JP2009242318A - Polyfunctional fluorine-containing compound, and method of producing the same - Google Patents

Abstract

The present invention provides a polyfunctional fluorine-containing compound, a process for producing the compound, a crosslinking agent comprising the compound, a curable composition containing the compound, and a cured product obtained by curing the composition. 1)
—S—CX ₂ CHF—Z—O—Rf (1)
[In the formula, Rf is a fluorine-containing alkyl group having 1 to 40 carbon atoms having a substituent, or a fluorine-containing alkyl group having 2 to 100 carbon atoms having a substituent, and the substituent is —OH, From —CH ₂ OH, —COOR ¹ , —CONR ² R ³ , —NH ₂ , —COCl, —SO ₂ F, —CN, —COOH, —COOH derivatives, —SO ₃ H and —SO ₃ H derivatives At least one selected from the group consisting of: R ¹ is an alkyl group or a fluorine-containing alkyl group; R ² and R ³ are the same or different and are H, an alkyl group or a fluorine-containing alkyl group; Differently, it is H or F, and Z is —CF ₂ — or a single bond. ]
A compound having two or more groups represented by [Selection] None

Description

  The present invention relates to a polyfunctional fluorine-containing compound, a method for producing the compound, a crosslinking agent comprising the compound, a curable composition containing the compound, and a cured product obtained by curing the composition.

  Fluorine-containing compounds having fluorine atoms in the molecule are excellent in light transmission and light durability, and materials containing fluorine-containing compounds are coating crosslinking agents, curable compositions, and optical device-related sealing. It is used as a material for members. The fluorine-containing compound used for these applications is desired to have a plurality of functional groups in the molecule that react with other components.

  However, the synthesis of the fluorine-containing compound requires a special raw material having a fluorine atom. In addition, since the reactivity of the fluorine-containing compound is often different from that of a general organic compound, it is difficult to obtain a target compound by a general organic synthesis method.

  In particular, a polyfunctional fluorine-containing compound having a plurality of functional groups in the molecule is not easy to synthesize, and when it becomes a polyfunctional fluorine-containing compound having 3 or more functional groups, there is no commercially available one.

Under such circumstances, a novel polyfunctional fluorine-containing compound having a plurality of functional groups in the molecule is demanded.
International Publication WO2004 / 016689 Pamphlet

  An object of the present invention is to provide a polyfunctional fluorine-containing compound, a method for producing the compound, a crosslinking agent comprising the compound, a curable composition containing the compound, and a cured product obtained by curing the composition.

  As a result of intensive studies to solve the above problems, the present inventors have conducted an enethiol reaction between a polyfunctional thiol compound and a fluorine-containing allyl compound having a functional group, or a fluorine-containing compound having a polyfunctional thiol compound and a functional group. It has been found that a novel polyfunctional fluorine-containing compound can be easily synthesized by an enethiol reaction with a vinyl ether compound.

  Since the obtained polyfunctional fluorine-containing compound has a plurality of reactive functional groups in the molecule, it can be suitably used as a crosslinking agent or additive for paints. Moreover, the polyfunctional fluorine-containing compound of the present invention having a plurality of functional groups in the molecule can be used as a curable composition, which can be cured to produce a cured product. The present invention has been completed based on such findings and further studies.

The present invention relates to a novel polyfunctional fluorine-containing compound shown in the following items 1 to 11, a method for producing the compound, a crosslinking agent comprising the compound, a curable composition containing the compound, and a cured product obtained by curing the composition. I will provide a.
Item 1. General formula (1)
—S—CX ₂ CHF—Z—O—Rf (1)
[In the formula, Rf is a fluorine-containing alkyl group having 1 to 40 carbon atoms having a substituent, or a fluorine-containing alkyl group having 2 to 100 carbon atoms having a substituent, and the substituent is —OH, From —CH ₂ OH, —COOR ¹ , —CONR ² R ³ , —NH ₂ , —COCl, —SO ₂ F, —CN, —COOH, —COOH derivatives, —SO ₃ H and —SO ₃ H derivatives At least one selected from the group consisting of: R ¹ is an alkyl group or a fluorine-containing alkyl group; R ² and R ³ are the same or different and are H, an alkyl group or a fluorine-containing alkyl group; Differently, it is H or F, and Z is —CF ₂ — or a single bond. ]
The compound which has two or more groups represented by these.
Item 2. General formula (1a)

[Wherein T is a hydrocarbon which may have at least one heteroatom selected from the group consisting of O, N and S, p is an integer of 2 or more, and X, Z and Rf are Each is the same or different and is the same as above. ]
The compound of claim | item 1 represented by these.
Item 3. General formula (1b)

Wherein R ⁴ is the same or different and is a single bond, —C _a H _2a —, —C _b H _2b —B—C _c H _2c — or —S—C _d H _2d —, a, b, c and d are the same or different and are an integer of 1 or more, B is —S—, —C (═O) O—, —OC (═O) — or —O—, and A is —C _e H _2e - or _{-C f H 2f -E-C g} H 2g - and is, e, f and g are the same or different integer of 1 or more, E is -S -, - C (= O ) O- , —OC (═O) — or —O—, wherein R ⁵ is H, an optionally substituted alkyl group, or —R ⁴ —S—CX ₂ CHF—Z—O—Rf Wherein R ⁶ is H, an alkyl group which may have a substituent, or a group represented by the formula: —R ⁴ —S—CX ₂ CHF—Z—O—Rf, Q is 0 or more Is a number, X, Z and Rf is as defined above the same or different. ]
The compound of claim | item 2 represented by these.
Item 4. General formula (1c)

[Wherein, Q has an optionally substituted aliphatic ring, an optionally substituted heteroaliphatic ring, an optionally substituted aromatic ring or a substituted group. Each of the substituents may be an alkyl group, —OH, —COOR ⁷ , —CONR ⁸ R ⁹ , —NH ₂ , —COCl, —SO ₂ F, —SO ₃ H and At least one selected from the group consisting of —CN, R ⁷ is H, an alkyl group or a fluorine-containing alkyl group, and R ⁸ and R ⁹ are the same or different and are H, an alkyl group or a fluorine-containing alkyl group. , R is an integer of 2 or more, and X, Z and Rf are the same as or different from each other. ]
The compound of claim | item 2 represented by these.
Item 5. Item 5. The compound according to any one of Items 1 to 4, wherein X is H and Z is —CF ₂ —.
Item 6. Item 5. The compound according to any one of Items 1 to 4, wherein X is F and Z is a single bond.
Item 7. Rf is a linear or branched fluorinated alkyl group having 1 to 20 carbon atoms having a substituent, or a linear or branched fluorinated alkyl group having an ether bond having 2 to 50 carbon atoms having a substituent. Any one of Items 1 to 6, wherein the substituent is at least one selected from the group consisting of —OH, —CH ₂ OH, —COOH, —COOR ¹ (wherein R ¹ is the same as above) and —CN. Compound described in 1.
Item 8. Two or more general formulas (1) in the molecule
—S—CX ₂ CHF—Z—O—Rf (1)
[In the formula, Rf is a fluorine-containing alkyl group having 1 to 40 carbon atoms having a substituent, or a fluorine-containing alkyl group having 2 to 100 carbon atoms having a substituent, and the substituent is —OH, ^{_{-CH 2 OH, -COOR 1, -CONR}} 2 R 3, -NH 2, -COCl, -SO 2 F, -SO 3 H, -CN, -COOH, a derivative of -COOH, -SO ₃ H and -SO _And at least one selected from the group consisting of ₃ H derivatives, R ¹ is an alkyl group or a fluorinated alkyl group, and R ² and R ³ are the same or different and are H, an alkyl group or a fluorinated alkyl group. , X are the same or different and are H or F, and Z is —CF ₂ — or a single bond. ]
Wherein the compound having two or more thiol groups in the molecule is represented by the general formula (2).
CX ₂ = CF—Z—O—Rf (2)
[Wherein, X, Z and Rf are the same as defined above. ]
The manufacturing method characterized by making it react with the compound represented by these.
Item 9. Item 7. A coating crosslinking agent comprising the compound according to any one of Items 1 to 6.
Item 10. The curable composition containing the compound in any one of claim | item 1 -6.
Item 11. Item 11. A cured product obtained by curing the curable composition according to Item 10.

Polyfunctional fluorine-containing compound The polyfunctional fluorine-containing compound of the present invention has the following general formula (1).
—S—CX ₂ CHF—Z—O—Rf (1)
[In the formula, Rf is a fluorinated alkyl group having 1 to 40 carbon atoms having a substituent, or a fluorinated alkyl group having an ether bond having 2 to 100 carbon atoms having a substituent,
The substituent is —OH, —CH ₂ OH, —COOR ¹ , —CONR ² R ³ , —NH ₂ , —COCl, —SO ₂ F, —CN, —COOH, a derivative of —COOH, —SO ₃ H and It is at least one selected from the group consisting of derivatives of -SO ₃ H,
R ¹ is an alkyl group or a fluorine-containing alkyl group,
R ² and R ³ are the same or different and are H, an alkyl group or a fluorine-containing alkyl group,
X is the same or different and is H or F;
Z is —CF ₂ — or a single bond. ]
It is a compound which has 2 or more groups represented by these.

