Episulfide compound and uses of same

Abstract

The purpose of the present invention is to provide a novel episulfide compound and uses of the same. Specifically, the purpose of the present invention is to provide: a novel episulfide compound; a composition which contains the episulfide compound and a curing agent and / or a curing accelerator; a composition which contains the episulfide compound and an ene compound that has a carbon-carbon double bond in each molecule; and an adhesive, a sealing agent, and a cured product which each contain these compositions. The present invention relates to an episulfide compound represented by chemical formula (I). (In the formula (I), R1 represents a methyl group or a hydroxy group, and when a plurality of R1 moieties are present, the moieties may be the same as or different from each other. R2 represents a hydrogen atom or a methyl group. Y represents a group represented by formulae (1) to (4). n represents an integer of 0 to 4.) (In the formulae (1) to (4), R11 represents a hydrogen atom or a methyl group, and when a plurality of R11 moieties are present, the moieties may be the same as or different from each other. R12 represents a hydrogen atom or a methyl group, and when a plurality of R12 moieties are present, the moieties may be the same as or different from each other. R13 represents a hydrogen atom or a methyl group, and when a plurality of R13 moieties are present, the moieties may be the same as or different from each other. R14 represents a hydrogen atom or a methyl group, and when a plurality of R14 moieties are present, the moieties may be the same as or different from each other. m1 represents an integer of 0 to 3, m2 represents an integer of 1 to 3, m3 represents an integer of 0 to 3, m4 represents an integer of 1 to 3, m5 represents an integer of 0 to 3, m6 represents an integer of 1 to 3, and m7 represents an integer of 1 to 3.)

Description

Episulfide compounds and their uses

[0001] This invention relates to episulfide compounds and their uses.

[0002] Epoxy resin compositions are widely used in electrical and electronic equipment components, automobile parts, aircraft parts, building materials, etc., due to their excellent adhesive strength to various materials and superior durability. However, the cured products of epoxy resin compositions used in such adhesives are hard and brittle, and have the problem of easily breaking when subjected to impact. Therefore, conventional research has been conducted to impart flexibility to epoxy resins without degrading their basic properties by adding elastomer components or using elastomer-modified epoxy resins.

[0003] For example, epoxy resin compositions have been proposed that contain an epoxy resin, a rubber-modified epoxy resin, a urethane resin in which the isocyanate at the end of the urethane prepolymer is blocked, and a curing agent, as well as compositions that contain an epoxy resin, a urethane-modified epoxy resin, an NBR-modified epoxy resin, a rubber particle-dispersed epoxy resin, and a latent curing agent (for example, Patent Documents 1 and 2).

[0004] However, increasing the amount of rubber-modified epoxy resin components, urethane resin components with blocked isocyanates at the ends of urethane prepolymers, or rubber particle-dispersed epoxy resins in the epoxy resin composition resulted in high viscosity and reduced workability, which presented a problem.

[0005] Furthermore, episulfide resins (compounds having a structure in which oxygen atoms of epoxy resin are replaced with sulfur atoms) are known as compounds with a structure similar to epoxy resin, and it has been proposed to use them to replace part or all of epoxy resin, but satisfactory performance has not yet been achieved (for example, Patent Documents 3 and 4). Therefore, from the viewpoint of improving work efficiency, there is a need for a material that has lower viscosity, excellent curability, and produces a cured product with excellent flexibility.

[0006] JP 2012-219223, JP 2-150484, JP 11-209576, JP 11-209689

[0007] An object of the present invention is to provide a novel episulfide compound and uses thereof. Specifically, it is an object to provide a novel episulfide compound, a composition containing the episulfide compound and a curing agent and / or a curing accelerator, a composition containing the episulfide compound and an ene compound having a carbon-carbon double bond in a molecule, an adhesive, a sealing agent and a cured product including these compositions.

[0008] The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, found that an episulfide compound having a heterocyclic ring containing two oxygen atoms is a novel compound, that the episulfide compound is useful as a resin material, and that a composition containing the episulfide compound is useful as an adhesive and a sealing material. They further conducted additional research based on this finding, and completed the present invention.

[0009] That is, the present invention includes the following embodiments. [1] An episulfide compound represented by chemical formula (I).

[0010] (wherein, R １ represents a methyl group or a hydroxy group, and when a plurality of R １ are present, they may be the same or different. R ２ represents a hydrogen atom or a methyl group. Y represents a group represented by any of formulas (1) to (4). n represents an integer of 0 to 4.)

[0011] (wherein, R １１ represents a hydrogen atom or a methyl group, and when a plurality of R １１ are present, they may be the same or different. R １２ represents a hydrogen atom or a methyl group, and when a plurality of R １２ are present, they may be the same or different. R １３ represents a hydrogen atom or a methyl group, and when a plurality of R １３ are present, they may be the same or different. R １４ represents a hydrogen atom or a methyl group, and R １４If there are multiple values, they may be the same or different. m1 represents an integer from 0 to 3, m2 represents an integer from 1 to 3, m3 represents an integer from 0 to 3, m4 represents an integer from 1 to 3, m5 represents an integer from 0 to 3, m6 represents an integer from 1 to 3, and m7 represents an integer from 1 to 3.

[0012] [2] A composition comprising the compound described in [1] and a curing agent and / or a curing accelerator. [3] A composition comprising the compound described in [1] and an ene compound having a carbon-carbon double bond in its molecule. [4] An adhesive comprising the composition described in [2] or [3]. [5] A sealant comprising the composition described in [2] or [3]. [6] A cured product of the composition described in [2] or [3].

[0013] The episulfide compound represented by chemical formula (I) of the present invention is a novel compound that can be used as a material for various resins. Compositions containing this episulfide compound exhibit low viscosity and excellent curability, improving workability during compounding and bonding processes, and enabling curing at low temperatures. Furthermore, the cured product obtained by reacting this composition is expected to have excellent flexibility. Therefore, when this composition is used as an adhesive, the adhesive strength can be improved. Accordingly, by including the composition of the present invention, adhesives and sealants with excellent adhesive strength can be obtained.

[0014] 1. Episulfide Compounds This invention relates to an episulfide compound represented by chemical formula (I) (hereinafter sometimes referred to as "the compound of the present invention").

[0015] (In the formula, R １ R represents a methyl group or a hydroxyl group. １ If there are multiple instances, they may be the same or different. ２ (where represents a hydrogen atom or a methyl group; Y represents the group shown in formulas (1) to (4); and n represents an integer from 0 to 4.)

[0016] (In the formula, R １１ R represents a hydrogen atom or a methyl group. １１ If there are multiple instances, they may be the same or different. １２R represents a hydrogen atom or a methyl group. １２ If there are multiple instances, they may be the same or different. １３ R represents a hydrogen atom or a methyl group. １３ If there are multiple instances, they may be the same or different. １４ R represents a hydrogen atom or a methyl group. １４ If there are multiple values, they may be the same or different. m1 represents an integer from 0 to 3, m2 represents an integer from 1 to 3, m3 represents an integer from 0 to 3, m4 represents an integer from 1 to 3, m5 represents an integer from 0 to 3, m6 represents an integer from 1 to 3, and m7 represents an integer from 1 to 3.

[0017] In the episulfide compound represented by chemical formula (I), preferred substituents are as follows: R ２ However, it is preferable that it is a hydrogen atom. Y is preferably a group represented by formulas (1) to (3), and more preferably a group represented by formula (1) or formula (3). n is preferably an integer between 0 and 1, and more preferably 0. R １１ ~R １４ However, it is preferable that it be a hydrogen atom. It is preferable that m1, m3, and m5 are integers from 0 to 2, and more preferably integers from 1 to 2. It is preferable that m2 and m4 are integers from 1 to 2.

[0018] Among the episulfide compounds represented by chemical formula (I), the compound represented by chemical formula (Ia) is preferred. (In the formula, Y ａ This is the base shown by equations (1) to (3). ) Y ａ However, it is preferable that the group is represented by formula (1) or the group represented by formula (3). In formula (1), R １１ R is preferably a hydrogen atom, m1 is preferably 1 or 2, and m2 is preferably 1 or 2. In formula (3), １３ For m5, a hydrogen atom is preferred; for m5, 1 or 2 is preferred; and for m6, 1 or 2 is preferred.

[0019] Examples of episulfide compounds represented by chemical formula (I) include those represented by chemical formulas (I-1) to (I-15).

[0020]

[0021] 2. Method for synthesizing episulfide compounds The episulfide compounds of the present invention can be synthesized by reacting an epoxy compound represented by chemical formula (II) with a thiatting agent. (See reaction scheme (A)).

[0022] (In the formula, R １ , R ２ n and Y are the same as described above.

[0023] Examples of epoxy compounds represented by chemical formula (II) include those represented by chemical formulas (II-1) to (II-15).

[0024]

[0025] These epoxy compounds can be synthesized, for example, according to the methods described in Organic & Biomolecular Chemistry (2013), 11(6), 905-913.

[0026] Examples of thiating agents include thiourea, trimethylthiourea, tetramethylthiourea, tetraethylthiourea, dimethylethylthiourea, ethylenethiourea, propylenethiourea, thiobarbitulic acid, dithiourazole, thiohydantoin, dithiohydantoin, sodium thiocyanate, potassium thiocyanate, ammonium thiocyanate, calcium thiocyanate, and lead thiocyanate.

[0027] The amount of thiazing agent used is preferably in an appropriate proportion within the range of 1 to 5 times the molar amount of the epoxy compound represented by chemical formula (II), and more preferably in an appropriate proportion within the range of 1 to 3 times the molar amount.

