JP2003055353A - Method for manufacturing thiol compound derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a new thiol compound derivative giving a rubber composition or a resin composition having excellent storage stability, processability and curing property. SOLUTION: The method for manufacturing a thiol compound derivative comprises allowing a thiol compound to come into contact with a vinyl ether to obtain the thiol compound derivative. A composition containing a thiol compound derivative has excellent storage stability and capable of performing curing quickly at an adequate timing. A cured product obtained from the composition has excellent physical properties.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thiol compound derivative and a method for producing the same. More specifically, it relates to a thiol compound derivative which is added to a polymer having reactivity with a thiol derivative substituent to give a curable composition.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Generally, when a diene rubber composition or a chlorine rubber composition to which a vulcanizing compounding agent such as a vulcanizing agent or a vulcanization accelerator is added is stored, vulcanization is gradually performed. As a result, the viscosity may increase, the scorch time may decrease, the vulcanization rate may decrease, and the processability of the composition into a product and the physical properties of the vulcanized product may deteriorate. From the viewpoint of maintaining storage stability, it is desirable that these changes are small. If no vulcanizing compounding agent is added, these changes are small, but from the viewpoint of productivity, a curable composition in which the vulcanizing compounding agent is added in advance is generally used, and the vulcanizing compounding agent is It is important to improve storage stability in the added state.

Conventionally, polythiol compounds such as dithiol compounds and trithiol compounds have been known as vulcanizing compounds such as diene rubber and chlorine rubber. However, since these polyvalent thiol compounds have high reactivity, they cause early vulcanization when kneading rubber and the vulcanizing compounding agent and processing, or perform kneading smoothly without early vulcanization. Even if it can be, it may gel during the subsequent storage, even if the resulting cured product has excellent physical properties,
There was a problem of lacking storage stability. For this reason,
Attempts have been made to improve storage stability by using an early vulcanization inhibitor in combination, but there are problems such as the use of an early vulcanization inhibitor in combination reduces the vulcanization rate and deteriorates heat resistance. It was

Therefore, the inventors of the present invention have conducted diligent research to solve the above problems, and use an early vulcanization inhibitor which adversely affects the physical properties of a cured product such as a diene rubber composition and a chlorine rubber composition. In addition, the inventors have found a novel thiol compound derivative that provides a rubber composition or a resin composition that is excellent in storage stability, processability and curability, and has completed the present invention.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for producing a novel thiol compound derivative which gives a rubber composition or resin composition having excellent storage stability, processability and curability.

[0006]

SUMMARY OF THE INVENTION The method for producing a thiol compound derivative of the present invention is characterized in that a thiol compound derivative is obtained by contacting a thiol compound with vinyl ethers. The thiol compound is preferably triazine thiol. In the method for producing a thiol compound of the present invention, vinyl ethers are monovinyl ether,
A vinyl ether selected from monovinyl thioethers and cyclic vinyl ethers is preferable, and the vinyl ethers are also preferably polyvalent vinyl ethers.

Further, in the method for producing a thiol compound of the present invention, it is also preferable that the thiol compound is triazine thiol and the vinyl ether is a polyvalent vinyl ether. When the thiol compound is triazine thiol, the triazine thiol has the following general formula (1)

[0008]

[Chemical 3]

Preferably, it is represented by The triazine thiol is also preferably represented by the following general formula (2).

[0010]

[Chemical 4]

[In the formula (2), R ¹ is one kind of group selected from the groups represented by the following (a) to (e): (a) hydrogen atom, alkyl group, alkenyl group, alkynyl A group selected from a group, a phenyl group, an aralkyl group and —NH ₂ ; (b) the following general formula (3) —NR ² R ³ ... (3) (wherein R ² and R ³ are an alkyl group or an alkenyl group) , An alkynyl group, an aralkyl group, a benzyl group, an allyl group, a cycloalkyl group, a fluoroalkyl group and a phenyl group, and R ² and R ³ may be the same or different. Dialkylamino group: (c) General formula (4) —NHR ⁴ (4) (wherein R ⁴ is an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, a benzyl group, an allyl group, a cycloalkyl group) Group, fluoroalkyl group, anilino group, hydroxyanili . Showing a group selected from the group and a phenyl group mono-alkylamino group represented by): (d) the following general formula ^{(5) -OR 5 ··· (5} ) ( provided that, R ⁵ is an alkyl group, an alkenyl group , An aralkyl group, a halogenophenyl group, a naphthyl group, a cycloalkyl group and a phenyl group.): (E) The following general formula (6) —SR ⁶ ... (6) ( However, R ⁶ represents a group selected from an alkyl group, an alkenyl group, an alkynyl group, a phenyl group, an aralkyl group, a halogenophenyl group, a naphthyl group and a cycloalkyl group.

The polyvalent vinyl ether is preferably at least one selected from divinyl ethers, trivinyl ethers and tetravinyl ethers. In the method for producing a thiol compound derivative of the present invention, it is preferable to bring the thiol compound and vinyl ethers into contact with each other in the presence of an acidic catalyst. It is also preferable that the thiol compound and the vinyl ether are brought into contact with each other in the presence of an acidic catalyst and then treated with hydrotalcite or metal alkoxide.

The acidic catalyst is preferably an acidic phosphoric acid ester. The metal of the metal alkoxide is
A metal selected from the group consisting of Ti, Al and Zr is preferable. The thiol compound derivative of the present invention is
It is obtained by contacting a thiol compound and vinyl ethers.

The curable composition of the present invention is characterized by containing a thiol compound derivative obtained by the method for producing a thiol compound derivative of the present invention.

[0015]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be specifically described below. In the present invention, a thiol compound is brought into contact with a vinyl ether to produce a thiol compound derivative. <Thiol Compound> The thiol compound used in the present invention is preferably one having two or more thiol groups bonded per molecule, and any thiol compound can be used as long as it is such a thiol.

Examples of such thiol compounds include phenylthiols such as dimercaptobenzene,
Thiocarboxylic acids, thiol compounds such as thiadiazole, mercaptoalkyltrialkoxysilanes such as γ-mercaptopropyltrimethoxysilane, aliphatic dithiols such as 1,10-dimercaptodecane, the following formula (1)
Examples include 1,3,5-triazine-2,4,6-trithiol represented by and triazinethiols represented by the following general formula (2).

