JP7199917B2 - Thiol compound, its synthesis method and use of said thiol compound - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel thiol compound, a method for synthesizing the thiol compound, and use of the thiol compound.

Compounds having multiple thiol groups in the molecule are known as curing agents for epoxy compounds (note: epoxy resin before curing).
For example, Patent Document 1 proposes an epoxy resin composition that uses a polythiol compound as a curing agent and contains a reaction product of an amine and an epoxy compound as a curing accelerator. This epoxy resin composition is said to have a long pot life and to cure rapidly at a relatively low temperature.
In Patent Document 2, a reaction product of an isocyanate compound having one or more isocyanate groups in the molecule and a compound having at least one primary and/or secondary amino group in the molecule is used to accelerate curing. Epoxy resin compositions containing as agents have been proposed. This epoxy resin composition is also said to have a long pot life and excellent curability.

In addition, compounds with multiple thiol groups in the molecule and ene compounds with a carbon-carbon double bond in the molecule are quickly polymerized (resinized) by a polymerization initiator, so they can be used in various applications. Usage is being considered.
For example, Patent Document 3 discloses that tris[(3-mercaptopropionyloxy)ethyl]isocyanurate having three thiol groups in the molecule rapidly reacts with an ene compound to obtain a cured product having excellent properties. It is said that

However, since these thiol compounds have an ester bond in the molecule, the ester bond is hydrolyzed in a humidified environment, and there is a problem in the moisture resistance of the resulting cured product.

In addition to these documents, Patent Documents 4 and 5 are cited as documents describing inventions related to the present invention.

JP-A-6-211969 JP-A-6-211970 JP 2014-58667 A U.S. Patent Application Publication No. 2017/0007505 WO 98/58294 pamphlet

The present invention provides a novel thiol compound, a method for synthesizing the thiol compound, a curing agent containing the thiol compound, a resin composition containing the thiol compound and an epoxy compound, and the thiol compound and carbon-carbon in the molecule. An object of the present invention is to provide a resin composition containing an ene compound having a double bond.
A further object is to provide adhesives and sealants containing these resin compositions as components.

As a result of intensive studies to solve the above problems, the present inventors have found that a thiol compound obtained by reacting a certain dialkene compound with thioacetic acid or thiobenzoic acid achieves the intended purpose. can be achieved, and the present invention has been completed.
That is, the first invention is a thiol compound represented by chemical formula (I), chemical formula (II) or chemical formula (III).

（式中、４つのＲ_１は、同一または異なって、水素原子、炭素数１～１０の直鎖状のアルキル基、炭素数３～１０の分岐鎖状のアルキル基、もしくはアリール基を表す。２つのＲ_２は、同一または異なって、炭素数２～１０の直鎖状のアルキレン基、炭素数３～１０の分岐鎖状のアルキレン基、炭素数２～１０の直鎖状のアルキレンオキシ基、炭素数３～１０の分岐鎖状のアルキレンオキシ基、または、以下の化学式（ａ）～化学式（ｆ）で示される２価の有機基を表し、２つのＲ_２の少なくとも１つが、酸素原子がベンゼン環に結合しているアルキレンオキシ基を表す。但し、２つのＲ _２ が、同時に炭素数２～１０の直鎖状のアルキレンオキシ基である場合を除く。）

(In the formula, the four R _1s are the same or different and represent a hydrogen atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or an aryl group. Two R ₂ are the same or different and are a linear alkylene group having 2 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or a linear alkyleneoxy group having 2 to 10 carbon atoms. , a branched alkyleneoxy group having 3 to 10 carbon atoms, or a divalent organic group represented by the following chemical formulas (a) to (f), wherein at least one of the two R ₂ is an oxygen atom represents an alkyleneoxy group bonded to a benzene ring, except when two R ₂ are both linear alkyleneoxy groups having 2 to 10 carbon atoms.)

（式中、Ｙは、同一または異なって、水素原子もしくはメチル基を表す。）

(In the formula, Y is the same or different and represents a hydrogen atom or a methyl group.)

（式中、４つのＲ_１および２つのＲ_２は、前記と同様である。）

(In the formula, four R ₁ and two R ₂ are the same as above.)

（式中、４つのＲ_１は、同一または異なって、水素原子、炭素数１～１０の直鎖状のアルキル基、炭素数３～１０の分岐鎖状のアルキル基、もしくはアリール基を表す。２つのＲ_２は、同一または異なって、炭素数２～１０の直鎖状のアルキレン基、炭素数３～１０の分岐鎖状のアルキレン基、炭素数２～１０の直鎖状のアルキレンオキシ基、炭素数３～１０の分岐鎖状のアルキレンオキシ基、または、前記の化学式（ａ）～化学式（ｆ）で示される２価の有機基を表し、２つのＲ_２の少なくとも１つが、酸素原子がベンゼン環に結合しているアルキレンオキシ基を表す。但し、２つのＲ_２が、同時に炭素数２～１０の直鎖状のアルキレンオキシ基である場合を除く。）

(In the formula, the four R _1s are the same or different and represent a hydrogen atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or an aryl group. Two R ₂ are the same or different and are a linear alkylene group having 2 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or a linear alkyleneoxy group having 2 to 10 carbon atoms. , a branched alkyleneoxy group having 3 to 10 carbon atoms, or a divalent organic group represented by the above chemical formulas (a) to (f), wherein at least one of the two R ₂ is an oxygen atom represents an alkyleneoxy group bonded to a benzene ring, except when two R ₂ are both linear alkyleneoxy groups having 2 to 10 carbon atoms.)

The second invention is characterized by reacting a dialkene compound represented by the chemical formula (IV), chemical formula (V) or chemical formula (VI) with thioacetic acid or thiobenzoic acid to produce the thiol compound of the first invention. Synthetic method.

（式中、４つのＲ_１は、同一または異なって、水素原子、炭素数１～１０の直鎖状のアルキル基、炭素数３～１０の分岐鎖状のアルキル基、もしくはアリール基を表す。２つのＲ_３は、同一または異なって、炭素数２～１０の直鎖状のアルケニル基、炭素数３～１０の分岐鎖状のアルケニル基、炭素数２～１０の直鎖状のアルケニルオキシ基、炭素数３～１０の分岐鎖状のアルケニルオキシ基、または、以下の化学式（ｇ）～化学式（ｌ）で示される炭素－炭素二重結合を有する有機基を表し、２つのＲ _３ の少なくとも１つが、酸素原子がベンゼン環に結合しているアルケニルオキシ基を表す。但し、２つのＲ_３が、同時に炭素数２～１０の直鎖状のアルケニルオキシ基である場合を除く。）

(In the formula, the four R _1s are the same or different and represent a hydrogen atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or an aryl group. Two R _3s are the same or different and are a linear alkenyl group having 2 to 10 carbon atoms, a branched alkenyl group having 3 to 10 carbon atoms, or a linear alkenyloxy group having 2 to 10 carbon atoms. , a branched alkenyloxy group having ₃ to 10 carbon atoms, or an organic group having a carbon-carbon double bond represented by the following chemical formulas (g) to (l) ; At least one represents an alkenyloxy group in which an oxygen atom is bonded to a benzene ring, except when two R ₃ are both straight-chain alkenyloxy groups having 2 to 10 carbon atoms.)

（式中、Ｙは、前記と同様である。）

(In the formula, Y is the same as described above.)

（式中、４つのＲ_１および２つのＲ_３は、前記と同様である。）

(In the formula, four R ₁ and two R ₃ are the same as above.)

（式中、４つのＲ_１は、同一または異なって、水素原子、炭素数１～１０の直鎖状のアルキル基、炭素数３～１０の分岐鎖状のアルキル基、もしくはアリール基を表す。２つのＲ_３は、同一または異なって、炭素数２～１０の直鎖状のアルケニル基、炭素数３～１０の分岐鎖状のアルケニル基、炭素数２～１０の直鎖状のアルケニルオキシ基、炭素数３～１０の分岐鎖状のアルケニルオキシ基、または、前記の化学式（ｇ）～化学式（ｌ）で示される炭素－炭素二重結合を有する有機基を表し、２つのＲ _３ の少なくとも１つが、酸素原子がベンゼン環に結合しているアルケニルオキシ基を表す。但し、２つのＲ_３が、同時に炭素数２～１０の直鎖状のアルケニルオキシ基である場合を除く。）

(In the formula, the four R _1s are the same or different and represent a hydrogen atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or an aryl group. Two R _3s are the same or different and are a linear alkenyl group having 2 to 10 carbon atoms, a branched alkenyl group having 3 to 10 carbon atoms, or a linear alkenyloxy group having 2 to 10 carbon atoms. , a branched alkenyloxy group having 3 to 10 carbon atoms, or an organic group having a carbon-carbon double bond represented by the above chemical formulas (g) to (l), and two R ₃ At least one represents an alkenyloxy group in which an oxygen atom is bonded to a benzene ring, except when two R ₃ are both straight-chain alkenyloxy groups having 2 to 10 carbon atoms.)