[0028] In carrying out this reaction, reaction accelerators (i) and reaction solvents (ii) may be used as appropriate, if necessary. Examples of reaction accelerators (i) include acids, acid anhydrides, and ammonium salts, which may be used individually or in combination of two or more.

[0029] Examples of acids 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, and tetrafluoroboric acid. These may be used individually or in combination of two or more.

[0030] Examples of acid anhydrides include acetic anhydride, propionic anhydride, butyric anhydride, succinic anhydride, maleic anhydride, benzoic anhydride, phthalic anhydride, pyromellitic anhydride, and trimellitic anhydride. These may be used individually or in combination of two or more.

[0031] Examples of ammonium salts include ammonium chloride, ammonium bromide, ammonium iodide, ammonium formate, ammonium acetate, ammonium propionate, ammonium benzoate, ammonium sulfate, ammonium nitrate, ammonium carbonate, ammonium phosphate, and ammonium hydroxide, with ammonium nitrate, ammonium sulfate, and ammonium chloride being preferred. These may be used individually or in combination of two or more.

[0032] The amount of reaction accelerator (i) used is preferably in an appropriate proportion within the range of 0.001 to 50 mol% relative to the amount of epoxy compound represented by chemical formula (II).

[0033] The reaction solvent (ii) is not particularly limited as long as it does not inhibit the reaction, and examples include water; alcohols such as methanol, ethanol, and isopropyl alcohol; aliphatic hydrocarbons such as hexane and heptane; esters such as ethyl acetate and butyl acetate; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, chlorotrifluoromethane, dichloroethane, chlorobenzene, and dichlorobenzene; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane, and diethylene glycol dimethyl ether; amides such as formamide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and hexamethylphosphorotriamide; and sulfoxides such as dimethyl sulfoxide. These may be used alone or in combination of two or more.

[0034] In this reaction, the reaction temperature is preferably set in the range of -10 to 150°C, more preferably in the range of 0 to 100°C, and even more preferably in the range of 0 to 60°C. The reaction time is set appropriately according to the set reaction temperature, but is preferably set in the range of 1 to 100 hours, more preferably in the range of 2 to 70 hours, and even more preferably in the range of 3 to 50 hours.

[0035] After the reaction is complete, the episulfide compound of the present invention, which is the target product of this invention, can be extracted from the resulting reaction solution by means of concentration, such as by distillation of the reaction solvent or by solvent extraction. Furthermore, if necessary, it can be purified by means of washing with water or the like, activated carbon treatment, silica gel chromatography, recrystallization, etc.

[0036] In this synthesis method, oligomers comprising the episulfide compound of the present invention as a constituent unit, and oligomers comprising the episulfide compound of the present invention and the epoxy compound represented by chemical formula (II) as constituent units (hereinafter, both may be collectively referred to simply as "oligomers") may be obtained (see reaction schemes (B) to (D)). Examples of oligomers include compounds represented by chemical formulas (III) to (V).

[0037] (In the formula, R １ , R ２ n and Y are the same as described above, and R １ , R ２ If n and Y are multiple, they may be the same or different. r represents an integer from 1 to 30. X １ and X ２ X represents an oxygen atom or a sulfur atom, either identical or different. ２ If there are multiple, they may be the same or different. However, X １ and X ２ (Except when all atoms are oxygen atoms.)

[0038] (In the formula, R １ , R ２ , n, Y and X ２ The same applies as described above, R １ , R ２ , n, Y, X ２ If each of them is multiple, they may be the same or different. Z ＋ represents a thia-inducing agent residue. r represents an integer from 1 to 30. However, X ２ (Except when all atoms are oxygen atoms.)

[0039] (In the formula, R １ , R ２ , n, Y and X ２ The same applies as described above, R １ , R ２ , n, Y, X ２ If each of them is multiple, they may be the same or different. Z ２ represents a thia-inducing agent residue. r represents an integer from 1 to 30. However, X ２ (Except when all atoms are oxygen atoms.)

[0040] Z ＋ The cheering agent residue shown is a substituent formed by the reaction of a cheering agent with an episulfide group or epoxy group, for example, -SC(=N ＋ R ｃ１ R ｃ２ ) (NR ｃ３ R ｃ４ The group shown in ) is an example. Note that R ｃ１ , R ｃ２ , R ｃ３ , R ｃ４ R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, either identical or different. ｃ１ or R ｃ２ And, R ｃ３ or R ｃ４ The two groups may bond together and form a ring with the adjacent group -N=C-N-. Also, Z ２ The cheering agent residue shown is a substituent formed by the reaction of a cheering agent with an episulfide group or epoxy group, for example, -SC(=NR ｄ１ ) (NR ｄ２ R ｄ３ The group shown in ) is an example. Note that R ｄ１ , R ｄ２ , R ｄ３ R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, either identical or different. ｄ１ and R ｄ２ or R ｄ３ These may bond together and form a ring with the adjacent group -N=C-N-.

[0041] Examples of compounds represented by chemical formula (III) include those represented by chemical formulas (III-1) to (III-32). These compounds may be included in the composition of the present invention.

[0042]

[0043]

[0044]

[0045]

[0046]

[0047] Examples of compounds represented by chemical formula (IV) include those represented by chemical formulas (IV-1) to (IV-10). These compounds may be included in the composition of the present invention.

[0048]

[0049] Examples of compounds represented by chemical formula (V) include those represented by chemical formulas (V-1) to (V-10). These compounds may be included in the composition of the present invention.

[0050]

[0051] When the composition of the present invention contains oligomers (compounds represented by chemical formulas (III) to (V)), the ratio of the oligomer content to the episulfide compound content of the present invention in the composition of the present invention is preferably 0.01 to 1.0, and more preferably 0.02 to 0.7. Two or more types of oligomers may be included. The ratio of the episulfide compound content to the oligomer content in the composition of the present invention is a value calculated using the peak area size of each component when the composition of the present invention or the raw materials before mixing are analyzed by liquid chromatography. See Examples.

[0052] 3. Compositions containing episulfide compounds The compositions of the present invention contain the compound of the present invention (hereinafter sometimes referred to as the "first curable compound") as an essential component, but may also contain one or more episulfide compounds of the present invention. The content of the compound of the present invention in the composition of the present invention is preferably 0.001 to 100% by weight, more preferably 0.001% by weight or more and less than 100% by weight, even more preferably 0.1% by weight or more and less than 100% by weight, and particularly preferably 10% by weight or more and less than 90% by weight.

[0053] A cured product can be obtained by polymerizing the compound of the present invention. In other words, since the composition of the present invention contains a compound having an episulfide group in its molecule, it can be said to be a polymerizable or curable composition. During this polymerization, by coexisting with another curable compound, a cured product can be obtained in which the compound of the present invention and the other curable compound are copolymerized. Examples of the other curable compound include epoxy compounds (referring to epoxy resin before curing) or other episulfide compounds (hereinafter, both may be collectively referred to as the "second curable compound"), and ene compounds having a carbon-carbon double bond in their molecule (hereinafter, may be referred to as the "third curable compound").

[0054] 3-1. First Composition The first composition of the present invention contains the compound of the present invention (first curable compound) and a curing agent or curing accelerator as essential components, and may optionally contain a second curable compound (epoxy compound and / or another episulfide compound). In other words, the first composition contains the compound of the present invention and a curing agent and / or curing accelerator, and may optionally include an epoxy compound, another episulfide compound, a stabilizer, etc. The second curable compound includes both polymerizable monomers and polymerizable oligomers (semi-cured products) having a structure in which polymerizable monomers are partially polymerized.

[0055] As for epoxy compounds, any compound having an epoxy group (glycidyl group) in its molecule can be used without particular limitations, for example: diepoxy resins such as polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, polytetramethylene ether glycol diglycidyl ether, glycerin diglycidyl ether, cyclohexane-type diglycidyl ether, and dicyclopentadiene-type diglycidyl ether; triepoxy resins such as trimethylolpropane triglycidyl ether and glycerin triglycidyl ether; and 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 and bisphenol F 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 glycoluryl compounds having two or more epoxy groups in the molecule, such as 1,3,4,6-tetraglycidyl glycoluryl; cyclic alicyclic epoxy resins such as 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, vinyl(3,4-cyclohexene)dioxide, and 2-(3,4-epoxycyclohexyl)-5,1-spiro-(3,4-epoxycyclohexyl)-m-dioxane; dicyclopentadiene-type diglycidyl ethers such as dicyclopentadiene dimethanol diglycidyl ether; cyclohexane-type diglycidyl ethers such as 1,4-cyclohexanedimethanol diglycidyl ether; Glycidylamine-type epoxy resins such as tetraglycidylbis(aminomethyl)cyclohexane; naphthalene skeleton-containing liquid epoxy resins such as 1,6-bis(glycidyloxy)naphthalene;Examples include epoxy resins having a silicone skeleton such as 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane; nitrogen-containing cyclic epoxy resins such as triglycidyl isocyanurate and hydantoin-type epoxy resins (e.g., 1,3-diglycidyl-5-methyl-5-ethylhydantoin); further, epoxidized phenol novolac resins (phenol novolac-type epoxy resins), epoxidized cresol novolac resins, epoxidized polyolefins, cyclic aliphatic epoxy resins, urethane-modified epoxy resins, and epoxy-modified organopolysiloxane compounds obtained by hydrosilylation addition reactions between organic compounds having a carbon-carbon double bond and a glycidyl group and silicon compounds having an SiH group (e.g., epoxy-modified organopolysiloxane compounds disclosed in Japanese Patent Publication No. 2004-99751 and Japanese Patent Publication No. 2006-282988), and these may be used in combination.

