Thiols and their uses

Abstract

This invention provides a novel thiol compound and its uses. Specifically, it provides a novel thiol compound, a curing agent containing the thiol compound, a resin composition containing the curing agent and an epoxy compound, a resin composition containing the curing agent and an alkene compound having a carbon-carbon double bond within its molecule, an adhesive, and a sealant containing such resin compositions. This invention relates to a dimer of the thiol compound shown in formula (II), a curing agent containing the resin of the dimer, a resin composition containing the curing agent and an epoxy compound, and the uses of the resin composition.

Description

[Technical Field]

[0001] This invention relates to thiols and their uses. [Previous Technology]

[0002] It is well known that compounds with multiple thiol groups within their molecules are suitable as curing agents for epoxy resins. For example, an epoxy resin composition has been proposed 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 has a long service life and can be cured rapidly at relatively low temperatures (see Patent Document 1).

[0003] Furthermore, an epoxy resin composition has been proposed, which comprises a reaction product of an isocyanate compound having one or more isocyanate groups in the molecule and a compound having one or more primary and / or secondary amine groups in the molecule, and uses the product as a curing accelerator. This epoxy resin composition has a long service life and excellent curing properties (see Patent Document 2).

[0004] Furthermore, it is currently known that when sulfur compounds containing ether bonds in their structure are used as epoxy resin curing agents, resin curing products with excellent flexibility and moisture resistance can be obtained. On the other hand, when used as adhesives, due to the flexibility of their structure, their adhesion strength to the adhered material is insufficient (see Patent Document 3).

[0005] [Prior Art Documents] [Patent Documents] [Patent Document 1] Japanese Unexamined Patent Publication No. 6-211969 [Patent Document 2] Japanese Unexamined Patent Publication No. 6-211970 [Patent Document 3] International Publication No. 2016 / 171072 [Summary of the Invention]

[0006] [Summary of the Invention] [Problem to be Solved by the Invention] The object of the present invention is to provide a novel thiol compound and its uses. Specifically, the object is to provide a novel thiol compound, a curing agent containing the thiol compound, a resin composition containing the curing agent and an epoxy compound, a resin composition containing the curing agent and an alkene compound having a carbon-carbon double bond in its molecule, and an adhesive and sealant containing such resin compositions.

[0007] [Means for Solving the Problem] As a result of repeated and in-depth research in order to solve the aforementioned problem, the inventors of this invention discovered a novel thiol compound, which is a dimer obtained by dimerizing a specific trithiol compound through oxidation; they also discovered that a composition containing this thiol compound is suitable as a curing agent, and a resin composition containing the curing agent and a predetermined resin is suitable as an adhesive and a sealant. Based on such knowledge and insights, further research was conducted repeatedly, and the present invention was finally completed.

[0008] That is, the present invention comprises the following states. [1] A dimer of a thiol compound of formula (II): [Chemical Formula 1] [2] The dimer of [1], which is selected from at least one compound of the group consisting of formulas (I-1) to (I-3): [Chemical Formula 2] [3] A composition comprising the compound of formula (II) and its dimer: [Chemical Formula 3] [4] The composition of [3], wherein the content of the dimer in the composition is in the ratio of the content of the compound of formula (II) to the content of the compound of formula (II) is 0.02 to 0.3, which is a value obtained by liquid chromatography from the ratio of the peak area of ​​the compound of formula (II) and the dimer. [5] A curing agent comprising the composition of [3] or [4]. [6] A resin composition comprising the curing agent of [5] and an epoxy compound. [7] The resin composition of [6] further comprising an amine as a curing accelerator. [8] A resin composition comprising a curing agent as described in [5] and an alkene compound having a carbon-carbon double bond within its molecule. [9] An adhesive comprising a resin composition as described in [6] or [8].

[10] A sealant comprising a resin composition as described in [6] or [8].

[11] A cured form of a resin composition, wherein the resin composition is a resin composition as described in [6] or [8].

[0009] [Effects of the Invention] The dimer of the thiol compound shown in Formula (II) of the present invention is a novel compound that can be used as a curing agent for various resins. The curing agent preferably contains the thiol compound shown in Formula (II) and its dimer. The cured product obtained by reacting a resin composition containing the curing agent and various resins exhibits improved toughness due to a reduced crosslinking density. Therefore, when this resin composition is used as an adhesive, problems with adhesion strength can be improved. Therefore, according to the present invention, by using this resin composition as a component, adhesives and sealants with particularly excellent adhesion strength can be obtained.

[0010] Furthermore, the hardener of the present invention has low viscosity, which improves the operability during formation when using resin compositions.

Implementation Method

[0012] (Thiol Compounds) The novel thiol compounds of the present invention are compounds with disulfide bonds (-SS-) obtained by oxidative polymerization of the trithiol compound (1,2,3-tris(3-mercaptopropoxy)propane) shown in formula (II), which belong to the category of polymers so-called oligomers. Typically, they are dimers obtained by oxidative dimerization of the trithiol compound shown in formula (II). These polymers (especially dimers) are suitable as curing agents for resins. [Chemical Formula 4]

[0013] Among the polymers of the trithiol compounds shown in formula (II), typical dimers include the thiol compounds shown in formulas (I-1) to (I-3), and at least one compound is selected from the group consisting of these compounds. [Chemical Formula 5]

[0014] Dimers of the trithiol compound shown in formula (II) can be produced, for example, by following the reaction formula. [Chemical Formula 6] (where R is the same or different, representing methyl, ethyl, propyl or phenyl.)

[0015] [Step (1)] Step (1) is the following step: reacting 1,2,3-triallyloxypropane as shown in formula (III) with thiocarboxylic acid as shown in formula (IV) to produce the compound shown in formula (V).

[0016] 1,2,3-triallyloxypropane as shown in formula (III) can be synthesized, for example, by the method described in Japanese Patent Application Publication No. 2012-184198.

[0017] Thiocarboxylic acids represented by formula (IV) include, for example, thioacetic acid, thiobutyric acid, and thiobenzoic acid. These thiocarboxylic acids can be purchased as commercially available reagents.

[0018] In step (1), the amount of thiocarboxylic acid shown in formula (IV) used (feed) should preferably be set to a suitable ratio of 2 to 40 moles relative to the allyl group of 1,2,3-triallyloxypropane.

[0019] In step (1), a free radical initiator (a) may also be used to promote the reaction. In addition, a reaction solvent (b) may also be used in order to facilitate the reaction. Free radical initiators (a) include, for example: azobisisobutyronitrile, t-hexylperoxyisopropyl monocarbonate, t-hexylperoxy2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy2-ethylhexanoate, t-butylperoxyneopentate, t-hexylperoxyneopentate, t-butylperoxyneopentate, t-hexylperoxyneopentate, 1,1,3,3-tetramethylbutylperoxyneopentate, 1,1-bis(t-hexylperoxy)cyclohexane, benzoyl peroxide, 3,5,5-trimethylhexylperoxide, dodecyl peroxide, 2,2′-azobis(2-methylbutyronitrile), dimethyl2,2′-azobis(2-methylpropionate), etc.

[0020] The amount of free radical initiator (a) used (feed) should preferably be set in a suitable ratio of 0.0001 to 10 moles relative to the amount of 1,2,3-triallyloxypropane used (feed).

[0021] Reaction solvent (b) may include, for example: water, methanol, ethanol, propanol, 2-propanol, butanol, ethyl acetate, propyl acetate, butyl acetate, tetrahydrofuran, dimethyl ether, acetonitrile, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphatamide, etc. One or more of these solvents may be used as reaction solvent (b).

[0022] In step (1), the reaction temperature should preferably be set to the range of 0~150℃. Also, the reaction time can be set appropriately according to the set reaction temperature, but should preferably be set to the range of 1~120 hours.