A third invention is a curing agent containing the thiol compound of the first invention.
The fourth invention is a resin composition containing the thiol compound and the epoxy compound of the first invention (hereinafter sometimes referred to as "first resin composition").
A fifth invention is the resin composition of the fourth invention containing an amine as a curing accelerator.
A sixth invention is the resin composition according to the fourth invention, which contains a reaction product of an epoxy compound and amines as a curing accelerator.
A seventh invention is a reaction product of a compound having one or more isocyanate groups in the molecule and a compound having at least one of a primary amino group and a secondary amino group in the molecule to promote curing. It is a resin composition of the fourth invention containing as an agent.
The eighth invention is a resin composition containing the thiol compound of the first invention and an ene compound having a carbon-carbon double bond in the molecule (hereinafter referred to as "second resin composition" there is).
A ninth invention is an adhesive containing the resin composition according to any one of the fourth to eighth inventions as a component.
A tenth invention is a sealant containing the resin composition according to any one of the fourth to eighth inventions as a component.

A thiol compound of the present invention is a novel compound having a benzene ring. Such thiol compounds are expected to be used as curing agents for resins and as intermediate raw materials for various sulfur-containing compounds. In addition, the thiol compound of the present invention is expected to have low volatility, and is expected to have excellent compatibility (low crystallinity) with epoxy compounds, ene compounds, and the like.
And, since the thiol compound of the present invention does not have an ester bond in the molecule, when it is used as a raw material for a resin, a cured product having excellent hydrolysis resistance can be obtained as compared with the case of using a conventional polythiol compound. expected to give. It is also expected to give a cured product with low elasticity.
Further, the adhesive and sealant of the present invention are expected to be excellent in moisture resistance, water resistance and the like.

1 is an IR spectrum chart of a yellow liquid obtained in Example 1. FIG. 4 is an IR spectrum chart of the yellow liquid obtained in Reference Example 2. FIG. 4 is an IR spectrum chart of the brown liquid obtained in Reference Example 3. FIG.

The present invention relates to a thiol compound represented by the above chemical formula (I), chemical formula (II) or chemical formula (III).
Examples of the thiol compound represented by the chemical formula (I) include thiol compounds represented by the chemical formulas (I-1) to (I-16).
Examples of the thiol compound represented by the chemical formula (II) include thiol compounds represented by the chemical formulas (II-1) to (II-6).
Examples of the thiol compound represented by the chemical formula (III) include thiol compounds represented by the chemical formulas (III-1) to (III-4).

In the present invention, two R ₂ appearing in each of chemical formula (I), chemical formula (II) and chemical formula (III) are the same or different and represent divalent organic groups, as described above. The divalent organic group is a linear alkylene group having 2 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, a linear alkyleneoxy group having 2 to 10 carbon atoms, a carbon number 3 to 10 branched alkyleneoxy groups or divalent organic groups represented by the following chemical formulas (a) to (f) are preferred. Further, in each of the two R ₂ appearing in chemical formula (I), chemical formula (II) and chemical formula (III), at least one of R ₂ is an alkyleneoxy group in which an oxygen atom is bonded to a benzene ring. is more preferred.

（式中、Ｙは、同一または異なって、水素原子もしくはメチル基を表す。）

(In the formula, Y is the same or different and represents a hydrogen atom or a methyl group.)

In the present invention, examples of aryl groups include
phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4- xylyl group, 3,5-xylyl group, 2,4,6-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,5-trimethylphenyl group, 2,3,5,6-tetramethylphenyl group, 1-naphthyl group, 2-naphthyl group and the like.

The thiol compound of the present invention is produced by reacting a dialkene compound represented by chemical formula (IV), chemical formula (V) or chemical formula (VI) with thioacetic acid or thiobenzoic acid (first step), followed by hydrolysis reaction or It can be synthesized by alcoholysis (step 2) (see reaction scheme (A) below). The dialkene compound represented by the chemical formula (IV) is a precursor of the thiol compound represented by the chemical formula (I), and the dialkene compound represented by the chemical formula (V) is a precursor of the thiol compound represented by the chemical formula (II). The dialkene compound represented by the chemical formula (VI) is a precursor of the thiol compound represented by the chemical formula (III).

Examples of the dialkene compounds represented by the chemical formula (IV) include dialkenes represented by the chemical formulas (IV-1) to (IV-16).
The dialkene compounds represented by the chemical formula (V) include, for example, the dialkenes represented by the chemical formulas (V-1) to (V-6).
The dialkene compounds represented by the chemical formula (VI) include, for example, the dialkenes represented by the chemical formulas (VI-1) to (VI-4).

In the present invention, two R ₃ appearing in each of chemical formula (IV), chemical formula (V) and chemical formula (VI) are the same or different, as described above, and are organic groups having a carbon-carbon double bond. show. The organic group is a linear alkenyl group having 2 to 10 carbon atoms, a branched alkenyl group having 3 to 10 carbon atoms, a linear alkenyloxy group having 2 to 10 carbon atoms, or 3 to 10 carbon atoms. or an organic group represented by the following chemical formulas (g) to (l).

（式中、Ｙは、前記と同様である。）

(In the formula, Y is the same as described above.)

These dialkene compounds are described, for example, in J. Am. Am. Chem. Soc. , vol. 81, pp. 2705-2715 (1959).

In the first step, the amount of thioacetic acid or thiobenzoic acid to be used (amount to be charged) is preferably an appropriate ratio within the range of 2 to 40 times the molar amount of the dialkene compound to be used (amount to be charged).

For example, the thiol compound of the present invention represented by the chemical formula (I-2) is reacted with the dialkene compound represented by the chemical formula (IV-2) and the thioacetic acid represented by the chemical formula (VII), followed by addition with methanol. An example synthesized by an alcoholysis reaction is shown in Reaction Scheme (A).

In the first step, a radical initiator (a) may be used to promote the reaction. In addition, a reaction solvent (b) may be used to facilitate the reaction.
As the radical initiator (a), for example,
azobisisobutyronitrile, t-hexylperoxyisopropyl monocarbonate, t-hexylperoxy 2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, t- Butyl peroxypivalate, t-hexyl peroxypivalate, t-butyl peroxyneodecanoate, t-hexyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecano ate, 1,1-bis(t-hexylperoxy)cyclohexane, benzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, lauroyl peroxide, 2,2′-azobis(2-methylbutyronitrile) , dimethyl 2,2'-azobis(2-methylpropionate) and the like.

The amount (amount to be charged) of the radical initiator (a) to be used (amount to be charged) is preferably an appropriate ratio within the range of 0.0001 to 10 times the amount (amount to be charged) of the dialkene compound.

As the reaction solvent (b), for example,
Water, methanol, ethanol, propanol, 2-propanol, butanol, ethyl acetate, propyl acetate, butyl acetate, tetrahydrofuran, dioxane, acetonitrile, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, dimethylformamide, dimethylacetamide, dimethyl Solvents such as sulfoxide and hexamethylphosphoric acid triamide are included. As the reaction solvent (ii), these may be used in combination.

In the first step, the reaction temperature is preferably set within the range of 0 to 150°C. The reaction time is appropriately set according to the set reaction temperature, but is preferably set within the range of 1 to 120 hours.

After the reaction in the first step is completed, the reaction solvent and the like are distilled off from the resulting reaction solution (reaction mixture), and the reaction product obtained as a residue may be subjected to the second step. After completion of the reaction in step 1, the obtained reaction solution may be directly subjected to step 2.

In the second step, the alcohol used for the alcoholysis reaction is, for example,
Methanol, ethanol, propanol, 2-propanol, butanol, ethylene glycol, propylene glycol, butylene glycol, glycerin and the like.

In the second step, it is preferred to use an acid (c) or a base (d) to promote the reaction. In addition, a reaction solvent (e) may be used to facilitate the reaction.
As the acid (c), for example,
Hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide, carbonic acid, formic acid, acetic acid, benzoic acid, oxalic acid, citric acid, phosphoric acid, hexafluorophosphoric acid, nitric acid, sulfuric acid, methanesulfonic acid, toluenesulfonic acid, trifluoromethanesulfonic acid, boric acid, boron trifluoride, tetrafluoroboric acid and the like.

The amount of acid (c) used (amount charged) is preferably an appropriate ratio within the range of 0.0001 to 10 times the amount used (amount produced) of the reaction product in the first step.

As the base (d), for example,
ammonia, trimethylamine, triethylamine, diisopropylethylamine, diazabicycloundecene, diazabicyclononene, pyridine, lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, Lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium hydrogen carbonate, trilithium phosphate, trisodium phosphate, tripotassium phosphate, tricesium phosphate, dilithium hydrogen phosphate, disodium hydrogen phosphate, phosphoric acid dipotassium hydrogen phosphate, dicesium hydrogen phosphate, lithium dihydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, cesium dihydrogen phosphate, lithium acetate, sodium acetate, potassium acetate, cesium acetate, sodium methoxide, sodium ethoxide, potassium t-butoxy, and the like.

The amount of the base (d) used (amount charged) is preferably an appropriate ratio within the range of 2 to 200 times the molar amount used (amount produced) of the reaction product in the first step.

As the reaction solvent (e), for example,
Solvents such as ethyl acetate, propyl acetate, butyl acetate, tetrahydrofuran, dioxane, acetonitrile, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, dimethylformamide, dimethylacetamide, dimethylsulfoxide, and hexamethylphosphoric acid triamide. As the reaction solvent (v), these may be used in combination.

