TW201715099A - Clathrate compound - Google Patents

Abstract

The present invention addresses the problem of providing a curing catalyst (clathrate compound) that suppresses a curing reaction at a low temperature, improving one-pack stability, and can effectively cure a resin by applying heat treatment. The clathrate compound according to the present invention contains a fluorene compound represented by formula (I) and an imidazole compound represented by formula (II).

Description

Crystal cage compound

The present invention relates to a novel crystal cage compound, a curing catalyst containing the crystal cage compound, a curing resin forming composition using the curing catalyst, a method for producing a cured resin using the curing resin forming composition, and A hardened resin obtained by the production method. The present application claims priority to Japanese Patent Application No. 2015-182752, filed on Sep.

Epoxy resins are widely used in various fields because of their excellent mechanical properties and thermal properties. As a hardener for hardening the epoxy resin, imidazole has been used in the industry, but the epoxy-imidazole mixture has a problem that the curing starts earlier and the single liquid stability is extremely poor. Therefore, as the curing agent, an imidazole acid addition salt obtained by adding hydroxybenzoic acid to imidazole has been proposed (see Patent Document 1), or a tetraphenol-based compound (for example, 1,1,2,2-tetra ( A crystal cage of 4-hydroxyphenyl)ethane (hereinafter referred to as TEP) and imidazole (see Patent Document 2). Although the imidazolium acid addition salt or crystal cage exhibits a certain effect, it is required to develop a function or function that is equivalent to the same. [Prior Art Document] [Patent Document] Patent Document 1: Japanese Patent Publication No. Hei 4-2638. Patent Document 2: Japanese Patent Laid-Open No. Hei 11-71449

[Problem to be Solved by the Invention] An object of the present invention is to provide a hardening catalyst (crystal cage) which can effectively improve the stability of a single liquid by suppressing a hardening reaction at a low temperature and which is effective in heat treatment by heat treatment. Compound). Further, an object of the present invention is to provide a cured resin-forming composition using the curing catalyst, a method for producing a cured resin using the cured resin-forming composition, and a cured resin obtained by the production method. [Means for Solving the Problems] The inventors of the present invention have diligently studied to solve the above problems, and as a result, have found that the above problems can be solved by using a specific cerium compound and a crystal cage compound of a specific imidazole compound, thereby completing the present invention. . That is, the present invention relates to the following, (1) a crystal cage compound containing the hydrazine compound represented by the formula (I) and the imidazole compound represented by the formula (II), [Chemical Formula 1] (wherein X ¹ each independently represents a halogeno group, an unsubstituted or substituted C1-6 alkyl group, a hydroxyl group, an unsubstituted or substituted C1-6 alkoxy group, an amine group, a nitro group Or cyano; m represents any integer from 0 to 4, n represents any integer from 0 to 4; X ² independently represents a halo group, an unsubstituted or substituted C1 to 6 alkyl group, a hydroxyl group , unsubstituted or substituted C 1 -6 alkoxy, amine, nitro, or cyano; p represents any integer from 0 to 4, q represents any integer from 0 to 4), [Chemical 2 ] (wherein R ¹ represents a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, or an unsubstituted or substituted C6-10 aryl group; and R ² to R ⁴ each independently represent a hydrogen atom; , halo, unsubstituted or substituted C1-6 alkyl, unsubstituted or substituted C6-10 aryl, nitro, or cyano); (2) as described in (1) a crystal cage compound, wherein the hydrazine compound represented by the formula (I) is 9,9-bis(4-hydroxyphenyl)fluorene; (3) a curing catalyst for an epoxy resin, which comprises (1) or ( 2) The crystal cage compound described above; (4) A composition for forming an epoxy resin, which comprises the following components (A) and (B): (A) an epoxy resin, and (B) a formula (I) a crystal cage compound represented by the hydrazine compound and the imidazole