  In Rf of the general formula (1), the fluorinated alkyl group of “the fluorinated alkyl group having 1 to 40 carbon atoms having a substituent” is preferably a fluorinated alkyl group having 1 to 20 carbon atoms, and 1 to 10 carbon atoms. The fluorine-containing alkyl group is more preferable. The fluorine-containing alkyl group may be linear, branched or cyclic.

  In Rf of the general formula (1), the alkyl group of “the fluorine-containing alkyl group having an ether bond having 2 to 100 carbon atoms having a substituent” is preferably a fluorine-containing alkyl group having an ether bond having 2 to 50 carbon atoms. A fluorine-containing alkyl group having an ether bond having 2 to 25 carbon atoms is more preferable. The fluorine-containing alkyl group may be linear, branched or cyclic.

In Rf of the general formula (1), as substituents of “a fluorine-containing alkyl group having 1 to 40 carbon atoms having a substituent” and “a fluorine-containing alkyl group having an ether bond having 2 to 100 carbon atoms having a substituent” Is, for example, —OH, —CH ₂ OH, —COOR ¹ , —CONR ² R ³ , —NH ₂ , —COCl, —SO ₂ F, —SO ₃ H, —CN, —COOH, —COOH derivatives, Derivatives of SO ₃ H and —SO ₃ H can be mentioned.

It suffices that at least one of these substituents in Rf of the general formula (1) exists in Rf, and two or more substituents may exist in Rf. That is, in Rf of the general formula (1), “a fluorine-containing alkyl group having 1 to 40 carbon atoms having a substituent” and “a fluorine-containing alkyl group having 2 to 100 carbon atoms having a substituent” , —OH, —CH ₂ OH, —COOR ¹ , —CONR ² R ³ , —NH ₂ , —COCl, —SO ₂ F, —CN, —COOH, —COOH derivatives, —SO ₃ H and —SO ₃ There is at least one substituent selected from the group consisting of derivatives of H.

  The polyfunctional fluorine-containing compound of the present invention having at least two of these substituents can be used as a crosslinking agent for paints because the substituents become functional groups.

Among these substituents, it is preferable to have at least one selected from the group consisting of —OH, —CH ₂ OH, —COOH, —COOR ¹ and —CN in Rf. From the viewpoint of solubility in a solvent, it is preferable to have —COOH as a substituent in Rf.

In the substituent —COOR ¹ in Rf, R ¹ is an alkyl group or a fluorine-containing alkyl group. As this alkyl group, a C1-C10 linear, branched or cyclic alkyl group is mentioned, for example. Moreover, as this fluorine-containing alkyl group, a C1-C10 linear, branched or cyclic fluorine-containing alkyl group is mentioned, for example.

Specific examples of the substituent —COOR ¹ include —COOCH ₃ , —COOCH ₂ CH ₃ , —COOCH ₂ CF ₃ , —COOCH ₂ CF ₂ CF _{3 and the} like. Among these, —COOCH ₃ is preferable in terms of ease of synthesis and high heat resistance. —COOCH ₂ CF ₃ is preferable from the viewpoint of ease of synthesis and low refractive index.

In the substituent —CONR ² R ³ , R ² and R ³ are the same or different and are H, an alkyl group, or a fluorine-containing alkyl group. As this alkyl group, a C1-C10 linear, branched or cyclic alkyl group is mentioned, for example. Moreover, as this fluorine-containing alkyl group, a C1-C10 linear, branched or cyclic fluorine-containing alkyl group is mentioned, for example.

Specific examples of the substituent —CONR ² R ³ include —CONH ₂ , —CONHCH ₃ , —CON (CH ₃ ) _{2 and the} like.

In addition, examples of the derivative of the substituent —COOH include salts of carboxylic acids such as —COONH ₄ , —COONa, —COOK, and —COOLi. Examples of the derivative of —SO ₃ H include sulfonic acid salts such as —SO ₃ NH ₄ , —SO ₃ Na, —SO ₃ K, and —SO ₃ Li.

  Specific examples of “a fluorine-containing alkyl group having 1 to 40 carbon atoms having a substituent” and “a fluorine-containing alkyl group having an ether bond having 2 to 100 carbon atoms having a substituent” in Rf of the general formula (1) As a structural formula, it can represent with the following structural formulas, for example. In the formula, the substituent is represented by Y.

[Wherein, l and m are the same or different and are an integer of 1 to 10, s, t and u are the same or different and are 0 or 1, n is an integer of 0 to 5, n ^a , n ^b and ^{n c} are the same or different integer of 0 or ^more, a ^{n a + n b + n c} = 1~10, X 1, X 4, X 5 and ^{X 7} F or CF ₃ identical or different X ² , X ³ and X ⁶ are the same or different and are H or F, and each repeating unit is not limited to this order, and may be a block or random. ]
Etc.

  Among these, Rf is preferably represented by the following structural formula.

[Wherein n is the same as defined above. ]
Further, among these, Rf is preferably represented by the following structural formula.

[Wherein, n and m are the same as above. ]
In general formula (1) -S—CX ₂ CHF—Z—O—Rf, X is the same or different and is H or F. In the general formula (1), Z -CF ₂ - is or a single bond. In the general formula (1), a compound in which X is H and Z is —CF ₂ —, or a compound in which X is F and Z is a single bond is preferable.

  Among the compounds represented by the general formula (1), the following general formula (1a)

[Wherein T is a hydrocarbon optionally having at least one heteroatom selected from the group consisting of O, N and S;
p is an integer greater than or equal to 2,
X, Z, and Rf are the same or different and are the same as described above. ]
The compound represented by these is preferable.

  In the general formula (1a), X, Z and Rf are the same or different and are the same as those of the compound represented by the general formula (1).

In the compound represented by the general formula (1a), there are p groups (p is an integer of 2 or more) represented by the formula: — (S—CX ₂ CHF—Z—O—Rf), Each is the same or different.

  p is usually an integer of 2 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 6.

  Specific examples of the compound represented by the general formula (1a) include, for example, the following general formula (1b)

[Wherein, R ⁴ is the same or different and is a single bond, -C _a H _2a- , -C _b H _2b -B-C _c H _2c -or -S-C _d H _2d- ,
a, b, c and d are the same or different and are an integer of 1 or more,
B is -S-, -C (= O) O-, -OC (= O)-or -O-,
A is _-C e _{H 2e} - or _{-C f H 2f -E-C g} H 2g - and is,
e, f and g are the same or different and are integers of 1 or more,
E is —S—, —C (═O) O—, —OC (═O) — or —O—;
R ⁵ is H, an alkyl group which may have a substituent, or a group represented by the formula: —R ⁴ —S—CX ₂ CHF—Z—O—Rf,
R ⁶ represents H, an alkyl group which may have a substituent, or a group represented by the formula: —R ⁴ —S—CX ₂ CHF—Z—O—Rf,
q is an integer of 0 or more,
X, Z and Rf are the same or different and are the same as above,
Group of the formula _{:-( S-CX 2 CHF-Z} -O-Rf) are the same or different. ]
The compound represented by these is mentioned.

  In the general formula (1b), X, Z and Rf are the same or different and are the same as those of the compound represented by the general formula (1).

In General Formula (1b), R ⁴ is the same or different and is a single bond, —C _a H _2a —, —C _b H _2b —B—C _c H _2c — or —S—C _d H _2d —. a, b, c and d are the same or different and are an integer of 1 or more, preferably an integer of 1 to 20, more preferably an integer of 1 to 10.

In the group in which R ⁴ is represented by —C _b H _2b —B—C _c H _2c —, B represents —S—, —C (═O) O—, —OC (═O) — or —O—. It is. However, in R ⁴ , -C _a H _2a- , -C _b H _2b -B-C _c H _2c -and -S-C _d H _2d -are each represented by the right side connector on the paper surface in the general formula (1b). Bonded to the S atom of —S—CX ₂ CHF—Z—O—Rf. Among these, B is preferably —OC (═O) —.

In the general formula (1b), A is _-C e _{H 2e} - or _{-C f H 2f -E-C g} H 2g - a.
e, f and g are the same or different and are an integer of 1 or more, preferably an integer of 1 to 20, more preferably an integer of 1 to 10. E is -S-, -C (= O) O-, -OC (= O)-or -O-. Among these, E is preferably -O-.

In General Formula (1b), R ⁵ is H, an alkyl group which may have a substituent, or a group represented by the formula: —R ⁴ —S—CX ₂ CHF—Z—O—Rf.

Examples of the alkyl group of the “optionally substituted alkyl group” represented by R ⁵ include linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms. Examples thereof include alkyl groups having 1 to 12 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl and cyclodecyl. . More preferably, it is a C1-C8 alkyl group. The alkyl group may be substituted, and the substituent is not particularly limited as long as it does not adversely affect the present invention. Examples of the substituent, for _{example, -OH, COOH, -COOCH 3,} -NH 2, -COOCH 2 CH 3, include -COOCH ₂ CF ₃ and the like. 1-3 alkyl groups may be substituted with at least one selected from these groups.