[0056] Other episulfide compounds can be used without particular restriction as long as they have an episulfide group (thiirane group) in their molecule, for example: aliphatic thioglycidyl ether type episulfide compounds such as 2,3-episulfidopropyl ether; thioglycidyl ester type episulfide compounds; thioglycidylamine type episulfide compounds; Aromatic thioglycidyl ether-type episulfide compounds such as bisphenol A-type episulfide compounds, bisphenol F-type episulfide compounds, bisphenol S-type episulfide compounds, biphenol-type episulfide compounds, phenol novolac-type episulfide compounds, cresol novolac-type episulfide compounds, cresol novolac-type episulfide compounds of bisphenol A, biphenyl novolac-type episulfide compounds, naphthalene-type episulfide compounds, fluorene-type episulfide compounds, anthracene-type episulfide compounds, phenol aralkyl-type episulfide compounds, naphthol aralkyl-type episulfide compounds, and episulfide compounds obtained from trisphenolmethane; hydrogenated bisphenol A-type episulfide resins such as hydrogenated bisphenol A-type episulfide resins; Isocyanurate compounds having an episulfide group, such as diallyl mono(2,3-episulfidopropyl) isocyanurate compounds, monoallyl di(2,3-episulfidopropyl) isocyanurate compounds (e.g., monoallyl di(2,3-episulfidopropyl) isocyanurate, 1-allyl-3,5-bis(2-methyl-2,3-episulfidopropyl) isocyanurate, 1-(2-methylpropenyl)-3,5-di(2,3-episulfidopropyl) isocyanurate, 1-(2-methylpropenyl)-3,5-bis(2-methyl-2,3-episulfidopropyl) isocyanurate, tri(2,3-episulfidopropyl) isocyanurate compounds; 2,2-bis[4-(2,3-episulfidepropoxy)cyclohexyl]propane; 2,2-bis[3,5-dimethyl-4-(2,3-episulfidepropoxy)cyclohexyl]propane;Examples include aliphatic episulfide resins such as dicyclopentadiene-type episulfide resins, tricyclodecane-type episulfide resins, and adamantane-type episulfide resins; and episulfide compounds represented by chemical formula (VI). These may be used in combination.

[0057] (In the formula, Y １ This represents an alkylene group with 1 to 5 carbon atoms, Y １ If there are multiple values, they may be the same or different. (s represents an integer from 1 to 3.)

[0058] Y １ Examples of alkylene groups having 1 to 5 carbon atoms represented by include methylene group, methylmethylene group, dimethylmethylene group, trimethylene group, ethylmethylene group, dimethylmethylene group, tetramethylene group, pentamethylene group, and the like.

[0059] The first composition of the present invention contains the compound of the present invention as an essential component, and may optionally contain the second curable compound described above. As the second curable compound, the polymerizable monomer and polymerizable oligomer described above can be used in combination. Different types of polymerizable monomers may be used as polymerizable monomers, and different types of polymerizable oligomers may also be used as polymerizable oligomers. Regarding the respective content ratios of the compound of the present invention and the second curable compound in the first composition of the present invention, it is preferable that the content of the second curable compound be in an appropriate ratio within the range of 0 to 1000 times (weight ratio) relative to the content of the compound of the present invention, and more preferably in an appropriate ratio within the range of 0.01 to 500 times (weight ratio).

[0060] The first composition of the present invention contains the compound of the present invention and a curing agent and / or a curing accelerator. Conventional known curing agents can be used as the curing agent. Examples of conventionally known curing agents include: thiol compounds; compounds having a phenolic hydroxyl group; acid anhydrides; organophosphine compounds such as triphenylphosphine, diphenylnaphthylphosphine, and diphenylethylphosphine; aromatic phosphonium salts; aromatic diazonium salts; aromatic iodonium salts; aromatic selenium salts, etc.

[0061] Examples of thiol compounds include aliphatic thiol compounds such as ethanedithiol, propanedithiol, hexamethylenedithiol, decamethylenedithiol, torylene-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 thiol compounds such as benzenedithiol, toluenedithiol, and xylenedithiol (p-xylenedithiol); cyclic sulfide compounds such as 1,4-dithiane ring-containing polythiol compounds represented by chemical formula (VII); and mercaptoalkyl sulfide compounds such as 3-thiapentane-1,5-dithiol and 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol. Mercaptopropionic acid esters such as pentaerythritol tetrakis(3-mercaptopropionate); epoxy resin-terminated mercapto compounds; 3,6-dioxa-1,8-octanedithiol, mercaptoalkyl ether disulfide compounds represented by chemical formula (VIII), 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-propanthol, 3-[2,2-bis[(3-mercaptopropoxy)methyl]butoxy]-1-propanthol, 3-(3-mercaptopropoxy)-2,2-bis[(3-mercaptopropoxy)methyl]-1-propanol, Examples include mercaptoalkyl ether compounds such as 2,2-bis[(3-mercaptopropoxy)methyl]-1-butanol and 3,3',3''-[propane-1,2,3-triyltris(oxy)]tri(propane-1-thiol); and 1,3,4,6-tetrakis(2-mercaptoethyl) glycoluryl and 1,3,4,6-tetrakis(3-mercaptopropyl) glycoluryl. One or more of these may be used in combination.

[0062] (In the formula, p represents an integer between 1 and 5.)

[0063] (In the formula, q represents an integer between 1 and 20.)

[0064] 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 novolac, cresol novolac, bisphenol A novolac, brominated phenol novolac, and resorcinol.

[0065] Examples of acid anhydrides include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, trimellitic anhydride, nadic anhydride, hymic anhydride, methylnadic anhydride, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid anhydride, bicyclo[2.2.1]heptane-2,3-dicarboxylic acid anhydride, and methylnorbornane-2,3-dicarboxylic acid.

[0066] The content of the curing agent in the first composition of the present invention is preferably 0.1 to 200 parts by weight, and more preferably 0.5 to 150 parts by weight, per 100 parts by weight of the curable compound (total of the first curable compound and the second curable compound).

[0067] Conventional known curing accelerators can be used. Examples of conventionally known 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 a primary amino group and a secondary amino group in the molecule. These may be used in combination.

[0068] (i) As for the amines, as is conventionally known, any amine that has at least one amino group selected from primary, secondary, and tertiary amino groups in its molecule is acceptable. Examples of such amines include: aliphatic amines such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, 4,4'-diaminodicyclohexylmethane, and dimethylbenzylamine; aromatic amines such as 4,4'-diaminodiphenylmethane and o-methylaniline; and nitrogen-containing heterocyclic compounds such as 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazoline, 2,4-dimethylimidazoline, piperidine, and piperazine.

[0069] In the first composition of the present invention, the content of the curing accelerator (particularly amines) is preferably 0.1 to 100 parts by weight, and more preferably 0.1 to 50 parts by weight, per 100 parts by weight of the curable compound (total of the first curable compound and the second curable compound).

[0070] (ii) The reaction products of epoxy compounds and amines are solids that are poorly soluble in epoxy resins at room temperature, but become solubilized (easily soluble) upon heating and function as curing accelerators, and are therefore also called latent curing accelerators (hereinafter, the reaction products of epoxy compounds and amines may be referred to as "latent curing accelerators").

[0071] Examples of epoxy compounds used as raw materials for latent curing accelerators include, in addition to the epoxy compounds mentioned above, glycidylamine compounds obtained by reacting 4,4'-diaminodiphenylmethane or m-aminophenol with epichlorohydrin; and monofunctional epoxy compounds such as butyl glycidyl ether, phenyl glycidyl ether, and glycidyl methacrylate.

[0072] The amines mentioned above can be used as raw materials for latent curing accelerators. Among these amines, those having a tertiary amino group in their molecule are raw materials that provide latent curing accelerators with excellent curing acceleration properties. Examples of such amines include amines such as dimethylaminopropylamine, diethylaminopropylamine, di-n-propylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, and N-methylpiperazine; amines having a tertiary amino group in their 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-methylimidazole Examples include alcohols, phenols, thiols, carboxylic acids, and hydrazides that have a tertiary amino group in their molecule, such as tilimimidazolin, 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-dimethylglycine hydrazide, N,N-dimethylpropionic acid hydrazide, nicotinic acid hydrazide, and isonicotinic acid hydrazide.

[0073] To further improve the storage stability of the first composition of the present invention, in addition to the epoxy compound and amines mentioned above, an active hydrogen compound having two or more active hydrogen atoms in its molecule may be used as a third component of the latent curing accelerator. Examples of active hydrogen compounds include: polyhydric phenols such as bisphenol A, bisphenol F, bisphenol S, hydroquinone, catechol, resorcinol, pyrogallol, and phenol novolac resin; polyhydric alcohols such as trimethylolpropane; polyhydric carboxylic acids such as adipic acid and phthalic acid; and 1,2-dimercaptoethane, 2-mercaptoethanol, 1-mercapto-3-phenoxy-2-propanol, mercaptoacetic acid, anthranilic acid, and lactic acid.

[0074] 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; and polyfunctional isocyanate compounds such as hexamethylene diisocyanate, toluene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, isophorone diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, and bicycloheptane triisocyanate.

[0075] Instead of this polyfunctional isocyanate compound, a compound containing a terminal isocyanate group obtained by the reaction of a polyfunctional isocyanate compound with an active hydrogen compound can also be used. Specifically, examples include an addition product having a terminal isocyanate group obtained by the reaction of toluene diisocyanate with trimethylolpropane, and an addition product having a terminal isocyanate group obtained by the reaction of toluene diisocyanate with pentaerythritol.