compound represented by the formula (II) as a main component, [Chemical 3] (wherein X ¹ each independently represents a halogeno group, an unsubstituted or substituted C1-6 alkyl group, a hydroxyl group, an unsubstituted or substituted C1-6 alkoxy group, an amine group, a nitro group Or cyano; m represents any integer from 0 to 4, n represents any integer from 0 to 4; X ² independently represents a halo group, an unsubstituted or substituted C1 to 6 alkyl group, a hydroxyl group , unsubstituted or substituted C 1 -6 alkoxy, amine, nitro, or cyano; p represents any integer from 0 to 4, q represents any integer from 0 to 4), ] (wherein R ¹ represents a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, or an unsubstituted or substituted C6-10 aryl group; and R ² to R ⁴ each independently represent a hydrogen atom; , halo, unsubstituted or substituted C1-6 alkyl, unsubstituted or substituted C6-10 aryl, nitro, or cyano); (5) as described in (4) The composition for forming an epoxy-hardening resin, wherein the imidazole compound represented by the formula (II) in the component (B) is 0.01 to 1.0 mol with respect to the epoxy ring 1 mol of the epoxy resin as the component (A). (6) The epoxy resin-forming composition according to (4) or (5), wherein the hydrazine compound represented by the formula (I) is 9,9-bis(4-hydroxyphenyl)fluorene; (7) A method for producing an epoxy resin, which is obtained by subjecting the epoxy resin-forming composition according to any one of (4) to (6) to heat treatment to cure the epoxy resin. (8) An epoxy-curable resin obtained by subjecting the epoxy resin-curable composition according to any one of (4) to (6) to heat treatment and curing the composition; (9) The epoxy resin-forming composition according to (4), further comprising a cyclic oxime compound, an acid anhydride, a ruthenium compound, a tertiary amine compound, an aromatic amine compound, an imidazole compound, and an organic phosphine compound. (10) The epoxy resin-forming composition according to (4), further comprising a curing agent; and (11) as described in (4) A composition for forming an epoxy resin, which further contains a filler. [Effect of the Invention] According to the curing catalyst (cage compound) of the present invention, the curing reaction at a low temperature is suppressed, and the stability of the single liquid is improved, and the resin can be effectively cured by heat treatment.

[茀 compound] The oxime compound represented by the formula (I) will be described. First, in the present invention, the term "unsubstituted" means only the base of the mother core. When there is no description together with the "substituent", and only the name of the base of the parent is described, it means "unsubstituted" unless otherwise specified. On the other hand, the term "having a substituent" means that any hydrogen atom which becomes a base of a mother nucleus is substituted with a group having the same or different structure as the mother nucleus. Therefore, the "substituent" is the other group that is bonded to the base of the mother nucleus. The substituent may be one or two or more. Two or more substituents may be the same or different. The terms "C1 to 6" indicate that the number of carbon atoms to be the base of the mother nucleus is 1 to 6. The number of carbon atoms does not include the number of carbon atoms present in the substituent. For example, a butyl group having an ethoxy group as a substituent is classified into a C2 alkoxy C4 alkyl group. The "substituent" is not particularly limited as long as it is chemically acceptable and has the effects of the present invention. Hereinafter, the basis of the "substituent" can be exemplified. Halogen group such as fluoro, chloro, bromo or iodo; methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, tert-butyl, n-pentyl C1～6 alkyl group such as benzyl or n-hexyl; vinyl, 1-propenyl, 2-propenyl (allyl), 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl a C 2-6 alkenyl group such as a 2-propenyl group or a 2-methyl-2-propenyl group; an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 1-butynyl group, a 2-butynyl group, C2-6 alkynyl group such as 3-butynyl group, 1-methyl-2-propynyl group; C3-8 cycloalkyl group such as cyclopropyl group, cyclobutyl group, cyclopentyl group or cyclohexyl group; phenyl group, naphthyl group C6～10 aryl; benzyl, phenethyl, etc. C6～10 aryl C1-6 