In General Formula (1b), R ⁶ is H, an alkyl group which may have a substituent, or a group represented by the formula: —R ⁴ —S—CX ₂ CHF—Z—O—Rf.

Examples of the alkyl group of the “optionally substituted alkyl group” represented by R ⁶ include linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms. Examples thereof include alkyl groups having 1 to 12 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl and cyclodecyl. . More preferably, it is a C1-C8 alkyl group. The alkyl group may be substituted, and the substituent is not particularly limited as long as it does not adversely affect the present invention. Examples of the substituent, for _{example, -OH, COOH, -COOCH 3,} -NH 2, -COOCH 2 CH 3, include -COOCH ₂ CF ₃ and the like. 1-3 alkyl groups may be substituted with at least one selected from these groups.

  In general formula (1b), q is an integer of 0 or more. q is preferably an integer of 0 to 10, more preferably an integer of 0 to 5, and particularly preferably 0 or 1.

  Among the compounds represented by the general formula (1b), particularly preferable compounds include compounds represented by the following general formula.

[Wherein, X, Z, Rf, b and c are the same or different and are the same as above. ]

[Wherein, X, Z, Rf, b, c, f and g are the same or different and are the same as above. ]

[Wherein, X, Z, Rf, b, c and e are the same or different and are the same as defined above. ]

[Wherein, X, Z, Rf, b and c are the same or different and are the same as defined above. ]

[Wherein, X, Z, Rf, b and c are the same as or different from each other, and R ⁵ is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms. ]
Furthermore, specific examples of the compound represented by the general formula (1a) include, for example, the following general formula (1c)

[Wherein, Q has an optionally substituted aliphatic ring, an optionally substituted heteroaliphatic ring, an optionally substituted aromatic ring or a substituted group. A heteroaromatic ring that may be
The substituent is at least one selected from the group consisting of an alkyl group, —OH, —COOR ⁷ , —CONR ⁸ R ⁹ , —NH ₂ , —COCl, —SO ₂ F, —SO ₃ H, and —CN. Yes,
R ⁷ is H, an alkyl group or a fluorine-containing alkyl group,
R ⁸ and R ⁹ are the same or different and are H, an alkyl group or a fluorine-containing alkyl group,
r is an integer greater than or equal to 2,
X, Z and Rf are the same or different and are the same as above,
Group of the formula _{:-( S-CX 2 CHF-Z} -O-Rf) are the same or different. ]
The compound represented by these is mentioned.

  In the general formula (1c), X, Z and Rf are the same or different and are the same as those of the compound represented by the general formula (1).

In the compound represented by the general formula (1c), r is an integer of 2 or more, and the group represented by — (S—CX ₂ CHF—Z—O—Rf) is represented by the general formula (1c). There are two or more in a given compound. r is an integer of usually 2 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 6.

In Q of the general formula (1c), the aliphatic ring which may have a substituent may be either a monocyclic ring or a bicyclic ring. Moreover, when it has a substituent, the substituent consists of an alkyl group, —OH, —COOR ⁷ , —CONR ⁸ R ⁹ , —NH ₂ , —COCl, —SO ₂ F, —SO ₃ H and —CN, respectively. It is at least one selected from the group.

In the substituent —COOR ⁷ , R ⁷ is H, an alkyl group, or a fluorine-containing alkyl group. As this alkyl group, a C1-C10 linear, branched or cyclic alkyl group is mentioned, for example. Moreover, as this fluorine-containing alkyl group, a C1-C10 linear, branched or cyclic fluorine-containing alkyl group is mentioned, for example.

In the substituent —CONR ⁸ R ⁹ , R ⁸ and R ⁹ are the same or different and are H, an alkyl group, or a fluorine-containing alkyl group. As this alkyl group, a C1-C10 linear, branched or cyclic alkyl group is mentioned, for example. Moreover, as this fluorine-containing alkyl group, a C1-C10 linear, branched or cyclic fluorine-containing alkyl group is mentioned, for example.

  Carbon number of the aliphatic ring which may have a substituent is about 3-100 normally, Preferably it is about 3-50, More preferably, it is about 3-12.

  Specific examples of the aliphatic ring which may have a substituent include an aliphatic ring represented by the following formula.

[Wherein each aliphatic ring may have the same substituent as in the general formula (1c), and r, X, Z and Rf are the same as those of the compound represented by the general formula (1). It is. ]
In Q of the general formula (1c), the heteroaliphatic ring which may have a substituent may be a monocyclic ring or a bicyclic ring. Moreover, when it has a substituent, the substituent consists of an alkyl group, —OH, —COOR ⁷ , —CONR ⁸ R ⁹ , —NH ₂ , —COCl, —SO ₂ F, —SO ₃ H and —CN, respectively. It is at least one selected from the group.

R ⁷ , R ⁸ and R ⁹ are the same as those of the aliphatic ring which may have the substituent.

  Carbon number of the heteroaliphatic ring which may have a substituent is about 2-100 normally, Preferably it is about 2-50, More preferably, it is about 2-12.

  Examples of the hetero atom contained in the heteroaliphatic ring include at least one selected from the group consisting of O, N, and S.

  Specific examples of the heteroaliphatic ring optionally having the substituent include heteroaliphatic rings represented by the following formula.

[Wherein, each heteroaliphatic ring may have the same substituent as in general formula (1c), and r, X, Z, and Rf are those of the compound represented by general formula (1). The same. ]
In Q of the general formula (1c), the aromatic ring which may have a substituent may be a single ring or multiple rings. Moreover, when it has a substituent, the substituent consists of an alkyl group, —OH, —COOR ⁷ , —CONR ⁸ R ⁹ , —NH ₂ , —COCl, —SO ₂ F, —SO ₃ H and —CN, respectively. It is at least one selected from the group.

R ⁷ , R ⁸ and R ⁹ are the same as those of the aliphatic ring which may have the substituent.

  Carbon number of the aromatic ring which may have a substituent is about 6-100 normally, Preferably it is about 6-50, More preferably, it is about 6-20.

  Specific examples of the aromatic ring which may have a substituent include aromatic rings represented by the following formula.

[Wherein each aromatic ring may have the same substituent as in the general formula (1c), and r, X, Z and Rf are the same as those of the compound represented by the general formula (1). It is. ]
In Q of the general formula (1c), the heteroaromatic ring which may have a substituent may be a single ring or multiple rings. Moreover, when it has a substituent, the substituent consists of an alkyl group, —OH, —COOR ⁷ , —CONR ⁸ R ⁹ , —NH ₂ , —COCl, —SO ₂ F, —SO ₃ H and —CN, respectively. It is at least one selected from the group.

R ⁷ , R ⁸ and R ⁹ are the same as those of the aliphatic ring which may have the substituent.

  Carbon number of the heteroaromatic ring which may have a substituent is about 4-100 normally, Preferably it is about 4-50, More preferably, it is about 4-20.

  Specific examples of the heteroaromatic ring which may have a substituent include heteroaromatic rings represented by the following formula.

[Wherein each heteroaromatic ring may have the same substituent as in the general formula (1c), and r, X, Z and Rf are those of the compound represented by the general formula (1). The same. ]
Production Method The production method of the present invention comprises a compound having two or more thiol groups in the molecule represented by the general formula (2).
CX ₂ = CF—Z—O—Rf (2)
[Wherein, X, Z and Rf are the same as defined above. ]
Is reacted with a compound represented by the general formula (1)
—S—CX ₂ CHF—Z—O—Rf (1)
[Wherein, Rf, X and Z are the same as defined above. ]
A compound having two or more groups represented by the formula is obtained.

  In the production method of the present invention, examples of the compound having two or more thiol groups in the molecule include the following general formula (3a):

[Wherein T is a hydrocarbon which may have at least one heteroatom selected from the group consisting of O, N and S, and p is an integer of 2 or more. ]
The compound represented by these is mentioned.

  In the general formula (3a), T and p are the same as those in the general formula (1a).

  Specific examples of the compound represented by the general formula (3a) include, for example, the following general formula (3b)

[Wherein R ^5b is H, an alkyl group which may have a substituent, or a group represented by the formula: —R ⁴ —SH, and R ^6b may be H or a substituent. A good alkyl group or a group represented by the formula: —R ⁴ —SH, wherein R ⁴ , A and q are the same as defined above. ]
The compound represented by these is mentioned.

In General Formula (3b), R ^5b is H, an alkyl group which may have a substituent, or a group represented by the formula: —R ⁴ —SH.