In the second step, the reaction temperature is preferably set within the range of 0 to 150°C. The reaction time is appropriately set according to the set reaction temperature, but is preferably set within the range of 1 to 120 hours.

After completion of the reaction in the second step, the target thiol compound of the present invention is removed from the resulting reaction solution (reaction mixture) by means of, for example, concentration of the reaction solution by distilling off the reaction solvent or solvent extraction. can be taken out.
Further, if necessary, purification can be carried out using means such as washing with water or the like, treatment with activated carbon, silica gel chromatography, and the like.

The thiol compound of the present invention is expected to be used as an intermediate raw material for various sulfur-containing compounds. It can also be used as a resin curing agent, that is, the curing agent of the present invention contains the thiol compound of the present invention.

(First resin composition)
The first resin composition of the present invention is obtained by incorporating the thiol compound of the present invention as a curing agent into an epoxy compound (note: epoxy resin before curing).
Any epoxy compound having an epoxy group (glycidyl group) in the molecule can be used without particular limitation.
Polyglycidyl ethers obtained by reacting polyhydric phenols such as bisphenol A, bisphenol F, bisphenol AD, catechol and resorcinol or polyhydric alcohols such as glycerin and polyethylene glycol with epichlorohydrin (for example, bisphenol A type epoxy resin);
Glycidyl ether esters obtained by reacting hydroxycarboxylic acids such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid with epichlorohydrin;
Polyglycidyl esters obtained by reacting polycarboxylic acids such as phthalic acid and terephthalic acid with epichlorohydrin;
Glycidyl glycoluril compounds having two or more epoxy groups in the molecule such as 1,3,4,6-tetraglycidyl glycoluril;
cyclic alicyclic epoxy resins such as 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate;
Nitrogen-containing cyclic epoxy resins such as triglycidyl isocyanurate and hydantoin-type epoxy resins;
Furthermore, epoxidized phenol novolak resin (phenol novolac type epoxy resin), epoxidized cresol novolac resin, epoxidized polyolefin, cycloaliphatic epoxy resin, urethane-modified epoxy resin,
An organic compound having a carbon-carbon double bond and a glycidyl group and an epoxy-modified organopolysiloxane compound obtained by a hydrosilylation addition reaction with a silicon compound having a SiH group (for example, JP-A-2004-99751 and JP-A-2006-282988 Epoxy-modified organopolysiloxane compounds disclosed in JP-A-2003-200214), etc., and these may be used in combination.

Regarding the content of the thiol compound of the present invention in the first resin composition of the present invention, the ratio (equivalent ratio) of the number of epoxy groups to the number of epoxy groups in the composition is 0.1. It is preferably set to be ~10.0.

In the first resin composition of the present invention, another thiol compound may be used in combination with the thiol compound of the present invention as a curing agent. Other thiol compounds include, for example,
ethanedithiol, propanedithiol, hexamethylenedithiol, decamethylenedithiol, tolylene-2,4-dithiol, 2,2-bis(mercaptomethyl)-1,3-propanedithiol, 2-(mercaptomethyl)-2-methyl- Aliphatic thiol compounds such as 1,3-propanedithiol and 2-ethyl-2-(mercaptomethyl)-1,3-propanedithiol;
aromatic thiol compounds such as benzenedithiol, toluenedithiol, and xylene dithiol (p-xylene dithiol);
Cyclic sulfide compounds such as 1,4-dithiane ring-containing polythiol compounds represented by the chemical formula (IX);
Mercaptoalkylsulfide compounds such as 3-thiapentane-1,5-dithiol and 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol;
Mercaptopropionate esters such as pentaerythritol tetrakis(3-mercaptopropionate);
epoxy resin terminated mercapto compound;
3,6-dioxa-1,8-octanedithiol, a mercaptoalkyl ether disulfide compound represented by the chemical formula (X),
2,2′-[[2,2-bis[(2-mercaptoethoxy)methyl]-1,3-propanediyl]bis(oxy)]bisethanethiol,
3,3′-[[2,2-bis[(3-mercaptopropoxy)methyl]-1,3-propanediyl]bis(oxy)]bis-1-propanethiol,
3-[2,2-bis[(3-mercaptopropoxy)methyl]butoxy]-1-propanethiol,
3-(3-mercaptopropoxy)-2,2-bis[(3-mercaptopropoxy)methyl]-1-propanol,
Mercaptoalkyl ether compounds such as 2,2-bis[(3-mercaptopropoxy)methyl]-1-butanol;
1,3,4,6-tetrakis(2-mercaptoethyl)glycoluril,
1,3,4,6-tetrakis(3-mercaptopropyl)glycoluril, which may be used in combination.

（式中、ｐは、１～５の整数を表す。）

(Wherein, p represents an integer of 1 to 5.)

（式中、ｑは、１～２０の整数を表す。）

(Wherein, q represents an integer of 1 to 20.)

Regarding the content of other thiol compounds in the first resin composition of the present invention, the number of thiol groups derived from the other thiol compounds in the composition is the number of thiol groups derived from the thiol compound of the present invention. It is preferable to set the ratio (equivalence ratio) from 0 to 100 with respect to the number of .

The first resin composition of the present invention may contain a conventionally known curing agent together with the thiol compound of the present invention. Conventionally known curing agents include, for example,
In addition to compounds with phenolic hydroxyl groups and acid anhydrides,
organic phosphine compounds such as triphenylphosphine, diphenylnaphthylphosphine and diphenylethylphosphine;
aromatic phosphonium salts;
aromatic diazonium salts;
aromatic iodonium salts;
aromatic selenium salts and the like.

Examples of compounds having a phenolic hydroxyl group include
Bisphenol A, bisphenol F, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol S, tetrachlorobisphenol A, tetrabromobisphenol A, dihydroxynaphthalene, phenol novolak, cresol novolak, bisphenol A novolak, brominated phenol Novolak, resorcinol and the like.

Examples of acid anhydrides include
Methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, trimellitic anhydride, nadic anhydride, hymic anhydride, methyl nadic anhydride product, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, bicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, methylnorbornane-2,3-dicarboxylic acid etc.

The first resin composition of the present invention may contain a conventionally known curing accelerator. As a curing accelerator, for example,
(i) amines, (ii) a reaction product of an epoxy compound and an amine, (iii) a compound having one or more isocyanate groups in the molecule, and a primary amino group and a secondary amino group in the molecule Examples thereof include reaction products with compounds having at least one amino group, and the like, and these may be used in combination.

(i) Amines, as conventionally known, have in the molecule at least one amino group selected from primary amino groups, secondary amino groups and tertiary amino groups. I wish I had.
Examples of such amines include
Aliphatic amines such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, 4,4'-diaminodicyclohexylmethane, dimethylbenzylamine;
aromatic amines such as 4,4′-diaminodiphenylmethane and o-methylaniline;
nitrogen-containing heterocyclic compounds such as 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine and piperazine;

The content of amines in the first resin composition of the present invention is preferably 0.1 to 100 parts by weight with respect to 100 parts by weight of the epoxy compound (epoxy resin).

(ii) The reaction product of an epoxy compound and an amine is a solid that is sparingly soluble in an epoxy resin at room temperature, and becomes soluble (easily soluble) by heating to function as a curing accelerator. Also called a latent curing accelerator (hereinafter, the reaction product of an epoxy compound and an amine may be referred to as a "latent curing accelerator").

Examples of the epoxy compound used as a raw material for the latent curing accelerator include, in addition to the above epoxy compounds, 4,4′-diaminodiphenylmethane and glycidylamine compounds obtained by reacting epichlorohydrin with m-aminophenol or the like;
Examples include monofunctional epoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, glycidyl methacrylate, and the like.

Examples of the amines used as raw materials for the latent curing accelerator include the amines described above. Among these amines, amines having a tertiary amino group in the molecule are raw materials that provide latent curing accelerators having excellent curing acceleration properties. Examples of such amines include
amines such as dimethylaminopropylamine, diethylaminopropylamine, di-n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, N-methylpiperazine;
Amines having a tertiary amino group in the molecule, such as imidazole compounds such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole,
2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, 1-(2-hydroxy- 3-phenoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazole , 1-(2-hydroxy-3-butoxypropyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-phenylimidazoline, 1-(2-hydroxy-3- butoxypropyl)-2-methylimidazoline, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, N-β-hydroxyethylformoline, 2-dimethylaminoethanethiol, 2- Mercaptopyridine, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 4-mercaptopyridine, N,N-dimethylaminobenzoic acid, N,N-dimethylglycine, nicotinic acid, isonicotinic acid, picolinic acid, N,N- Alcohols, phenols, thiols, carboxylic acids, hydrazides having a tertiary amino group in the molecule, such as dimethylglycine hydrazide, N,N-dimethylpropionic acid hydrazide, nicotinic acid hydrazide, and isonicotinic acid hydrazide etc.