[0076] Furthermore, the acidic substance used for surface treatment of the latent curing accelerator may be a gas, liquid, or solid, and may be either an inorganic or organic acid. Examples of such acidic substances include carbon dioxide, sulfur dioxide, 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.

[0077] Latent curing accelerators can be easily obtained by mixing epoxy compounds, amines, and optionally active hydrogen compounds, reacting them at temperatures ranging from room temperature to 200°C, then solidifying and pulverizing the mixture, or by reacting the mixture in a solvent such as methyl ethyl ketone, dioxane, or tetrahydrofuran, removing the solvent, and then pulverizing the solid.

[0078] Alternatively, commercially available latent curing accelerators can be used. Examples of commercially available products include: "Amicure PN-23 (product name)", "Amicure PN-H (product name)", "Amicure PN-50 (product name)", "Amicure PN-23J (product name)", "Amicure PN-40J (product name)", and "Amicure MY-24 (product name)" from Ajinomoto Fine Techno Co., Ltd.; "NovaCure HX-3088 (product name)", "NovaCure HX-3721 (product name)", "NovaCure HX-3722 (product name)", "NovaCure HX-3742 (product name)", "NovaCure HX-3941HP (product name)", and "NovaCure HXA3922HP (product name)" from Asahi Kasei Corporation; and T&K Examples include the "Fujicure FXR-1030 (product name)", "Fujicure FXR-1081 (product name)", and "Fujicure FXR-1121 (product name)" manufactured by TOKA Corporation.

[0079] The content of the latent curing accelerator in the first composition of the present invention is preferably 0.1 to 100 parts by weight, more preferably 0.5 to 80 parts by weight, and even more preferably 1 to 50 parts by weight, per 100 parts by weight of the curable compound (total of the first curable compound and the second curable compound).

[0080] (iii) The reaction product of a compound having one or more isocyanate groups in its molecule and a compound having at least one of a primary amino group and a secondary amino group in its molecule can be obtained by reacting the two in an organic solvent such as dichloromethane.

[0081] 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, hexamethyl Examples include diisocyanate, 2,4-toluylene diisocyanate, 2,6-toluylene diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane-4,4'-diisocyanate, 2,2-dimethyldiphenylmethane-4,4'-diisocyanate, toridine diisocyanate, isophorone diisocyanate, xylylene diisocyanate, 1,3-bis(isocyanate methyl)cyclohexane, p-phenylene diisocyanate, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris-(3-isocyanato-4-methylphenyl) isocyanurate, tris-(6-isocyanatohexyl) isocyanurate, and the like.

[0082] Examples of compounds having at least one of a primary amino group and a secondary amino group in their 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, and 1,1-dimethylhydrazine.

[0083] In the first composition of the present invention, the content of the reaction product between a compound having one or more isocyanate groups in its molecule and a compound having at least one of a primary amino group and a secondary amino group in its molecule is preferably 0.1 to 100 parts by weight per 100 parts by weight of the curable compound (total of the first curable compound and the second curable compound).

[0084] The first composition of the present invention may contain conventionally known stabilizers, as long as they do not inhibit the effects of the present invention. Examples of stabilizers include liquid borate ester compounds, aluminum chelates (such as aluminum trisacetylacetonate), and organic acids (such as acetic acid, propionic acid, butyric acid, succinic acid, malic acid, citric acid, and barbituric acid).

[0085] Examples of liquid borate ester compounds include trimethyl borate, triethyl borate, tri-n-propyl borate, triisopropyl borate, triallyl borate, tri-n-butyl borate, tripentyl borate, trihexyl borate, tricyclohexyl borate, trioctyl borate, trinonyl borate, tridecyl borate, tridodecyl borate, trihexadecyl borate, trioctadecyl borate, tris(2-ethylhexyloxy)borane, triphenyl borate, tri-o-tolyl borate, tri-m-tolyl borate, tripenzyl borate, triethanolamine borate, and 2,2'-oxybis(5,5'-dimethyl-1,3,2-oxaborinane). Since liquid borate ester compounds are liquid at room temperature, they can suppress the increase in viscosity of the composition.

[0086] The amount of stabilizer in the first composition of the present invention is preferably 0.1 to 10% by weight, more preferably 0.1 to 8% by weight, and even more preferably 0.1 to 6% by weight, based on the total amount of the first composition.

[0087] The first composition of the present invention may contain triphenylsilanol. By containing triphenylsilanol, the pot life of the first composition of the present invention can be maintained, and the curing completion temperature when curing the composition can be lowered.

[0088] The content of triphenylsilanol in the first composition of the present invention is preferably 0.1 to 10% by weight, more preferably 0.1 to 8% by weight, and even more preferably 0.1 to 6% by weight, based on the total amount of the first composition.

[0089] The first composition of the present invention may contain talc. By including talc, the heat resistance, low thermal expansion, and impact resistance of the first composition of the present invention can be improved. The shape of the talc is preferably plate-like or flat. Furthermore, the aspect ratio of the talc is preferably 5 to 20.

[0090] The talc content in the first composition of the present invention is preferably 0 to 20 parts by weight, and more preferably 0.1 to 15 parts by weight, per 100 parts by weight of the curable compound (total of the first curable compound and the second curable compound).

[0091] The first composition of the present invention may contain a filler. The inclusion of a filler lowers the coefficient of thermal expansion of the cured product, resulting in improved moisture resistance and thermal cycling resistance. Examples of fillers include silica fillers (e.g., fused silica, spherical silica, etc.), alumina fillers (e.g., spherical alumina, crushed alumina, etc.), kaolin, clay, mica, barium sulfate, lithopone, gypsum, zinc stearate, perlite, quartz, quartz glass, 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, and carbon-based materials such as diamond and carbon. The average particle size of the filler is preferably 0.005 to 10 μm, and more preferably 0.1 to 6 μm. The shape of the filler can be spherical, amorphous, or flake-shaped. If the filler is not spherical in shape, the average particle size of the filler refers to the average maximum diameter of the filler.

[0092] The filler content in the first composition of the present invention is preferably 0 to 400 parts by weight, more preferably 5 to 300 parts by weight, and even more preferably 5 to 200 parts by weight, based on 100 parts by weight of the entire first composition (total amount) excluding the filler.

[0093] The first composition of the present invention may contain calcium carbonate. The inclusion of calcium carbonate improves the drop impact resistance of the cured product. The average particle size of the calcium carbonate is not particularly limited, but is preferably 0.1 to 15 μm.

[0094] The calcium carbonate content in the first composition of the present invention is preferably 0 to 200 parts by weight, and more preferably 0.1 to 150 parts by weight, per 100 parts by weight of the curable compound (total of the first curable compound and the second curable compound).

[0095] The first composition of the present invention may contain a reactive diluent. In this specification, a reactive diluent is a compound having one epoxy group (glycidyl group) and having a relatively low viscosity at room temperature. Depending on the purpose, the reactive diluent may have other polymerizable functional groups in addition to the epoxy group, such as alkenyl groups such as vinyl and allyl; or unsaturated carboxylic acid residues such as acryloyl and methacryloyl.

[0096] Examples of reactive diluents include monoepoxide compounds such as n-butylglycidyl ether, 2-ethylhexylglycidyl ether, phenylglycidyl ether, cresylglycidyl ether, p-s-butylphenylglycidyl ether, styrene oxide, and α-pinene oxide; and monoepoxide compounds having other functional groups such as allylglycidyl ether, glycidyl methacrylate, and 1-vinyl-3,4-epoxycyclohexane.

[0097] The content of the reactive diluent in the first composition of the present invention is preferably 0 to 200 parts by weight, and more preferably 0.1 to 150 parts by weight, per 100 parts by weight of the curable compound (total of the first curable compound and the second curable compound).

[0098] The first composition of the present invention, insofar as it does not impede the effects of the present invention, contains pigments (titanium white, cyanine blue, watching red, red iron oxide, carbon black, aniline black, manganese blue, iron black, ultramarine blue, Hansa red, chrome yellow, chrome green, etc.), thermoplastic resins and / or thermosetting resins (various high-density, medium-density, and low-density polyethylenes, polypropylene, polybutene, polypentene and other homopolymers, ethylene-propylene copolymers, polyamide resins such as nylon-6, nylon-6,6, 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, fluororesins, various elastomer resins such as acrylic rubber, urethane rubber, graft copolymers such as methyl methacrylate-butadiene-styrene graft copolymers and acrylonitrile-butadiene-styrene graft copolymers, etc.), reinforcing agents (glass fibers, carbon fibers, etc.), Additives (modifiers) such as anti-sagging agents (hydrogenated castor oil, fine particle anhydrous silicic acid, etc.), matting agents (fine silica powder, 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 stearic acid amide, fatty acid esters, polyolefin wax, paraffin wax, etc.), surfactants, leveling agents, defoaming agents, viscosity-adjusting diluents (organic solvents), flexibility-imparting agents, coupling agents (silane coupling agents such as glycidylsilane coupling agents, titanium coupling agents, etc.), fragrances, flame retardants, antioxidants, etc. may be included in amounts of 0.01 to 50% by weight of the entire first composition (total amount) as needed. Furthermore, if an isocyanate group-containing compound is included as an additive (modifier) ​​in the first composition of the present invention, the adhesive strength can be improved while suppressing a decrease in the curability of the composition.

[0099] Examples of isocyanate group-containing compounds 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, and bicycloheptane triisocyanate.