[0023] After the reaction in step (1) is completed, the reaction solvent can be distilled off from the obtained reaction solution (reaction mixture) and the reaction product of the obtained residue can be supplied to step (2). Alternatively, after the reaction in step (1) is completed, the obtained reaction solution can be directly supplied to step (2).

[0024] [Step (2)] Step (2) is the following steps: decompose the compound shown in formula (V) with a solvent (e.g., hydrolysis or alcohol decomposition reaction (alcoholization)) to produce a mixture (composition) containing 1,2,3-tris(3-mercaptopropoxy)propane and its dimer shown in formula (II).

[0025] In step (2), the alcohol used for the alcohol decomposition reaction can be, for example, methanol, ethanol, propanol, 2-propanol, butanol, ethylene glycol, propylene glycol, butanediol, glycerol, etc.

[0026] In step (2), an acid (c) or a base (d) is preferably used to promote the reaction. Also, a reaction solvent (e) may be used to facilitate the reaction. Examples of acids (c) include hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide, carbonic acid, formic acid, acetic acid, benzoic acid, oxalic acid, citric acid, phosphoric acid, hexafluorophosphate, nitric acid, sulfuric acid, methanesulfonic acid, toluenesulfonic acid, trifluoromethanesulfonic acid, boric acid, boron trifluoride, tetrafluoroboric acid, etc.

[0027] The amount of acid (c) used (feed) should be set to a suitable ratio of 0.0001 to 10 moles relative to the amount of reaction product used (generated) in step (1).

[0028] Bases (d) include, 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 bicarbonate, sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, trilithium phosphate, trisodium phosphate, tripotassium phosphate, tricesium phosphate, dilithium hydrogen phosphate, disodium hydrogen phosphate, 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-butoxide, etc.

[0029] The amount of alkali (d) used (feed) should be set to a suitable ratio of 2 to 200 moles relative to the amount of reaction product used (generated) in step (1).

[0030] In the solvent decomposition reaction, from the viewpoint of suppressing the amount of dimer formation, it is advisable to use an alkali.

[0031] Reaction solvents (e) may include, for example, ethyl acetate, propyl acetate, butyl acetate, tetrahydrofuran, dimethyl ether, acetonitrile, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphatamide, etc. These reaction solvents (e) may also be used in combination.

[0032] In step (2), the reaction temperature should preferably be set in the range of 0~150°C. Furthermore, the reaction time can be appropriately set according to the set reaction temperature, but should preferably be set in the range of 1~120 hours. After the solvent decomposition reaction is completed, the mixture (composition) of the compound shown in formula (II) and its dimer can be extracted from the obtained reaction solution by means such as distilling off the reaction solvent to concentrate the reaction solution or solvent extraction. This mixture (composition) can be used as a hardener for resins.

[0033] [Step (3)] After step (2) is completed, the dimer can be further separated or purified by means of washing with water, activated carbon treatment, silicone chromatography, etc., as needed.

[0034] (Curing Agent) The dimer of the compound shown in Formula (II) can be used as a curing agent for resins. It can also be used as an intermediate raw material for various other sulfur-containing compounds. The curing agent of the present invention contains a dimer of the compound shown in Formula (II). It is preferably a composition containing the compound shown in Formula (II) and its dimer. When the curing agent is a composition containing the compound shown in Formula (II) and its dimer, from the viewpoint of the viscosity of the resin composition and the adhesion strength of the cured product, the ratio of the dimer content to the compound shown in Formula (II) in this composition is generally 0.02 to 0.30, preferably 0.05 to 0.25, and more preferably 0.10 to 0.25. The content ratio of each component in the composition is a value calculated using the peak area of ​​each component when the composition used as the curing agent is analyzed by liquid chromatography. See the examples for details.

[0035] (First Resin Composition) The first resin composition of the present invention is an epoxy compound (meaning the epoxy resin before curing) containing the curing agent of the present invention. That is, the first resin composition contains the curing agent and epoxy compound of the present invention, and may further contain curing accelerators, stabilizers, etc., as needed.

[0036] This epoxy compound can be used without restriction if it has an intramolecular epoxy group (epoxypropyl group). Examples include: polyepoxypropyl ethers (e.g., bisphenol A type epoxy resin) obtained by reacting polyphenols such as bisphenol A, bisphenol F, bisphenol AD, catechol, and resorcinol, or polyols such as glycerol and polyethylene glycol, with epichlorohydrin; epoxypropyl ether esters obtained by reacting hydroxycarboxylic acids such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid with epichlorohydrin; polyepoxypropyl esters obtained by reacting polycarboxylic acids such as phthalic acid and terephthalic acid with epichlorohydrin; epoxypropyl acetylenide compounds with two or more intramolecular epoxy groups, such as 1,3,4,6-tetraepoxypropylacetylenide; 3′,4′-epoxycyclohexylmethyl- Cyclic alicyclic epoxy resins such as 3,4-epoxycyclohexane carboxylate; nitrogen-containing cyclic epoxy resins such as triepoxypropyl triisocyanate and vinyl urea-type epoxy resin; as well as epoxidized phenolic resins (phenolic resins), epoxidized cresol resins, epoxidized polyolefins, cyclic aliphatic epoxy resins, and polyurethane-modified epoxy resins. In addition, organic compounds having carbon-carbon double bonds and epoxypropyl groups, and epoxy-modified organopolysiloxane compounds obtained by hydrogenation silanization addition reaction with silicon compounds having SiH groups (e.g., epoxy-modified organopolysiloxane compounds disclosed in Japanese Patent Application Publication No. 2004-99751 and Japanese Patent Application Publication No. 2006-282988), can also be used in combination.

[0037] In the first resin composition of the present invention, the content of the curing agent of the present invention is generally 0.1 to 60% by weight, preferably 1 to 50% by weight, and more preferably 2 to 30% by weight. In the first resin composition, the content of the curing agent of the present invention is preferably set in such a way that the ratio (equivalent ratio) of the number of thiol groups in the curing agent of the present invention to the number of epoxy groups in the composition is 0.1 to 10, and further preferably 0.1 to 1.

[0038] The first resin composition of the present invention may contain other thiol compounds as curing agents in addition to the curing agent of the present invention. Other thiols include, for example, aliphatic thiols such as ethanedithiol, propanedithiol, hexamethylenedithiol, decamethyldithiol, toluene-2,4-dithiol, 2,2-bis(mercaptomethyl)-1,3-propanedithiol, 2-(mercaptomethyl)-2-methyl-1,3-propanedithiol, and 2-ethyl-2-(mercaptomethyl)-1,3-propanedithiol; aromatic thiols such as benzenedithiol, toluenedithiol, and xylenedithiol (p-xylenedithiol); cyclic sulfides such as polythiols containing a 1,4-dithiane ring as shown in formula (VI); mercaptoalkyl sulfides such as 3-thiopentane-1,5-dithiol and 4-mercaptomethyl-3,6-dithio-1,8-octanedithiol; mercaptopropionates such as neopentyltetroxide tetra(3-mercaptopropionate); and epoxy resin terminal mercapto compounds. Compounds; 3,6-dioxo-1,8-octanedithiol, mercaptoalkyl ether disulfides of formula (VII), 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, 2,2-bis[(3-mercaptopropoxy)methyl]-1-butanol and other mercaptoalkyl ether compounds; 1,3,4,6-tetra(2-mercaptoethyl)ethynurea, 1,3,4,6-tetra(3-mercaptopropyl)ethynurea, etc. One or more of these compounds can also be used in combination.

[0039] [Chemical Formula 7] (In the formula, p represents an integer from 1 to 5.)

[0040] [Chemical Formula 8] (In the formula, q represents an integer from 1 to 20.)