In order to further improve the storage stability of the first resin composition of the present invention, in addition to the above epoxy compound and amines as raw materials for the latent curing accelerator, two active hydrogens are added to the molecule as a third component. Active hydrogen compounds having one or more may also be used.
Examples of active hydrogen compounds include
Polyphenols such as bisphenol A, bisphenol F, bisphenol S, hydroquinone, catechol, resorcinol, pyrogallol, and phenol novolac resin;
Polyhydric alcohols such as trimethylolpropane;
Polyvalent carboxylic acids such as adipic acid and phthalic acid,
1,2-dimercaptoethane, 2-mercaptoethanol, 1-mercapto-3-phenoxy-2-propanol, mercaptoacetic acid, anthranilic acid, lactic acid and the like.

Furthermore, the latent curing accelerator may be surface-treated with an isocyanate compound or an acidic compound. Examples of isocyanate compounds include
Monofunctional isocyanate compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, and benzyl isocyanate;
Hexamethylene diisocyanate, toluylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate and polyfunctional isocyanate compounds such as

A terminal isocyanate group-containing compound obtained by reacting a polyfunctional isocyanate compound with an active hydrogen compound can also be used instead of this polyfunctional isocyanate compound. Specific examples include an addition reaction product having a terminal isocyanate group obtained by the reaction of toluylene diisocyanate and trimethylolpropane, and an addition reaction product having a terminal isocyanate group obtained by the reaction of toluylene diisocyanate and pentaerythritol.

The acidic substance used for the surface treatment of the latent curing accelerator may be gaseous, liquid or solid, and may be inorganic acid or organic acid. Examples of this acidic substance include:
Carbon dioxide gas, sulfurous acid gas, sulfuric acid, hydrochloric acid, oxalic acid, phosphoric acid, acetic acid, formic acid, propionic acid, adipic acid, caproic acid, lactic acid, succinic acid, tartaric acid, sebacic acid, p-toluenesulfonic acid, salicylic acid, boric acid, Tannic acid, alginic acid, polyacrylic acid, polymethacrylic acid, phenol, pyrogallol, phenolic resin, resorcinol resin and the like.

The latent curing accelerator is obtained by mixing an epoxy compound, amines, and, if necessary, an active hydrogen compound, reacting the reaction at a temperature from room temperature to 200° C., solidifying and pulverizing, or using methyl ethyl ketone, dioxane, tetrahydrofuran. It can be easily obtained by reacting in a solvent such as , and pulverizing the solid content after removal of the solvent.

A commercially available latent curing accelerator can also be used. Commercially available products include, for example,
"Amicure PN-23 (trade name)", "Amicure PN-H (trade name)", "Amicure MY-24 (trade name)" manufactured by Ajinomoto Fine Techno Co., Ltd., "Novacure HX-3721 (trade name)" manufactured by Asahi Kasei Corporation name)”, “Novacure HX-3742 (trade name)”, and the like.

The content of the latent curing accelerator in the first resin composition of the present invention is preferably 0.1 to 1000 parts by weight with respect to 100 parts by weight of the epoxy compound (epoxy resin).

(iii) the reaction product of a compound having one or more isocyanate groups in the molecule and a compound having at least one of a primary amino group and a secondary amino group in the molecule; It can be obtained by reacting in an organic solvent.

Examples of isocyanate compounds having one or more isocyanate groups in the molecule include
n-butyl isocyanate, isopropyl isocyanate, 2-chloroethyl isocyanate, phenyl isocyanate, p-bromophenyl isocyanate, m-chlorophenyl isocyanate, o-chlorophenyl isocyanate, p-chlorophenyl isocyanate, 2,5-dichlorophenyl isocyanate, 3,4-dichlorophenyl isocyanate, 2,6-dimethylphenyl isocyanate, o-fluorophenyl isocyanate, p-fluorophenyl isocyanate, m-tolyl isocyanate, p-tolyl isocyanate, o-trifluoromethylphenyl isocyanate, m-trifluoromethylphenyl isocyanate, benzyl isocyanate , hexamethylene diisocyanate, 2,4-toluylene diisocyanate, 2,6-toluylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, 2,2-dimethyldiphenylmethane-4,4'-diisocyanate , tolidine diisocyanate, isophorone diisocyanate, xylylene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, p-phenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris-(3-isocyanato- 4-methylphenyl)isocyanurate, tris-(6-isocyanatohexyl)isocyanurate and the like.

Examples of compounds having at least one of a primary amino group and a secondary amino group in the molecule include:
dimethylamine, diethylamine, di-n-propylamine, di-n-butylamine, di-n-hexylamine, di-n-octylamine, di-n-ethanolamine, dimethylaminopropylamine, diethylaminopropylamine, morpholine, piperidine, 2,6-dimethylpiperidine, 2,2,6,6-tetramethylpiperidine, piperazine, pyrrolidine, benzylamine, N-methylbenzylamine, cyclohexylamine, metaxylylenediamine, 1,3-bis(aminomethyl ) cyclohexane, isophoronediamine, N-aminoethylpiperazine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-phenylimidazole, 1,1-dimethylhydrazine and the like.

Reaction of a compound having one or more isocyanate groups in the molecule with a compound having at least one of a primary amino group and a secondary amino group in the molecule in the first resin composition of the present invention. The content of the product is preferably 1 to 10 parts by weight with respect to 100 parts by weight of the epoxy compound (epoxy resin).

The first resin composition of the present invention, as long as it does not inhibit the effects of the present invention,
Pigments (titanium white, cyanine blue, watching red, iron oxide, carbon black, aniline black, manganese blue, iron black, ultramarine blue, hansa red, chrome yellow, chrome green, etc.),
Inorganic fillers (calcium carbonate, kaolin, clay, talc, mica, barium sulfate, lithopone, gypsum, zinc stearate, perlite, quartz, quartz glass, fused silica, silica powder such as spherical silica, spherical alumina, crushed alumina , oxides such as magnesium oxide, beryllium oxide and titanium oxide; nitrides such as boron nitride, silicon nitride and aluminum nitride; carbides such as silicon carbide; hydroxides such as aluminum hydroxide and magnesium hydroxide; Metals and alloys such as copper, silver, iron, aluminum, nickel and titanium, carbon-based materials such as diamond and carbon, etc.),
Thermoplastic resin and / or thermosetting resin (high density, medium density, low density polyethylene, polypropylene, polybutene, homopolymer such as polypentene, ethylene-propylene copolymer, nylon-6, nylon-6,6 Polyamide resins, vinyl chloride resins, nitrocellulose resins, vinylidene chloride resins, acrylic resins, acrylamide resins, styrene resins, vinyl ester resins, polyester resins, phenolic resins (phenolic compounds), silicone Elastomer resins such as system resins, fluororesins, acrylic rubbers, urethane rubbers, etc., and graft copolymers such as methyl methacrylate-butadiene-styrene-based graft copolymers and acrylonitrile-butadiene-styrene-based graft copolymers.) ,
reinforcing agents (glass fiber, carbon fiber, etc.),
Anti-sagging agents (hydrogenated castor oil, fine silica anhydride, etc.),
Matting agents (micronized silica, paraffin wax, etc.),
Abrasives (such as zinc stearate),
Internal release agents (fatty acids such as stearic acid, fatty acid metal salts of calcium stearate, fatty acid amides such as stearamide, fatty acid esters, polyolefin waxes, paraffin waxes, etc.),
Additives (modifiers) such as surfactants, leveling agents, antifoaming agents, diluents for adjusting viscosity (organic solvents), flexibility imparting agents, coupling agents, fragrances, flame retardants, antioxidants, etc. may be contained in a proportion of 0.01 to 50% by weight with respect to the entire (total amount) of the first resin composition, if necessary.
Further, in the first resin composition of the present invention, when an isocyanate group-containing compound is contained as an additive (modifier), it is possible to improve the adhesive strength while suppressing the deterioration of the curability of the resin composition. can be done.

Examples of the isocyanate group-containing compound include
n-butyl isocyanate, isopropyl isocyanate, 2-chloroethyl isocyanate, phenyl isocyanate, p-chlorophenyl isocyanate, benzyl isocyanate, hexamethylene diisocyanate, 2-ethylphenyl isocyanate, 2,6-dimethylphenyl isocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, tolidine diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate and the like.

The content of the isocyanate group-containing compound in the first resin composition of the present invention is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the epoxy compound (epoxy resin).

The method for preparing (mixing) the first resin composition of the present invention is not particularly limited. It is possible to mix while heating if necessary.

The method for curing the first resin composition of the present invention is not particularly limited, and conventionally known curing apparatuses such as closed curing furnaces and tunnel furnaces capable of continuous curing can be employed. The heating source is also not particularly limited, and conventionally known means such as hot air circulation, infrared heating, and high-frequency heating can be employed. Curing temperature and curing time may be appropriately set.

(Second resin composition)
The second resin composition of the present invention contains the thiol compound of the present invention and an ene compound having a carbon-carbon double bond in its molecule (hereinafter sometimes simply referred to as "ene compound").
The ene compound includes both a polymerizable monomer and a polymerizable oligomer (semi-cured product) having a structure in which the polymerizable monomer is partially polymerized.