[0017]

[Chemical 5]

[0018]

[Chemical 6]

In addition to these trithiol compounds and dithiol compounds, it is also possible to use, as the thiol compound, a monothiol compound in which one of the thiol groups (--SH) of the general formula (2) is further substituted with R ^1. it can. formula
In (2), R ¹ includes one kind of group selected from the groups represented by the following (a) to (e). (a) A group selected from a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a phenyl group, an aralkyl group and -NH ₂ .

Of these, a hydrogen atom, an alkyl group and a phenyl group are preferred. The alkyl group preferably has 1 to 25 carbon atoms, more preferably 1 to 1 carbon atoms.
8 alkyl groups can be mentioned. Examples of such an alkyl group include linear, branched, and cyclic groups, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a te group.
rt-butyl group, pentyl group, hexyl group, heptyl group,
Examples thereof include an octyl group, a 2-ethylhexyl group, a decyl group, a cetyl group, a stearyl group and a 1-menthyl group.
Of these, a methyl group and an ethyl group are preferable.

The alkenyl group is preferably an alkenyl group having 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms. As such an alkenyl group,
For example, propanedienyl group, isopropenyl group, 3
Examples thereof include a methyl-2-butenyl group, an allyl group, and a 2-methylallyl group. Of these, the isopropenyl group is preferred.

The alkynyl group is preferably an alkynyl group having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. As such an alkynyl group,
For example, a propargyl group, a 1-phenylpropargyl group and the like can be mentioned. Of these, the propargyl group is preferred. As the aralkyl group, an aralkyl group having preferably 1 to 20 and preferably 1 to 10 carbon atoms can be mentioned. Examples of such an aralkyl group include a 4-phenylbutyl group and the like.

As the phenyl group, a phenyl group (C ₆ H ₅
-), Methoxyphenyl group, o-tolyl group, p-nitrophenyl group, 2-nitrophenyl group, 3-nitrophenyl group, p-
Fluorophenyl group, p-methoxyphenyl group, p-aminophenyl group, N-methylaminophenyl group, p- (dimethylamino) phenyl group, 4-acetylphenyl group, p-iodophenyl group, p-chlorophenyl group, 2 -Piperidinoethyl group, 2,4,6-trichlorophenyl group, 2,4,6-trimethylphenyl group, 2,4,6-tribromophenyl group, 2,4-dichlorophenyl group, 2,4-dibromophenyl group, Examples include 2,4-dimethylphenyl group. Of these, a phenyl group is preferred. (b) A dialkylamino group represented by the following general formula (3) —NR ² R ³ (3). However, R ² and R ³ are groups selected from an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, a benzyl group, an allyl group, a cycloalkyl group and a fluoroalkyl group, and R ² and R ³ are the same as each other. Or they may be different. Of these,
An alkyl group and an alkenyl group are preferable.

The alkyl group is preferably an alkyl group having 1 to 25 carbon atoms, more preferably 1 to 18 carbon atoms. As such an alkyl group, a straight chain,
Both branched and cyclic, for example, a methyl group,
Ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group,
Pentyl group, hexyl group, heptyl group, octyl group, 2
Examples thereof include an ethylhexyl group, a decyl group, a cetyl group, a stearyl group and a 1-menthyl group. Of these, a methyl group and an ethyl group are preferred.

The alkenyl group is preferably an alkenyl group having 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms. As such an alkenyl group,
For example, propanedienyl group, isopropenyl group, 3
Examples thereof include a methyl-2-butenyl group, an allyl group, and a 2-methylallyl group. Among these, an isopropenyl group and the like are preferable.

The alkynyl group is preferably an alkynyl group having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. As such an alkynyl group,
For example, a propargyl group, a 1-phenylpropargyl group and the like can be mentioned. Of these, the propargyl group is preferred. As the aralkyl group, an aralkyl group having preferably 1 to 20 and preferably 1 to 10 carbon atoms can be mentioned. Examples of such an aralkyl group include a methylbenzyl group and the like.

Examples of the benzyl group include a benzyl group and a 1-phenylethyl group. Examples of the cycloalkyl group include a cyclohexyl group and a cyclopentyl group. A tetrafluoroethyl group is mentioned as a fluoroalkyl group. (c) A monoamino group represented by the following general formula (4) —NHR ⁴ (4). However, R ⁴ is an alkyl group,
A group selected from an alkenyl group, an alkynyl group, an aralkyl group, a benzyl group, an allyl group, a cycloalkyl group, a fluoroalkyl group, an anilino group and a hydroxyanilino group is shown.

Of these, alkyl groups are preferred. Examples of the alkyl group, alkenyl group, alkynyl group, aralkyl group, benzyl group, allyl group, cycloalkyl group and fluoroalkyl group include the same groups as the groups represented by R ⁶ and R ⁷ . Examples of the anilino group include anilino group and p-methylanilino group.

The hydroxyanilino group includes o-, m-,
Examples include groups derived from p-hydroxyaniline derivatives. (j) Group represented by the following general formula (5) -OR ⁵ ... (5). However, R ⁵ represents a group selected from an alkyl group, a phenyl group, an alkenyl group, an aralkyl group, a halogenophenyl group, a naphthyl group and a cycloalkyl group. Of these, alkyl groups and phenyl groups are preferred.

The alkyl group is preferably an alkyl group having 1 to 25 carbon atoms, and more preferably 1 to 18 carbon atoms. As such an alkyl group, a straight chain,
Both branched and cyclic, for example, a methyl group,
Ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group,
Pentyl group, hexyl group, heptyl group, octyl group, 2
Examples thereof include an ethylhexyl group, a decyl group, a cetyl group, a stearyl group and a 1-menthyl group. Of these, a methyl group and an ethyl group are preferred.

The alkenyl group is preferably an alkenyl group having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. As such an alkenyl group,
For example, propanedienyl group, isopropenyl group, 3
Examples thereof include a methyl-2-butenyl group, an allyl group, and a 2-methylallyl group. Among these, an isopropenyl group and the like are preferable.

The aralkyl group is preferably an aralkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Examples of such an aralkyl group include a 4-phenylbutyl group and the like. The halogenophenyl group, p-iodophenyl group, p-chlorophenyl group, p-bromophenyl group, 2,4-dichlorophenyl group, 2,4-dibromophenyl group, 2,4-diiodophenyl group, 2,4 Examples thereof include a 6,6-trichlorophenyl group and a 2,4,6-tribromophenyl group. Of these, p-chlorophenyl group is preferable.