[0041] In the first resin composition of the present invention, the content of other thiol compounds shall be set in such a way that the number of thiol groups derived from other thiol compounds in the composition shall be in a ratio of 0 to 100 (equivalent ratio) to the number of thiol groups derived from the curing agent of the present invention.

[0042] The first resin composition of the present invention may contain the curing agent of the present invention, as well as conventionally known curing agents. Conventionally known curing agents include, for example, compounds having phenolic hydroxyl groups, acid anhydrides, and organophosphorus compounds such as triphenylphosphine, diphenylnaphthylphosphine, and diphenylethylphosphine; aromatic phosphonium salts; aromatic diazonium salts; aromatic phosphonium salts; and aromatic selenium salts.

[0043] Compounds having phenolic hydroxyl groups include, for example: bisphenol A, bisphenol F, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol S, tetrachlorobisphenol A, tetrabromobisphenol A, dihydroxynaphthalene, phenolic aldehyde, cresol aldehyde, bisphenol A aldehyde, brominated phenolic aldehyde, resorcinol, etc.

[0044] Examples of acid anhydrides include: methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, trimellitic anhydride, nadic anhydride, hemicryl anhydride, methylnadic anhydride, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, bicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, methylnorbornene-2,3-dicarboxylic acid, etc.

[0045] The first resin composition of the present invention may also contain conventionally known curing accelerators. Examples of curing accelerators include: (i) amines, (ii) reaction products of epoxy compounds and amines, and (iii) reaction products of compounds having one or more isocyanate groups in the molecule and compounds having at least one of primary and secondary amine groups in the molecule. These may also be used in combination.

[0046] (i) As previously known, amines are those having at least one amino group selected from primary, secondary, and tertiary amino groups within the molecule. Examples of such amines include: aliphatic amines such as diethyltriamine, triethyltetraamine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, 4,4′-diaminodicyclohexylmethane, and dimethylbenzylmethylamine; aromatic amines such as 4,4′-diaminodiphenylmethane and o-methylaniline; and nitrogen-containing heterocyclic compounds such as 2-ethyl-4-methylimidazolium, 2-methylimidazolium, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine, and piperazine.

[0047] In the first resin composition of the present invention, the content of the curing accelerator (especially amines) is preferably 0.1 to 30 parts by weight relative to 100 parts by weight of the curing agent of the present invention.

[0048] (ii) The reaction product of epoxy compounds and amines is a solid that is insoluble in epoxy resin at room temperature, but can be soluble by heating (easily soluble), and can play the role of curing accelerator. Therefore, it is also called a potential curing accelerator (hereinafter, the reaction product of epoxy compounds and amines is sometimes referred to as "potential curing accelerator").

[0049] In addition to the aforementioned epoxy compounds, epoxy compounds used as raw materials for potential hardening accelerators include: epoxypropylamine compounds obtained by reacting 4,4′-diaminodiphenylmethane, m-aminophenol, etc. with epichlorohydrin; monofunctional epoxy compounds such as butyl epoxypropyl ether, phenyl epoxypropyl ether, and epoxypropyl methacrylate.

[0050] The aforementioned amines can be cited as raw materials for potential hardening accelerators. Furthermore, among these amines, those with tertiary amino groups within the molecule can serve as raw materials for potential hardening accelerators with excellent hardening promoting properties. Examples of such amines include: dimethylaminopropylamine, diethylaminopropylamine, di-n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, N-methylpiperazine, etc.; imidazole compounds such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, etc., which contain a tertiary amino group within the molecule; 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, etc. azole, 1-(2-hydroxy-3-butoxypropyl)-2-ethyl-4-methylimidazol, 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-hydroxyethylmorpholine, 2-dimethylaminoethanethiol, 2- Mercaptopyridine, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 4-mercaptopyridine, N,N-dimethylaminobenzoic acid, N,N-dimethylglycine, nicotinic acid, isonicotinic acid, pyridine-2-carboxylic acid, N,N-dimethylglycine acehydrazide, N,N-dimethylpropionic acid acehydrazide, nicotinic acid acehydrazide, isonicotinic acid acehydrazide, etc. These are alcohols, phenols, thiols, carboxylic acids, acehydrazides, etc., that contain a tertiary amino group.

[0051] To further improve the storage stability of the first resin composition of the present invention, in addition to the aforementioned epoxy compounds and amines, active hydrogen compounds having two or more active hydrogen atoms in their molecules can also be used as the third component as raw materials for potential curing accelerators. Examples of active hydrogen compounds include: bisphenol A, bisphenol F, bisphenol S, hydroquinone, catechol, resorcinol, pyrogallol, phenolic resins, and other polyphenols; trimethylolpropane and other polyols; adipic acid, phthalic acid and other polycarboxylic acids; 1,2-dimercaptoethane, 2-mercaptoethanol, 1-mercapto-3-phenoxy-2-propanol, mercaptoacetic acid, o-aminobenzoic acid, lactic acid, etc.

[0052] Furthermore, the potential hardening accelerator can also be surface-treated using isocyanate compounds and acidic compounds. Examples of isocyanate compounds include: monofunctional isocyanate compounds such as n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, and benzyl isocyanate; and polyfunctional isocyanate compounds such as hexamethylene diisocyanate, toluene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4′-diisocyanate, isoflavone diisocyanate, toluene diisocyanate, p-toluene diisocyanate, 1,3,6-hexamethylene triisocyanate, and dicycloheptane triisocyanate.

[0053] Alternatively, a compound with a terminal isocyanate group obtained by reacting a polyfunctional isocyanate compound with an active hydrogen compound can be used instead of the polyfunctional isocyanate compound. Examples include: an addition reaction product with a terminal isocyanate group obtained by reacting toluene diisocyanate with trihydroxymethylpropane; and an addition reaction product with a terminal isocyanate group obtained by reacting toluene diisocyanate with neopentyl tertrol.

[0054] Furthermore, the acidic substance used for surface treatment of the potential hardening accelerator can be any of a gas, liquid, or solid, and can be any of an inorganic acid or an organic acid. Examples of such acidic substances include: carbon dioxide gas, sulfurous acid gas, sulfuric acid, hydrochloric acid, oxalic acid, phosphoric acid, acetic acid, formic acid, propionic acid, adipic acid, hexanoic 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, phenol resin, resorcinol resin, etc.

[0055] Potential curing accelerators can be easily obtained by mixing epoxy compounds, amines, and active hydrogen compounds as needed, reacting them at a temperature from room temperature to 200°C, and then curing and pulverizing them; or by reacting them in solvents such as methyl ethyl ketone, dimethyl ether, and tetrahydrofuran, removing the solvent, and then pulverizing the solid components.

[0056] Alternatively, commercially available latent hardening accelerators may be used. Examples of commercially available products include: Ajinomoto Fine-Techno's "Amicure PN-23", "Amicure PN-H", and "Amicure MY-24", and Asahi Kasei's "Novacure HX-3721" and "Novacure HX-3742".

[0057] In the first resin composition of the present invention, the content of the potential curing accelerator is preferably 0.1 to 1000 parts by weight relative to 100 parts by weight of epoxy compound (epoxy resin).

[0058] (iii) The reaction product of a compound having one or more isocyanate groups in its molecule and a compound having at least one of primary amine groups and secondary amine groups in its molecule can be obtained by reacting the two in an organic solvent such as dichloromethane.

[0059] Isocyanate compounds having one or more isocyanate groups in their molecule, for example, 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, and benzyl isocyanate. Esters, hexamethylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4′-diisocyanate, 2,2-dimethyldiphenylmethane-4,4′-diisocyanate, dimethylbiphenyl diisocyanate, isoflavone diisocyanate, xylene diisocyanate, 1,3-bis(isocyanate methyl)cyclohexane, p-xylene diisocyanate, 1,3,6-hexamethylene triisocyanate, dicycloheptane triisocyanate, tri-(3-isocyanate-4-methylphenyl)triisocyanate, tri-(6-isocyanate hexyl)triisocyanate, etc.