^Examples of the alkyl group of the “optionally substituted alkyl group” represented by R ^5b include linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms. Examples thereof include alkyl groups having 1 to 12 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl and cyclodecyl. . More preferably, it is a C1-C8 alkyl group. The alkyl group may be substituted, and the substituent is not particularly limited as long as it does not adversely affect the present invention. Examples of the substituent, for _{example, -OH, COOH, -COOCH 3,} -NH 2, -COOCH 2 CH 3, include -COOCH ₂ CF ₃ and the like. 1-3 alkyl groups may be substituted with at least one selected from these groups.

In General Formula (3b), R ^6b is H, an alkyl group which may have a substituent, or a group represented by the formula: —R ⁴ —SH.

^Examples of the alkyl group of the “optionally substituted alkyl group” represented by R ^6b include linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms. Examples thereof include alkyl groups having 1 to 12 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl and cyclodecyl. . More preferably, it is a C1-C8 alkyl group. The alkyl group may be substituted, and the substituent is not particularly limited as long as it does not adversely affect the present invention. Examples of the substituent, for _{example, -OH, COOH, -COOCH 3,} -NH 2, -COOCH 2 CH 3, include -COOCH ₂ CF ₃ and the like. 1-3 alkyl groups may be substituted with at least one selected from these groups.

  Among the compounds represented by the general formula (3b), particularly preferable compounds include compounds represented by the following general formula.

  [Wherein, b and c are the same or different and are the same as defined above. ]

  [Wherein b, c and e are the same or different and are the same as defined above. ]

  [Wherein, b, c, f and g are the same or different and are the same as defined above. ]

  [Wherein, b and c are the same or different and are the same as defined above. ]

[Wherein, b and c are the same as or different from each other, and R ⁵ is a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms. ]
Examples of the compound represented by the general formula (3b) include 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptopros Pionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), 1,2-dimercaptoethane, 1,2-dimercaptopropane, 1,3- Dimercaptopropane, dimercaptobutane, dimercaptohexane, tetrakismercaptomethylmethane, dimercaptomethane, trimercaptomethane, 1,2,3-trimercaptopropane, 1,2,3,4-tetramercaptobutane, dimercaptomethane 1,1-dimercaptoe 1,2-dimercaptoethane, 1,1-dimercaptopropane, 1,2-dimercaptopropane, 1,3-dimercaptopropane, 2,2-dimercaptopropane, 1,1-dimercaptobutane, 1,2-dimercaptobutane, 1,3-dimercaptobutane, 1,4-dimercaptobutane, 2,2-dimercaptobutane, 2,3-dimercaptobutane, 1,2-dimercaptobutane-3 -Mercaptopropane, 1,2-bis-2-mercaptoethylthio-3-mercaptopropane, bis (mercaptomethyl) sulfide, bis (2-mercaptoethyl) sulfide, bis (mercaptomethylthio) methane, 2,3-dimercapto- 1-propanol etc. are mentioned.

  Specific examples of the compound represented by the general formula (3a) include, for example, the following general formula (3c)

[Wherein, Q and r are the same as those in the general formula (1c). ]
The compound represented by these is mentioned.

In general formula (3c), Q has an aliphatic ring which may have the same substituent as in general formula (1c), a heteroaliphatic ring which may have a substituent, and a substituent. An aromatic ring which may be substituted or a heteroaromatic ring which may have a substituent. The substituent is at least one selected from the group consisting of an alkyl group, —OH, —COOR ⁷ , —CONR ⁸ R ⁹ , —NH ₂ , —COCl, —SO ₂ F, —SO ₃ H, and —CN. is there.

In Q of the general formula (3c), the aliphatic ring which may have a substituent may be either a monocyclic ring or a bicyclic ring. Moreover, when it has a substituent, the substituent consists of an alkyl group, —OH, —COOR ⁷ , —CONR ⁸ R ⁹ , —NH ₂ , —COCl, —SO ₂ F, —SO ₃ H and —CN, respectively. It is at least one selected from the group.

In the substituent —COOR ⁷ , R ⁷ is H, an alkyl group, or a fluorine-containing alkyl group. As this alkyl group, a C1-C10 linear, branched or cyclic alkyl group is mentioned, for example. Moreover, as this fluorine-containing alkyl group, a C1-C10 linear, branched or cyclic fluorine-containing alkyl group is mentioned, for example.

In the substituent —CONR ⁸ R ⁹ , R ⁸ and R ⁹ are the same or different and are H, an alkyl group, or a fluorine-containing alkyl group. As this alkyl group, a C1-C10 linear, branched or cyclic alkyl group is mentioned, for example. Moreover, as this fluorine-containing alkyl group, a C1-C10 linear, branched or cyclic fluorine-containing alkyl group is mentioned, for example.

  In the compound represented by the general formula (3c), r is an integer of 2 or more, and two or more groups represented by-(SH) are present in the compound represented by the general formula (3c). r is an integer of usually 2 to 20, preferably an integer of 2 to 10, more preferably an integer of 2 to 6.

  Carbon number of the aliphatic ring which may have a substituent is about 3-100 normally, Preferably it is about 3-50, More preferably, it is about 3-12.

  Specific examples of the aliphatic ring which may have a substituent include an aliphatic ring represented by the following formula.

[Wherein each aliphatic ring may have the same substituent as in general formula (3c), and the substituent and r are the same as those of the compound represented by general formula (1c). . ]
In Q of the general formula (3c), the heteroaliphatic ring which may have a substituent may be a single ring or multiple rings. Moreover, when it has a substituent, the substituent consists of an alkyl group, —OH, —COOR ⁷ , —CONR ⁸ R ⁹ , —NH ₂ , —COCl, —SO ₂ F, —SO ₃ H and —CN, respectively. It is at least one selected from the group.

R ⁷ , R ⁸ and R ⁹ are the same as those of the aliphatic ring which may have the substituent.

  Carbon number of the heteroaliphatic ring which may have a substituent is about 2-100 normally, Preferably it is about 2-50, More preferably, it is about 2-12.

  Examples of the hetero atom contained in the heteroaliphatic ring include at least one selected from the group consisting of O, N, and S.

  Specific examples of the heteroaliphatic ring which may have a substituent include heteroaliphatic rings represented by the following formula.

[Wherein each heteroaliphatic ring may have the same substituent as in the general formula (3c), and the substituent and r are the same as those in the compound represented by the general formula (1c). is there. ]
Specific examples of the compound in which Q is a heteroaliphatic ring which may have a substituent in the general formula (3c) include 2,5-dimercaptomethyl-1,4-dithiane, 4,5-dithiane Examples include mercaptomethyl-1,3-dithiane.

In Q of the general formula (3c), the aromatic ring which may have a substituent may be a monocyclic ring or a multicyclic ring. Moreover, when it has a substituent, the substituent consists of an alkyl group, —OH, —COOR ⁷ , —CONR ⁸ R ⁹ , —NH ₂ , —COCl, —SO ₂ F, —SO ₃ H and —CN, respectively. It is at least one selected from the group.

R ⁷ , R ⁸ and R ⁹ are the same as those of the aliphatic ring which may have the substituent.

  Carbon number of the aromatic ring which may have a substituent is about 6-100 normally, Preferably it is about 6-50, More preferably, it is about 6-20.

  Specific examples of the aromatic ring which may have a substituent include aromatic rings represented by the following formula.

[Wherein each aromatic ring may have the same substituent as in the general formula (3c), and the substituent and r are the same as those of the compound represented by the general formula (1c). ]
Specific examples of the compound in which Q in the general formula (3c) is an aromatic ring which may have a substituent include 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4- Dimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2-dimercaptotoluene, 1,3-dimercaptotoluene, 1,4-dimercaptotoluene, 1,3,5-trimercaptotoluene, 1, Examples include 2-dimercaptoxylene, 1,3-dimercaptoxylene, 1,4-dimercaptoxylene, 1,3-dimercaptotolylene, 1,3,5-trimercaptotolylene, and the like.

In Q of the general formula (1c), the heteroaromatic ring which may have a substituent may be a single ring or multiple rings. Moreover, when it has a substituent, the substituent consists of an alkyl group, —OH, —COOR ⁷ , —CONR ⁸ R ⁹ , —NH ₂ , —COCl, —SO ₂ F, —SO ₃ H and —CN, respectively. It is at least one selected from the group.

R ⁷ , R ⁸ and R ⁹ are the same as those of the aliphatic ring which may have the substituent.

  Carbon number of the aromatic ring which may have a substituent is about 4-100 normally, Preferably it is about 4-50, More preferably, it is about 4-20.

  Examples of the hetero atom contained in the heteroaromatic ring include at least one selected from the group consisting of O, N, and S.

[Wherein each heteroaromatic ring may have the same substituent as in general formula (3c), and the substituent and r are the same as those in the compound represented by general formula (1c). . ]
The compound having two or more thiol groups (—SH group, mercapto group) in the molecule of the present invention is a compound obtained by a conventionally known production method, and a commercially available product can also be used. The compound having two or more thiol groups in the molecule of the present invention can be synthesized, for example, according to the method described in The Chemistry of the thiol group (Chemistry of Functional Groups) By Saul Patai: John Wiley and Sons Ltd. Can do. For example, there is an isothiuronium salt method in which thiourea is reacted, isothiuronium salified and hydrolyzed.