alkyl; 3-6-membered heterocyclic; 3- to 6-membered heterocyclic C1-6 alkyl; hydroxy; methoxy a C1-6 alkoxy group such as a ethoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a second butoxy group, an isobutoxy group or a third butoxy group; a vinyloxy group; a C2-6 alkenyloxy group such as an allyloxy group, a propenyloxy group or a butenyloxy group; a C6-10 aryloxy group such as a phenoxy group or a naphthyloxy group; a C6-10 which is a benzyloxy group or a phenethyloxy group; Aryl C1 ~ 6 alkoxy a 3- to 6-membered heterocyclic oxy group; a 3 to 6-membered heterocyclic C 1 -6 alkoxy group; a chloromethyl group, a chloroethyl group, a trifluoromethyl group, a 1,2-dichloro-n-propyl group, and 1 a C1 to 6 haloalkyl group such as a fluoro-n-butyl group or a perfluoro-n-pentyl group; a C1 to 6 haloalkoxy group such as a trifluoromethoxy group, a 2-chloro-n-propoxy group or a 2,3-dichlorobutoxy group; a C1-6 alkylamino group such as a methylamino group, a dimethylamino group or a diethylamino group; a C6-10 arylamino group such as an anilino group or a naphthylamino group; a benzylamino group and a phenethylamino group; C6～10 aryl C1-6 alkyl amino group; fluorenyl; methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, second butylthio, a C1-6 alkylthio group such as a tributylthio group; a C1-6 alkylsulfonyl group such as a methylsulfonyl group, an ethylsulfonyl group or a third butasulfonyl group; a C6-10 group such as a phenylthio group or a naphthylthio group; Arylthio; 3-6-membered heterocyclylthio; C6-10 sulfonyl phenylsulfonyl; 3-6-membered heterocyclylsulfonyl; cyano; nitro. Further, with respect to these "substituents", any one of the substituents may be substituted by a group having a different structure. Examples of the "substituent" in this case include a halogen group, a C1-6 alkyl group, a C1-6-6 halogenated alkyl group, a C1-6 alkoxy group, a C1-6-6 halogenated alkoxy group, a cyano group, a nitro group and the like. Further, the "3- to 6-membered heterocyclic group" includes a cyclic group selected from the group consisting of one to four hetero atoms in a group consisting of a nitrogen atom, an oxygen atom and a sulfur atom as a constituent atom of the ring. Examples of the "3- to 6-membered heterocyclic group" include a 3- to 6-membered saturated heterocyclic group, a 5- to 6-membered heteroaryl group, and a 5- to 6-membered partially unsaturated heterocyclic group. Examples of the 3- to 6-membered saturated heterocyclic group include aziridine group, epoxy group, pyrrolidinyl group, tetrahydrofuranyl group, thiazolidinyl group, piperidinyl group, and piperazine. A group, a morpholinyl group, a dioxolyl group, a dioxanyl group, and the like. Examples of the 5-membered heteroaryl group include a pyrrolyl group, a furyl group, a thienyl group, an imidazolyl group, and a pyrazolyl group. Azolyl, different Azyl, thiazolyl, isothiazolyl, triazolyl, A oxazolyl group, a thiadiazolyl group, a tetrazolyl group or the like. As the 6-membered heteroaryl group, a pyridyl group or a pyridyl group is exemplified. Base, pyrimidinyl, oxime Base, three Base. Examples of the 5-membered partially unsaturated heterocyclic group include a pyrrolinyl group, a dihydrofuranyl group, an imidazolinyl group, and a pyrazolinyl group. Oxazolinyl and the like. As a 6-membered partially unsaturated heterocyclic group, a An oxazoline group, a dihydropiperidyl group or the like. [X ¹ , X ² ] In the formula (I), X ¹ each independently represents a halogeno group, an unsubstituted or substituted C1-6 alkyl group, a hydroxyl group, an unsubstituted or substituted C1-6 Alkoxy, amine, nitro, or cyano. m represents any integer from 0 to 4, and n represents any integer from 0 to 4. X ² independently represents a halo group, an unsubstituted or substituted C 1-6 alkyl group, a hydroxy group, an unsubstituted or substituted C 1-6 alkoxy group, an amine group, a nitro group, or a cyano group. . p represents any integer from 0 to 4, and q represents any integer from 0 to 4. Examples of the "halo group" in X ¹ and X ² include a fluorine group, a chlorine group, a bromine group, and an iodine group. X X ^{2 1} and of the "C1 ~ 6 alkyl group" may be linear, may be branched. Examples of the C1-6 alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, isopropyl group, isobutyl group, second butyl group, and third butyl group. Butyl, neopentyl, 2-methylbutyl, 