[0060] A compound having at least one of a primary amino group and a secondary amino group in its molecule, for example: 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, piperidine, pyrrolidine, benzylamine, N-methylbenzylamine, cyclohexylamine, m-xylyldiamine, 1,3-bis(aminomethyl)cyclohexane, isophorone diamine, N-aminoethylpiperidine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-phenylimidazole, 1,1-dimethylhydrazine, etc.

[0061] In the first resin composition of the present invention, the content of the reaction product of the compound having one or more isocyanate groups in the molecule and the compound having at least one of primary amine groups and secondary amine groups in the molecule is preferably 1 to 10 parts by weight relative to 100 parts by weight of epoxy compound (epoxy resin).

[0062] The first resin composition of the present invention may also contain conventionally known stabilizers, provided that the effects of the present invention are not impaired. Examples of stabilizers include: liquid borate compounds (trimethylborate, triethylborate, tri-n-propylborate, triallylborate, trihexylborate, etc.), and organic acids (acetic acid, propionic acid, butyric acid, succinic acid, malic acid, citric acid, etc.).

[0063] The first resin composition of the present invention may, as long as it does not impair the effect of the present invention, contain, as required, the following components in a weight percentage of 0.01 to 50% relative to the total weight of the first resin composition: pigments (titanium dioxide, cyan blue, uranium red, iron oxide red, carbon black, aniline black, manganese blue, iron black, ultramarine blue, sunshine red, chrome yellow, chrome green, etc.), inorganic fillers (calcium carbonate, kaolin, clay, talc, mica, barium sulfate, zinc barium white, gypsum, zinc stearate, iron oxide, quartz, quartz glass, fused silica, etc.). Spherical silica powder, spherical alumina, crushed alumina, magnesium oxide, beryllium oxide, titanium oxide and other oxides, boron nitride, silicon nitride, aluminum nitride and other nitrides, silicon carbide and other carbides, aluminum hydroxide, magnesium hydroxide and other hydroxides, copper, silver, iron, aluminum, nickel, titanium and other metals, alloys, diamond, carbon and other carbon-based materials, etc.), thermoplastic resins and / or thermosetting resins (high-density, medium-density, low-density various polyethylene, polypropylene, polybutene, polypentene and other homopolymers, ethylene-propylene copolymers, nylon, etc. This includes polyamide resins such as Nylon-6 and Nylon-6, vinyl chloride resins, nitrocellulose resins, vinylidene chloride resins, acrylic resins, acrylamide resins, styrene resins, vinyl ester resins, polyester resins, phenolic resins (phenolic compounds), silicone resins, fluorine resins, acrylic rubber, polyurethane rubber and other elastomer resins, methyl methacrylate-butadiene-styrene graft copolymers, acrylonitrile-butadiene-styrene graft copolymers, etc. The additives (modifiers) include: reinforcing agents (glass fiber, carbon fiber, etc.), anti-drip agents (hydrogenated castor oil, micronized anhydrous silica, etc.), matting agents (micronized silica, paraffin wax, etc.), abrasives (zinc stearate, etc.), internal release agents (fatty acids such as stearic acid, fatty acid metal salts of calcium stearate, fatty acid amides such as stearylamine, fatty acid esters, polyolefin waxes, paraffin wax, etc.), surfactants, leveling agents, defoamers, viscosity adjusters (organic solvents), flexibility enhancers, coupling agents, fragrances, flame retardants, antioxidants, etc. Furthermore, when the first resin composition of this invention contains a compound containing isocyanate groups as an additive (modifier), it can inhibit the decrease in the curing properties of the resin composition and simultaneously improve its adhesion.

[0064] Examples of compounds containing isocyanate groups 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, dimethylbiphenyl diisocyanate, isoflavone diisocyanate, xylylene diisocyanate, p-xylylene diisocyanate, 1,3,6-hexamethylene triisocyanate, dicycloheptane triisocyanate, etc.

[0065] In the first resin composition of the present invention, the content of the compound containing isocyanate groups is preferably 0.1 to 20 parts by weight relative to 100 parts by weight of epoxy compound (epoxy resin).

[0066] There are no particular limitations on the method of preparing (mixing) the first resin composition of the present invention. A predetermined amount of each of the aforementioned components can be measured and a suitable mixing device such as a three-roller mixer or a planetary mixer can be used, and heating can be performed while mixing as needed.

[0067] There are no particular limitations on the method for curing the first resin composition of the present invention, and conventionally known curing devices such as closed curing furnaces and tunnel furnaces capable of continuous curing can be used. There are also no particular limitations on the heating source, and conventionally known methods such as hot air circulation, infrared heating, and high-frequency heating can be used. The curing temperature and curing time can be set appropriately.

[0068] (Second Resin Composition) The second resin composition of this invention contains the curing agent of this invention and an alkene compound having carbon-carbon double bonds within its molecule (hereinafter, sometimes simply referred to as "alkene compound"). That is, the second resin composition contains the curing agent and the alkene compound of this invention, and may further contain photopolymerization initiators, stabilizers, etc., as needed. The alkene compound includes both polymerizable monomers and polymerizable oligomers (semi-cured compounds) having a structure formed by partial polymerization of polymerizable monomers.

[0069] This polymerizable monomer can be exemplified by: (1) (meth)acrylate alkyl ester monomers, (2) hydroxyl-containing monomers, (3) carboxyl-containing monomers, (4) amino-containing monomers, (5) acetyl-acetyl monomers, (6) isocyanate-containing monomers, (7) epoxypropyl monomers, (8) monomers containing one aromatic ring, (9) monomers containing alkoxy and oxoalkyl groups, (10) alkoxyalkyl (meth)acrylamide monomers, (11) (meth)acrylamide monomers, (12) monofunctional unsaturated compounds, (13) polyfunctional unsaturated compounds, etc.

[0070] (1) Alkyl methacrylate monomers, for example: meth (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, dodecyl (meth)acrylate, hexadecyl (meth)acrylate, octadecyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, etc.

[0071] (2) Hydroxyl-containing monomers, for example, include: 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate and other hydroxyalkyl (meth)acrylates; caprolactone-modified monomers such as 2-hydroxyethyl (meth)acrylate modified with caprolactone; diethylene glycol (meth)acrylate, polyethylene glycol (meth)acrylate and other oxyalkylene-modified monomers; and 2-acryloyloxyethyl-2-hydroxyethyl Phthalic acid, N-hydroxymethyl (meth)acrylamide, hydroxyethylacrylamide, etc. contain primary hydroxy monomers; 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, propylene glycol digoxypropyl ether-epoxy di(meth)acrylate, phenol glycidyl ether-epoxy di(meth)acrylate, bisphenol A digoxypropyl ether-epoxy di(meth)acrylate, etc. contain secondary hydroxy monomers; 2,2-dimethyl-2-hydroxyethyl (meth)acrylate, etc. contain tertiary hydroxy monomers, etc.

[0072] (3) Contains carboxyl monomers, for example: (meth)acrylic acid, acrylic acid dimer, crotonic acid, maleic acid, maleic anhydride, fumaric acid, citralic acid, pentenoic acid, itconic acid, acrylamide N-glycolic acid, cinnamic acid, etc.

[0073] (4) Contains amino monomers, for example: tert-butylaminoethyl (meth) acrylate, ethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, etc.

[0074] (5) Contains acetyl acetoyl monomers, for example: 2-(acetyl acetooxy) ethyl (meth) acrylate, allyl acetoacetate, etc.

[0075] (6) Monomers containing isocyanate groups, for example, 2-acryloyloxyethyl isocyanate, 2-methylacryloyloxyethyl isocyanate, and their epoxide adducts.

