more than 1, The order of existence of R ²¹ and R ²² is arbitrary in the formula]. The thiol compound containing a fluoropolyether group as described in any one of claims 1 to 18 has a number average molecular weight of 1,000 to 100,000. The thiol compound containing a fluoropolyether group as described in any one of claims 1 to 20 has a viscosity of 100 to 10000 cP. A curable composition containing the thiol compound containing a fluoropolyether group as described in any one of claims 1 to 21. The curable composition according to claim 22, further comprising an unsaturated compound containing a fluoropolyether group containing a group having a carbon-carbon double bond. The curable composition according to claim 23, wherein the number of the aforementioned groups having carbon-carbon double bonds is 2 to 8. The curable composition according to claim 23 or 24, wherein the group having a carbon-carbon double bond is an allyl group, a vinyl group, or a (meth)acrylyl group. The curable composition according to any one of claims 23 to 25, wherein the group having a carbon-carbon double bond is an allyl group. The curable composition according to any one of claims 23 to 26, wherein the group having a carbon-carbon double bond is present on both ends of the fluoropolyether group. The curable composition according to any one of claims 23 to 27, wherein 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 _δ (4) [In the formula: 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 by more than 1 fluorine atom, Rf ² is a C _1-6 alkylene group which may be substituted by more than one fluorine atom, R ^F are each independently a divalent fluoropolyether group, p is 0 or 1, q is each independently 0 or 1, X ^B is each independently a single bond or an organic group with 2 to 10 valences, R ^D are each independently a group having a carbon-carbon double bond, γ1 is an integer from 1 to 9, γ2 is an integer from 1 to 9, δ is each independently an integer from 1 to 9]. The curable composition according to claim 28, wherein the aforementioned group having a carbon-carbon double bond is a group represented by the following formula: -Y-A [In the formula: Y is a single bond, oxygen atom or divalent organic group, A is -CR ⁴¹ =CH ₂ , R ⁴¹ is each independently a hydrogen atom or C _1-3 alkyl group]. The curable composition as described in claim 28 or 29, wherein Y is -CR ⁴² ₂ - or -CO-, R ⁴² is each independently a hydrogen atom or a C _1-6 alkyl group. The curable composition according to any one of claims 28 to 30, wherein R ^D is a base represented by the following formula (D1), (D2), (D3), (D4) or (D5), -Y-A (D1)

-SiR ^a1 _k1 R ^b1 _l1 R ^c1 _m1 (D3) -CR ^d1 _k2 R ^e1 _l2 R ^f1 _m2 (D4) -NR ^g1 R ^h1 (D5) [In the formula, Y is a single bond, oxygen atom or divalent organic group, A is -CR ⁴¹ =CH ₂ , R ⁴¹ is each independently a hydrogen atom or a C _1-3 alkyl group, Each time X ¹⁰ appears, it is independently a single bond or a divalent organic radical. R ¹³ is independently a hydrogen atom or a monovalent organic group each time it appears, Each occurrence of t is independently an integer above 2, Each occurrence of R ¹⁴ is independently a hydrogen atom or a halogen atom, R ^a1 is independently -Z ¹ -SiR ^a2 _p1 R ^a3 _q1 R ^a4 _r1 on each occurrence, Z ¹ is independently a single bond, an oxygen atom or a divalent organic group each time it appears, R ^a2 is independently -Z ^1' -SiR ^a3' _q1' R ^a4' _r1' on each occurrence, Z ^1' is independently a single bond, an oxygen atom or a divalent organic group each time it appears, R ^a3' is independently -Z ² -YA on each occurrence, Each occurrence of R ^a4' is independently a hydrogen atom, a hydroxyl group or a monovalent organic group, Each time Z ² appears, it is independently a single bond, an oxygen atom or a divalent organic group, q1’ is independently an integer from 0 to 3 each time it appears, r1’ is independently an integer from 0 to 3 on each occurrence, Here, the total of q1' and r1' is 3 in the (SiR ^a3' _q1' R ^a4' _r1' ) unit, R ^a3 is independently -Z ² -YA on each occurrence, Each occurrence of R ^a4 is independently a hydrogen atom, a hydroxyl group or a monovalent organic group, p1 is independently an integer from 0 to 3 on each occurrence, q1 is independently an integer from 0 to 3 on each occurrence, r1 is independently an integer from 0 to 3 on each occurrence, Here, the total of p1, q1 and r1 is 3 in the (SiR ^a2 _p1 R ^a3 _q1 R ^a4 _r1 ) unit, R ^b1 is independently -Z ² -YA on each occurrence, Each time R ^c1 appears, it is independently a hydrogen atom, a hydroxyl group or a monovalent organic group, k1 is independently an integer from 0 to 3 on each occurrence, l1 is independently an integer from 0 to 3 each time it appears, m1 is independently an integer from 0 to 3 on each occurrence, Here, the total of k1, l1, and m1 is 3 in the (SiR ^a1 _k1 R ^b1 _l1 R ^c1 _m1 ) unit, In formula (D3), there is at least 1 -Y-A, R ^d1 is independently -Z ³ -CR ^d2 _p2 R ^d3 _q2 R ^d4 _r2 on each occurrence, Each time Z ³ appears, it is independently a single bond, an oxygen atom or a divalent organic group, R ^d2 is independently -Z ^3' -CR ^d3' _q2' R ^d4' _r2' on each occurrence, Z ^3' is independently an oxygen atom or a divalent organic group each time it appears, R ^d3' is