2,2-dimethylpropyl, isohexyl and the like. The substituent on the "C1-6 alkyl group" is preferably a halogen group, a hydroxyl group, a C1-6 alkoxy group, a C3-8 cycloalkyl group, a C6-10 aryl group, or a cyano group. Specific examples of the "C1-6 alkyl group having a substituent" include a fluoromethyl group, a chloromethyl group, a bromomethyl group, a difluoromethyl group, a dichloromethyl group, a dibromomethyl group, and a trifluoromethyl group. Base, trichloromethyl, tribromomethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 4-fluorobutyl, 4-chlorobutyl , 3,3,3-trifluoropropyl, 2,2,2-trifluoro-1-trifluoromethylethyl, perfluorohexyl, perchlorohexyl, 2,4,6-trichlorohexyl, etc. C1～ 6 haloalkyl; hydroxymethyl, 2-hydroxyethyl and the like hydroxy C1-6 alkyl; methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, methoxy n-propyl C1-6 alkoxy group such as ethoxymethyl, ethoxyethyl, n-propoxymethyl, isopropoxyethyl, second butoxymethyl or tert-butoxyethyl C1-6 alkyl group; cyclopropylmethyl, 2-cyclopropylethyl, cyclopentylmethyl, 2-cyclohexylethyl, 2-cyclooctylethyl, etc. C3-8 cycloalkyl C1-6 An alkyl group; a C7 to 11 aralkyl group such as a benzyl group or a phenethyl group; a cyano C1-6 alkyl group such as a cyanomethyl group or a cyanoethyl group; and the like. As in the ¹ X X ² and "C1 ~ 6 alkoxy group" include: methoxy, ethoxy, n-propoxy, n-butoxy, n-pentyloxy, n-hexyloxy, isopropoxy Base, isobutoxy, second butoxy, tert-butoxy, isohexyloxy and the like. The substituent on the "C1-6 alkoxy group" is preferably a halogen group, a C1-6 alkoxy group, a C3-8 cycloalkyl group, or a C6-10 aryl group. Specific examples of the "C1 to 6 alkoxy group having a substituent" include a chloromethoxy group, a dichloromethoxy group, a difluoromethoxy group, a trichloromethoxy group, and a trifluoromethoxy group. A C1 to 6 haloalkoxy group such as a 1-fluoroethoxy group, a 1,1-difluoroethoxy group, a 2,2,2-trifluoroethoxy group or a pentafluoroethoxy group. Specific examples of the hydrazine compound represented by the formula (I) include 9,9-bis(4-hydroxyphenyl)fluorene<9,9-Bis(4-hydroxyphenyl)fluorene>, 9,9-double (4-hydroxy-3-methylphenyl)fluorene <9,9-Bis(4-hydroxy-3-methylphenyl)fluorene>, 2,7-dibromo-9,9-bis(4-hydroxyphenyl)茀<2,7-Dibromo-9,9-bis(4-hydroxyphenyl)fluorene>,9,9-bis(3-amino-4-hydroxyphenyl)fluorene<9,9-Bis(3-amino- 4-hydroxyphenyl)fluorene>, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene <9,9-Bis(4-hydroxy-3,5-dimethylphenyl)fluorene>, 9, 9-bis(4-hydroxy-2,6-dibromophenyl)fluorene <9,9-Bis(4-hydroxy-2,6-dibromolphenyl)fluorene>. [Imidazole compound] Next, the imidazole compound represented by the formula (II) will be described. [R ¹ ] In the formula (II), R ¹ represents a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, or an unsubstituted or substituted C6-10 aryl group. Examples of the "C1 to 6 alkyl group" in R ¹ include the same as those exemplified in the above X ¹ . The substituent on the "C1-6 alkyl group" is preferably a halogen group, a hydroxyl group, a C1-6 alkoxy group, a C3-8 cycloalkyl group, a C6-10 aryl group, or a cyano group. The "C6 to 10 aryl group" in R ¹ may be either a single ring or a polycyclic ring. As long as at least one ring is an aromatic ring, the remaining ring may be either a saturated alicyclic ring, an unsaturated alicyclic ring or an aromatic ring. Examples of the "C6 to 10 aryl group" in R ¹ include a phenyl group, a naphthyl group, an anthracenyl group, an anthracenyl group, a dihydroindenyl group, and a tetrahydronaphthyl group. Examples of the substituent on the "C6-10 aryl group" include a halogen group, a C1-6 alkyl group, a hydroxyl group, a C1-6 alkoxy group, a C1-6-6 halogenated alkoxy group, a cyano group, and a nitro group. [R ² to R ⁴ ] In the formula (II), R ² to R ⁴ each independently represent a hydrogen atom, a halogeno group, an unsubstituted or substituted C 1 to 6 alkyl group, an unsubstituted or substituted group. C6-10 aryl, nitro, or cyano. Examples of the "halo group", the "C1 to 6 alkyl group", and the "C6 to 10 aryl group" in R ² to R ⁴ are the same as those exemplified in the above X ¹ . The substituent on the "C1-6 alkyl group" is preferably a halogen group, a hydroxyl group, a C1-6 alkoxy group, a C3-8 cycloalkyl group, a C6-10 aryl group, or a cyano group. Examples of the substituent on the "C6-10 aryl group" include a halogen group, a C1-6 alkyl