In the production method of the present invention, the above compound having two or more thiol groups in the molecule is reacted with the compound CX ₂ = CF—Z—O—Rf represented by the general formula (2). A polyfunctional fluorine-containing compound is obtained. X, Z and Rf of the compound represented by the general formula (2) are the same as those of the compound represented by the general formula (1).

As the compound represented by the general formula (2), as in the compound represented by the general formula (1), a substituent present in Rf (a fluorine-containing alkyl group having 1 to 40 carbon atoms having a substituent, or —OH, —CH ₂ OH, —COOR ¹ , —CONR ² R ³ , —NH ₂ , —COCl, —SO, which are substituents of a fluorine-containing alkyl group having a C 2-100 ether bond having a substituent ₂ F, —SO ₃ H, —CN, —COOH, a derivative of —COOH, —SO ₃ H or —SO ₃ H) are represented by Y, for example.

[Wherein, n is an integer of 0 to 5. ]

[Wherein n is the same as defined above. ]
Furthermore, among these compounds, those represented by the following structural formula are particularly preferable.

[Wherein, m is an integer of 1 to 10, and n is the same as described above. ]
The compound represented by General formula (2) of this invention is a compound obtained by a conventionally well-known manufacturing method, and can also use a commercial item.

  As a manufacturing method of the compound represented by General formula (2) of this invention, the method described in the international publication WO95 / 33782 pamphlet is specifically mentioned, for example.

  In addition, it can be produced according to a specific synthesis route described in Sankyo Publishing “Introduction to Fluorine Chemistry” edited by the Japan Society for the Promotion of Science Fluorine Chemistry 155th Committee.

  In the manufacturing method of this invention, the compound represented by General formula (2) may be used individually by 1 type, and 2 or more types may be mixed and used for it.

  In the production method of the present invention, the amount of the compound having two or more thiol groups in the molecule varies depending on the number of thiol groups in the molecule, and is represented by the general formula (2) for one thiol group, for example. It is sufficient to use an amount sufficient for one compound to react. In this specification, this amount is called equivalent. In a compound having two thiol groups in the molecule, the equivalent is ½ of the molecular weight, and in the same manner, in an compound having three thiol groups in the molecule, the equivalent is ３ of the molecular weight.

  The amount of the compound having two or more thiol groups in the molecule is usually about 2 to 0.1 equivalent, preferably 1.2 to 0.2 equivalent, relative to the compound represented by the general formula (2). The amount is about 1 to 0.5 equivalent. In other words, the amount of the compound represented by the general formula (2) is usually about 0.5 to 10 mol, preferably 0.83 with respect to 1 mol of the thiol group of the compound having two or more thiol groups in the molecule. About 5 mol, more preferably about 1-2 mol may be used.

In the production method of the present invention, the compound having two or more thiol groups in the molecule and the compound represented by the general formula (2) undergo an enethiol reaction (addition reaction), whereby two or more thiol groups in the molecule. H on S of the compound having the following formula (4)
—CX ₂ CHF—Z—O—Rf (4)
[Wherein X, Z and Rf are the same as above]
Is substituted with a group represented by

  That is, in the enethiol reaction of the present invention, the carbon-carbon double bond present in the compound represented by the general formula (2) undergoes an addition reaction with the thiol group in the compound having two or more thiol groups in the molecule. . On the other hand, the substituent in Rf present in the compound represented by the general formula (2) does not substantially react and becomes a reactive functional group of the polyfunctional fluorine-containing compound of the present invention.

  Since the polyfunctional fluorine-containing compound of the present invention has a plurality of reactive functional groups derived from the above substituents in the compound represented by the general formula (2) in the molecule, It can be used suitably. Moreover, it can be set as the curable composition containing the polyfunctional fluorine-containing compound of this invention, this can be hardened, and hardened | cured material can also be manufactured.

  When an unreacted thiol group is present in the polyfunctional fluorine-containing compound of the present invention obtained by the enethiol reaction, the unreacted thiol group is obtained when the polyfunctional fluorine-containing compound of the present invention is used as a curable composition. Acts as a curing reactive group.

  In the production method of the present invention, compounds having two or more thiol groups in the molecule may be used singly or in combination of two or more.

  The enethiol reaction easily proceeds by irradiating a mixture of a compound having two or more thiol groups in the molecule and a compound represented by the general formula (2) with ultraviolet rays.

The irradiation amount of ultraviolet rays is usually about 0.1 to 10 J / cm ² , preferably about 0.5 to ⁸ J / cm ² , more preferably about 1 to 6 J / cm ² .

  The reaction temperature for the enethiol reaction is usually about 5 to 60 ° C, preferably about 10 to 55 ° C, more preferably about 20 to 50 ° C.

  In the production method of the present invention, a photopolymerization initiator may be used in addition to the compound having two or more thiol groups in the molecule and the compound represented by the general formula (2). Even if the photopolymerization initiator is not used, the polyfunctional fluorine-containing compound of the present invention can be obtained. However, by using the photopolymerization initiator, the enethiol reaction proceeds in a shorter time, and the desired polyfunctional compound is contained. A fluorine compound is obtained.

  The kind of photoinitiator is not specifically limited, What is necessary is just to use a conventionally well-known thing, and a commercial item can be obtained easily.

  Examples of the photopolymerization initiator include acetophenone compounds such as acetophenone, chloroacetophenone, diethoxyacetophenone, hydroxyacetophenone, α-aminoacetophenone; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl Benzoin compounds such as dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, benzophenone compounds such as 4-phenylbenzophenone, hydroxybenzophenone, hydroxy-propylbenzophenone, acrylated benzophenone, Michler ketone; thioxanthone, chlorothioxanthone, Methylthioxanthone, diethylthioxanthone, dimethylthioxa Thioxanthones such as Son; benzyl, alpha-acyl oxime esters, acylphosphine oxide, glycidyl oxy ester, 3-ketocoumarin, 2-ethyl anthraquinone, camphorquinone, and a photopolymerization initiator such as anthraquinone. Examples of commercially available photopolymerization initiators include Irgacure 907, Irgacure 127, Irgacure 369, and Irgacure 819 manufactured by Nagase Sangyo Co., Ltd. A photoinitiator may be used individually by 1 type and may be used in mixture of 2 or more types.

  Moreover, you may add well-known photoinitiator adjuvants, such as amines, sulfones, and sulfines, to a photoinitiator as needed.

  When using a photoinitiator, the usage-amount of a photoinitiator is not specifically limited, What is necessary is just to adjust suitably, For example, it is normal with respect to 100 mass parts of compounds represented by General formula (2). About 0.01 to 10 parts by mass, preferably about 0.5 to 7 parts by mass, more preferably about 1 to 5 parts by mass.

  In the production method of the present invention, a solvent may be further used. When a solvent is used, a conventionally known solvent that is generally used and does not hinder the progress of the enethiol reaction may be used as the solvent. As the solvent, for example, methanol, ethanol, isopropanol, HCFC225 (dichloropentafluoropropane), methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK) or the like may be used.

  In the production method of the present invention, other components may be added as necessary. Examples of other components include an antioxidant, a leveling agent, an inorganic filler, and an organic filler.

  When using antioxidant, the usage-amount is about 0.01-10 mass parts normally with respect to 100 mass parts of compounds represented by General formula (2), Preferably it is about 0.1-2 mass parts, More preferably, it is about 0.5-1 mass part.

  What is the enthiol reaction? In particular, the reaction can proceed by generating radicals by an appropriate method even without irradiation with ultraviolet rays.

  As a method of generating radicals, for example, a method of generating radicals by heating using a known radical polymerization initiator is preferable.

  As the radical polymerization initiator, known peroxides, azo initiators, and the like can be used.

  The amount of the radical polymerization initiator is usually about 0.01 to 10 parts by mass, preferably about 0.05 to 7 parts by mass, more preferably 100 parts by mass of the compound represented by the general formula (2). Is about 0.5 to 3 parts by mass.

Crosslinking agent and additive for coating material Since the polyfunctional fluorine-containing compound of the present invention has a plurality of crosslinkable functional groups in the molecule, it can be suitably used as a crosslinking agent and additive for coating material.

Examples of paints that can use the polyfunctional fluorine-containing compound of the present invention as a crosslinking agent include acrylic, urethane, epoxy, and fluorine paints. The polyfunctional fluorine-containing compound of the present invention can be used by adding the crosslinking agent to the coating material described in Example 1 of JP-A-2004-204205, for example. In Example 1, an isocyanate curing agent is used. When the polyfunctional fluorine-containing compound of the present invention is used as a crosslinking agent for an isocyanate-based curing agent as described in Example 1, the substituent of the polyfunctional fluorine-containing compound of the present invention is —OH, —CH _2. OH, —COOH and the like are preferable. When the substituent is —CH ₂ OH, the addition amount is about 0.01 to 10 parts by mass, preferably about 0.05 to 7 parts by mass, more preferably about 1 to 5 parts by mass with respect to the solid content in the paint. do it.