independently -Z ² -YA on each occurrence, Each time R ^d4' appears, it is independently a hydrogen atom, a hydroxyl group or a monovalent organic group, q2’ is independently an integer from 0 to 3 each time it appears, r2’ is independently an integer from 0 to 3 on each occurrence, Here, the total of q2' and r2' is 3 in the (CR ^d3' _q2' R ^d4' _r2' ) unit, R ^d3 is independently -Z ² -YA on each occurrence; R ^d4 is independently a hydrogen atom, a hydroxyl group or a monovalent organic group each time it appears; p2 is independently an integer from 0 to 3 each time it appears; q2 is independently an integer from 0 to 3 each time it appears; r2 is independently an integer from 0 to 3 on each occurrence; Here, the total of p2, q2 and r2 in the (CR ^d2 _p2 R ^d3 _q2 R ^d4 _r2 ) unit is 3, R ^e1 is independently -Z ² -YA on each occurrence, Each occurrence of R ^f1 is independently a hydrogen atom, a hydroxyl group or a monovalent organic group, k2 is independently an integer from 0 to 3 on each occurrence, l2 is independently an integer from 0 to 3 each time it appears, m2 is independently an integer from 0 to 3 on each occurrence, Here, the total of k2, l2, and m2 is 3 in the (CR ^d1 _k2 R ^e1 _l2 R ^f1 _m2 ) unit, In formula (D4), there is at least 1 A, Each occurrence of R ^g1 and R ^h1 is independently -Z ⁴ -YA, -Z ⁴ -SiR ^a1 _k1 R ^b1 _l1 R ^c1 _m1 , or -Z ⁴ -CR ^d1 _k2 R ^e1 _l2 R ^f1 _m2 , Z ⁴ is independently a single bond, an oxygen atom or a divalent organic radical each time it appears. In formula (D5), there is at least 1 A]. The curable composition according to any one of claims 28 to 31, wherein X ^B is each independently a divalent group represented by the following formula, -{(R ³¹ ) _p' -(X ^a ) _q' }-R ³² - [In the formula: R ³¹ is a single bond, -(CH ₂ ) _s' -or ortho-, meta- or p-phenylene group, R ³² is a single bond, -(CH ₂ ) _t' -or ortho-, meta- or p-phenylene group, s’ is an integer from 1 to 20, t’ is an integer from 1 to 20, X ^a represents -(X ^b ) _r' -, _Each occurrence ^of o-, m- or p-phenylene, -C(O)O-, -CONR ³⁴ -, -O-CONR ³⁴ -, -NR ³⁴ -, -Si(R ³³ ) ₂ -, -(Si (R ³³ ) ₂ O) _m' -Si(R ³³ ) ₂ -, and -(CH ₂ ) _n' -, R ^33, on each occurrence, is independently phenyl, C _1-6 alkyl or C _1-6 alkoxy, Each occurrence of R ³⁴ is independently a hydrogen atom, a phenyl group or a C _1-6 alkyl group, Each occurrence of m’ is independently an integer from 1 to 100, n’ is independently an integer from 1 to 20 on each occurrence, r’ is an integer from 1 to 10, p’ is 0 or 1, q’ is 0 or 1, Here, at least one of p' and q' is 1, and the order in which the repeating units enclosed in parentheses of p' or q' exists is arbitrary]. The curable composition according to any one of claims 23 to 32, wherein the mass ratio of the thiol compound containing a fluoropolyether group and the unsaturated compound containing a fluoropolyether group is 0.1:100 to 100 :0.1. The curable composition according to any one of claims 22 to 33, further containing a polymerization initiator. The curable composition according to claim 34, wherein the polymerization initiator is a radical polymerization initiator. The curable composition according to claim 34, wherein the polymerization initiator is a radical photopolymerization initiator. The curable composition according to claim 34, wherein the polymerization initiator has 1 to 3 aromatic ring structures. The curable composition according to any one of claims 22 to 37, further containing a fluorine-containing oil. The curable composition according to claim 38, wherein the fluorine-containing oil is a compound represented by the following formula (5), Rf ⁵ -(OC ₄ F ₈ ) _a' -(OC ₃ F ₆ ) _b' -(OC ₂ F ₄ ) _c' -(OCF ₂ ) _d' -Rf ⁶ ． ． ． (5) [In the formula: Rf ⁵ is a C _1-16 alkyl group which may be substituted by more than one fluorine atom, Rf ⁶ is a C _1-16 alkyl group, a fluorine atom or a hydrogen atom that may be substituted by more than one fluorine atom, a’, b’, c’ and d’ are each independently an integer between 0 and 300, The order of existence of each repeating unit enclosed in parentheses of the subscript a', b', c' or d' is arbitrary in the formula]. The curable composition according to any one of claims 22 to 39, which is solvent-free. The curable composition as described in any one of claims 22 to 39 has a viscosity of 100 to 10000 cP. A hardened material obtained by hardening the curable composition described in any one of claims 22 to 41. The hardened material according to claim 42 has a tensile elastic modulus of 0.5 to 500 MPa. The hardened material according to claim 42, which is a sealing material. The hardened material according to claim 42, which is a sealing material for electronic equipment. An article includes a base material and a layer on the base material hardened by the curable composition according to any one of claims 22 to 41. A compound represented by formula (c1), (OH-X ¹² ) ₂ NCO-X ¹¹ -R ^F2 -X ¹¹ -CON(X ¹² -OH) ₂ (c1) [In the formula: R ^F2 is -Rf ² _p -R ^F -O _q -, Rf ² is a C _1-6 alkylene group which may be substituted by more than one fluorine atom, R ^F are each independently a divalent fluoropolyether group, p is 0 or 1, q is each independently 0 or 1, X ¹¹ is a single bond or a divalent hydrocarbon group, X ¹² is a divalent hydrocarbon group].