[0076] (7) Contains an epoxypropyl monomer, for example: epoxypropyl acrylate (meth)acrylate, ethylene glycol digoxypropyl ether-epoxy(meth)acrylate, resorcinol digoxypropyl ether-epoxy(meth)acrylate, bis(4-hydroxyphenyl) sulfide digoxypropyl ether-epoxy(meth)acrylate, phenolic epoxy resin-(meth)acrylate, cresol phenolic epoxy resin-(meth)acrylate, bisphenol (e.g., The products of the reaction between epoxy compounds such as bisphenol A and bisphenol F type epoxy resins-(meth)acrylates, bisphenol (e.g., 3,3′,5,5′-tetramethylbisphenol) type epoxy resins-(meth)acrylates, and tris(2,3-epoxypropyl)triisocyanate-(meth)acrylates and (meth)acrylic acid are epoxy (meth)acrylates, 4-hydroxybutyl (meth)acrylate glycidyl ether, and other glycidyl (meth)acrylates.

[0077] (8) Monomers containing one aromatic ring, for example: phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, styrene, α-methylstyrene, etc.

[0078] (9) Monomers containing alkoxy and oxoalkyl groups, 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, octyloxypolyethylene glycol-polypropylene glycol-mono(meth) acrylate, dodecyloxypolyethylene glycol mono(meth) acrylate, octadecyloxypolyethylene glycol mono(meth) acrylate, etc.

[0079] (10) Alkoxyalkyl (meth)acrylamide monomers, for example: methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, isopropoxymethyl (meth)acrylamide, n-butoxymethyl (meth)acrylamide, isobutoxymethyl (meth)acrylamide, etc.

[0080] (11) (Meth)acrylamide is a monomer, for example: (meth)acrylamide morpholine, dimethyl (meth)acrylamide, diethyl (meth)acrylamide, (meth)acrylamide N-hydroxymethyl (meth)acrylamide, etc.

[0081] (12) Monofunctional unsaturated compounds, for example, (meth)acrylate compounds containing a biphenyl structure, more specifically, include: o-biphenyl (meth)acrylate, m-biphenyl (meth)acrylate, p-biphenyl (meth)acrylate, etc.; 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, p-biphenyloxypropyl (meth)acrylate, etc., biphenyloxyalkyl (meth)acrylates. Esters; (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, (p-biphenyloxy)polypropylene glycol (meth)acrylate, etc., biphenyloxy polyalkyl glycol (meth)acrylates.

[0082] (13) Multifunctional unsaturated compounds, for example, monomers with 2 functional groups, monomers with 3 or more functional groups, polyurethane (meth) acrylates, the aforementioned epoxy (meth) acrylates, polyester (meth) acrylates, polyether (meth) acrylates, etc.

[0083] Furthermore, specific examples of the 2-functionalized monomers include: 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, butanediol 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... Methacrylates, 1,6-hexanediol di(meth)acrylates, 1,6-hexanediol ethylene oxide modified di(meth)acrylates, glycerol di(meth)acrylates, neopentyltetrol di(meth)acrylates, ethylene glycol diglycidyl ether di(meth)acrylates, diethylene glycol diglycidyl ether di(meth)acrylates, phthalic acid diglycidyl ester di(meth)acrylates, hydroxytert-valerate modified neopentyl glycol di(meth)acrylates, ethylene oxide modified isocyanate diacrylates, 2-(meth)acrylic acid oxyethyl acid phosphate diester, etc.

[0084] Furthermore, specific examples of monomers with 3 or more functional groups include: trimethylolpropane tri(meth)acrylate, neopentyltetramethylol tri(meth)acrylate, neopentyltetramethylol tetra(meth)acrylate, dinepentyltetramethylol tri(meth)acrylate, dinepentyltetramethylol tetra(meth)acrylate, dinepentyltetramethylol penta(meth)acrylate, dinepentyltetramethylol hexa(meth)acrylate, tri(meth)acryloxyethoxytrimethylolpropane, glycerol polyoxypropylene Elemental ether poly(meth)acrylate, tris(2-(meth)acryloxyethyl)triisocyanate, ethylene oxide modified tri(meth)acrylate, ethylene oxide modified dinepentetrene penta(meth)acrylate, ethylene oxide modified dinepentetrene hexa(meth)acrylate, ethylene oxide modified neopentetrene tri(meth)acrylate, ethylene oxide modified neopentetrene tetra(meth)acrylate, succinic acid modified neopentetrene tri(meth)acrylate, etc.

[0085] In addition to the aforementioned polymerizable monomers, the following may also be included: divinylbenzene, isoprene, isoprene, pentadiene, vinylcyclohexene, chloroprene, butadiene, methylbutadiene, cyclopentadiene, methylpentadiene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, vinyl stearate, vinyl chloride, vinylidene chloride, alkyl vinyl ethers, ethylene toluene, vinylpyridine, vinylpyrrolidone, dialkyl isonate, dialkyl transbutenedioic acid, allyl alcohol, acrylamide chloride, methyl vinyl ketone, N- Acrylamide methyl trimethylammonium chloride, allyl trimethylammonium chloride, dimethyl allyl ketone, 2-chloroethyl vinyl ether, triallyl triisocyanate, tetraallyl ethynyl urea, N-vinylpyrrolidone, N-vinylcaprolactam, ethylene glycol diallyl carbonate, triallyl trimellitate, trifluoroethyl (meth)acrylate, tribromophenylmethyl (meth)acrylate, perfluorooctyl ethyl (meth)acrylate, sulfur-containing (meth)acrylate, (meth)acryloxypropyltris(methoxy)silane, etc.

[0086] In the second resin composition of the present invention, the olefin compound can be used in combination with the aforementioned polymerizable monomers and polymerizable oligomers. The polymerizable monomers can be used in combination with the polymerizable monomers mentioned above (different types of polymerizable monomers can be combined). The polymerizable oligomers can also be used in combination with different types of polymerizable oligomers.

[0087] In the second resin composition of the present invention, the content ratio (proportion) of the curing agent and the olefin compound of the present invention should preferably be set to a suitable proportion in the range of 0.01 to 1000 times the content of the olefin compound relative to the content of the curing agent of the present invention (by weight), and more preferably in the range of 0.1 to 100 times the content of the olefin compound (by weight).

[0088] In the second resin composition of the present invention, the aforementioned other thiol compounds and the curing agent of the present invention may also be used together. In the second resin composition of the present invention, the content ratio (proportion) of the curing agent of the present invention and other thiol compounds should preferably be set to a suitable proportion in the range of 0 to 100 times the content of the other thiol compounds relative to the content of the curing agent of the present invention (by weight), and more preferably a suitable proportion in the range of 0.1 to 10 times the content (by weight).

[0089] Methods for polymerizing (curing) the second resin composition of the present invention include photocuring and thermocuring methods. Photocuring can be achieved by irradiating with active energy rays, preferably using a photopolymerization initiator. Active energy rays can include light, radiation, electromagnetic waves, electron beams, etc., preferably electron beams or light in the ultraviolet-infrared wavelength region. Light sources can be, for example, ultra-high pressure mercury light sources or metal halide light sources for irradiating ultraviolet light; metal halide light sources or halogen light sources for irradiating visible light; and halogen light sources for irradiating infrared light. Alternatively, lasers, LEDs, and other light sources that emit light at various wavelengths and have been widely used in recent years can also be used. The irradiation amount of the active energy rays can be appropriately set according to the type of light source.

[0090] The photopolymerization initiator can be either a photoradical polymerization initiator or a photoanionic polymerization initiator, so that the second resin composition contains either one. In addition, in order to improve production efficiency and the properties of the cured product, thermal polymerization (thermal curing) can also be used in photocuring.