Examples of the cycloalkyl group include cyclohexyl group and cyclopentyl group. (e) Group represented by the following general formula (6) —SR ⁶ ... (6). However, R ⁶ represents a group selected from an alkyl group, an alkenyl group, an alkynyl group, a phenyl group, an aralkyl group, a halogenophenyl group, a naphthyl group and a cycloalkyl group. Of these, alkyl groups are preferred.

Examples of the alkyl group, alkenyl group, aralkyl group, halogenophenyl group, naphthyl group and cycloalkyl group are the alkyl group, alkenyl group, aralkyl group, halogenophenyl group, naphthyl group and cycloalkyl group represented by R ^5. The same thing as is mentioned.
The alkynyl group preferably has 1 to 2 carbon atoms.
There are 0, and more preferably 1 to 10 alkynyl groups. Examples of such an alkynyl group include a propargyl group and a 1-phenylpropargyl group. Of these, the propargyl group is preferred.

As the phenyl group, a phenyl group (C ₆ H ₅
-), Methoxyphenyl group, o-tolyl group, p-nitrophenyl group, 2-nitrophenyl group, 3-nitrophenyl group, p-
Fluorophenyl group, p-methoxyphenyl group, p-aminophenyl group, N-methylaminophenyl group, p- (dimethylamino) phenyl group, 4-acetylphenyl group, p-iodophenyl group, p-chlorophenyl group, 2 -Piperidinoethyl group, 2,4,6-trichlorophenyl group, 2,4,6-trimethylphenyl group, 2,4,6-tribromophenyl group, 2,4-dichlorophenyl group, 2,4-dibromophenyl group, Examples include 2,4-dimethylphenyl group. Of these, a phenyl group and a methoxyphenyl group are preferred.

Specific examples of the dithiol compound represented by the above general formula (2) include s-triazine-2,4 dithiol, 6-methyl-s-triazine-2,4 dithiol, 6-phenyl-s-triazine-2,4 dithiol, 6-amino-s-triazine-
2,4 dithiol, 6-dihexylamino-s-triazine-2,4 dithiol, 6- [bis (2-hexyl)
Amino] -s-triazine-2,4 dithiol, 6-diethylamino-s-triazine-2,4 dithiol, 6
-Dicyclohexylamino-s-triazine-2,4 dithiol, 6-diphenylamino-s-triazine-
2,4 dithiol, 6-dibenzylamino-s-triazine-2,4 dithiol, 6-diallylamino-s-triazine-2,4 dithiol, 6-didodecylamino-
s-Triazine-2,4 dithiol, 6-dibutylamino-s-triazine-2,4 dithiol, 6-dimethylamino-s-triazine-2,4 dithiol, 6-phenylamino-s-triazine-2,4 dithiol , 2-
(3,5-Di-tert-butyl-4-hydroxyanilino) -s-triazine-2,4dithiol, 6-stearylamino-s-triazine-2,4dithiol, 6-
Ethylamino-s-triazine-2,4 dithiol, 6
-Hexylamino-s-triazine-2,4 dithiol, 6- (cis-9-octadecenylamino) -s-triazine-2,4 dithiol, 6-cyclohexylamino-
s-triazine-2,4 dithiol, 6- (4-anilino-N-isopropylanilino) -s-triazine-
2,4 dithiol, 6-methoxy-s-triazine-
2,4 dithiol, 6- (1-naphthyloxy) -s-
Triazine-2,4 dithiol, 6- (m-chlorophenoxy) -s-triazine-2,4 dithiol, 6-
(2,4-Dimethylphenoxy) -s-triazine-
2,4 dithiol, 6-phenoxy-s-triazine-
2,4 dithiol etc. are mentioned.

Of these, 6-phenyl-s-triazine-2,4 dithiol is preferred. <Vinyl ethers> As the vinyl ethers used in the present invention, any vinyl ethers containing one or more vinyl groups per molecule can be used.
Monovinyl ethers, monovinyl thioethers, monovinyl ethers such as pyran derivatives and furan derivatives which are cyclic vinyl ethers, and polyvalent vinyl ethers such as divinyl ether, trivinyl ether and tetravinyl ether can be used.

Examples of monovinyl ethers include those represented by the following general formula (7).

[0039]

[Chemical 7]

In the formula (7), A is an oxygen atom or a sulfur atom, R ⁷ is a hydrogen atom, an alkyl group or a phenyl group, and R ⁸ is a group consisting of the following (f) to (k). R ⁹ is a hydrogen atom, an alkyl group or a phenyl group, and R ⁷ and R ⁸ may form a ring: (f) an alkyl group or a halogenated alkyl group. , At least 1
One group selected from an alkyl group having one hydroxyl group, an alkenyl group, an alkynyl group and an aralkyl group; (g) an alkylene glycol, a dialkylene glycol,
One hydroxyl group-containing compound selected from trialkylene glycol, tetraalkylene glycol, allyl alcohols, ketoxime, alkanolamines, dialkanolamines, trialkanolamines, trialkylsilanols, alicyclic alcohols and naphthyl alcohols From which the hydroxyl group is removed; (h) General formula (8) —CHY—CH ₂ X (8) (wherein, X is a halogen atom, an alkoxy group, an alkoxyalkoxy group, or a dialkyl group). A group represented by any of an amino group, a trialkylsilyl group, an acetoxy group or a piperidino group, and Y represents a hydrogen atom or a halogen atom); (i) the following general formula (9)

[0041]

[Chemical 8]

(In the formula (9), Z is a hydrogen atom, a halogen atom,
Represents a nitro group, an amino group, an alkoxy group, an alkylamino group, a dialkylamino group, an alkyl group or an acyl group, n is an integer of 1 to 3, and a phenyl group skeleton represented by the formula (9) The number of the substituents Z bonded to is shown. Groups represented _{by); (j) -CH 2 -C} 6 H 5 or -CHCH ₃ -C ₆ group represented by H _5; (k) the following general formula ^{(10) -R 10 -ACH = CH} 2 ... (10) or the following general formula (11)

[0043]

[Chemical 9]

(In the formula (11), R ¹ and R ³ are respectively the above-mentioned formulas.
The same as R ⁷ and R ^{9 in} (7), and in the formulas (10) and (11),
A is an oxygen atom or a sulfur atom, and R ¹⁰ is -C.
_{H 2 -, - CH 2 CH} 2 -, - CH 2 CH 2 CH 2 -, - CH
_{2 CH 2 CH 2 CH 2 -} , - CH 2 CH 2 OCH 2 CH 2 -, -
_{CH 2 CH 2 OCH 2 CH 2} OCH 2 CH 2 -,

[0045]

[Chemical 10]

One of the following is shown. ) Is a group represented by. R ⁷ and R ^{8 in} the general formula (7) may form a ring. When R ⁷ and R ⁸ form a ring, both R ⁷ and R ⁸ are preferably an alkyl group, and the alkyl group may have a substituent. In this case, R ⁹ is preferably a hydrogen atom.