  The polyfunctional fluorine-containing compound of the present invention undergoes curing crosslinking with an isocyanate-based curing agent under normal conditions as described in Examples of JP-A-2004-204205.

  Since the polyfunctional fluorine-containing compound of the present invention has a plurality of functional groups, an effect of improving the crosslinking density can be obtained when it is used as a crosslinking agent or additive for paints. In addition, unlike the functional group-containing fluoropolymer described in JP-A-2004-204205, the polyfunctional fluorine-containing compound of the present invention has a low molecular weight, so that the viscosity does not increase.

Moreover, since the polyfunctional fluorine-containing compound of the present invention is liquid at room temperature, a solventless curable composition can also be produced. Furthermore, since the type of functional group of the polyfunctional fluorine-containing compound can be easily changed, the functional group can be selected according to the curing system of various paints. For example, in the case of urethane _paint, -OH, -CH 2 OH, -COOH, etc., _-CH 2 OH in the case of epoxy-based coating, -COOH, etc., _-CH 2 OH, etc. For the acrylic paint, using An appropriate functional group can be selected according to the composition of the paint to be applied.

  Moreover, it has the characteristic that the fluorine content rate of hardened | cured material can be designed high by using a polyfunctional fluorine-containing compound with a high fluorine content rate. As a result, the obtained cured product has properties unique to fluorine. That is, by using the polyfunctional fluorine-containing compound of the present invention as a crosslinking agent, the cured product has features such as a refractive index lowering effect, an improvement in heat resistance, an effect of water and oil repellency, and an improvement in chemical resistance. Can be granted.

  According to the present invention, a new polyfunctional thiol compound can be easily formed by an ene thiol reaction between a polyfunctional thiol compound and a fluorinated allyl compound having a functional group, or an ene thiol reaction between a polyfunctional thiol compound and a fluorinated vinyl ether compound having a functional group. Fluorine compounds can be synthesized. Since the obtained polyfunctional fluorine-containing compound has a plurality of crosslinkable functional groups in the molecule, it can be suitably used as a crosslinking agent or additive for paints. Moreover, since the obtained polyfunctional fluorine-containing compound has two or more functional groups which have curability in a molecule | numerator, a curable composition and hardened | cured material can also be manufactured.

  EXAMPLES Hereinafter, the present invention will be further clarified by giving examples of the present invention, but the present invention is not limited to these examples.

In the examples of the present invention, (1) measurement of fluorine content, (2) measurement of refractive index (n _D ), (3) infrared absorption analysis (IR analysis), (4) measurement of ¹⁹ F-NMR and (5) Compatibility (solubility) was measured by the following method.

(1) Measurement of fluorine content A 10 mg sample is burned by the oxygen flask combustion method, the decomposition gas is absorbed in 20 ml of deionized water, and the fluorine ion concentration in the absorption liquid is determined by the fluorine selective electrode method (fluorine ion meter, manufactured by Orion). 901 type) to determine the fluorine content in the sample (mass%).

(2) Measurement of refractive index (n _D ) Using a sodium D line (589 nm) as a light source, the refractive index (n _D ) of the sample at 25 ° C. is measured using an Abbe refractometer (manufactured by Atago Optical Instruments Co., Ltd.). did.

(3) Infrared absorption analysis (IR analysis)
An infrared absorption analysis of the sample was performed at room temperature using a Fourier transform infrared spectrophotometer 1760X manufactured by Perkin Elmer.

⁽⁴⁾ 19 using the F-NMR measurement manufactured by BRUKER NMR measurement apparatus was measured ¹⁹ F-NMR of the sample.
¹⁹ F-NMR measurement conditions: 282 MHz (trichlorofluoromethane: 0 ppm).

(5) Measurement of compatibility (solubility) The sample and acetone were mixed at a mass ratio of 1: 1, and the compatibility was visually confirmed. In the evaluation of the compatibility, the compatibility was evaluated as ○, and the two-phase separation was evaluated as ×.

  The structural formulas and abbreviations of the fluorine-containing allyl ether compound and polyfunctional thiol compound used in this example are shown below.

Fluorine-containing allyl ether compound

Multifunctional thiol compound

(Karenzu MT BD1 Showa Denko)

(Karenz MT PE1 Showa Denko)

(TMMP (Trimethylolpropane tris-3-mercaptopropionate) manufactured by Sakai Chemical Co., Ltd.)

(PEMP (Pentaerythritol tetrakis-3-mercaptopropionate) manufactured by Sakai Chemical Co., Ltd.)

(DPMP (Dipentaerythritolhexa-3-mercaptopropionate) manufactured by Sakai Chemical Co., Ltd.).

  QE-340M: (Polythiol QE-340M Toray Fine Chemical Co., Ltd. structural formula is not disclosed).

Example 1
(1) Preparation of mixed solutions (a1) to (a3) Mixed solutions (a1) to (a3) were prepared according to the following formulation.

Mixed solution (a1)
(i) AEH-1 100 parts by mass
(ii) 33 parts by mass of TMMP
(iii) Irgacure 907 (photopolymerization initiator, Nagase Sangyo Co., Ltd.) 4 parts by mass.

Mixed solution (a2)
(i) AEH-1: 100 parts by mass
(ii) 33 parts by mass of TMMP
(iii) Irgacure 127 (photopolymerization initiator, Nagase Sangyo Co., Ltd.) 4 parts by mass.

Mixed solution (a3)
(i) AEH-1 100 parts by mass
(ii) TMMP 33 parts by mass.

(2) Reaction and IR absorption measurement of mixed solution (a2) 1 g of mixed solution (a2) was put into a 5 ml glass sample bottle. Without the lid, the mixed solution (a2) was irradiated with ultraviolet rays having an intensity of 2000 mJ / cm ² U and 5000 mJ / cm ² U, respectively, from above the sample bottle using a high-pressure mercury lamp (under normal temperature and normal pressure).

  Thereafter, the IR absorption change of the obtained solution (a2) was measured. FIG. 1 and FIG. 2 show changes in IR absorption based on —SH group and C═C bond, which are supposed to be changed by enethiol reaction between AEH-1 and TMMP, respectively.

  As can be seen from FIG. 1 and FIG. 2, the enethiol reaction between AEH-1 and TMMP proceeded by ultraviolet irradiation, confirming a decrease in SH groups and a decrease in C═C bonds in solution (a2). On the other hand, there was no change in IR absorption of the —OH group derived from AEH-1 before and after ultraviolet irradiation.

  Moreover, the viscosity of the solution (a2) after ultraviolet irradiation rose to such an extent that it could be visually confirmed as compared with the mixed solution (a2) before ultraviolet irradiation. The solution (a2) after ultraviolet irradiation was colorless and transparent.

(3) Reaction of mixed solution (a1)-(a3) and calculation of reaction rate Each 1g of mixed solution (a1)-(a3) was put into a 5 ml glass sample bottle, respectively. Without covering, each mixed solution was irradiated with ultraviolet rays having an intensity of 500 mJ / cm ² U, 2000 mJ / cm ² U, and 5000 mJ / cm ² U from above the sample bottle using a high-pressure mercury lamp.

The reaction rate of AEH-1 and TMMP was calculated from the change in the integrated intensity of the absorption of fluorine bonded to the C═C double bond by ¹⁹ F-NMR measurement of each obtained solution. The results are shown in Table 1 below.

  When IR absorption of each solution was measured before and after UV irradiation, there was no change in IR absorption of the OH group derived from AEH-1. Moreover, the viscosity of each solution after ultraviolet irradiation rose to such an extent that it could be visually confirmed as compared with each mixed solution before ultraviolet irradiation.

  The solutions (a2) and (a3) after the ultraviolet irradiation were colorless and transparent. On the other hand, the solution (a1) after the ultraviolet irradiation was transparent but pale yellow. It seems that the cause of pale yellow is the color of Irgacure 907, which is a photopolymerization initiator.

(4) Measurement of fluorine content, refractive index and compatibility of solution (a1) after ultraviolet irradiation of solution (a1) obtained in (3) above after irradiation with ultraviolet light having an intensity of 5000 mJ / cm ² U Fluorine content, refractive index and compatibility were measured. The results are shown in Table 2.

Comparative Example 1
(1) Preparation of mixed solutions (b1) to (b3) Mixed solutions (b1) to (b3) were prepared according to the following formulation.

Mixed solution (b1)
(i) AEH-1 100 parts by mass
(ii) Irgacure 907 4 parts by mass.

Mixed solution (b2)
(i) AEH-1 100 parts by mass
(ii) Irgacure 127 4 parts by mass.

Mixed solution (b3)
(i) AEH-1 100 parts by mass.

(2) Reaction of mixed solutions (b1) to (b3), IR absorption measurement and ¹⁹ F-NMR measurement 1 g of each of the mixed solutions (b1) to (b3) was placed in a 5 ml glass sample bottle. Without the lid, each mixed solution was irradiated with ultraviolet rays of 5000 mJ / cm ² U intensity from above the sample bottle using a high-pressure mercury lamp (under normal temperature and normal pressure).