Examples of the polymerizable monomer include
(1) (meth)acrylic acid alkyl ester-based monomer,
(2) a hydroxyl group-containing monomer,
(3) a carboxyl group-containing monomer,
(4) an amino group-containing monomer,
(5) an acetoacetyl group-containing monomer,
(6) an isocyanate group-containing monomer,
(7) a glycidyl group-containing monomer,
(8) a monomer containing one aromatic ring;
(9) a monomer containing an alkoxy group and an oxyalkylene group;
(10) alkoxyalkyl (meth)acrylamide-based monomers,
(11) (meth) acrylamide-based monomer,
(12) monofunctional unsaturated compounds,
(13) polyfunctional unsaturated compounds and the like.

(1) Examples of (meth)acrylic acid alkyl ester-based monomers include:
methyl (meth)acrylate,
ethyl (meth)acrylate,
n-butyl (meth)acrylate,
iso-butyl (meth)acrylate,
tert-butyl (meth)acrylate,
n-propyl (meth)acrylate,
n-hexyl (meth)acrylate,
2-ethylhexyl (meth)acrylate,
n-octyl (meth)acrylate,
isodecyl (meth)acrylate,
Lauryl (meth)acrylate,
cetyl (meth)acrylate,
stearyl (meth)acrylate,
cyclohexyl (meth)acrylate,
isobornyl (meth)acrylate and the like.

(2) Examples of hydroxyl group-containing monomers include:
2-hydroxyethyl (meth)acrylate,
4-hydroxybutyl (meth)acrylate,
5-hydroxypentyl (meth)acrylate,
6-hydroxyhexyl (meth)acrylate,
(meth)acrylic acid hydroxyalkyl esters such as 8-hydroxyoctyl (meth)acrylate;
caprolactone-modified monomers such as caprolactone-modified 2-hydroxyethyl (meth)acrylate;
diethylene glycol (meth)acrylate,
Oxyalkylene-modified monomers such as polyethylene glycol (meth)acrylate;
In addition, 2-acryloyloxyethyl 2-hydroxyethyl phthalate,
N-methylol (meth)acrylamide,
Primary hydroxyl group-containing monomers such as hydroxyethylacrylamide;
2-hydroxypropyl (meth)acrylate,
2-hydroxybutyl (meth)acrylate,
3-chloro 2-hydroxypropyl (meth)acrylate,
propylene glycol diglycidyl ether-epoxy di(meth)acrylate,
phenol glycidyl ether-epoxy (meth)acrylate,
Secondary hydroxyl group-containing monomers such as bisphenol A diglycidyl ether-epoxy di(meth)acrylate;
Examples thereof include tertiary hydroxyl group-containing monomers such as 2,2-dimethyl 2-hydroxyethyl (meth)acrylate.

(3) Examples of carboxyl group-containing monomers include
(Meth)acrylic acid, acrylic acid dimer, crotonic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid, glutaconic acid, itaconic acid, acrylamido-N-glycolic acid, cinnamic acid and the like.

(4) Examples of amino group-containing monomers include
tert-butylaminoethyl (meth)acrylate,
ethylaminoethyl (meth)acrylate,
dimethylaminoethyl (meth)acrylate,
diethylaminoethyl (meth)acrylate and the like.

(5) Examples of acetoacetyl group-containing monomers include
2-(acetoacetoxy)ethyl (meth)acrylate,
and allyl acetoacetate.

(6) Examples of isocyanate group-containing monomers include
2-acryloyloxyethyl isocyanate,
2-methacryloyloxyethyl isocyanate, alkylene oxide adducts thereof, and the like.

(7) Examples of glycidyl group-containing monomers include
In addition to glycidyl (meth)acrylate,
ethylene glycol diglycidyl ether-epoxy (meth)acrylate,
resorcinol diglycidyl ether-epoxy (meth)acrylate,
bis(4-hydroxyphenyl)sulfide diglycidyl ether-epoxy(meth)acrylate,
phenolic novolac type epoxy resin-(meth)acrylate,
cresol novolak type epoxy resin-(meth)acrylate,
bisphenol (e.g., bisphenol A, bisphenol F) type epoxy resin-(meth)acrylate,
biphenol (for example, 3,3′,5,5′-tetramethylbiphenol) type epoxy resin-(meth)acrylate,
epoxy (meth)acrylates which are reaction products of epoxy compounds such as tris(2,3-epoxypropyl)isocyanurate-(meth)acrylate and (meth)acrylic acid;
Examples include glycidyl (meth)acrylates such as 4-hydroxybutyl (meth)acrylate glycidyl ether.

(8) Examples of monomers containing one aromatic ring include
phenyl (meth)acrylate,
benzyl (meth)acrylate,
phenoxyethyl (meth)acrylate,
phenoxydiethylene glycol (meth)acrylate,
2-hydroxy-3-phenoxypropyl (meth)acrylate,
styrene,
and α-methylstyrene.

(9) Monomers containing an alkoxy group and an oxyalkylene group include, for example,
2-methoxyethyl (meth)acrylate,
2-ethoxyethyl (meth)acrylate,
3-methoxybutyl (meth)acrylate,
2-butoxyethyl (meth)acrylate,
2-butoxydiethylene glycol (meth)acrylate,
methoxydiethylene glycol (meth)acrylate,
methoxytriethylene glycol (meth)acrylate,
ethoxydiethylene glycol (meth)acrylate,
methoxydipropylene glycol (meth)acrylate,
methoxypolyethylene glycol (meth)acrylate,
octoxypolyethylene glycol-polypropylene glycol-mono(meth)acrylate,
lauroxypolyethylene glycol mono(meth)acrylate,
stearoxypolyethylene glycol mono(meth)acrylate and the like.

(10) Examples of alkoxyalkyl (meth)acrylamide-based monomers include
methoxymethyl (meth)acrylamide,
ethoxymethyl (meth)acrylamide,
propoxymethyl (meth)acrylamide,
isopropoxymethyl (meth)acrylamide,
n-butoxymethyl (meth)acrylamide,
isobutoxymethyl (meth)acrylamide and the like.

(11) Examples of (meth)acrylamide-based monomers include
(meth)acryloylmorpholine,
dimethyl (meth)acrylamide,
diethyl (meth)acrylamide,
(Meth)acrylamide N-methylol (meth)acrylamide and the like.

(12) Monofunctional unsaturated compounds include, for example, biphenyl structure-containing (meth)acrylate compounds, more specifically,
o-biphenyl (meth)acrylate,
m-biphenyl (meth)acrylate,
biphenyl (meth)acrylates such as p-biphenyl (meth)acrylate;
o-biphenyloxymethyl (meth)acrylate,
m-biphenyloxymethyl (meth)acrylate,
p-biphenyloxymethyl (meth)acrylate,
o-biphenyloxyethyl (meth)acrylate,
m-biphenyloxyethyl (meth)acrylate,
p-biphenyloxyethyl (meth)acrylate,
o-biphenyloxypropyl (meth)acrylate,
m-biphenyloxypropyl (meth)acrylate,
Biphenyloxyalkyl (meth)acrylates such as p-biphenyloxypropyl (meth)acrylate;
(o-biphenyloxy) diethylene glycol (meth)acrylate,
(m-biphenyloxy) diethylene glycol (meth)acrylate,
(p-biphenyloxy) diethylene glycol (meth)acrylate,
(o-biphenyloxy) dipropylene glycol (meth)acrylate,
(m-biphenyloxy) dipropylene glycol (meth)acrylate,
(p-biphenyloxy) dipropylene glycol (meth)acrylate,
(o-biphenyloxy) polyethylene glycol (meth)acrylate,
(m-biphenyloxy) polyethylene glycol (meth)acrylate,
(p-biphenyloxy) polyethylene glycol (meth)acrylate,
(o-biphenyloxy) polypropylene glycol (meth)acrylate,
(m-biphenyloxy)polypropylene glycol (meth)acrylate,
Biphenyloxy polyalkylene glycol (meth)acrylates such as (p-biphenyloxy) polypropylene glycol (meth)acrylate can be mentioned.

(13) Polyfunctional unsaturated compounds include, for example, bifunctional monomers, trifunctional or higher monomers, urethane (meth)acrylates, the aforementioned epoxy (meth)acrylates, polyester (meth)acrylates, poly ether (meth)acrylates and the like.

And, as a specific example of the bifunctional monomer,
ethylene glycol di(meth)acrylate,
diethylene glycol di(meth)acrylate,
triethylene glycol di(meth)acrylate,
tetraethylene glycol di(meth)acrylate,
polyethylene glycol di(meth)acrylate,
propylene glycol di(meth)acrylate,
dipropylene glycol di(meth)acrylate,
polypropylene glycol di(meth)acrylate,
butylene glycol di(meth)acrylate,
neopentyl glycol di(meth)acrylate,
ethylene oxide-modified bisphenol A type di(meth)acrylate,
Propylene oxide-modified bisphenol A type di(meth)acrylate,
1,6-hexanediol di(meth)acrylate,
1,6-hexanediol ethylene oxide-modified di(meth)acrylate,
glycerine di(meth)acrylate,
pentaerythritol di(meth)acrylate,
ethylene glycol diglycidyl ether di(meth)acrylate,
diethylene glycol diglycidyl ether di(meth)acrylate,
phthalate diglycidyl ester di(meth)acrylate,
hydroxypivalic acid-modified neopentyl glycol di(meth)acrylate,
isocyanuric acid ethylene oxide modified diacrylate,
2-(meth)acryloyloxyethyl acid phosphate diester and the like.