Specific examples of such a vinyl ether include the compounds shown below. Methyl-1 phenyl vinyl ether, ethyl-1 phenyl vinyl ether, methyl-1 methyl vinyl ether, ethyl-1 ethyl vinyl ether, ethyl-1 methyl vinyl ether, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, sec-butyl vinyl ether, tert-butyl vinyl ether, pentyl vinyl ether, hexyl vinyl ether, heptyl vinyl ether, octyl vinyl ether, 2-ethylhexyl vinyl ether, decyl vinyl ether, cetyl vinyl ether, stearyl vinyl ether, propadienyl vinyl ether, isopropenyl vinyl ether, 2-propynyl vinyl ether, 3-butynyl bi Ether, 3-methyl-2-butenyl vinyl ether, allyl vinyl ether, ethylene glycol monovinyl ether, diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, triethanolamine monovinyl ether, 1-chloroethyl vinyl ether, 2-chloroethyl vinyl ether, acetone oxime Vinyl ether,
2-methylallyl vinyl ether, 3-phenylpropargyl vinyl ether, cyclohexyl vinyl ether, 2-bromoethyl vinyl ether, methoxyethyl vinyl ether, 2-butoxyethyl vinyl ether,
Diethylene glycol methyl vinyl ether, 2-acetoxyethyl vinyl ether, dimethylaminoethyl vinyl ether, 2- (diethylamino) ethyl vinyl ether, aminoethyl vinyl ether, 3-dimethylaminopropyl vinyl ether, trimethylsiloxyethyl vinyl ether, trimethylsilyl vinyl ether,
Triethylsilyl vinyl ether, 1-menthyl vinyl ether, 2-methoxyphenyl vinyl ether, o-
Tril vinyl ether, p-nitrophenyl vinyl ether, 2-naphthyl vinyl ether, phenyl vinyl ether, p-fluorophenyl vinyl ether, p-methoxyphenyl vinyl ether, p-aminophenyl vinyl ether, 2,4,6-trichlorophenyl vinyl ether, 2,4,6 -Trimethylphenyl vinyl ether, 2,4-dichlorophenyl vinyl ether, 2,
4,6-tribromophenyl vinyl ether, N-methylaminophenyl vinyl ether, p- (dimethylamino) phenyl vinyl ether, 4-acetylphenyl vinyl ether, 2-nitrophenyl vinyl ether, 3
-Nitrophenyl vinyl ether, p-iodophenyl vinyl ether, p-chlorophenyl vinyl ether,
1-phenylethyl vinyl ether, benzyl vinyl ether, 2-piperidinoethyl vinyl ether and the like can be mentioned.

Specific examples of the cyclic monovinyl ether include 2,3-dihydrofuran, 3,4-dihydrofuran, 2,3-dihydro-2H-pyran, 3, and the like.
4-dihydro-2H-pyran, 3,4-dihydro-2-
Methoxy-2H-pyran, 3,4-dihydro-4,4-
Dimethyl-2H-pyran-2-one, 3,4-dihydro-2-ethoxy-2H-pyran and the like can be mentioned.

Examples of the polyvalent vinyl ethers include divinyl ether, trivinyl ether, tetravinyl ether and the like. Specific examples of the divinyl ether include divinyl ether, divinyl formal, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, triethanolamine divinyl ether, 1,3-propanediol divinyl ether,
Examples thereof include 1,4-butanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, 4,4′-dihydroxyazobenzene divinyl ether, hydroquinone divinyl ether and bisphenol A divinyl ether.

Specific examples of the trivinyl ether include glycerol trivinyl ether and the like. Specific examples of the tetravinyl ether include pentaerythritol tetravinyl ether and the like. When the polyvalent vinyl ether is used for the production, the polyvalent vinyl ether may crosslink with a plurality of thiol compounds to form a polymer compound depending on the production conditions.

Examples of the vinyl thioether include vinyl thioethers corresponding to the above vinyl ethers and cyclic monovinyl ethers. Specific examples of such vinyl thioether include 3- (trimethylsilyl) propyl vinyl thioether, 2-hydroxyethyl vinyl thioether, 2- (N-morpholino) ethyl-S-vinyl thioether, and 2- (N- β-hydroxyethyl) aminoethyl-S-vinyl thioether, 2-aminoethyl vinyl thioether, p-chlorophenyl thioether, phenyl vinyl thioether, divinyl thioether and the like.

<Catalyst> When the thiol compound derivative according to the present invention is produced by reacting the thiol compound with vinyl ethers or the like, a catalyst can be used if necessary. As the catalyst, an acidic catalyst is preferable, and as the acidic catalyst, acidic phosphoric acid ester, hydrogen chloride, thionyl chloride, zinc chloride and the like can be used. Of these, acidic phosphoric acid esters can be preferably used.

As such an acidic phosphoric acid ester,
For example, the following general formula (12)

[0054]

[Chemical 11]

In the formula (12), R ¹¹ is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group or an allyl group,
m is 1 or 2. Such an acidic phosphoric acid ester is a phosphoric acid monoester or phosphoric acid diester of a primary alcohol or a secondary alcohol, and specific examples of the primary alcohol include 1-propanol, 1-butanol, and 1-butanol. -Hexanol, 1-octanol, 2-ethylhexyl alcohol, etc. are mentioned, and as the secondary alcohol, 2-propanol, 2-
Butanol, 2-hexanol, 2-octanol, cyclohexanol, etc. are mentioned.

Such acidic phosphates may be used alone or in combination of two or more. When using the said acidic phosphoric acid ester, the usage-amount is about 0.05-5 weight% preferably with respect to the said thiol compound. If the amount of acidic phosphoric acid ester used is small, the reaction rate may become slow. <Reaction Solvent> The reaction between the thiol compound and vinyl ethers can be carried out without solvent or in a solvent. From the viewpoint of reaction rate and operability, it is preferably carried out in a solvent. As such a solvent, a known organic solvent can be used, and examples thereof include hydrocarbons, ethers, esters, and ketones. Specifically, benzene,
Examples thereof include toluene, xylene, ethylbenzene, dioxane, tetrahydrofuran, diethyl ether, dipropyl ether, methyl acetate, ethyl acetate, butyl acetate, isopropyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone and methyl propyl ketone.