group, a hydroxyl group, a C1-6 alkoxy group, a C1-6-6 halogenated alkoxy group, a cyano group, and a nitro group. Specific examples of the imidazole compound represented by the formula (II) include imidazole, 2-ethyl-4-methylimidazole, 1-methylimidazole, 2-methylimidazole, 4-methylimidazole, and 1 -benzyl-2-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2 -phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2 - phenylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, and the like. [Crystal Cage Compound] The crystal cage compound of the present invention is not particularly limited as long as it is a crystal cage compound containing the hydrazine compound represented by the formula (I) and the imidazole compound represented by the formula (II). The cage compound of the present invention may contain a third component such as a solvent, and the third component is preferably 40 mol% or less, more preferably 20 mol% or less, and still more preferably 10 mol% or less. The cage compound of the present invention can be used as a resin hardener for a polyester resin, an epoxy resin, an epoxy-polyester resin, a urethane resin or the like, and can be preferably used as a hardener for an epoxy resin. Further, the cage compound of the present invention may be a liquid which is dissolved in a solvent, and is preferably a powder (precipitated in a solvent). By being in the form of a powder, for example, it can be used for a powder coating. The crystal cage compound of the present invention can be added to a solvent by adding the hydrazine compound represented by the formula (I) and the imidazole compound represented by the formula (II), and then heating or refluxing, if necessary, while stirring. It is obtained by recrystallization and precipitation. Further, in consideration of the solubility in the solvent, it is preferred to dissolve the hydrazine compound represented by the formula (I) and the imidazole compound represented by the formula (II) in a solvent, and then to mix the solutions. As the solvent, water, methanol, ethanol, isopropanol, ethyl acetate, methyl acetate, diethyl ether, dimethyl ether, tetrahydrofuran, 1,4-two can be used. Alkane, acetone, methyl ethyl ketone, acetonitrile, benzene, toluene, hexane, chloroform, dichloromethane, carbon tetrachloride, and the like. The addition ratio of the hydrazine compound represented by the formula (I) and the imidazole compound represented by the formula (II) at the time of production of the cage compound of the present invention is relative to the hydrazine compound (main body) represented by the formula (I). The imidazole compound (guest) represented by the formula (II) is preferably from 0.1 to 5.0 mols, more preferably from 0.5 to 3.0 mols. [Epoxy-hardening resin-forming composition] The epoxy-curable resin-forming composition of the present invention contains an epoxy resin (component (A)) and the above-described cage compound (component (B) of the present invention. There is no particular restriction on the component), and the component (B) is as described above. [Epoxy Resin] As the epoxy resin of the component (A), various conventionally known polyepoxy compounds can be used, and examples thereof include bis(4-hydroxyphenyl)propane diglycidyl ether and bis(4-hydroxy-). 3,5-Dibromophenyl)propane diglycidyl ether, bis(4-hydroxyphenyl)ethane diglycidyl ether, bis(4-hydroxyphenyl)methane diglycidyl ether, resorcinol condensed water Glycerol ether, phloroglucin triglycidyl ether, trihydroxybiphenyl triglycidyl ether, tetraglycidyl benzophenone, bis resorcinol tetraglycidyl ether, tetramethyl bisphenol A diglycidyl ether , bisphenol C diglycidyl ether, bisphenol hexafluoropropane diglycidyl ether, 1,3-bis[1-(2,3-epoxypropoxy)-1-trifluoromethyl-2,2 ,2-trifluoroethyl]benzene, 1,4-bis[1-(2,3-epoxypropoxy)-1-trifluoromethyl-2,2,2-trifluoromethyl]benzene An aromatic glycidyl ether compound such as 4,4'-bis(2,3-epoxypropoxy)octafluorobiphenyl or a phenolic novolac type diepoxide; alicyclic diepoxy condensation An alicyclic aldehyde, an alicyclic diepoxy adipate, an alicyclic diepoxy carboxylic acid ester, a cyclohexene ethylene oxide or the like Polyepoxy compound; diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, dimethyl glycidyl phthalate, hexahydroortho a glycidyl ester compound such as dimethyl glycidyl phthalate, diglycidyl p-hydroxybenzoate, cyclopentane-1,3-dicarboxylic