[0091] Photoradical polymerization initiators can be used without particular restrictions for general users. Examples include acetophenones such as 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-hydroxycyclohexylphenyl one, and 2-methyl-1-{4-(methylthio)phenyl}-2-morpholinopropane-1-one; benzoin derivatives such as benzyl dimethyl ketal; diphenyl ones such as 4-phenyldiphenyl one and hydroxydiphenyl one; oxysulfur derivatives such as isopropyl oxysulfur and 2,4-diethyl oxysulfur; and methyl phenyl glyoxylates, etc., which can also be used in combination. In addition, photoradical polymerization initiators can also be used in combination with known photopolymerization promoters such as benzoic acid such as 4-dimethylaminobenzoic acid and tertiary amines, depending on the requirements.

[0092] Photo-ion polymerization initiators, which can be used without particular restrictions for general users, include: onium salts, carbamates, etc. Examples of onium salts include: 1,2-diisopropyl-3-(bis(dimethylamino)methylene)guanidine salt 2-(3-benzophenyl)propionate, 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidine salt n-butyltriphenylborate, etc. Examples of carbamates include: 2-nitrophenylmethylpiperidine-1-carboxylic acid ester, 1-(anthraquinone-2-yl)ethylimidazolium carboxylic acid ester, 1-(3-(2-hydroxyphenyl)-2-propenyl)piperidine, 9-anthramethyldiethylcarbamate, etc.

[0093] Furthermore, when photocuring the second resin composition of the present invention, sensitizers such as pyrene, perylene, acridine orange, oxysulfuron, 2-chlorooxysulfuron, and benzoxanthin can be used.

[0094] In the second resin composition of the present invention, the content of photopolymerization initiator relative to the total amount of the second resin composition is preferably 0.001 to 20% by weight, and more preferably 0.01 to 10% by weight.

[0095] On the other hand, a method for thermosetting the second resin composition of the present invention can be exemplified by using a method employing a thermal polymerization initiator. The thermal polymerization initiator can be selected from thermal free radical polymerization initiators and thermal anionic polymerization initiators, and the resin composition may contain either one. The thermosetting conditions can be appropriately set to a heating temperature / heating time, but preferably within a range of 60~130°C / 30~240 minutes, and more preferably within a range of 70~125°C / 30~120 minutes.

[0096] Thermal free radical polymerization initiators can be used without special restrictions for general users. Examples include: diisopropyl peroxydicarbonate, benzoyl peroxide, t-butyl peroxyisobutyrate, t-hexyl peroxyisopropyl monocarbonate, t-hexyl peroxy2-ethylhexanoate, 1,1,3,3-tetramethylbutyl peroxy2-ethylhexanoate, t-butyl peroxyneopentate, t-hexyl peroxyneopentate, t-butyl peroxyneopentate, etc. Peroxides such as decanoate, t-hexylperoxynedecanoate, 1,1,3,3-tetramethylbutylperoxynedecanoate, 1,1-bis(t-hexylperoxy)cyclohexane, benzoyl peroxide, 3,5,5-trimethylhexyl peroxide, dodecyl peroxide, azobisisobutyronitrile, 2,2′-azobis(2-methylbutyronitrile), and dimethyl 2,2′-azobis(2-methylpropionate) can also be used in combination.

[0097] Thermal anionic polymerization initiators can be used without particular restrictions for general users. Examples include amines and imidazoles, which can also be used in combination. Examples of amines include: diethyltriamine, triethyltetraamine, isophorone diamine, xylyltriamine, diaminodiphenylmethane, 1,3,4,6-tetra(3-aminopropyl)ethynylurea, etc. Examples of imidazoles include: 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, etc.

[0098] In the second resin composition of the present invention, the content of the thermal polymerization initiator relative to the total amount of the second resin composition is preferably 0.001 to 20% by weight, and more preferably 0.01 to 10% by weight.

[0099] Furthermore, 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 also be used. Photocationic polymerization initiators can be used without particular restriction by general users, and examples include onium salts and organometallic complexes. Examples of onium salts include diazonium salts, strontium salts, and iodonium salts; examples of organometallic complexes include iron-aromatic complexes, titanocene complexes, and arylsilyl-aluminum complexes. Commercially available photocationic polymerization initiators include, for example, DEKA OPTOMER SP-150 and DEKA OPTOMER SP-170 manufactured by ADEKA, UVE-1014 manufactured by General Electric, CD-1012 manufactured by SARTOMER, and CPI-100P manufactured by SAN-APRO. Paired anions of photocationic polymerization initiators include SbF6-, AsF6-, B(C6F5)4-, and PF6-.

[0100] Thermal cationic polymerization initiators can be used without particular restrictions for general users. Examples include various onium salts such as quaternary ammonium salts, phosphonium salts, and strontium salts, as well as organometallic complexes, which can also be used in combination. Commercially available onium salts include, for example, ADEKA OPTON CP-66 and ADEKA OPTON CP-77 manufactured by ADEKA Corporation; SAN-AID SI-60L, SAN-AID SI-80L, and SAN-AID SI-100L manufactured by Sanshin Chemical Industry Co., Ltd.; and the CI series manufactured by Nippon Soda Corporation. Organometallic complexes include alkoxysilane-aluminum complexes.

[0101] The second resin composition of the present invention may be further incorporated with stabilizers, additives (modifiers), etc., as described in the items of the first resin composition, provided that the effect of the present invention is not impaired. It may also contain additives (modifiers) in a proportion of 0.01 to 50% by weight relative to the total amount of the second resin composition, depending on specific requirements.

[0102] There are no particular limitations on the preparation (mixing) of the second resin composition of the present invention. For example, it can be prepared by mixing the curing agent, olefin compound, photopolymerization initiator and / or thermal polymerization initiator of the present invention, other thiol compounds added as needed, and additives. The mixing method can be a known method (e.g., the method described in the section on the first resin composition). In addition, the curing agent of the present invention (together with other thiol compounds added as needed) can be dissolved or dispersed in a viscosity-adjusting diluent (organic solvent) beforehand.

[0103] (Uses of the Resin Composition) It is expected that the first and second resin compositions of the present invention (sometimes referred to collectively as "the resin compositions of the present invention") containing the curing agent of the present invention can provide cured products with excellent mechanical strength. That is, compared with resin compositions containing conventional thiol compounds, the resin compositions of the present invention can provide cured products with excellent adhesive strength, and are therefore suitable for use as adhesives and sealants. In other words, the adhesives and sealants of the present invention use the aforementioned resin compositions of the present invention as components.

[0104] The adhesive and sealant of the present invention may also contain additives. Examples of additives include: flow behavior modifiers such as silica, magnesium silicate, and barium sulfate; thermal conductivity imparting agents such as alumina; electrical conductivity imparting agents such as silver and carbon; coloring agents such as pigments and dyes. These additives may be incorporated when preparing the resin composition of the present invention. Furthermore, they may also be mixed with a pre-prepared resin composition of the present invention. The mixing method may employ known methods (e.g., the method described in the first resin composition section).

[0105] The adhesives and sealants of the present invention have no particular limitations in their application and can be used in a wide variety of fields. Examples of applications for the adhesive include: adhesives for flexible printed circuit boards; interlayer adhesives for multilayer substrates such as laminated substrates; adhesives for bonding optical components; adhesives for optical disc bonding; adhesives for mounting printed circuit boards; die-attach adhesives; semiconductor adhesives such as filler adhesives; adhesives for mounting BGA reinforcement filler adhesives, anisotropic conductive films (ACF), anisotropic conductive pastes (ACP), etc.; adhesives for optical pickups; adhesives for optical path bonding; adhesives used between exterior materials, base materials, ceiling materials, and interior materials; adhesives for bonding exterior wall materials, base materials, tiles, and stone. Adhesives; adhesives for bonding various wood flooring materials, polymer-based flooring sheets, and floor tiles; adhesives for structural materials, bodies, and parts of automobiles and aircraft; adhesives for automotive interiors; adhesives for steel plate joints, etc. Sealant applications include: sealants for joints in various metal plates, edge plates, and other exterior materials; sealants used between exterior materials, base materials, ceiling materials, and interior materials; sealants for joints in various concrete products such as roads, bridges, tunnels, and breakwaters; sealants for structural materials, bodies, and parts of automobiles and aircraft; sealants for steel plate joints; sealants for medical machines, etc.