Of these, acetone can be preferably used. <Treatment> In the method for producing a thiol compound derivative of the present invention, when the thiol compound and vinyl ethers are reacted in the presence of an acidic catalyst, hydrotalcite or metal alkoxide is optionally added after the reaction. May be processed. When such a treatment is performed, the catalyst mixed in the obtained thiol compound derivative is removed or deactivated, and the storage stability of the obtained thiol compound derivative is improved, which is preferable.

When an active catalyst is mixed in the obtained thiol compound derivative, the obtained thiol compound derivative may be hydrolyzed depending on storage conditions. Therefore, in the method for producing a thiol compound derivative of the present invention, when a thiol compound and a vinyl ether are reacted in the presence of a catalyst, the catalyst mixed in the reaction product is removed or deactivated. Is preferred. When the mixed catalyst is removed or deactivated,
Even when stored in the air for a long period of time, the thiol compound derivative is less likely to be decomposed, is stable, has excellent storability, and is more practical.

A thiol compound and vinyl ethers,
When the thiol compound derivative is obtained by contacting in the presence of an acidic catalyst, particularly an acidic phosphoric acid ester, it is desirable to treat with hydrotalcite or metal alkoxide. In the treatment with hydrotalcite, a reaction product containing an acidic catalyst such as an acidic phosphoric acid ester is brought into contact with hydrotalcite to adsorb the acidic catalyst on the hydrotalcite. The catalyst adsorbed on the hydrotalcite can be easily removed from the reaction product by a method such as filtration or precipitation.

In the treatment with metal alkoxide, metal alkoxide is added to the reaction product containing an acidic catalyst such as acidic phosphoric acid ester. As a result, the acid groups of the acidic catalyst (such as the phosphoric acid group of the acidic phosphoric acid ester) can be destroyed, and the catalyst mixed in the reaction product can be deactivated. The metal alkoxide metal used is Ti, A
Preferably, it is a metal selected from the group consisting of 1 and Zr.

<Production of thiol compound derivative> In the present invention, specifically, in the above solvent or without solvent, if necessary, in the presence of an acidic solvent such as an acidic phosphoric acid ester,
A thiol compound derivative can be produced by bringing the thiol compound and the vinyl ether into contact with each other, preferably in a temperature range of room temperature to 180 ° C. The reaction time is usually preferably about 1 to 60 minutes.

In the production of such a thiol compound derivative, the thiol compound and vinyl ethers may be contacted with each other in the presence of an acidic catalyst, and then treated with hydrotalcite or metal alkoxide, if necessary. . When the treatment is performed with a metal alkoxide, the metal of the metal alkoxide is preferably a metal selected from the group consisting of Ti, Al and Zr.

In the thiol compound derivative obtained by the method of the present invention in which the thiol compound and the vinyl ethers are brought into contact with each other, all or some of the hydrogen atoms of the thiol group of the starting thiol compound are substituted with vinyl ethers. A desired thiol compound derivative can be obtained by controlling the compounding ratio of a thiol compound and vinyl ethers. Specifically, for example, the reaction may be performed in the following mixing ratio.

When the above-mentioned trithiol compound (1) is used as a raw material and all the hydrogen atoms of the three thiol groups (--SH) are substituted with vinyl ethers to obtain a thiol compound derivative, 1 mol of the trithiol compound (1) is used. Thus, it is desirable to use vinyl ethers in an amount of preferably 3 to 5 mol. Using the trithiol compound (1) as a raw material, two of the hydrogen atoms of three thiol groups (-SH) are used.
When one is substituted with vinyl ether or the like to obtain a thiol compound derivative, it is desirable to use the vinyl ether in an amount of preferably 1.8 to 2.3 mol with respect to 1 mol of the trithiol compound (1).

Further, in the case of obtaining a thiol compound derivative in which the hydrogen atom of the thiol group is substituted with an alkali metal, an aqueous solution of the trithiol compound (1) and sodium hydroxide or potassium hydroxide is added to 1 mol of the trithiol compound (1). It is obtained by reacting 1.8 to 2.3 moles of vinyl ethers with the salt obtained by reacting 1 to 1.1 moles.

Using the dithiol compound (2) as a raw material,
When all the hydrogen atoms of two thiol groups (-SH) are substituted with vinyl ethers or the like to obtain a thiol compound derivative, vinyl ethers are preferably contained in an amount of 2 to 5 moles per 1 mole of dithiol compound (2). Is preferred. When the dithiol compound (2) is used as a raw material and one of the hydrogen atoms of two thiol groups (-SH) is substituted with vinyl ether or the like to obtain a thiol compound derivative, 1 mol of the dithiol compound (2) is used. Thus, it is desirable to use the vinyl ether in an amount of preferably 0.8 to 1.3 mol.

Further, when a thiol compound derivative in which the hydrogen atom of the thiol group is substituted with an alkali metal is obtained, an aqueous solution of the dithiol compound (2) and sodium hydroxide or potassium hydroxide is added to 1 mol of the dithiol compound (2). It can be obtained by reacting 0.8 to 1.3 mol of vinyl ether with the salt obtained by reacting 1 to 1.1 mol.

When the vinyl ethers are polyvalent vinyl ethers, the polyvalent vinyl ethers are usually
Further, it reacts with another triazine thiol to form a crosslinked structure, and the obtained thiol compound derivative becomes a polymer. Using triazine thiol as a thiol compound,
When using a polyvalent vinyl ether as the vinyl ethers, the blending ratio of the triazine thiol and the polyvalent vinyl ether is usually different depending on the triazine thiol and the polyvalent vinyl ether used, so the following describes the preferred blending ratio for each triazine thiol. To do.

The polyvalent vinyl ether may be used alone or in combination of two or more. this house,
It is preferable to use one kind alone. (1) Reaction of triazine thiol (1) with polyvalent vinyl ether Using the triazine thiol (1) as a raw material, all or part of the hydrogen atoms of three thiol groups (-SH) are replaced with divinyl ether to give a thiol. When a compound derivative is obtained, divinyl ether is preferably added in an amount of 1.5 to 20 mol per 1 mol of triazine trithiol (1),
More preferably, it is desirable to use it in an amount of 3 to 10 mol. In this case, the divinyl ethers may form a crosslinked structure with triazine thiol, but the divinyl ethers do not form a crosslink, for example, a thiol compound derivative represented by the following general formula (13) is formed. May be.