[0100] In the first composition of the present invention, the content of the isocyanate group-containing compound is preferably 0.1 to 20 parts by weight per 100 parts by weight of the curable compound (total of the first curable compound and the second curable compound).

[0101] There are no particular restrictions on the method of preparing (mixing) the first composition of the present invention. The aforementioned components can be measured in predetermined amounts and mixed using an appropriate stirring and mixing device such as a three-roll mixer or a planetary mixer, while heating as necessary.

[0102] There are no particular limitations on the method for curing the first 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 means such as hot air circulation, infrared heating, and high-frequency heating can be used. The curing temperature and curing time can be set as appropriate.

[0103] 3-2. Second Composition The second composition of the present invention contains the compound of the present invention and a third curable compound (an ene compound having a carbon-carbon double bond in its molecule (hereinafter sometimes simply referred to as "ene compound")). In other words, the second composition contains the compound of the present invention and an ene compound, and may further include a second curable compound, a photopolymerization initiator, a curing accelerator, a stabilizer, etc., as needed. The ene compound includes both polymerizable monomers and polymerizable oligomers (semi-cured products) having a structure in which polymerizable monomers are partially polymerized.

[0104] Examples of polymerizable monomers include: (1) alkyl (meth)acrylate monomers, (2) monomers containing hydroxyl groups, (3) monomers containing carboxyl groups, (4) monomers containing amino groups, (5) monomers containing acetoacetyl groups, (6) monomers containing isocyanate groups, (7) monomers containing glycidyl groups, (8) monomers containing one aromatic ring, (9) monomers containing alkoxy groups and oxyalkylene groups, (10) alkoxyalkyl (meth)acrylamide monomers, (11) (meth)acrylamide monomers, (12) monofunctional unsaturated compounds, and (13) polyfunctional unsaturated compounds.

[0105] (1) Examples of alkyl (meth)acrylate 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, etc.

[0106] (2) Examples of hydroxyl group-containing monomers include: hydroxyalkyl (meth)acrylate esters such as 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 8-hydroxyoctyl (meth)acrylate; caprolactone-modified monomers such as caprolactone-modified 2-hydroxyethyl (meth)acrylate; oxyalkylene-modified monomers such as diethylene glycol (meth)acrylate and polyethylene glycol (meth)acrylate; other primary hydroxyl group-containing monomers such as 2-acryloyloxyethyl 2-hydroxyethyl phthalic acid, N-methylol (meth)acrylamide, and hydroxyethyl acrylamide; 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, propylene glycol diglycidyl ether epoxy di(meth)acrylate, Examples include secondary hydroxyl group-containing monomers such as phenol glycidyl ether-epoxy (meth)acrylate and bisphenol A diglycidyl ether-epoxy di(meth)acrylate; and tertiary hydroxyl group-containing monomers such as 2,2-dimethyl 2-hydroxyethyl (meth)acrylate.

[0107] (3) Examples of carboxyl group-containing monomers include (meth)acrylic acid, acrylate dimer, crotonic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid, glutaconic acid, itaconic acid, acrylamide N-glycolic acid, cinnamic acid, etc.

[0108] (4) Examples of amino group-containing monomers include tert-butylaminoethyl (meth)acrylate, ethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, and diethylaminoethyl (meth)acrylate.

[0109] (5) Examples of acetoacetyl group-containing monomers include 2-(acetoacetoxy)ethyl (meth)acrylate and allyl acetoacetate.

[0110] (6) Examples of isocyanate group-containing monomers include 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and alkylene oxide adducts thereof.

[0111] (7) Examples of glycidyl group-containing monomers include, in addition to glycidyl (meth)acrylate, epoxy (meth)acrylates which are reaction products of epoxy compounds such as ethylene glycol diglycidyl ether - epoxy (meth)acrylate, resorcinol diglycidyl ether - epoxy (meth)acrylate, bis(4-hydroxyphenyl) sulfide diglycidyl ether - epoxy (meth)acrylate, phenol novolac type epoxy resin - (meth)acrylate, cresol novolac type epoxy resin - (meth)acrylate, bisphenol (e.g., bisphenol A, bisphenol F) type epoxy resin - (meth)acrylate, biphenol (e.g., 3,3',5,5'-tetramethylbiphenol) type epoxy resin - (meth)acrylate, tris(2,3-epoxypropyl) isocyanurate - (meth)acrylate and (meth)acrylate, and epoxy (meth)acrylates which are reaction products of epoxy compounds and (meth)acrylic acid. Examples include glycidyl (meth)acrylates such as 4-hydroxybutyl (meth)acrylate glycidyl ether.

[0112] (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, α-methylstyrene, etc.

[0113] (9) Examples of monomers containing alkoxy groups and oxyalkylene groups include 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.

[0114] (10) Examples of alkoxyalkyl (meth)acrylamide monomers include methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, isopropoxymethyl (meth)acrylamide, n-butoxymethyl (meth)acrylamide, isobutoxymethyl (meth)acrylamide, and the like.

[0115] (11) Examples of (meth)acrylamide monomers include (meth)acryloylmorpholine, dimethyl(meth)acrylamide, diethyl(meth)acrylamide, and (meth)acrylamide N-methylol(meth)acrylamide.

[0116] (12) Examples of monofunctional unsaturated compounds include biphenyl structure-containing (meth)acrylate compounds, more specifically, biphenyl (meth)acrylates such as o-biphenyl (meth)acrylate, m-biphenyl (meth)acrylate, and p-biphenyl (meth)acrylate; biphenyloxyalkyl (meth)acrylates such as 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, and p-biphenyloxypropyl (meth)acrylate; (o-biphenyloxy)diethylene glycol (meth)acrylate, Examples of biphenyloxy polyalkylene glycol (meth)acrylates include (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, and (p-biphenyloxy)polypropylene glycol (meth)acrylate.

[0117] (13) Examples of polyfunctional unsaturated compounds include bifunctional monomers, monomers with three or more functions, urethane (meth)acrylates, the aforementioned epoxy (meth)acrylates, polyester (meth)acrylates, polyether (meth)acrylates, and the like.

[0118] Specific examples of difunctional 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, 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, tricyclodecanedimethanol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,6-hexanediol ethylene oxide-modified di(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, Examples include ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, diglycidyl phthalate di(meth)acrylate, hydroxypivalic acid-modified neopentyl glycol di(meth)acrylate, ethylene oxide isocyanurate-modified diacrylate, and 2-(meth)acryloyloxyethyl acid phosphate diester.

[0119] Furthermore, specific examples of monomers with three or more functionalities 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, isocyanurate ethylene oxide-modified tri(meth)acrylate, ethylene oxide-modified dipentaerythritol penta(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, Examples include ethylene oxide-modified pentaerythritol tri(meth)acrylate, ethylene oxide-modified pentaerythritol tetra(meth)acrylate, succinic acid-modified pentaerythritol tri(meth)acrylate, and the like.

[0120] In addition to the polymerizable monomers mentioned above, 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-acrylamide methyltrimethylammonium chloride Examples include hydrates, allyltrimethylammonium chloride, dimethylallyl vinyl ketone, 2-chloroethyl vinyl ether, triallyl isocyanurate, tetraallyl glycoluryl, N-vinylpyrrolidone, N-vinylcaprolactam, ethylene glycol diallyl carbonate, trimellitic acid trialyl ester, trifluoroethyl (meth)acrylate, tribromobenzyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, sulfur-containing (meth)acrylate, and (meth)acryloyloxypropyltris(methoxy)silane.

[0121] In the second composition of the present invention, the third curable compound (ene compound) may be a combination of the polymerizable monomer and polymerizable oligomer described above, the polymerizable monomer may be a combination of the polymerizable monomers exemplified above (a combination of different types of polymerizable monomers may be used), and the polymerizable oligomer may also be a combination of different types of polymerizable oligomers.

[0122] Regarding the ratio of the content of the compound of the present invention and the third curable compound in the second composition of the present invention, it is preferable that the content of the third curable compound be in an appropriate ratio within the range of 0.01 to 1000 times (weight ratio) relative to the content of the compound of the present invention, and more preferably in an appropriate ratio within the range of 0.1 to 500 times (weight ratio).

[0123] The second composition of the present invention may contain the second curable compound described in section 3-1. First Composition above. In the second composition of the present invention, the content of the second curable compound is preferably 0 to 1000 parts by weight, and more preferably 0.01 to 500 parts by weight, based on 100 parts by weight of the total of the first curable compound and the third curable compound.

[0124] The second composition of the present invention may contain the thiol compound described in section 3-1, "First Composition," as a curing agent. In the second composition of the present invention, the content of the curing agent (thiol compound) is preferably 0.1 to 200 parts by weight, and more preferably 0.5 to 150 parts by weight, per 100 parts by weight of the curable compound (total of the first curable compound and the third curable compound).

[0125] Methods for polymerizing (curing) the second composition of the present invention include photocuring and thermal curing. Methods for photocuring include irradiation with active energy rays, preferably in combination with a photopolymerization initiator. Examples of active energy rays include light, radiation, electromagnetic waves, and electron beams, with electron beams or light in the ultraviolet to infrared wavelength range being preferred. As light sources, for example, a high-pressure mercury light source or a metal halide light source can be used for ultraviolet irradiation, a metal halide light source or a halogen light source for visible light irradiation, and a halogen light source for infrared irradiation. Furthermore, light sources such as lasers and LEDs, which have become increasingly popular in recent years and are capable of emitting light at various wavelengths, may also be used. The amount of active energy ray irradiation can be appropriately set according to the type of light source.