[0106] The resin composition of the present invention, in addition to the aforementioned adhesive and sealant, can be used as a raw material for products (parts, components), electrical or electronic, optical, construction, civil engineering, automotive or aircraft, medical fields, and daily necessities or general merchandise, etc., in various fields where the material is resin.

[0107] Examples of parts, components, and materials in the electrical or electronic fields include: resin-coated copper foil, prepreg, copper laminate, printed circuit boards, solder resist ink, conductive paste, interlayer insulating materials, sealing materials, LED sealing materials, insulating materials, thermally conductive materials, hot melt adhesive materials, coatings, potting compounds, etc. More specifically, examples include: interlayer insulating films, wiring films, etc., printed circuit boards, sealing materials for electronic components, layer forming materials; color filters, thin films for flexible displays, photoresist materials, alignment films, etc., forming materials for display devices; photoresist materials, buffer coatings, etc., forming materials for semiconductor devices; holographic, waveguide, optical circuit, optical circuit components, anti-reflective films, etc., forming materials for optical components. Examples include: rigid wiring boards for semiconductor mounting, forming materials for flexible printed wiring boards; mounting materials for semiconductor mounting, sealing materials for semiconductors, sealing materials for solar cells, insulating films for semiconductors, covering films for flexible printed circuit protection, and coating agents for wiring sheaths.

[0108] Examples of materials in the field of optics include fiber core materials, cover materials, lenses, and wear-resistant coatings for lenses (e.g., hard coating liquids).

[0109] Examples of materials in the construction field include: coating materials and primers for various metal plates, edge panels and other exterior materials; injection molding materials, shock-absorbing materials, sound-insulating materials, conductive materials for electromagnetic wave shielding, and lime plaster materials used between exterior materials, base materials, ceiling materials and interior materials; adhesives for bonding wood flooring boards, polymer flooring sheets, floor tiles to various types of flooring; injection molding materials for repairing cracks in various exterior and interior materials, etc.

[0110] Examples of materials in the civil engineering field include: coating materials, primers, paints, lime plaster materials, injection materials, spraying materials, and molding materials for various concrete products such as roads, bridges, tunnels, and breakwaters.

[0111] Examples of materials used in the automotive or aircraft industry include: structural materials, body materials, parts covering materials, cushioning materials, shock-absorbing materials, sound insulation materials, spray materials; adhesives, covering materials, and foaming materials used in automotive interiors; and covering materials used for steel plate joints.

[0112] Examples of materials in the medical field include: artificial bone materials, dental mold materials, medical rubber materials, and medical adhesives.

[0113] [Examples] Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the present invention is not limited thereto. The main raw materials used are as described below.

[0114] ・1,2,3-Triallyloxypropane (the compound shown in formula (III) synthesized according to the method described in Japanese Patent Application Publication No. 2012-184198.)・Thioacetic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)・48% aqueous solution of sodium hydroxide (manufactured by Wako Pure Chemical Industries Co., Ltd.)・Sulfuric acid (manufactured by Wako Pure Chemical Industries Co., Ltd.)

[0115] (A) Hardener • 1,2,3-Tris(3-mercaptopropoxy)propane (Refer to Synthesis Example 1. Compound shown in Formula (II).) • Trihydroxymethylpropane tris(3-mercaptopropionate) (Manufactured by SC Organic Chemicals Co., Ltd., trade name "TMMP", compound shown in Formula (VIII), thiol equivalent: 133) [Chemical Formula 9]

[0116] (B) Curing accelerator: Dimethylbenzylmethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) (C) Epoxy compound (epoxy resin): Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name "jER828", epoxy equivalent: 187.0) Glyceryl trioxypropyl ether (manufactured by Anhui Xinyuan Technology Co., Ltd., trade name "XY633", epoxy equivalent: 149.9)

[0117] The methods for determining the storage modulus of elasticity and the method for determining the adhesion strength in the evaluation tests used in the examples and comparative examples are as follows.

[0118] [Viscosity Measurement] The viscosity of the compound used as a hardener and the epoxy resin composition at 25°C was measured using a viscometer (UBM, "Rheosol-G5000"). The lower the viscosity (lower viscosity), the better the operability when preparing the epoxy resin composition and when using the resin composition as an adhesive.

[0119] [Determination of Storage Modulus of Elasticity] The epoxy resin composition was cured (80°C / 1 hour), and the storage modulus of elasticity G′ (MPa) of the cured material (test piece: 25mm long × 5mm wide × 1mm thick) at 25°C was measured using a dynamic viscoelasticity measuring device (UBM Corporation, "Rheosol-G5000") (frequency: 1Hz). The smaller this storage modulus of elasticity (low elasticity), the better the impact resistance of the cured material.

[0120] [Determination of Adhesion Strength] An epoxy resin composition (adhesive) was applied to two SUS plates (100 mm long × 25 mm wide × 1.6 mm thick), forming a 12.5 mm long × 25 mm wide area measured from any end (length direction) on one side of each SUS plate. The two SUS plates were then bonded together with the coated surfaces in contact with each other, and a test piece was prepared by heating (to harden the epoxy resin composition at 80°C for 1 hour). The tensile shear strength (MPa) of this test piece was determined according to JIS K6850. The higher the shear strength, the more suitable the epoxy resin composition is as an adhesive.

[0121] <Synthesis of Thiol Compounds> [Example 1] 50.95 g (240.0 mmol) of 1,2,3-triallyloxypropane and 190.00 g of butyl acetate were fed into a 500 ml three-necked flask and heated to 50 °C. Then, 73.07 g (960.0 mmol) of thioacetic acid was added dropwise and the mixture was stirred at 67 °C for 44 hours. Next, the reaction mixture was concentrated, and 66.00 g (792.0 mmol) of 48% sodium hydroxide aqueous solution and 920.0 g of deionized water were added to the resulting reaction product. The mixture was stirred at 70 °C for 24 hours. After neutralizing the resulting reaction mixture with sulfuric acid, the washing operation was repeated 5 times with a butyl acetate / deionized water ratio of 2 / 1 (by weight). The organic layer after washing was concentrated to obtain 66.12 g of a brown liquid (crude product). The crude product was further purified by silicone column chromatography (chloroform / ethyl acetate = 12 / 1 (volume ratio)) to obtain 0.10 g of pale yellow liquid (column yield: 1.6%).

[0122] The 1H-NMR spectrum data of this pale yellow liquid is shown below. ・ 1H-NMR (CDCl 3) δ: 3.69 (quin., 4H), 3.50 (dd, 18H), 2.75 (t, 4H), 2.62 (q, 8H), 1.95 (quin., 4H), 1.86 (quin., 8H), 1.38 (t, 4H). The IR spectrum data of this pale yellow liquid is shown in Figure 1. Based on these spectral data, specifically, by the integral ratio of the 1.38 peak (-SH) in 1H-NMR and the absorption peak at 755 cm⁻¹ in IR (-CSSC- of -CS- absorption peak), the obtained pale yellow liquid was identified as an oxidized dimer of the thiol compound shown in formula (II).