IR absorption measurement and ¹⁹ F-NMR measurement of each solution after ultraviolet irradiation were performed, but no decrease in C = C bond was observed, and changes in integrated intensity of absorption of fluorine bonded to C = C double bond were also observed. I couldn't. In addition, the change in viscosity before and after the ultraviolet irradiation was not visually observed.

Example 2
(1) Adjustment of mixed solutions (a4) to (a6), calculation of reaction and reaction rate Mixed solutions (a4) to (a6) were prepared according to the following formulation.

Mixed solution (a4)
(i) AEC-1 76 parts by mass
(ii) 24 parts by mass of TMMP
(iii) Irgacure 907 4 parts by mass.

Mixed solution (a5)
(i) AEC-1 78 parts by mass
(ii) PMP 22 parts by mass
(iii) Irgacure 907 4 parts by mass.

Mixed solution (a6)
(i) AEC-1 76 parts by mass
(ii) DPMP 24 parts by mass
(iii) Irgacure 907 4 parts by mass.

1 g of each of the mixed solutions (a4) to (a6) was placed in a 5 ml glass sample bottle. Without a lid, each mixture was irradiated with ultraviolet rays having an intensity of 500 mJ / cm ² U, 2000 mJ / cm ² U and 5000 mJ / cm ² U using a high-pressure mercury lamp from above the sample bottle (normal temperature normal temperature) Reduction).

From the ¹⁹ F-NMR measurement of each solution obtained, the reaction rates of AEC-1, TMMP, PEMP, and DPMP were calculated based on the change in the integrated intensity of absorption of fluorine bonded to the C═C double bond. The results are shown in Table 3.

  The viscosity of each solution after ultraviolet irradiation increased to such an extent that it could be visually confirmed as compared with each mixed solution before ultraviolet irradiation.

(4) Measurement of fluorine content, refractive index, compatibility and IR absorption of solutions (a4) to (a6) after ultraviolet irradiation Solutions (a4) to (a6) after ultraviolet irradiation with an intensity of 5000 mJ / cm ² U ) Was measured for fluorine content, refractive index and compatibility. The results are shown in Table 4 below.

  There was no change in IR absorption of -COOH group derived from AEC-1 in each solution before and after UV irradiation.

Example 3
(1) Preparation of mixed solutions (a7) to (a11) Mixed solutions (a7) to (a11) were prepared according to the following formulation.

Mixed solution (a7)
(i) AEH-0 62 parts by mass
(ii) 38 parts by weight of MTBD
(iii) Irgacure 907 4 parts by mass.

Mixed solution (a8)
(i) 68 parts by mass of AEC-0
(ii) 32 parts by weight of MTPE
(iii) Irgacure 907 4 parts by mass.

Mixed solution (a9)
(i) 82 parts by mass of AEC-2
(ii) TMMP 18 parts by mass
(iii) Irgacure 907 4 parts by mass.

Mixed solution (a10)
(i) 54 parts by mass of AEC-0
(ii) 46 parts by mass of QE-340M
(iii) Irgacure 907 4 parts by mass.

Mixed solution (a11 )
(i) 74 parts by mass of AEHFIP-0
(ii) 26 parts by mass of TMMP
(iii) Irgacure 907 4 parts by mass.
(2) Reaction of mixed solutions (a7) to (a11), fluorine content, refractive index and IR absorption measurement 1 g of each of the mixed solutions (a7) to (a11) was put into a 5 ml glass sample bottle. Without a lid, each mixture was irradiated with ultraviolet rays having an intensity of 5000 mJ / cm ² U from above the sample bottle using a high-pressure mercury lamp (under normal temperature and normal pressure). The fluorine content and refractive index of each solution after ultraviolet irradiation were measured. The results are shown in Table 5 below.

  When IR absorption of each solution before and after ultraviolet irradiation was measured, a decrease in SH groups and a decrease in C═C bonds were confirmed. Furthermore, there was no change in IR absorption of -OH groups derived from AEH-0 and AEHFIP-0 and -COOH groups derived from AEC-0 and AEC-2 before and after ultraviolet irradiation.

  Moreover, the viscosity of each solution after ultraviolet irradiation rose to such an extent that it could be visually confirmed as compared with each mixed solution before ultraviolet irradiation.

Example 4
(1) Preparation of mixed solutions (a12) to (a16) Mixed solutions (a12) to (a16) were prepared according to the following formulation.

Mixed solution (a12)
(i) 80 parts by mass of AEHFIP-1
(ii) TMMP 20 parts by mass
(iii) Irgacure 907 4 parts by mass
(iv) 100 parts by mass of HCFC225.

Mixed solution (a13)
(i) AEH-1 37 parts by mass
(ii) 39 parts by mass of AEE-1
(iii) 24 parts by mass of TMMP
(iv) Irgacure 907 4 parts by mass
(v) 100 parts by mass of HCFC225.

Mixed solution (a14)
(i) 28 parts by mass of AEC-0
(ii) 44 parts by mass of AECN-1
(iii) TMMP 28 parts by mass
(iv) Irgacure 907 4 parts by mass
(v) 100 parts by mass of HCFC225.

Mixed solution (a15)
(i) AEH-2 53 parts by mass
(ii) 22 parts by mass of AEH-0
(iii) 25 parts by mass of TMMP
(iv) Irgacure 907 4 parts by mass
(v) 100 parts by mass of HCFC225.

Mixed solution (a16)
(i) AEH-3 59 parts by mass
(ii) AEH-0 20 parts by mass
(iii) TMMP 21 parts by mass
(iv) Irgacure 907 4 parts by mass
(v) 100 parts by mass of HCFC225.

(2) Reaction of mixed solutions (a12) to (a16), fluorine content, refractive index and IR absorption measurement 1 g of each of the mixed solutions (a12) to (a16) was placed in a 5 ml glass sample bottle. Without the lid, each mixed solution was irradiated with ultraviolet rays having an intensity of 5000 mJ / cm ² U from above the sample bottle using a high-pressure mercury lamp (under normal temperature and normal pressure). The resulting solution was air dried at room temperature to remove HCFC225. Thereafter, the fluorine content and refractive index of the obtained solution were measured. The results are shown in Table 6 below.

  When IR absorption of each solution before and after UV irradiation was measured, a decrease in SH groups and a decrease in C═C bonds in the solution were confirmed. Furthermore, before and after UV irradiation, AEH-0, AEH-1, AEH-2, AEH-3 and AEHFIP-1 derived -OH groups, AEC-0 derived -COOH groups, AECN-1 derived -CN groups and There was no change in IR absorption of the -C (= O) O-bond derived from AEE-1.

  Moreover, the viscosity of each solution after drying rose to such an extent that it could be visually observed as compared with each mixed solution (without HCFC225) before ultraviolet irradiation.

Example 5 ( Preparation of curable composition)
The OH group-containing fluorine compound obtained in Example 1 (mixed solution (a1)) is A. The COOH group-containing fluorine-containing compound obtained in Example 2 (mixed solution (a4)) is designated as B.

  Moreover, the following reagents were used for preparation of the curable composition.

Fluorine-containing paint: GK-510 manufactured by Daikin Industries
Acrylic monomer: TMPA (trimethylolpropane triacrylate)
Hydroxyl group-containing acrylic polymer: UH-2032 manufactured by Toa Gosei Co., Ltd.
Curing agent: Sumidur N3300 (aliphatic polyisocyanate) (hereinafter N3300) manufactured by Sumika Bayer Urethane Co., Ltd.
Photopolymerization initiator: Irgacure 907 manufactured by Nagase & Co.
Cross-linking agent: YX-8000 (hydrogenated bisphenol epoxy) manufactured by Japan Epoxy Resin Co., Ltd.
Acid anhydride: manufactured by Hitachi Chemical Co., Ltd. HN-5500 (alicyclic acid anhydride)
Curing accelerator: UCAT-5003 manufactured by San Apro.

  Each component was mixed with the following mixing | blending, and the curable composition was created (thermosetting).

Curable composition (c1)
(I) A 5 parts by mass (ii) GK570 50 parts by mass (iii) N3300 10 parts by mass.

Curable composition (c2)
(I) B 5 parts by mass (ii) GK570 50 parts by mass (iii) N3300 10 parts by mass.

Curable composition (c3)
(I) A 5 parts by mass (ii) B 5 parts by mass (iii) GK570 50 parts by mass (iv) N3300 12 parts by mass.

Curable composition (c4)
(I) A 10 parts by mass (ii) GK570 50 parts by mass (iii) N3300 12 parts by mass.

Curable composition (c5)
(I) B 12 parts by mass (ii) YX-8000 50 parts by mass (iii) HN-500 40 parts by mass (iv) UCAT-5003 2 parts by mass.

  The obtained curable compositions (c1) to (c5) were all uniform and transparent compositions.

  Next, each component was mixed with the following mixing | blending, and the curable composition was created (photocurability).