acid diglycidyl ester or dimer acid glycidyl ester; diglycidylglycerol Glycidylamine compounds such as aniline, diglycidyltoluidine, triglycidylaminophenol, tetraglycidyldiaminodiphenylmethane, diglycidyltribromoaniline; diglycidyl carbendazim And a heterocyclic epoxy compound such as glycidyl glycidoxyalkyl carbendazim or isocyanuric acid triglycidyl ester. The ratio of the imidazole compound represented by the formula (II) in the (A) component and the component (B) in the epoxy resin-forming composition of the present invention to the epoxy ring of the epoxy resin as the component (A) 1 mole, preferably containing 0.01 to 1.0 mole of the imidazole compound represented by the formula (II) in the component (B), more preferably 0.1 to 1.0 mole, and still more preferably 0.3 to 1.0 mole. Further, the epoxy resin-forming composition of the present invention can be produced by mixing the components (A) and (B). However, in order to form a sufficiently mixed state, it is usually heated to room temperature to about 100 ° C to be mixed. . In the production of an epoxy hardening resin, the stability of the single liquid at the temperature at this time becomes important. In the composition of the present invention, in addition to the above components, the following components may be added in order to impart desired properties. (1) A curing catalyst for an epoxy resin In the composition of the present invention, in addition to the above-mentioned curing catalyst, a known curing catalyst may be used in combination. For example, 1,5-diazabicyclo[4.3.0]-5-pinene, 1,8-diazabicyclo[5.4.0]-7-undecene, 5,6-dibutyl group a cyclic guanidine compound such as amino-1,8-diazabicyclo[5.4.0]-7-undecene; phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, Anhydride such as maleic anhydride or trimellitic anhydride; 1,4-benzoquinone, 2,5-methylphenylhydrazine, 1,4-naphthoquinone, 2,3-dimethylphenylhydrazine, 2,6 - dimethyl benzoquinone, 2,3-dimethoxy-5-methyl-1,4 phenylhydrazine, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4- Anthracene compound such as benzoquinone; tertiary amine compound such as triethylamine, dimethylbenzylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol; o-phenylenediamine , an aromatic amine compound such as m-phenylenediamine, p-phenylenediamine, diaminodiphenylmethane, diaminodiphenylanthracene or m-xylylenediamine; imidazole, 2-methylimidazole, 2-ethyl- Imidazole compounds such as 4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole; trimethylphosphine, triethyl Phosphine, triphenylphosphine, diphenyl (p-tolyl) phosphine, etc. Phosphine compounds and the like. (2) Hardener Further, a known hardener for hardening an epoxy resin can be used. For example, resorcin, catechol, bisphenol A, and bisphenol F are equivalent to a compound having two phenolic hydroxyl groups in one molecule; a phenolic novolak resin, a cresol novolak resin, and a cresol aralkyl A polyphenol resin such as a base resin, a phenol aralkyl resin, a biphenyl aralkyl resin, a dicyclopentadiene type phenol resin, or a naphthol aralkyl resin. (3) Filler In addition, in order to control the viscosity or the physical properties of the hardened material, the filler may also be formulated. As the filler, an insulating inorganic filler or whiskers or a resin filler can be used. Examples of the insulating inorganic filler include glass, cerium oxide, aluminum oxide, titanium oxide, carbon black, mica, and boron nitride. Examples of the whiskers include aluminum borate, aluminum titanate, zinc oxide, calcium citrate, magnesium sulfate, and boron nitride. As the resin filler, a polyurethane resin, a polyimide resin, or the like can be used. Further, metal particles such as gold, silver, copper, nickel, and solder, and conductive filler such as carbon may be used in the case of forming an adhesive for bonding electronic parts. (4) Other Additives Further, in the range which does not hinder the desired target characteristics of the present invention, a mold release agent, a leveling agent, a decane coupling agent, a flame retardant, an antioxidant, a colorant, an anthrone may be blended. Known additives such as a sling agent and an ion scavenger. [Epoxy-Cured Resin] The method for producing the epoxy-curable resin of the present invention is not particularly limited as long as it is a method of heat-treating the epoxy-curable resin-forming composition, and is