[0123] Furthermore, the crude product was analyzed by liquid chromatography (extraction solution: 20 mM sodium dihydrogen phosphate aqueous solution / acetonitrile = 1 / 3 (weight ratio), column: Shim-Pack CLC-ODS, detector: PDA (210 nm)). It was confirmed that the crude product contained the thiol compound shown in formula (II) (dissolution time: peak at 5.6 minutes) as the main component, and also contained its oxidized dimer (dissolution times: 12.6 minutes, 12.9 minutes, and 16.0 minutes with 3 peaks). By the peak area ratio of the thiol compound shown in formula (II) and its oxidized dimer (the sum of the 3 peaks), it was confirmed that the content of the oxidized dimer relative to the content of the thiol compound shown in formula (II) was 0.20 (20% in percentage).

[0124] Furthermore, when performing LC / MS analysis (extraction solution: 5 mM ammonium formate aqueous solution / acetonitrile = 1 / 3 (volume ratio), column: Aquity UPLC BEH C18, detector: PDA (210 nm)), the peak detected at 5.6 minutes by liquid chromatography had an m / z of 315.1115 (H+ adduct); the peaks detected at 12.6 minutes, 12.9 minutes, and 16.0 minutes each had an m / z of 644.2272 (NH4+ adduct), confirming that the respective peaks were thiols and oxidized dimers (3 isomers) as shown in formula (II).

[0125] [Synthesis Example 1] (Synthesis of 1,2,3-(3-mercaptopropyloxy)propane) 50.95 g (240.0 mmol) of 1,2,3-triallyloxypropane and 190.00 g of butyl acetate were fed into a 500 mL three-necked flask and heated to 50 °C. Then, 73.07 g (960.0 mmol) of thioacetic acid was added dropwise, and the mixture was stirred at 67 °C for 44 hours. Next, the reaction mixture was concentrated, and 1.17 g (12.0 mmol) of sulfuric acid and 250.00 g of methanol were added to the resulting reaction product. The mixture was stirred at 50 °C for 48 hours. The resulting reaction mixture was cooled, and butyl acetate / deionized water at a ratio of 2 / 1 (by weight) was added below 20 °C. The washing process was then repeated five times with deionized water. The concentrated organic layer after washing was purified by silicone column chromatography (chloroform / toluene = 3 / 1 (volume ratio)) to obtain 18.89 g of colorless and transparent liquid (column yield: 28.6%).

[0126] The 1H-NMR spectrum data of this colorless and transparent liquid is shown below. ・ 1H-NMR (CDCl 3) δ: 3.69 (t, 2H), 3.56 (m, 5H), 3.50 (t, 4H), 2.64 (q, 6H), 1.87 (quin., 6H), 1.39 (t, 3H). Based on the 1H-NMR spectrum data, the obtained colorless and transparent liquid was identified as the thiol compound (1,2,3-(3-mercaptopropyloxy)propane) shown in formula (II).

[0127] In addition, the colorless and transparent liquid was analyzed by liquid chromatography (extraction solution: 20 mM sodium dihydrogen phosphate aqueous solution / acetonitrile = 1 / 3 (weight ratio), column: Shim-Pack CLC-ODS, detector: PDA (210 nm)), and the thiol compound shown in formula (II) was detected (dissolution time: peak at 5.6 minutes), but its oxidized dimer was not detected (dissolution time: 3 peaks at 12.6 minutes, 12.9 minutes and 16.0 minutes).

[0128] <Evaluation of Epoxy Resin Composition> [Example 2] An epoxy resin composition was prepared by mixing 66.8 parts by weight of the crude product obtained in Example 1 (thiol equivalent: 125.0) as a curing agent, 3.3 parts by weight of dimethylbenzylmethylamine as a curing accelerator, and 100.0 parts by weight of jER828 as an epoxy compound. Furthermore, the amount of curing accelerator used was adjusted to 5.0% by weight relative to the curing agent. Evaluation tests (viscosity measurement, storage modulus of elasticity measurement of the cured product, and adhesion strength measurement when used as an adhesive) were conducted on this epoxy resin composition. The test results are shown in Table 1.

[0129] [Example 3, Comparative Examples 1-4] The situation was the same as in Example 2. Epoxy resin compositions having the composition shown in Table 1 were prepared, and evaluation tests were conducted on these epoxy resin compositions. The test results are shown in Table 1.

[0130] [Table 1]

[0131] It was confirmed from Table 1 that when using jER828 as the epoxy compound, the case of using the crude product of Example 1 (containing 1,2,3-tris(3-mercaptopropoxy)propane and its dimer) as the curing agent (Example 2) is superior to the case of using only 1,2,3-tris(3-mercaptopropoxy)propane (Comparative Example 1) because the curing agent and epoxy resin composition have low viscosity and thus excellent workability, the cured product has low storage modulus of elasticity and thus excellent impact resistance, and the cut strength is high, thus making it an excellent adhesive.

[0132] Furthermore, it was confirmed that: when using the crude material of Example 1 as a hardener (Example 2), compared with the case of using TMMP (Comparative Example 2), the case of using the crude material of Example 1 as a hardener has excellent workability due to the low viscosity of the hardener and epoxy resin composition, excellent impact resistance due to the low storage modulus of elasticity of the hardened material, and excellent adhesive performance due to the high shear strength.

[0133] Furthermore, it was confirmed that when XY633 is used as an epoxy compound, the case of using the crude product of Example 1 as a hardener (Example 3) has better workability due to the lower viscosity of the hardener and epoxy resin composition, better impact resistance due to the lower storage modulus of elasticity of the hardened product, and better performance as an adhesive due to the higher shear strength compared to the case of using only 1,2,3-tris(3-mercaptopropoxy)propane (Comparative Example 3).

[0134] Furthermore, it was confirmed that when the crude material of Example 1 was used as a hardener (Example 3), compared with the case of using TMMP (Comparative Example 4), the hardener and epoxy resin composition had excellent workability due to their low viscosity, excellent impact resistance due to their low storage modulus of elasticity, and excellent adhesive properties due to their high shear strength.

[0135] [Industrial Applicability] The oxidized dimer of the compound shown in formula (II) of the present invention is suitable for use as a curing agent for resins and as an intermediate raw material for various sulfur-containing compounds. Furthermore, compositions containing the compound shown in formula (II) of the present invention and its oxidized dimer are suitable for use as curing agents for epoxy resins, etc. Furthermore, resin compositions containing the curing agent and epoxy compounds, etc., are suitable for various applications such as bonding, sealing, sealing, casting, molding, coating, and application. [Simplified Explanation of the Diagram]

[0011] Figure 1 is the IR spectrum of the pale yellow liquid obtained in Example 1.

Claims

1. A dimer of a thiol compound of formula (II): [Chemical Formula 1].

2. The dimer of claim 1 is selected from at least one compound of the group consisting of formulas (I-1) to (I-3): [Chemical Formula 2].

3. A composition comprising the compound of formula (II) and its dimer: [Chemical Formula 3] .

4. As in claim 3, wherein, In the composition, the ratio of the content of the dimer to the content of the compound shown in formula (II) is 0.02 to 0.

3. This ratio is obtained by liquid chromatography from the peak area ratio of the compound shown in formula (II) and the dimer.

5. A hardener comprising the composition as claimed in claim 3 or 4.

6. A resin composition comprising a hardener as claimed in claim 5 and an epoxy compound.

7. The resin composition of claim 6 further contains amines as curing accelerators.

8. A resin composition comprising a curing agent as claimed in claim 5 and an alkene compound having an intramolecular carbon-carbon double bond.

9. An adhesive comprising the resin composition of claim 6.

10. An adhesive comprising the resin composition of claim 8.

11. A sealant comprising a resin composition as claimed in claim 6.

12. A sealant comprising a resin composition as claimed in claim 8.

13. A cured form of a resin composition, wherein the resin composition is the resin composition of claim 6.

14. A cured resin composition, wherein the resin composition is the resin composition of claim 8.

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