[0070]

[Chemical 12]

In the formula (13), X ¹ , X ² and X ³ are the following general formulas.
(14)

[0072]

[Chemical 13]

In the formula, X ¹ , X ² and X ³ may be the same or different and are preferably the same. formula
In (14), A is an oxygen atom or a sulfur atom, and R
¹² is a hydrogen atom, an alkyl group or a phenyl group,
R ¹³ is a hydrogen atom, an alkyl group or a phenyl group, and R ¹⁴ is —CH ₂ —, —CH ₂ CH ₂ —, —CH ₂ CH.
_{2 CH 2 -, - CH 2} CH 2 CH 2 CH 2 -, - CH 2 CH 2 O
_{CH 2 CH 2 -, - CH} 2 CH 2 OCH 2 CH 2 OCH 2 CH 2
-,

[0074]

[Chemical 14]

Either of the above is shown. ) Is any group represented by. Of these, R ¹⁴ is —CH
_{2 -, - CH 2 CH 2} -, - CH 2 CH 2 OCH 2 CH 2 - and the like are preferable. In addition, such a non-crosslinked thiol compound derivative can be isolated by a method such as distillation.

The triazine thiol 3 of the above (1) is also used.
Two of the hydrogen atoms of one thiol group (-SH) are replaced by divinyl ethers, leaving one thiol group (15)

[0077]

[Chemical 15]

A thiol compound derivative represented by may be produced. Incidentally, the substituents X ^1, X ^2, the formula (13) are the same as the substituents X ^1, X ^2, and also identical to each other or different, are preferably the same. As described above, it is speculated that the divinyl ethers reacted with triazine thiol further react with other trithiol compounds to form a crosslinked structure. Specifically, for example, it is assumed that the terminal vinyl group of the general formula (13) reacts with other triazine thiol. When the triazine thiol (1) is used as a raw material and trivinyl ethers are used as the polyvalent vinyl ether,
It is desirable to use trivinyl ethers in an amount of preferably 1 to 15 mol, more preferably 3 to 10 mol, based on 1 mol of triazine thiol (1). in this case,
As in the case of using divinyl ether, it is speculated that trivinyl ethers form a cross-linking structure with triazine thiol, and the resulting product contains a thiol compound derivative in which trivinyl ethers do not form cross-links. May be. When the triazine thiol (1) is used as a raw material and tetravinyl ethers are used as the polyvalent vinyl ether, tetravinyl ethers are preferably 0.75 to 10 mol, and more preferably 3 to 1 mol with respect to 1 mol of the triazine thiol (1). It is desirable to use an amount of 7 moles.
In this case, as in the case of using divinyl ethers,
It is speculated that tetravinyl ethers form a crosslinked structure with triazine thiol. In addition, a thiol compound derivative in which tetravinyl ethers do not form crosslinks may be mixed in the obtained product.

Thus, the thiol compound derivative obtained from triazine thiol (1) and polyvalent vinyl ether is
It is a composition having a plurality of kinds of molecular weights having a crosslinked structure, and usually exhibits an oligomeric or polymeric state. Such a thiol compound derivative has a viscosity of preferably 10 to 10,000 cps, more preferably 10
It is preferably in the range of 0 to 1000 cps.

The weight average molecular weight of such a thiol compound derivative is preferably in the range of 400 to 10000, more preferably 1000 to 5000. (2) Reaction of triazine thiol (2) with polyvalent vinyl ether Using the triazine thiol (2) as a raw material, all or part of the hydrogen atoms of the two thiol groups (-SH) are replaced with divinyl ethers, When obtaining a thiol compound derivative, it is desirable to use the divinyl ether in an amount of preferably 1 to 20 mol, more preferably 3 to 10 mol, based on 1 mol of the triazinedithiol (2). In this case, the divinyl ethers may form a crosslinked structure with the triazine thiol, but a thiol compound derivative in which the divinyl ethers do not form a crosslink may be formed. When the triazine thiol (2) is used as a raw material and trivinyl ethers are used as the polyvalent vinyl ether,
It is desirable to use the trivinyl ethers in an amount of preferably 0.7 to 10 mol, more preferably 3 to 7 mol, based on 1 mol of the triazine thiol (2). In this case, as in the case of using divinyl ethers, trivinyl ethers are presumed to form a crosslinked structure with triazine thiol, and in the resulting product, trivinyl ethers do not form a crosslinked thiol compound. The derivative may be mixed. When the triazine thiol (2) is used as a raw material and tetravinyl ethers are used as the polyvalent vinyl ether, tetravinyl ethers are preferably 0.5 to 7 mol, and more preferably 1 to 1 mol of the triazine thiol (2). It is desirable to use an amount of 5 moles.

Thus, the thiol compound derivative obtained from the triazine thiol (2) and the polyvalent vinyl ether is
It is a composition having a plurality of kinds of molecular weights having a crosslinked structure, and usually exhibits an oligomeric or polymeric state. Such a thiol compound derivative has a viscosity of preferably 10 to 10,000 cps, more preferably 10
It is preferably in the range of 0 to 1000 cps.

The weight average molecular weight of such a thiol compound derivative is preferably in the range of 400 to 10000, more preferably 1000 to 5000. <Use of Thiol Compound Derivative> The curable composition according to the present invention contains the thiol compound derivative obtained by the production method of the present invention. The thiol compound derivative is useful as a crosslinking agent for the curable composition. The thiol compound derivative according to the present invention is a thiol group (-SH).
Is protected by a group derived from vinyl ether, or is protected by being cross-linked by a group derived from vinyl ether, therefore, when used as a vulcanizing agent such as chlorine-containing acrylic rubber, good storage stability,
For example, gelation during processing or subsequent storage can be suppressed. Further, at the time of vulcanization molding or cross-linking formation of chlorine-containing acrylic rubber or the like, the protecting group derived from vinyl ether can be eliminated by heating or the like to easily regenerate the thiol compound having a —SH group. It is possible to easily restore the reactivity and effectively vulcanize or crosslink a chlorine-containing acrylic rubber, an epoxy group-containing resin or the like to obtain a crosslinked product having excellent physical properties.

The elimination of the protective group derived from vinyl ether is preferably carried out using an acid catalyst. Examples of such an acid catalyst include halogenocarboxylic acid, sulfonic acid, sulfuric acid monoester, phosphoric acid monoester, phosphoric acid diester, boric acid monoester, boric acid diester, and the like. The thiol compound derivative according to the present invention can be used for addition to a double bond, addition to an epoxy ring, and substitution of organic chlorine after regeneration of a thiol group.