Further, specific examples of tri- or higher functional monomers include:
trimethylolpropane tri(meth)acrylate,
pentaerythritol tri(meth)acrylate,
pentaerythritol tetra(meth)acrylate,
dipentaerythritol tri(meth)acrylate,
dipentaerythritol tetra(meth)acrylate,
dipentaerythritol penta(meth)acrylate,
dipentaerythritol hexa(meth)acrylate,
tri(meth)acryloyloxyethoxytrimethylolpropane,
glycerin polyglycidyl ether poly(meth)acrylate,
tris(2-(meth)acryloyloxyethyl)isocyanurate,
isocyanuric acid ethylene oxide modified tri(meth)acrylate,
ethylene oxide-modified dipentaerythritol penta(meth)acrylate,
ethylene oxide-modified dipentaerythritol hexa(meth)acrylate,
ethylene oxide-modified pentaerythritol tri(meth)acrylate,
ethylene oxide-modified pentaerythritol tetra(meth)acrylate,
succinic acid-modified pentaerythritol tri(meth)acrylate and the like.

In addition to the above polymerizable monomers,
Divinylbenzene, piperylene, isoprene, pentadiene, vinylcyclohexene, chloroprene, butadiene, methylbutadiene, cyclopentadiene, methylpentadiene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, vinyl stearate, vinyl chloride, vinylidene chloride, alkyl vinyl ether , vinyltoluene, vinylpyridine, vinylpyrrolidone, dialkyl itaconate, dialkyl fumarate, allyl alcohol, acryloyl chloride, methyl vinyl ketone, N-acrylamidomethyltrimethylammonium chloride, allyltrimethylammonium chloride, dimethyl allyl vinyl ketone, 2- Chlorethyl vinyl ether, triallyl isocyanurate, tetraallyl glycoluril,
N-vinylpyrrolidone, N-vinylcaprolactam, ethylene glycol diallyl carbonate, triallyl trimellitate,
trifluoroethyl (meth)acrylate,
tribromobenzyl (meth)acrylate,
perfluorooctylethyl (meth)acrylate,
sulfur-containing (meth)acrylate,
(Meth)acryloyloxypropyltris(methoxy)silane and the like.

In the second resin composition of the present invention, the above-mentioned polymerizable monomer and polymerizable oligomer may be used in combination as the ene compound, and the polymerizable monomers exemplified above may be used in combination as the polymerizable monomer. (different types of polymerizable monomers may be used in combination), and as for polymerizable oligomers, different types of polymerizable oligomers may be used in combination.

Regarding the content ratio (percentage) of the thiol compound of the present invention and the ene compound in the second resin composition of the present invention, the content of the ene compound is An appropriate ratio within the range of 0.01 to 1000 times the amount (weight ratio) is preferable, and an appropriate ratio within the range of 0.1 to 100 times the amount (weight ratio) is more preferable.

In the second resin composition of the present invention, the other thiol compound may be used in combination with the thiol compound of the present invention.
Regarding the ratio (percentage) of the content of the thiol compound of the present invention and the other thiol compound in the second resin composition of the present invention, the content of the other thiol compound is the content of the thiol compound of the present invention. The ratio is preferably 0 to 100 times the amount (weight ratio), more preferably 0.1 to 10 times (weight ratio).

The method of polymerizing (curing) the second resin composition of the present invention includes photocuring and thermal curing.
A method of photocuring includes a method of irradiating with an active energy ray, preferably a method of using a photopolymerization initiator in combination. Examples of active energy rays include light, radiation, electromagnetic waves, electron beams, and the like, and electron beams or light in the ultraviolet to infrared wavelength range are preferred. As the light source, for example, an ultra-high pressure mercury light source or a metal halide light source is used for ultraviolet irradiation, a metal halide light source or a halogen light source is used for visible light irradiation, and a halogen light source is used for infrared irradiation. can do. In addition, light sources such as lasers and LEDs that emit light of various wavelengths, which have been widely used in recent years, may also be used.
The dose of active energy rays can be appropriately set according to the type of light source and the like.

The photopolymerization initiator can be selected from photoradical polymerization initiators and photoanion polymerization initiators, and both of them may be contained in the second resin composition. In the photocuring, thermal polymerization (thermosetting) may be used together in order to improve the production efficiency and the properties of the cured product.

As the radical photopolymerization initiator, any commonly used one can be used without particular limitation.
Acetophenones such as 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-{4-(methylthio)phenyl}-2-morpholinopropan-1-one kind;
Benzoins such as benzyl dimethyl ketal;
Benzophenones such as benzophenone, 4-phenylbenzophenone, hydroxybenzophenone;
Thioxanthones such as isopropylthioxanthone and 2,4-diethylthioxanthone,
In addition, methylphenyl glyoxylate and the like can be mentioned, and these may be used in combination.
If necessary, the photoradical polymerization initiator may be used in combination with known photopolymerization accelerators such as benzoic acids such as 4-dimethylaminobenzoic acid and tertiary amines.

Any commonly used photoanionic polymerization initiator can be used without particular limitation, and examples thereof include onium salts and carbamates.
Onium salts include, for example, 1,2-diisopropyl-3-(bis(dimethylamino)methylene)guanidinium 2-(3-benzoylphenyl)propionate, 1,2-dicyclohexyl-4,4,5,5-tetramethyl biguanidium n-butyltriphenylborate and the like,
Examples of carbamates include 2-nitrophenylmethylpiperidine-1-carboxylate, 1-(anthraquinone-2-yl)ethylimidazole carboxylate, 1-(3-(2-hydroxyphenyl)-2-propenoyl)piperidine , 9-anthranylmethyldiethylcarbamate and the like.

When photocuring the second resin composition of the present invention, sensitizers such as pyrene, perylene, acridine orange, thioxanthone, 2-chlorothioxanthone, and benzoflavin can be used.

The content of the photopolymerization initiator in the second resin composition of the present invention is preferably a ratio of 0.001 to 20% by weight with respect to the entire second resin composition (total amount), A proportion of 0.01 to 10% by weight is more preferred.

On the other hand, as a method of thermosetting the second resin composition of the present invention, a method of using a thermal polymerization initiator in combination can be mentioned. The thermal polymerization initiator can be selected from thermal radical polymerization initiators and thermal anionic polymerization initiators, both of which may be contained in the resin composition.
Regarding the conditions for thermosetting, the heating temperature/heating time can be appropriately set, but it is preferable to set the temperature within the range of 60 to 130°C/30 to 240 minutes, and the range of 70 to 125°C/30 to 120 minutes. is more preferable.

Any commonly used thermal radical polymerization initiator can be used without particular limitation. Oxyisopropyl monocarbonate, t-hexylperoxy 2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, t-butylperoxypivalate, t-hexylperoxy pivalate, t-butyl peroxyneodecanoate, t-hexyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, 1,1-bis(t-hexyl peroxy)cyclohexane, benzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, lauroyl peroxide and other peroxides, azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile ), dimethyl 2,2'-azobis(2-methylpropionate) and other azo compounds, which may be used in combination.

As the thermal anionic polymerization initiator, any commonly used one can be used without particular limitation. Examples thereof include amines, imidazoles, etc., and these may be used in combination.
Examples of amines include diethylenetriamine, triethylenetetramine, isophoronediamine, xylylenediamine, diaminodiphenylmethane, 1,3,4,6-tetrakis(3-aminopropyl)glycoluril, and the like.
Examples of imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and the like.

The content of the thermal polymerization initiator in the second resin composition of the present invention is preferably 0.001 to 20% by weight with respect to the entire second resin composition (total amount), A proportion of 0.01 to 10% by weight is more preferred.

When the second resin composition of the present invention contains an epoxy resin (epoxy compound) as an additive (modifier), a photocationic polymerization initiator or a thermal cationic polymerization initiator may be used. .
As the photocationic polymerization initiator, if it is generally used, it can be used without particular limitation, and examples thereof include onium salts and organometallic complexes.
Onium salts include, for example, diazonium salts, sulfonium salts, iodonium salts,
Examples of organometallic complexes include iron-allene complexes, titanocene complexes, arylsilanol-aluminum complexes, and the like.
Examples of commercially available photocationic polymerization initiators include "ADEKA Optomer SP-150 (trade name)" and "ADEKA Optomer SP-170 (trade name)" manufactured by ADEKA, and "UVE- 1014 (trade name)”, “CD-1012 (trade name)” manufactured by Sartomer, and “CPI-100P (trade name)” manufactured by San-Apro.
Counter anions of the photocationic polymerization initiator include SbF ₆ ⁻ , AsF ₆ ⁻ , B(C ₆ F ₅ ) ₄ ⁻ , PF ₆ ^{− and} the like.

As the thermal cationic polymerization initiator, if it is generally used, it can be used without particular limitation. and may be used in combination.
Examples of commercially available onium salts include "Adeka Opton CP-66 (trade name)" and "ADEKA Opton CP-77 (trade name)" manufactured by ADEKA, and "San-Aid SI-60L (trade name)" manufactured by Sanshin Chemical Industry Co., Ltd. )”, “San-Aid SI-80L (trade name)”, “San-Aid SI-100L (trade name)”, “CI Series (trade name)” manufactured by Nippon Soda Co., Ltd., and the like.
Further, examples of organic metal complexes include alkoxysilane-aluminum complexes.