[0126] The photopolymerization initiator can be selected from photoradical polymerization initiators and photoanionic polymerization initiators, and either can be included in the second composition. In addition, in photocuring, thermal polymerization (thermosetting) may be used in combination to improve production efficiency and the properties of the cured product.

[0127] As photoradical polymerization initiators, any commonly used ones can be used without particular limitations. Examples include acetophenones such as 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, and 2-methyl-1-{4-(methylthio)phenyl}-2-morpholinopropan-1-one; benzoins such as benzyldimethylketal; benzophenones such as benzophenone, 4-phenylbenzophenone, and hydroxybenzophenone; thioxanthones such as isopropylthioxanthone and 2,4-diethylthioxanthone, and methylphenylglyoxylate, and these may be used in combination. In addition, known photopolymerization accelerators such as benzoic acids such as 4-dimethylaminobenzoic acid and tertiary amines may be used in combination with the photoradical polymerization initiator as needed.

[0128] As photoanionic polymerization initiators, any commonly used ones can be used without particular limitations, such as onium salts and carbamates. Examples of onium salts include 1,2-diisopropyl-3-(bis(dimethylamino)methylene)guanidium 2-(3-benzoylphenyl)propionate and 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidium n-butyltriphenylborate. Examples of carbamates include 2-nitrophenylmethylpiperidine-1-carboxylate, 1-(anthraquinone-2-yl)ethylimidazole carboxylate, 1-(3-(2-hydroxyphenyl)-2-propenoyl)piperidine and 9-anthranylmethyldiethylcarbamate.

[0129] Furthermore, when photocuring the second composition of the present invention, sensitizers such as pyrene, perylene, acridine orange, thioxanthone, 2-chlorothioxanthone, and benzoflavin can be used.

[0130] In the second composition of the present invention, the content of the photopolymerization initiator is preferably 0.001 to 20% by weight, and more preferably 0.01 to 10% by weight, based on the total amount of the second composition.

[0131] On the other hand, a method for thermally curing the second composition of the present invention is to use a thermal polymerization initiator in combination. The thermal polymerization initiator can be selected from thermal radical polymerization initiators and thermal anionic polymerization initiators, and either can be included in the composition. The conditions for thermal curing can be set appropriately by adjusting the heating temperature and heating time, but it is preferable to set them in the range of 60 to 130°C / 30 to 240 minutes, and more preferably in the range of 70 to 125°C / 30 to 120 minutes.

[0132] As a thermal radical polymerization initiator, any commonly used one can be used without particular limitations, for example, diisopropyl peroxydicarbonate, benzoyl peroxide, t-butyl peroxyisobutyrate, t-hexyl peroxyisopropyl monocarbonate, t-hexyl peroxy 2-ethylhexanoate, 1,1,3,3-tetramethylbutyl peroxy 2-ethylhexanoate, t-butyl peroxypivalate, t-hexyl peroxypivalate, t-butyl peroxyneodecanoate Examples of peroxides include 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 azo compounds such as azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), and dimethyl-2,2'-azobis(2-methylpropionate), and these may be used in combination.

[0133] As the thermal anionic polymerization initiator, any commonly used initiator can be used without particular limitation. Examples thereof include amines, imidazoles, and the like, and these may be used in combination. Examples of the amines include diethylenetriamine, triethylenetetramine, isophoronediamine, xylylenediamine, diaminodiphenylmethane, 1,3,4,6-tetrakis(3-aminopropyl)glycoluril, and the like. Examples of the imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and the like.

[0134] The content of the thermal polymerization initiator in the second composition of the present invention is preferably 0.001 to 20% by weight relative to the entire (total amount of) the second composition, and more preferably 0.01 to 10% by weight.

[0135] In the case where the second 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, any commonly used initiator can be used without particular limitation, and examples thereof include onium salts, organometallic complexes, and the like. Examples of the onium salts include diazonium salts, sulfonium salts, and iodonium salts. Examples of the organometallic complexes include iron-arene 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 Corporation, "UVE-1014 (trade name)" manufactured by General Electronics, "CD-1012 (trade name)" manufactured by Sartomer, "CPI-100P (trade name)" manufactured by San-Apro Ltd., and the like. As the counter anion for the photocationic polymerization initiator, SbF ６ － , AsF ６ － , B(C ６ F ５ ) ４ － , PF ６ －These are some examples.

[0136] As a thermal cationic polymerization initiator, any commonly used one can be used without particular restrictions. Examples include various onium salts such as quaternary ammonium salts, phosphonium salts, and sulfonium salts, as well as organometallic complexes, which may be used in combination. Examples of commercially available onium salts include "ADEKA Opton CP-66" and "ADEKA Opton CP-77" from ADEKA Corporation, "San-Aid SI-60L," "San-Aid SI-80L," and "San-Aid SI-100L" from Sanshin Chemical Industry Co., Ltd., and the "CI Series" from Nippon Soda Co., Ltd. Examples of organometallic complexes include alkoxysilane-aluminum complexes.

[0137] The second composition of the present invention may further contain the curing accelerator, stabilizer, triphenylsilanol, talc, filler, calcium carbonate, additives (modifiers), etc., as described in section 3-1. First Composition, as long as they do not inhibit the effects of the present invention. The additives (modifiers) may be contained in an amount of 0.01 to 50% by weight of the entire second composition (total amount), if necessary.

[0138] There are no particular limitations on the method for preparing (mixing) the second composition of the present invention. For example, it can be prepared by mixing the compound of the present invention, an ene compound, a photopolymerization initiator and / or a thermal polymerization initiator, and optionally a second curable compound, a curing agent (thiol compound), and an additive. Known methods (for example, the methods described in section 3-1. First Composition) can be used as means of mixing. The compound of the present invention may be dissolved or dispersed in a viscosity-adjusting diluent (organic solvent) beforehand.

[0139] 4. Uses of the Compositions The first and second compositions of the present invention containing the compound of the present invention (these compositions may be collectively referred to as "the compositions of the present invention") exhibit low viscosity and excellent curability. Furthermore, the compositions of the present invention are expected to provide cured products with excellent flexibility. In other words, compared to conventional compositions containing epoxy compounds or episulfide compounds, the compositions of the present invention exhibit low viscosity and excellent curability, as well as providing cured products with excellent flexibility and adhesive strength, making them suitable for use as adhesives and sealants. That is, the adhesives and sealants of the present invention consist of the compositions of the present invention described above.

[0140] The adhesives and sealants of the present invention may contain additives. Examples of additives include flow behavior modifiers such as silicic acid, magnesium silicate, and barium sulfate; thermal conductivity imparters such as alumina; conductivity imparters such as silver and carbon; and colorants such as pigments and dyes. These additives can be incorporated during the preparation of the composition of the present invention. They may also be mixed with compositions of the present invention that have already been prepared. Known methods (for example, the methods described in section 3-1. First Composition) can be used as means of mixing.

[0141] The adhesives and sealants of the present invention are not particularly limited in their use and can be applied to a variety of fields. Examples of adhesive applications include: adhesives for flexible printed circuit boards; interlayer adhesives for multilayer substrates such as build-up substrates; adhesives for bonding optical components; adhesives for bonding optical discs; adhesives for image sensors; adhesives for mounting printed circuit boards; die bonding adhesives; adhesives for semiconductors such as underfills; adhesives for mounting BGA reinforcement underfills, anisotropic conductive films (ACF), anisotropic conductive pastes (ACP), etc.; adhesives for optical pickups; adhesives for optical path coupling; adhesives used between exterior materials, substrates, ceiling materials and interior materials; and adhesives for bonding tiles and stone to exterior wall materials and substrates. Adhesives include those for bonding wood flooring materials, polymer-based floor sheets, and floor tiles to various types of flooring; adhesives for structural materials, bodies, and parts of automobiles and aircraft; adhesives for automobile interiors; and adhesives for steel plate joints. Examples of sealant applications include, for example, sealants for joints of exterior materials such as various metal panels and siding boards; sealants used between exterior materials, substrates, ceiling materials, and interior materials; sealants for joints of 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; and sealants for medical devices.

[0142] In recent years, with the miniaturization of electronic components and modules, adhesives and encapsulants used in electronic components are sometimes injected into confined spaces using jet dispensers. In such cases, the composition used for the adhesive or encapsulant is required to have low viscosity. The composition of the present invention is particularly suitable for these applications because it has low viscosity. Furthermore, the adhesive of the present invention exhibits good adhesion to engineering plastics, ceramics, and metals.

[0143] Engineering plastics are plastics that maintain a tensile strength of 49 MPa or higher and a flexural modulus of 2.5 GPa or higher even under harsh conditions of 100°C / 100h. Examples of engineering plastics include thermoplastic engineering plastics such as polyacetal, polyamide, polycarbonate, modified polyphenylene ether, polybutylene terephthalate, glass fiber reinforced polyethylene terephthalate, ultra-high molecular weight polyethylene, and syndiotactic polystyrene; thermosetting engineering plastics such as epoxy, glass epoxy (FR-4), phenol, and silicone; and super engineering plastics such as amorphous polyarylate, polysulfone, polyethersulfone, polyphenylene sulfide, polyetheretherketone, polyimide, polyetherimide, polyamideimide, fluororesin, and liquid crystal polymer. Super engineering plastics are defined as engineering plastics that maintain a tensile strength of 49 MPa or higher and a flexural modulus of 2.5 GPa or higher even under harsh conditions of 150°C / 100h. These engineering plastics are suitably used as VoiceCoilMotors (VCMs) in image sensor modules having optical components.