Such a thiol compound derivative can be used alone or in combination with an accelerator, a dehalogenating agent and the like. Examples of the rubber and resin having the double bond include natural rubber (NR) and isoprene rubber (I
R), styrene-butadiene rubber (SBR), butadiene rubber (BR), nitrile rubber (NBR), ethylene propylene rubber (EPDM), unsaturated polyester resin, acrylic rubber having double bonds introduced, and the like.

Examples of the rubber or resin having an epoxy group include an epoxy resin oligomer and an epoxy group-containing acrylic rubber. As the rubber or resin containing organic chlorine, acrylic rubber, chloroprene rubber (CR), epichlorohydrin rubber (CO, EC
O), chlorinated polyethylene, polyvinyl chloride and the like.

The thiol compound derivative according to the present invention can be used alone or as a mixture of a plurality of these rubbers or resins in the form of a blend or a multilayer structure. The rubber or resin containing the compound derivative is co-crosslinked, co-vulcanized,
It is useful for molding as a composite material that is vulcanized and bonded to a metal.

[0087]

The thiol compound derivative according to the present invention is
It is useful as a cross-linking agent for a curable composition composed of rubber, resin, etc., and a composition containing the thiol compound derivative according to the present invention has a suppressed storage stability before molding and curing because the reaction of the thiol compound is suppressed. Are better. Further, during molding of the composition, the highly reactive thiol compound can be easily regenerated by heat, so that the curing can be carried out timely and promptly. Further, by using the thiol compound derivative according to the present invention as a vulcanizing agent for a curable composition, an early vulcanization inhibitor for controlling the preservability or curability which may impair various physical properties of the cured product is added. Since it is not necessary to do so, it is possible to obtain a cured product having excellent physical properties.

[0088]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples. In the following Examples, the IR absorption spectrum was measured using a JASCO Corporation FT / IR-7000 type Fourier transform infrared spectrophotometer, and the liquid sample was a KRS-5 cell. After coating, each solid sample was measured by the KBr tablet method.

[0089]

Example 1 A four-necked flask equipped with a thermometer, a reflux condenser and a stirrer was charged with 35.46 g (0.2 mol) of 1,3,5-triazine-2,4,6-trithiol and butyl acid phosphate. (A
P-4 (manufactured by Daihachi Chemical Industry Co., Ltd.) (0.3 g), isobutyl vinyl ether (72.1 g (0.72 mol)) and acetone (190 g) were charged, and the mixture was reacted at 65 ° C. for 16 hours. After the reaction was completed, the insoluble matter was filtered off and the filtrate was concentrated to obtain 91 g of a viscous yellow liquid.

The viscous yellow liquid thus obtained was applied to a KRS-5 cell, the IR absorption spectrum was measured, and the measurement result chart is shown in FIG. In addition, the raw material 1,3,5-triazine-2,4,
The IR absorption spectrum of 6-trithiol was measured by the KBr tablet method, and the measurement result chart is shown in FIG. In Figure 1,
1621 on the absorption of double bonds in isobutyl vinyl ether
It can be seen that the absorption around cm ^-1 has disappeared. Also,
Regarding the absorption around 1,590 cm ⁻¹ related to the absorption of SH bond (enol structure) or C═S bond (keto structure) of 1,3,5-triazine-2,4,6-trithiol shown in FIG. Figure
It can be seen that it disappeared in 1. From this result, the obtained product is an adduct of 1,3,5-triazine-2,4,6-trithiol and isobutyl vinyl ether, that is, a thiol compound derivative in which a thiol group is added to a vinyl group. confirmed. The product yield was 93% based on 1,3,5-triazine-2,4,6-trithiol.

The obtained product, viscous yellow liquid, was applied to a slide glass in a thickness of about 1 mm, and the temperature was 23 ± 2 ° C. and the humidity was
When left in 50 ± 5% air for 70 days, it turned into a yellow solid. The IR absorption spectrum of this yellow solid was measured by the KBr tablet method using the above infrared spectrophotometer, and the results shown in FIG. 3 were obtained. Figure 3 shows that 1,3,5-triazine-2,4,6-trithiol, which is the raw material for synthesis, is assigned.
It was found that there was absorption near 590 cm ⁻¹ and the product had decomposed.

[0092]

Example 2 In a four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, 35.46 g (0.2 mol) of 1,3,5-triazine-2,4,6-trithiol and butyl acid phosphate were added. (A
P-4 (manufactured by Daihachi Chemical Industry Co., Ltd.) (0.3 g), isobutyl vinyl ether (72.1 g (0.72 mol)) and acetone (190 g) were charged, and the mixture was reacted at 65 ° C. for 16 hours. After completion of the reaction, synthetic hydrotalcite (Kyoward 500SH, Kyowa Chemical Industry Co., Ltd.)
(Made in Japan) 4.0 g, stirred at 40 ° C. for 10 hours, filtered,
The filtrate was concentrated to obtain 80 g of a viscous yellow liquid.

The viscous yellow liquid thus obtained was applied to a KRS-5 cell, the IR absorption spectrum was measured, and the measurement result chart is shown in FIG. In FIG. 4, it can be seen that the absorption around 1621 cm ⁻¹ related to the absorption of the double bond of isobutyl vinyl ether has disappeared. In addition, as shown in Fig. 2, SH bond of 1,3,5-triazine-2,4,6-trithiol (enol structure)
Or 1590 cm ^-1 related to absorption of C = S bond (keto structure)
As for absorption in the vicinity, it can be seen that it disappears in FIG. From this result, the obtained product is an adduct of 1,3,5-triazine-2,4,6-trithiol and isobutyl vinyl ether, that is, a thiol compound derivative in which a thiol group is added to a vinyl group. confirmed. The product yield was 84% based on 1,3,5-triazine-2,4,6-trithiol.

The obtained product, viscous yellow liquid, was applied to a slide glass in a thickness of about 1 mm, and the temperature was 23 ± 2 ° C. and the humidity was
After leaving it in the air of 50 ± 5% for 70 days, there was no change in appearance such as turbidity. Moreover, when the viscous yellow liquid after standing for 70 days was applied to a KRS-5 cell and the IR absorption spectrum was measured, the results shown in FIG. 5 were obtained. In FIG. 5, there was no absorption around 1590 cm ^−1, which was attributed to the synthetic raw material 1,3,5-triazine-2,4,6-trithiol, and no decomposition of the product was observed.