The second resin composition of the present invention further contains the above-mentioned additive (modifier) (see paragraph 0081 ) as long as it does not inhibit the effects of the present invention. It may be contained in a ratio of 0.01 to 50% by weight with respect to the (total amount).

There is no particular limitation on the method of preparing (mixing) the second resin composition of the present invention. It can be prepared by mixing an initiator and an additive. As a mixing means, a known method (for example, the method described in paragraph 0084 ) can be adopted. The thiol compound of the present invention (in combination with other thiol compounds, if necessary) may be dissolved or dispersed in advance in a viscosity-adjusting diluent (organic solvent).

The first resin composition and the second resin composition of the present invention containing the thiol compound of the present invention (these resin compositions may be collectively referred to as the "resin composition of the present invention") are It is expected to give a cured product with excellent hydrolysis resistance (moisture resistance).
That is, the resin composition of the present invention can be suitably used as an adhesive or a sealing agent because it gives a cured product having excellent moisture resistance as compared with a conventional resin composition containing a thiol compound. That is, the adhesive and sealant of the present invention contain the above resin composition of the present invention as a component.

The adhesive and sealant of the present invention may contain additives. Additives include, for example, flow behavior modifiers such as silicic acid, magnesium silicate, and barium sulfate, thermal conductivity imparting agents such as alumina, conductivity imparting agents such as silver and carbon, and coloring agents such as pigments and dyes. mentioned. These additives can be blended during preparation of the resin composition of the present invention. It may also be mixed with the resin composition of the present invention that has already been prepared. As a mixing means, a known method (for example, the method described in paragraph 0084) can be adopted.

The adhesives and sealants of the present invention are not particularly limited in their uses, and can be applied to various fields. Uses of adhesives include, for example, adhesives for flexible printed wiring boards; interlayer adhesives for multilayer boards such as build-up boards; adhesives for bonding optical components; adhesives for bonding optical discs; and adhesives for mounting printed wiring boards. ; Die bonding adhesive; Semiconductor adhesive such as underfill; Mounting adhesive such as BGA reinforcing underfill, anisotropic conductive film (ACF), anisotropic conductive paste (ACP); Adhesives; Optical path coupling adhesives; Adhesives used between exterior materials, base materials, ceiling materials and interior materials; Adhesives for adhering tiles and stone materials to exterior wall materials and base materials; Adhesives for adhesion of floor sheets and floor tiles of materials and polymer materials; adhesives for structural materials, bodies and parts of automobiles and aircraft; adhesives for automotive interiors;
Applications of sealants include, for example, sealants for joints of exterior materials such as various metal panels and siding boards; sealants used between exterior materials, base materials, ceiling materials and interior materials; roads, bridges, tunnels, Sealing agents for joints of various concrete products such as breakwaters; sealing agents for structural materials, bodies and parts of automobiles, aircraft, etc.; sealing agents for joints of steel plates; sealing agents for medical equipment.

The resin composition of the present invention can be applied to products (parts and members) in various fields that may be made of resin, in addition to the adhesives and sealants described above. , automobiles, aircraft, medical fields, and other materials for daily use and miscellaneous goods.

For example, examples of parts, members and materials in the electrical and electronic fields include resin-coated copper foils, prepregs, copper clad laminates, printed wiring boards, solder resist inks, conductive pastes, interlayer insulating materials, sealing materials, Examples include LED sealing materials, insulating materials, thermally conductive materials, hot melt materials, paints, potting agents, etc. More specifically, printed wiring such as interlayer insulating films and wiring coating films Sealing materials and layer forming materials for plates and electronic parts;
Materials for forming display devices such as color filters, films for flexible displays, resist materials, and alignment films;
Forming materials for semiconductor devices such as resist materials and buffer coat films;
Examples include materials for forming optical components such as holograms, optical waveguides, optical circuits, optical circuit components, and antireflection films.
Forming materials for rigid wiring boards and flexible printed wiring boards for semiconductor mounting, mounting materials for semiconductor mounting, sealing materials for semiconductors, sealing materials for solar cells, insulating films for semiconductors, coverlay films for protecting flexible printed circuits , a wiring coating agent, and the like.

Examples of materials in the field of optics include core materials for optical fibers, clad materials, lenses, wear-resistant coating agents for lenses (eg, hard coat forming liquids), and the like.

Examples of materials in the construction field include coating materials and primers for exterior materials such as various metal panels and siding boards; injection materials, damping materials, and soundproofing materials used between exterior materials, base materials, ceiling materials, and interior materials. , conductive materials for electromagnetic shielding, putty materials; wooden flooring materials for various floors, polymer floor sheets, adhesives for floor tile adhesion; injection materials for repairing cracks in various exterior and interior materials, etc. .

Examples of materials in the field of civil engineering include coating materials, primers, paints, putty materials, grouting materials, spraying materials, molding materials, etc. for various concrete products such as roads, bridges, tunnels and breakwaters.

Examples of materials in the automobile and aircraft fields include structural materials, coating materials for bodies and parts, cushioning materials, damping materials, soundproofing materials, and spraying materials; adhesives, coating materials, and foam materials for automotive interiors; and the like.

Examples of materials in the medical field include artificial bones, dental impression materials, medical rubber materials, medical adhesives, and the like.

EXAMPLES The present invention will be described in more detail below with reference to Examples (synthesis tests and evaluation tests) , Reference Examples (synthesis tests) and Comparative Examples (evaluation tests), but the present invention is not limited thereto.
The main raw materials used in the synthesis test are as follows.

[Main raw material]
- 1-allyl-2-allyloxybenzene (synthesized according to the method described in J. Am. Chem. Soc., Vol. 81, pp. 2705-2715 (1959). See chemical formula (IV-2))
- 1,3-bisallyloxybenzene (synthesized according to the method described in J. Am. Chem. Soc., Vol. 130, pp. 237-244 (2008). See chemical formula (V-3))
· 1,3-bis(3-butenyl-1-oxy)benzene (European Polymer Journal, Vol. 95, pp. 503-513 (2017), synthesized according to the method described. Chemical formula (V-6) reference)
・Thioacetic acid (manufactured by Tokyo Chemical Industry Co., Ltd., see chemical formula (VII))
・Azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.)

The main raw materials (excluding the thiol compound of the present invention) used in the evaluation test are as follows.
[Main raw material]
(A) Curing agent 1,3,4,6-tetrakis(2-mercaptoethyl) glycoluril (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name “TS-G”, see chemical formula (XI), thiol equivalent: 100.4 )
- Pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd., trade name "PEMP", see chemical formula (XII), thiol equivalent: 122.2)

(B) Curing accelerator, dimethylbenzylamine (manufactured by Wako Pure Chemical Industries, Ltd.)
・Microcapsule-type amine adduct (manufactured by Asahi Kasei Corporation, latent curing type, trade name “Novacure HXA3922HP”)
(C) epoxy compound (epoxy resin)
- Phenolic novolac type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name "jER152", epoxy equivalent: 174.0)
- Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name "jER828", epoxy equivalent: 187.0)

The method for measuring the storage elastic modulus and the method for measuring the adhesive strength in the evaluation tests employed in Examples and Comparative Examples are as follows.

[Measurement of storage modulus]
The epoxy resin composition was cured (80° C./1 hour), and the obtained cured product (specimen: length 20 mm×width 5 mm×thickness 1 mm) was subjected to a dynamic viscoelasticity measurement device (manufactured by UBM, “Rheosol- G5000”) was used to measure the storage modulus E′ (GPa) at 25° C. (frequency: 1 Hz).
It is determined that the smaller the storage elastic modulus (lower elasticity), the more excellent the impact resistance of the cured product.

[Measurement of adhesive strength (moisture resistance test)]
For two blasted aluminum plates (length 100 mm x width 25 mm x thickness 1.6 mm), on one side of each aluminum plate, an area (length) in the range of 12.5 mm from either end (longitudinal direction) An epoxy resin composition (adhesive) was applied to the 12.5 mm (height)×25 mm (width).
Subsequently, two aluminum plates were pasted together so that these coated surfaces were in contact with each other, and then heated (cured at 80° C. for 1 hour to cure the epoxy resin composition) to prepare a test piece.
The tensile shear bond strength (MPa) of this test piece was measured according to JIS K6850 before and after high-temperature and high-pressure steam treatment (PCT treatment, 121° C./48 hours) in an autoclave.
From the measured values obtained, the residual rate of tensile shear bond strength after PCT treatment (hereinafter sometimes referred to as "strength residual rate") was calculated by the following formula.
Strength residual rate (%) = (tensile shear bond strength after PCT treatment) / (tensile shear bond strength before PCT treatment) x 100
It is judged that the higher the residual strength ratio, the better the moisture resistance of the cured product, and the epoxy resin composition is recognized as being suitable as an adhesive.
In addition, when the adhesive layer was eluted by the PCT treatment and the tensile shear adhesive strength could not be measured, it was described as "N.D.".