[0144] Examples of ceramics include alumina, aluminum nitride, silicon carbide, silicon nitride, boron nitride, and glass. Alumina and silicon nitride are preferred from the viewpoint of thermal conductivity, coefficient of thermal expansion, and chemical durability. These ceramics are suitably used as substrates for image sensor modules having an image sensor.

[0145] Examples of metals include stainless steel, nickel and its alloys, titanium and its alloys, copper and its alloys, tin and its alloys, aluminum and its alloys, and solder. From the viewpoint of chemical stability such as oxidation resistance, stainless steel, nickel and its alloys are preferred.

[0146] Tables 1 and 2 show preferred formulations of the compositions of the present invention when used in adhesives (particularly one-component adhesives). Table 1 shows an example of the formulation of the first composition, and Table 2 shows an example of the formulation of the second composition.

[0147]

[0148]

[0149] When using the composition of the present invention as a one-component adhesive, the adhesive is applied to the area to be bonded and then heat-cured. The heating temperature and heating time can be set as appropriate, but it is preferable to set them in the range of 80°C / 10 to 180 minutes, and more preferably in the range of 80°C / 30 to 60 minutes.

[0150] The compositions of the present invention are applicable to products (parts and components) in various fields, including adhesives and sealants as described above, and may be made of resin. They can be used as raw materials for electrical or electronic, optical, construction, civil engineering, automotive or aerospace, medical, and other everyday or general merchandise items.

[0151] For example, examples of components, materials, and parts in the electrical or electronic field include resin-coated copper foil, prepregs, copper-clad laminates, printed circuit boards, solder resist inks, conductive pastes, interlayer insulating materials, encapsulants, LED encapsulants, insulating materials, thermally conductive materials, hot melt materials, paints, potting agents, etc. More specifically, examples include encapsulant materials and layer-forming materials for printed circuit boards and electronic components such as interlayer insulating films and wiring coating films; forming materials for display devices such as color filters, flexible display films, resist materials, and alignment films; forming materials for semiconductor devices such as resist materials and buffer coating films; and forming materials for optical components such as holograms, optical waveguides, optical circuits, optical circuit components, and anti-reflective films. In addition, examples include forming materials for rigid circuit boards and flexible printed circuit boards for semiconductor mounting, mounting materials for semiconductor mounting, semiconductor encapsulants, solar cell encapsulants, semiconductor insulating films, coverlay films for flexible printed circuit protection, and coating agents for wiring coating.

[0152] Examples of materials in the field of optics include core materials for optical fibers, cladding materials, lenses, and wear-resistant coatings for lenses (e.g., hard coat forming solutions).

[0153] Examples of materials in the construction field include coatings and primers for exterior materials such as various metal panels and siding boards; injection materials, vibration damping materials, soundproofing materials, conductive materials for electromagnetic shielding, and putty materials used between exterior materials, substrates, ceiling materials, and interior materials; wood flooring materials, polymer-based floor sheets, and adhesives for floor tile bonding; and injection materials for crack repair in various exterior and interior materials.

[0154] Examples of materials used in civil engineering include coatings, primers, paints, putties, injection materials, spray materials, and mold covers for various concrete products such as roads, bridges, tunnels, and breakwaters.

[0155] Examples of materials used in the automotive or aerospace sectors include structural materials, coatings for bodies and parts, cushioning materials, vibration damping materials, soundproofing materials, and spray materials; adhesives, coatings, and foams for automotive interiors; and coatings for steel plate joints.

[0156] Examples of materials used in the medical field include artificial bones, dental impression materials, medical rubber materials, and medical adhesives.

[0157] The present invention will be described in more detail below using examples and comparative examples, but the present invention is not limited thereto. The main raw materials used are as follows.

[0158] • 2-(oxyranylmethoxy)methyl-1,4-benzodioxane (synthesized according to the method described in Synthesis, 1983, (2), 117-119. See chemical formula (II-2).) • Thiourea (manufactured by Fujifilm Wako Pure Chemical Industries) • 2-(2-(oxyranylmethoxy)ethoxy)methyl-1,4-benzodioxane (synthesized by the method of Synthesis Example 1. See chemical formula (II-13).) • 2-[(2,3-dihydro-1,4-benzodioxin-2-yl)methoxy]ethanol (synthesized according to the method described in Advanced Synthesis & Catalesis, 2019, 361(15), 3639-3644. See chemical formula (A).) • Benzyltrimethylammonium chloride (manufactured by Fujifilm Wako Pure Chemical Industries) • Epichlorohydrin (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0159]

[0160] The methods for measuring the reaction initiation temperature and peak top temperature, which are evaluation tests used in the examples and comparative examples, are as follows.

[0161] [Measurement of Reaction Initiation Temperature and Peak Top Temperature] The curability of the curable composition was evaluated by measuring the reaction initiation temperature and peak top temperature. The measurements were performed using a differential scanning calorimeter (Hitachi High-Tech Science, "DSC7020") under the following conditions. Note that the reaction initiation temperature is the onset temperature of the exothermic peak. ・Temperature profile: -30°C to 250°C ・Heating condition: 10°C / min. ・Nitrogen flow (20 ml / min.)

[0162] [Example 1] <Synthesis of 2-(thiiranylmethoxy)methyl-1,4-benzodioxane (compound represented by chemical formula (I-2))> Into a 2000 mL capacity four-necked eggplant flask, 111.12 g (500.0 mmol) of 2-(oxiranylmethoxy)methyl-1,4-benzodioxane and 700 g of methanol were charged, 41.87 g (550.0 mmol) of thiourea was added at 25°C, and the mixture was stirred at 25°C for 24 hours. After the obtained reaction solution was concentrated under reduced pressure, washing operation with chloroform / deionized water = 2 / 1 (weight ratio) was repeated 5 times. Thereafter, the organic layer was concentrated under reduced pressure to obtain 116.77 g of a colorless transparent liquid (yield: 98%).

[0163] The obtained colorless transparent liquid was analyzed by gel permeation chromatography (eluent: tetrahydrofuran, column: PLgel Guard (7.5×50 mm, 3.0 μm) + PLgel MIXED-E (7.5×300 mm, 3.0 μm×2), detector: PDA (210 nm)). This colorless transparent liquid contains, as a main component, the compound represented by chemical formula (I-2) (peak with elution time: 36.5 minutes), and further contains an oligomer represented by chemical formula (III) (in the formula, R ２ are all hydrogen atoms, all n are 0, all Y are -CH ２ OCH ２ -, and X １ and X ２ are the same or different and are oxygen atoms or sulfur atoms).

[0164] The elution times for the oligomer represented by chemical formula (III) were as follows: • Oligomer represented by chemical formula (III) with r = 1 (hereinafter sometimes referred to as "dimer"): Peak at 33.7 min • Oligomer represented by chemical formula (III) with r = 2 (hereinafter sometimes referred to as "trimer"): Peak at 33.0 min • Oligomer represented by chemical formula (III) with r = 3 (hereinafter sometimes referred to as "tetramer"): Peak at 31.9 min • Oligomer represented by chemical formula (III) with r = 4 (hereinafter sometimes referred to as "pentamer"): Peak at 31.2 min • Oligomer represented by chemical formula (III) with r = 5 (hereinafter sometimes referred to as "hexamer"): Peak at 30.6 min • Oligomer represented by chemical formula (III) with r = 6 II) The oligomer shown in (I) (hereinafter sometimes referred to as "heptamer"): The oligomer shown in chemical formula (III) with a peak r of 7 at 30.3 min (hereinafter sometimes referred to as "octamer"): The oligomer shown in chemical formula (III) with a peak r of 8 at 29.8 min (hereinafter sometimes referred to as "nocaper"): The oligomer shown in chemical formula (III) with a peak r of 9 to 10 at 29.5 min (hereinafter sometimes referred to as "decaper-decaper"): The oligomer shown in chemical formula (III) with a peak r of 11 or more at 28.1 to 29.3 min (hereinafter sometimes referred to as "decaper or more"): Peak at 26.5 to 28.1 min)

[0165] From the peak area ratio of the dimer to the compound represented by chemical formula (I-2), it was confirmed that the ratio of the dimer content to the compound represented by chemical formula (I-2) is 0.005. From the peak area ratio of the trimer to the compound represented by chemical formula (I-2), it was confirmed that the ratio of the trimer content to the compound represented by chemical formula (I-2) is 0.007. From the peak area ratio of the tetramer to the compound represented by chemical formula (I-2), it was confirmed that the ratio of the tetramer content to the compound represented by chemical formula (I-2) is 0.008. From the peak area ratio of the pentamer to the compound represented by chemical formula (I-2), it was confirmed that the ratio of the pentamer content to the compound represented by chemical formula (I-2) is 0.008. From the peak area ratio of the hexamer to the compound represented by chemical formula (I-2), it was confirmed that the ratio of the hexamer content to the compound represented by chemical formula (I-2) is 0.008. From the peak area ratio of the heptamer to the compound represented by chemical formula (I-2), it was confirmed that the ratio of the heptamer content to the content of the compound represented by chemical formula (I-2) is 0.011. From the peak area ratio of the octamer to the compound represented by chemical formula (I-2), it was confirmed that the ratio of the octamer content to the content of the compound represented by chemical formula (I-2) is 0.014. From the peak area ratio of the nenamer to the compound represented by chemical formula (I-2), it was confirmed that the ratio of the nenamer content to the content of the compound represented by chemical formula (I-2) is 0.018. From the peak area ratio of the decamer-elevenmer to the compound represented by chemical formula (I-2), it was confirmed that the ratio of the decamer-elevenmer content to the content of the compound represented by chemical formula (I-2) is 0.019. From the peak area ratio of the compound represented by chemical formula (I-2) to the compound represented by chemical formula (I-2), it was confirmed that the ratio of the content of the compound represented by chemical formula (I-2) to the content of the compound represented by chemical formula (I-2) was 0.006. Therefore, the ratio of the content of the oligomer (dimer or more) represented by chemical formula (III) to the content of the compound represented by chemical formula (I-2) was 0.104.