[0095]

Example 3 In a four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, 35.46 g (0.2 mol) of 1,3,5-triazine-2,4,6-trithiol and butyl acid phosphoric acid ester were placed. (A
P-4 (manufactured by Daihachi Chemical Industry Co., Ltd.) (0.3 g), isobutyl vinyl ether (72.1 g (0.72 mol)) and acetone (190 g) were charged, and the mixture was reacted at 65 ° C. for 16 hours. After completion of the reaction, 1.0 g of tetra (2-ethylhexyl) titanate (Organix TA-30, manufactured by Matsumoto Pharmaceutical Co., Ltd.) was added and concentrated to obtain 90 g of a viscous brown liquid.

The viscous yellow liquid thus obtained was applied to a KRS-5 cell, the IR absorption spectrum was measured, and the measurement result chart is shown in FIG. In FIG. 6, it can be seen that the absorption around 1621 cm ⁻¹ related to the absorption of the double bond of isobutyl vinyl ether has disappeared. In addition, as shown in Fig. 2, the raw materials 1,
3,5-triazine-2,4,6-trithiol absorption of SH bond (enol structure) or C = S bond (keto structure)
It can be seen in FIG. 6 that the absorption around 1590 cm ⁻¹ has also disappeared. From this result, the obtained product was 1,
It was confirmed that it is an adduct of 3,5-triazine-2,4,6-trithiol and isobutyl vinyl ether, that is, a thiol compound derivative in which a thiol group is added to a vinyl group. The product yield was 93% based on 1,3,5-triazine-2,4,6-trithiol.

The resulting product, viscous brown liquid, was applied on a slide glass to a thickness of about 1 mm, and the temperature was 23 ± 2 ° C. and the humidity was
After leaving it in the air of 50 ± 5% for 70 days, there was no change in appearance such as turbidity in the viscous brown liquid after standing. In addition, the IR absorption spectrum of the viscous brown liquid after standing for 70 days,
When applied to a KRS-5 cell and measured, the results shown in FIG. 7 were obtained. In Figure 7, the raw material 1,3,5-triazine-2,4,
There was no absorption around 1590 cm ^-1 attributed to 6-trithiol, and no decomposition of the product was observed.

[Brief description of drawings]

FIG. 1 is an IR absorption spectrum chart of the synthetic product obtained in Example 1.

FIG. 2 is a chart of an IR absorption spectrum of 1,3,5-triazine-2,4,6-trithiol which is a synthetic raw material of Examples 1 to 3.

FIG. 3 is a chart of an IR absorption spectrum of a sample obtained by allowing the composition obtained in Example 1 to stand in the air.

FIG. 4 is an IR absorption spectrum chart of the synthetic product obtained in Example 2.

FIG. 5 is an IR absorption spectrum chart of a sample obtained by allowing the composition obtained in Example 2 to stand in the air.

FIG. 6 is an IR absorption spectrum chart of the synthetic product obtained in Example 3.

FIG. 7 is an IR absorption spectrum chart of a sample obtained by allowing the composition obtained in Example 3 to stand in the air.

Claims (15)

[Claims] 1. A method for producing a thiol compound derivative, which comprises contacting a thiol compound with vinyl ethers to obtain a thiol compound derivative. 2. The method for producing a thiol compound derivative according to claim 1, wherein the thiol compound is triazine thiol. 3. The method for producing a thiol compound derivative according to claim 1, wherein the vinyl ether is a vinyl ether selected from monovinyl ether, monovinyl thioether and cyclic vinyl ethers. 4. The method for producing a thiol compound derivative according to claim 1, wherein the vinyl ether is a polyvalent vinyl ether. 5. The method for producing a thiol compound derivative according to claim 1, wherein the thiol compound is triazine thiol and the vinyl ethers are polyvalent vinyl ethers. 6. The triazine thiol is represented by the following general formula:
(1) [Chemical 1] The method for producing a thiol compound derivative according to claim 2 or 5, characterized in that 7. The triazine thiol has the following general formula:
(2) [Chemical 2] The method for producing a thiol compound derivative according to claim 2 or 5, wherein R ¹ is selected from the groups represented by the following (a) to (e): It is one kind of group: (a) a group selected from a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a phenyl group, an aralkyl group and —NH ₂ ; (b) the following general formula (3) —NR ² R ³ (3) (wherein R ² and R ³ are groups selected from an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, a benzyl group, an allyl group, a cycloalkyl group, a fluoroalkyl group and a phenyl group, and R ² and R ³ may be the same or different from each other.): (C) General formula (4) —NHR ⁴ ... (4) (wherein R ⁴ is Alkyl group, alkenyl group, alkynyl group, aralkyl group, benzyl group, allyl group Cycloalkyl group, a fluoroalkyl group, an anilino group, a monoalkylamino group represented by) represents a group selected from hydroxyanilino group and a phenyl group:. (D) the following general formula (5) -OR ⁵ · · · (5) (wherein R ⁵ represents a group selected from an alkyl group, an alkenyl group, an aralkyl group, a halogenophenyl group, a naphthyl group, a cycloalkyl group and a phenyl group): (e) the following general Formula (6) —SR ⁶ (6) (wherein R ⁶ represents a group selected from an alkyl group, an alkenyl group, an alkynyl group, a phenyl group, an aralkyl group, a halogenophenyl group, a naphthyl group and a cycloalkyl group. Group represented by. 8. The method for producing a thiol compound derivative according to claim 4, wherein the polyvalent vinyl ether is at least one selected from divinyl ethers, trivinyl ethers and tetravinyl ethers. 9. A thiol compound and vinyl ethers,
The method for producing a thiol compound derivative according to any one of claims 1 to 8, wherein the thiol compound derivative is contacted in the presence of an acidic catalyst. 10. The method for producing a thiol compound derivative according to claim 9, wherein the thiol compound and the vinyl ether are brought into contact with each other in the presence of an acidic catalyst and then treated with hydrotalcite or metal alkoxide. 11. The method for producing a thiol compound derivative according to claim 9, wherein the acidic catalyst is an acidic phosphoric acid ester. 12. The metal of metal alkoxide is Ti or A.
The method for producing a thiol compound derivative according to claim 10, which is a metal selected from the group consisting of 1 and Zr. 13. A thiol compound derivative obtained by contacting a thiol compound with vinyl ethers. 14. A curable composition comprising a thiol compound derivative obtained by the method for producing a thiol compound derivative according to any one of claims 1 to 12. 15. A curable composition comprising the thiol compound derivative according to claim 13.