Curable composition (c6)
(I) A 12 parts by mass (ii) 50 parts by mass of UH-2032 (iii) 50 parts by mass of TMPA (iv) Irgacure 907 3 parts by mass.

Curable composition (c7)
(I) B 12 parts by mass (ii) UH-2032 50 parts by mass (iii) TMPA 50 parts by mass (iv) Irgacure 907 3 parts by mass.

  The obtained curable compositions (c6) and (c7) were both uniform and transparent compositions.

Example 6 (Preparation of coated product (acid anhydride))
The thermosetting compositions (c1) to (c5) obtained in Example 5 were applied onto a slide glass by bar coating at room temperature, and vacuum dried at room temperature for 5 minutes. At this time, the type of the bar was selected so that the film thickness after drying was 10 μm.

  Moreover, the applicability at the time of application | coating by a bar coat was evaluated on the following reference | standard. The results are shown in Table 7.

  ○: There is no coating unevenness.

  Δ: Some coating unevenness is observed.

  ×: Cannot be applied.

Example 7 (Measurement of physical properties of cured film)
The curable compositions (c1) to (c5) applied in Example 6 were cured. The curable composition (c5) was heat-cured by heat-treating the dried film in a 90 ° C. dryer for 2 hours and subsequently in a 140 ° C. dryer for 3 hours to prepare a cured film. The curable compositions (c1) to (c4) were cured at room temperature for 4 days to prepare a cured film.

  The physical properties of the cured film were evaluated by the following methods. The results are shown in Table 7.

Appearance was evaluated visually.
○: Transparent uniform Δ: Partially, non-uniform ×: Cloudy.

Fluorine content as described above.

The state (dissolution or peeling) of the coating film surface after rubbing the coating film surface with a cotton cloth impregnated with chemical-resistant methanol was visually observed. Evaluation of chemical resistance was performed as follows.
○: No change △: Partially dissolved or peeled ×: Dissolved or peeled

Example 8 (Preparation of coated product (photocuring))
The photocurable compositions (c6) and (c7) obtained in Example 5 were coated on an untreated surface acrylic plate with a spin coater at room temperature and dried in vacuum at room temperature for 5 minutes. At this time, the rotation speed of the spin coater was adjusted (500 to 2000 rotations) so that the film thickness after drying was 1 μm. The applicability during application by a spin coater was evaluated according to the following criteria. The results are shown in Table 8.
○: No coating unevenness Δ: Some coating unevenness is observed ×: Cannot be applied.

Example 9 (Measurement of physical properties of cured film)
The photocurable compositions (c6) and (c7) applied in Example 8 were cured by photocuring by irradiating ultraviolet rays with an intensity of 5000 mJ / cm ² at room temperature using a high-pressure mercury lamp for the dried film. A coating was prepared. The physical properties of the photocured film were evaluated by the following methods. The results are shown in Table 8.

Appearance was evaluated visually.
○: Transparent uniform Δ: Partially, non-uniform ×: Cloudy.

Fluorine content as described above.

The state (dissolution or peeling) of the coating film surface after rubbing the coating film surface with a cotton cloth impregnated with chemical-resistant methanol was visually observed. Evaluation of chemical resistance was performed as follows.
○: No change Δ: Partially dissolved or peeled ×: Dissolved or peeled

Using a contact angle meter for water contact (CA-DT manufactured by Kyowa Interface Chemical Co., Ltd.), 3 μl of pure water was brought into contact with the surface of the substrate at room temperature to form droplets. The angle between the droplet and the surface generated at this time was measured to determine the contact angle with water. The results are shown in Table 8.

Comparative Example 2
A mixed solution having the following composition was prepared (photocuring system).

Curable composition (d1)
(I) 50 parts by mass of UH-2032 (ii) 50 parts by mass of TMPA (iii) 3 parts by mass of Irgacure 907.

  The obtained curable composition (d1) was applied and cured in the same manner as in Examples 8 and 9, and the coating film was evaluated. The results are shown in Table 8.

The graph which shows the measurement result (-SH group) of IR absorption (Before ultraviolet irradiation, the mixed solution (a2) after ultraviolet irradiation of intensity 2000 mJ / cm < ² > U and 5000 mJ / cm < ² > U) The graph which shows the measurement result (C = C coupling | bonding) of IR absorption (The mixed solution (a2) after ultraviolet irradiation of 2000 mJ / cm < ² > U and 5000 mJ / cm < ² > U intensity | strength before ultraviolet irradiation)

Claims (11)

General formula (1)
—S—CX ₂ CHF—Z—O—Rf (1)
[In the formula, Rf is a fluorine-containing alkyl group having 1 to 40 carbon atoms having a substituent, or a fluorine-containing alkyl group having 2 to 100 carbon atoms having a substituent, and the substituent is —OH, From —CH ₂ OH, —COOR ¹ , —CONR ² R ³ , —NH ₂ , —COCl, —SO ₂ F, —CN, —COOH, —COOH derivatives, —SO ₃ H and —SO ₃ H derivatives At least one selected from the group consisting of: R ¹ is an alkyl group or a fluorine-containing alkyl group; R ² and R ³ are the same or different and are H, an alkyl group or a fluorine-containing alkyl group; Differently, it is H or F, and Z is —CF ₂ — or a single bond. ]
The compound which has two or more groups represented by these. General formula (1a)

[Wherein T is a hydrocarbon which may have at least one heteroatom selected from the group consisting of O, N and S, p is an integer of 2 or more, and X, Z and Rf are Each is the same or different and is the same as above. ]
The compound of Claim 1 represented by these. General formula (1b)

Wherein R ⁴ is the same or different and is a single bond, —C _a H _2a —, —C _b H _2b —B—C _c H _2c — or —S—C _d H _2d —, a, b, c and d are the same or different and are an integer of 1 or more, B is —S—, —C (═O) O—, —OC (═O) — or —O—, and A is —C _e H _2e - or _{-C f H 2f -E-C g} H 2g - and is, e, f and g are the same or different integer of 1 or more, E is -S -, - C (= O ) O- , —OC (═O) — or —O—, wherein R ⁵ is H, an optionally substituted alkyl group, or —R ⁴ —S—CX ₂ CHF—Z—O—Rf Wherein R ⁶ is H, an alkyl group which may have a substituent, or a group represented by the formula: —R ⁴ —S—CX ₂ CHF—Z—O—Rf, Q is 0 or more Is a number, X, Z and Rf is as defined above the same or different. ]
The compound of Claim 2 represented by these. General formula (1c)

[Wherein, Q has an optionally substituted aliphatic ring, an optionally substituted heteroaliphatic ring, an optionally substituted aromatic ring or a substituted group. Each of the substituents may be an alkyl group, —OH, —COOR ⁷ , —CONR ⁸ R ⁹ , —NH ₂ , —COCl, —SO ₂ F, —SO ₃ H and At least one selected from the group consisting of —CN, R ⁷ is H, an alkyl group or a fluorine-containing alkyl group, and R ⁸ and R ⁹ are the same or different and are H, an alkyl group or a fluorine-containing alkyl group. , R is an integer of 2 or more, and X, Z and Rf are the same as or different from each other. ]
The compound of Claim 2 represented by these. X is H, Z is -CF ₂ - A compound according to claim 1 in which.   The compound according to any one of claims 1 to 4, wherein X is F and Z is a single bond. Rf is a linear or branched fluorinated alkyl group having 1 to 20 carbon atoms having a substituent, or a linear or branched fluorinated alkyl group having an ether bond having 2 to 50 carbon atoms having a substituent. The substituent is at least one selected from the group consisting of —OH, —CH ₂ OH, —COOH, —COOR ¹ (wherein R ¹ is the same as above) and —CN. A compound according to claim 1. Two or more general formulas (1) in the molecule
—S—CX ₂ CHF—Z—O—Rf (1)
[In the formula, Rf is a fluorine-containing alkyl group having 1 to 40 carbon atoms having a substituent, or a fluorine-containing alkyl group having 2 to 100 carbon atoms having a substituent, and the substituent is —OH, ^{_{-CH 2 OH, -COOR 1, -CONR}} 2 R 3, -NH 2, -COCl, -SO 2 F, -SO 3 H, -CN, -COOH, a derivative of -COOH, -SO ₃ H and -SO _And at least one selected from the group consisting of ₃ H derivatives, R ¹ is an alkyl group or a fluorinated alkyl group, and R ² and R ³ are the same or different and are H, an alkyl group or a fluorinated alkyl group. , X are the same or different and are H or F, and Z is —CF ₂ — or a single bond. ]
Wherein the compound having two or more thiol groups in the molecule is represented by the general formula (2).
CX ₂ = CF—Z—O—Rf (2)
[Wherein, X, Z and Rf are the same as defined above. ]
The manufacturing method characterized by making it react with the compound represented by these.   The crosslinking agent for coating materials which consists of a compound in any one of Claims 1-6.   The curable composition containing the compound in any one of Claims 1-6.   A cured product obtained by curing the curable composition according to claim 10.

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