[Example 1]
<Synthesis of 1-(3-mercaptopropyl)-2-(3-mercaptopropyloxy)benzene>
13.42 g (100.0 mmol) of 1-allyl-2-allyloxybenzene, 0.17 g (1.0 mmol) of azobisisobutyronitrile, and 100.00 g of ethyl acetate were charged into a 300 ml four-necked eggplant flask, After heating to 50° C., 16.75 g (220.0 mmol) of thioacetic acid was added dropwise and stirred at 60° C. for 15 hours. Then, the reaction solution was concentrated, 0.49 g (5.0 mmol) of sulfuric acid and 100.00 g of methanol were added to the obtained reaction product, and the mixture was stirred at 60° C. for 24 hours. The obtained reaction solution was concentrated and purified by silica gel column chromatography (ethyl acetate/methanol=20/1 (v/v)) to obtain 14.74 g of a yellow liquid (yield: 60.8%). .

¹ H-NMR spectrum data of this yellow liquid was as follows.
・¹ H-NMR (d ₆ -DMSO) δ: 7.15 (t, 1 H), 7.12 (d, 1 H), 6.94 (d, 1 H), 6.85 (t, 1 H), 4.05 (t, 2 H), 2.65 ( m, 4H), 2.47(t, 2H), 2.39(t, 1H), 2.27(t, 1H), 2.01(quin., 2H), 1.78(quin., 2H).
Moreover, the IR spectrum data of this yellow liquid was as shown in the chart shown in FIG.
From these spectral data, the obtained yellow liquid was identified as the title thiol compound represented by the chemical formula (I-2).

[ Reference example 2]
<Synthesis of 1,3-bis(3-mercaptopropyloxy)benzene>
19.02 g (100.0 mmol) of 1,3-bisallyloxybenzene, 0.17 g (1.0 mmol) of azobisisobutyronitrile, and 100.00 g of butyl acetate were placed in a 300 ml four-necked eggplant flask. After heating to °C, 16.75 g (220.0 mmol) of thioacetic acid was added dropwise, and the mixture was stirred at 60°C for 15 hours. Then, the reaction solution was concentrated, 0.49 g (5.0 mmol) of sulfuric acid and 100.00 g of methanol were added to the obtained reaction product, and the mixture was stirred at 60° C. for 24 hours. The resulting reaction solution was concentrated and purified by silica gel column chromatography (toluene/hexane=8/2 (v/v)) to obtain 21.29 g of a yellow liquid (yield: 82.4%).

¹ H-NMR spectrum data of this yellow liquid was as follows.
・¹ H-NMR (d ₆ -DMSO) δ: 7.16(t, 1H), 6.52(d, 2H), 6.49(s, 1H), 4.03(t, 4H), 2.62(dt, 4H)，2.42( t, 2H), 1.96(quin., 4H).
Moreover, the IR spectrum data of this yellow liquid was as shown in the chart shown in FIG.
From these spectral data, the obtained yellow liquid was identified as the title thiol compound represented by the chemical formula (II-3).

[ Reference Example 3]
<Synthesis of 1,3-bis(4-mercaptobutyloxy)benzene>
21.82 g (100.0 mmol) of 1,3-bis(3-butenyl-1-oxy)benzene, 0.17 g (1.0 mmol) of azobisisobutyronitrile, and butyl acetate are placed in a 300 ml four-necked eggplant flask. After preparing 100.00 g and heating to 50° C., 16.75 g (220.0 mmol) of thioacetic acid was added dropwise and stirred at 60° C. for 15 hours. Then, the reaction solution was concentrated, 0.49 g (5.0 mmol) of sulfuric acid and 100.00 g of methanol were added to the obtained reaction product, and the mixture was stirred at 60° C. for 24 hours. The resulting reaction solution was concentrated and purified by silica gel column chromatography (toluene/hexane=8/2 (v/v)) to obtain 20.02 g of brown liquid (yield: 69.9%).

¹ H-NMR spectrum data of this brown liquid was as follows.
・¹ H-NMR (d ₆ -DMSO) δ: 7.14(t, 1H), 6.49(d, 2H), 6.46(s, 1H), 3.94(t, 4H), 2.53(dt, 4H), 2.28( t, 2H), 1.76(quin., 4H) , 1.66(quin., 4H).
Moreover, the IR spectrum data of this brown liquid was as shown in the chart shown in FIG.
From these spectral data, the obtained brown liquid was identified as the title thiol compound represented by the chemical formula (II-6).

[Example 4]
131.8 parts by weight of the thiol compound (thiol equivalent: 131.8) synthesized in Example 1 as a curing agent, 6.1 parts by weight of dimethylbenzylamine as a curing accelerator, and 174.0 parts of jER152 as an epoxy compound. parts by weight to prepare an epoxy resin composition. The amount of curing accelerator used was adjusted so that the gelation time (80° C.) of the epoxy resin composition was 2 minutes±20 seconds.
This epoxy resin composition was subjected to an evaluation test (measurement of the storage modulus of the cured product and measurement of the adhesive strength when used as an adhesive), and the test results obtained are shown in Table 1. there were.

[Examples 5-8, Comparative Examples 1-2]
Epoxy resin compositions having the compositions shown in Table 1 were prepared in the same manner as in Example 4, and evaluation tests were conducted on these epoxy resin compositions. was as shown.

The thiol compound of the present invention is expected to be used as a curing agent for resins and as an intermediate raw material for various sulfur-containing compounds.
Moreover, the resin composition containing the thiol compound of the present invention is suitable for various uses such as adhesion, sealing, encapsulation, casting, molding, painting and coating.

Claims (10)

A thiol compound represented by chemical formula (I), chemical formula (II) or chemical formula (III).

(In the formula, the four R _1s are the same or different and represent a hydrogen atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or an aryl group. Two R ₂ are the same or different and are a linear alkylene group having 2 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or a linear alkyleneoxy group having 2 to 10 carbon atoms. , a branched alkyleneoxy group having 3 to 10 carbon atoms, or a divalent organic group represented by the following chemical formulas (a) to (f), wherein at least one of the two R ₂ is an oxygen atom represents an alkyleneoxy group bonded to a benzene ring, except when two R ₂ are both linear alkyleneoxy groups having 2 to 10 carbon atoms.)

(In the formula, Y is the same or different and represents a hydrogen atom or a methyl group.)

(In the formula, four R ₁ and two R ₂ are the same as above.)

(In the formula, the four R _1s are the same or different and represent a hydrogen atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or an aryl group. Two R ₂ are the same or different and are a linear alkylene group having 2 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or a linear alkyleneoxy group having 2 to 10 carbon atoms. , a branched alkyleneoxy group having 3 to 10 carbon atoms, or a divalent organic group represented by the above chemical formulas (a) to (f), wherein at least one of the two R ₂ is an oxygen atom represents an alkyleneoxy group bonded to a benzene ring, except when two R ₂ are both linear alkyleneoxy groups having 2 to 10 carbon atoms.) 2. The method for synthesizing a thiol compound according to claim 1, wherein the dialkene compound represented by the chemical formula (IV), chemical formula (V) or chemical formula (VI) is reacted with thioacetic acid or thiobenzoic acid.

(In the formula, the four R _1s are the same or different and represent a hydrogen atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or an aryl group. Two R _3s are the same or different and are a linear alkenyl group having 2 to 10 carbon atoms, a branched alkenyl group having 3 to 10 carbon atoms, or a linear alkenyloxy group having 2 to 10 carbon atoms. , a branched alkenyloxy group having ₃ to 10 carbon atoms, or an organic group having a carbon-carbon double bond represented by the following chemical formulas (g) to (l) ; At least one represents an alkenyloxy group in which an oxygen atom is bonded to a benzene ring, except when two R ₃ are both straight-chain alkenyloxy groups having 2 to 10 carbon atoms.)

(In the formula, Y is the same as described above.)

(In the formula, four R ₁ and two R ₃ are the same as above.)

(In the formula, the four R _1s are the same or different and represent a hydrogen atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or an aryl group. Two R _3s are the same or different and are a linear alkenyl group having 2 to 10 carbon atoms, a branched alkenyl group having 3 to 10 carbon atoms, or a linear alkenyloxy group having 2 to 10 carbon atoms. , a branched alkenyloxy group having 3 to 10 carbon atoms, or an organic group having a carbon-carbon double bond represented by the above chemical formulas (g) to (l), and two R ₃ At least one represents an alkenyloxy group in which an oxygen atom is bonded to a benzene ring, except when two R ₃ are both straight-chain alkenyloxy groups having 2 to 10 carbon atoms.) A curing agent containing the thiol compound according to claim 1 . A resin composition containing the thiol compound according to claim 1 and an epoxy compound. 5. The resin composition according to claim 4, which contains an amine as a curing accelerator. 5. The resin composition according to claim 4, which contains a reaction product of an epoxy compound and amines as a curing accelerator. A curing accelerator containing a reaction product of a compound having one or more isocyanate groups in the molecule and a compound having at least one of a primary amino group and a secondary amino group in the molecule. 5. The resin composition according to 4. A resin composition comprising the thiol compound according to claim 1 and an ene compound having a carbon-carbon double bond in the molecule. An adhesive comprising the resin composition according to any one of claims 4 to 8 as a component. A sealant comprising the resin composition according to any one of claims 4 to 8 as a component.

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