[0166] [Example 2] A curable composition was prepared by uniformly mixing 100 parts by weight of a mixture mainly consisting of the episulfide compound (compound shown by chemical formula (I-2)) synthesized in Example 1 with 2 parts by weight of 2-ethyl-4-methylimidazole (manufactured by Shikoku Chemicals Co., Ltd.). An evaluation test (measurement of reaction start temperature and peak top temperature) was performed on this curable composition, and the test results obtained are shown in Table 3.

[0167] [Comparative Example 1] A curable composition was prepared in the same manner as in Example 2, except that the mixture mainly composed of the compound represented by chemical formula (I-2) was changed to 2-(oxyranylmethoxy)methyl-1,4-benzodioxane (the compound represented by chemical formula (II-2)). An evaluation test (measurement of reaction start temperature and peak top temperature) was performed on this curable composition, and the test results obtained are shown in Table 3.

[0168]

[0169] Table 3 shows that the curable composition of Example 2 had a lower reaction initiation temperature and peak top temperature compared to a conventional epoxy compound (a curable composition using the compound represented by chemical formula (II-2) in Comparative Example 1). Therefore, it is considered that the compound of the present invention can be cured at a lower temperature than conventional epoxy compounds.

[0170] [Synthesis Example 1] <Synthesis of 2-(2-(oxyranylmethoxy)ethoxy)methyl-1,4-benzodioxane (compound shown by chemical formula (II-13))> 145.21 g (690.7 mmol) of 2-[(2,3-dihydro-1,4-benzodioxin-2-yl)methoxy]ethanol, 1.28 g (6.91 mmol) of benzyltrimethylammonium chloride, and 172.68 g of dimethyl sulfoxide were charged into a 1000 mL four-necked round-bottom flask. At 25°C, 143.90 g (1.73 mol) of 48% sodium hydroxide aqueous solution and 479.30 g (5.18 mol) of epichlorohydrin were added in that order, and the mixture was stirred at 25°C for 17 hours. After concentrating the resulting reaction solution under reduced pressure, the washing operation was repeated five times with toluene / deionized water = 1 / 1 (by weight). Subsequently, the organic layer was concentrated under reduced pressure to obtain 159.80 g of a brown liquid. The obtained brown liquid was purified by distillation to obtain 128.75 g of a colorless, transparent liquid (yield: 70%).

[0171] The resulting colorless, transparent liquid １ The H-NMR spectral data was as follows: １ H-NMR (CDCl ３ δ: 6.90–6.82 (m, 4H), 4.35 (d, 1H), 4.31 (d, 1H), 4.08 (dd, 1H), 3.83–3.77 (m, 2H), 3.73–3.66 (m, 5H), 3.43 (dd, 1H), 3.16 (quin., 1H), 2.80 (t, 1H), 2.61 (dd, 1H). From this spectral data, the obtained colorless transparent liquid was identified as the compound shown by chemical formula (II-13).

[0172] [Example 3] <Synthesis of 2-(2-(thyranylmethoxy)ethoxy)methyl-1,4-benzodioxane (compound shown by chemical formula (I-13))> 10.00 g (37.6 mmol) of 2-(2-(oxyranylmethoxy)ethoxy)methyl-1,4-benzodioxane and 60 g of methanol were charged into a 100 mL three-necked round-bottom flask. 3.15 g (41.4 mmol) of thiourea was added at 25°C and the mixture was stirred at 25°C for 24 hours. The resulting reaction mixture was concentrated under reduced pressure, and then washed five times with chloroform / deionized water = 2 / 1 (by weight). Subsequently, the organic layer was concentrated under reduced pressure to obtain 10.38 g of a colorless, transparent liquid (yield: 98%).

[0173] The obtained colorless, transparent liquid was analyzed by gel permeation chromatography (eluent: tetrahydrofuran, column: PLgel Guard (7.5 × 50 mm, 3.0 μm) + PLgel MIXED-E (7.5 × 300 mm, 3.0 μm × 2), detector: PDA (210 nm)). This colorless, transparent liquid mainly contained the compound represented by chemical formula (I-13) (peak at elution time: 36.4 minutes), and further contained the oligomer represented by chemical formula (III) (wherein R ２ All of them are hydrogen atoms, all n is 0, and all Y is -CH ２ OCH ２ CH ２ OCH ２ - and X １ and X ２ However, it was confirmed that the oligomers contained either the same or different oxygen or sulfur atoms.

[0174] The elution times for the oligomer represented by chemical formula (III) were as follows: • Oligomer represented by chemical formula (III) with r = 1 (hereinafter sometimes referred to as "dimer"): Peak at 33.6 minutes • Oligomer represented by chemical formula (III) with r = 2 (hereinafter sometimes referred to as "trimer"): Peak at 32.8 minutes • Oligomer represented by chemical formula (III) with r = 3 (hereinafter sometimes referred to as "tetramer"): Peak at 31.6 minutes • Oligomer represented by chemical formula (III) with r = 4 (hereinafter sometimes referred to as "pentamer"): Peak at 31.0 minutes • Oligomer represented by chemical formula (III) with r = 5 or more (hereinafter sometimes referred to as "hexamer or more"): Peak between 27.5 minutes and 30.0 minutes

[0175] From the peak area ratio of the dimer to the compound represented by chemical formula (I-13), it was confirmed that the ratio of the dimer content to the compound represented by chemical formula (I-13) is 0.009 (0.9%). From the peak area ratio of the trimer to the compound represented by chemical formula (I-13), it was confirmed that the ratio of the trimer content to the compound represented by chemical formula (I-13) is 0.009 (0.9%). From the peak area ratio of the tetramer to the compound represented by chemical formula (I-13), it was confirmed that the ratio of the tetramer content to the compound represented by chemical formula (I-13) is 0.009 (0.9%). From the peak area ratio of the pentamer to the compound represented by chemical formula (I-13), it was confirmed that the ratio of the pentamer content to the compound represented by chemical formula (I-13) is 0.009 (0.9%). From the peak area ratio of the hexamer or larger and the compound represented by chemical formula (I-13), it was confirmed that the ratio of the content of the hexamer or larger to the content of the compound represented by chemical formula (I-13) was 0.016 (1.6%). Therefore, the ratio of the content of the oligomer (dimer or larger) represented by chemical formula (III) to the content of the compound represented by chemical formula (I-13) was 0.052 (5.2%).

[0176] [Example 4] A curable composition was prepared by uniformly mixing 100 parts by weight of a mixture mainly composed of the episulfide compound (compound shown by chemical formula (I-13)) synthesized in Example 3 with 2 parts by weight of 2-ethyl-4-methylimidazole (manufactured by Shikoku Chemicals Co., Ltd.). An evaluation test (measurement of reaction start temperature and peak top temperature) was performed on this curable composition, and the test results obtained are shown in Table 4.

[0177] [Comparative Example 2] A curable composition was prepared in the same manner as in Example 4, except that the mixture mainly composed of the compound represented by chemical formula (I-13) was changed to 2-(2-(oxyranylmethoxy)ethoxy)methyl-1,4-benzodioxane (the compound represented by chemical formula (II-13)). An evaluation test (measurement of reaction start temperature and peak top temperature) was performed on this curable composition, and the test results obtained are shown in Table 4.

[0178]

[0179] Table 4 shows that the curable composition of Example 4 has a lower reaction initiation temperature and peak top temperature compared to a conventional epoxy compound (a curable composition using the compound represented by chemical formula (II-13) in Comparative Example 2). Therefore, it is considered that the compound of the present invention can be cured at a lower temperature than conventional epoxy compounds.

[0180] The episulfide compounds of the present invention are useful as resin materials and intermediate raw materials for various sulfur-containing compounds. Furthermore, compositions containing the episulfide compounds of the present invention are suitable for various applications such as bonding, sealing, encapsulation, casting, molding, painting, and coating.

Claims

1. An episulfide compound represented by chemical formula (I). (wherein, R １ represents a methyl group or a hydroxy group, and when there are plural R １ , they may be the same or different. R ２ represents a hydrogen atom or a methyl group. Y represents a group represented by any one of formula (1) to formula (4). n represents an integer of 0 to 4.) (wherein, R １１ represents a hydrogen atom or a methyl group, and when there are plural R １１ , they may be the same or different. R １２ represents a hydrogen atom or a methyl group, and when there are plural R １２ , they may be the same or different. R １３ represents a hydrogen atom or a methyl group, and when there are plural R １３ , they may be the same or different. R １４ represents a hydrogen atom or a methyl group, and when there are plural R １４ , they may be the same or different. m1 represents an integer of 0 to 3, m2 represents an integer of 1 to 3, m3 represents an integer of 0 to 3, m4 represents an integer of 1 to 3, m5 represents an integer of 0 to 3, m6 represents an integer of 1 to 3, and m7 represents an integer of 1 to 3.) 2. A composition comprising the compound described in claim 1 and a curing agent and / or a curing accelerator.

3. A composition comprising the compound described in claim 1 and an ene compound having a carbon-carbon double bond in its molecule.

4. An adhesive comprising the composition according to claim 2 or claim 3.

5. A sealant comprising the composition according to claim 2 or claim 3.

6. A cured product of the composition according to claim 2 or claim 3.

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