usually heated. The heating temperature for the treatment is 60 to 250 ° C, preferably 100 to 200 ° C, and it is preferred to carry out curing at this temperature for a short period of time. [Use for Use] The crystal cage of the present invention is an epoxy resin hardening catalyst excellent in potential. The epoxy resin-containing composition containing the same is stable for a long period of time when stored at around room temperature, and can be rapidly cured at a relatively low temperature when it is cured. The use of the epoxy resin-forming composition of the present invention is not particularly limited, and examples thereof include an underfill, a thermosetting prepreg, a casting material, a structural adhesive, and a powder coating. In particular, a prepreg for a printed circuit board, a semiconductor, a sealing material for an electronic component, an adhesive for an electronic component, a conductive adhesive, a resist ink, an insulating material, or the like can be used. EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the technical scope of the present invention is not limited to the examples. [Example 1] (Preparation of crystal cage compound) 4.40 g of 9,9-bis(4-hydroxyphenyl)fluorene and 2.76 g of 2-ethyl-4-methylimidazole were added to a flask (hereinafter, 2E4MZ) and 43.0 g of a hexane-ethyl acetate mixed solvent were heated and refluxed for 3 hours while stirring. After cooling to room temperature, it was filtered and dried under reduced pressure to give 6.46 g of product. For the obtained product, XRD (X Ray Diffraction), TG-DSC (Thermogravimetry-Differential Scanning Calorimetry), and ¹ H-NMR (Nuclear Magnetic Resonance, It was confirmed by nuclear magnetic resonance to confirm that it is a crystal cage compound A having a molar ratio of 9,9-bis(4-hydroxyphenyl)fluorene to 2E4MZ of 1:2. The results of these measurements are shown in FIGS. 1A to 1C. The measurement conditions of each spectrum are as follows (the same applies to other examples). [XRD measurement] Apparatus: Ultima IV (manufactured by Rigaku Co., Ltd.) X-ray source: Cu 40 kV/40 mA Measurement method: concentrating filter: Kβ filter scanning speed: 5°/min. [TG-DSC measurement] Device: TGA-DSC1 (manufactured by Mettler-Toledo) Al PAN seal measurement temperature range: room temperature to 500 ° C Temperature increase rate: 20 ° C / min Sample size: about 3 mg [ ¹ H-NMR measurement] Device: JNM-AL400 (Japan Ethylene company manufacture) Deuterated solvent: CD ₃ OD Cumulative number: 16 times (XRD measurement) The diffraction pattern of 9,9-bis(4-hydroxyphenyl)fluorene and 2E4MZ disappeared as a raw material, and a novel winding was observed. The pattern was shot, and thus the crystal cage was confirmed (Fig. 1A). (Measurement by TG-DSC) Regarding the onset temperature of the endothermic peak accompanying melting, 9,9-bis(4-hydroxyphenyl)fluorene was 221 ° C, and 2E4MZ was 48 ° C. On the other hand, the cage compound was 120 °C. Further, regarding the initial temperature at which the weight is reduced, 9,9-bis(4-hydroxyphenyl)anthracene is 326 ° C, and 2E4MZ is 162 ° C. In contrast, the weight loss of the crystal cage compound derived from 2E4MZ is 165 ° C. By moving to the high temperature side, it is understood that the thermal stability of 2E4MZ is improved by the crystal cage. (FIG. 1B) ⁽¹ H-NMR measurement), and the peak integration value according fluorenyl attributed to 9,9-bis (4-hydroxyphenyl) 2E4MZ, the known 9,9-bis (4-hydroxyphenyl) fluorene and 2E4MZ It was crystallized in the form of 1 to 2 (Fig. 1C). [Example 2] (Preparation of a composition for forming an epoxy-curable resin) 5 g of an epoxy resin (trade name: Epotohto (registered trademark) YD-128, manufactured by Toho Chemical Co., Ltd.) in terms of 2E4MZ After the crystal cage compound A was added in an amount of 0.2 g (corresponding to 4 phr), the mixture was kneaded at 25 ° C for 10 minutes to obtain a composition A for forming an epoxy resin. (DSC measurement of the epoxy resin-forming composition) The epoxy resin-hardening resin composition was measured by the DSC measuring apparatus (DSC1, the Mettler-Toledo company) so that it may be about 8-10 mg in the aluminum container. A, under nitrogen purge (nitrogen flow rate: 50 mL/min), from 30 ° C to 250 ° C (heating rate: 10 k / min), and determination of the hardening reaction based on the epoxy resin forming composition A heat. The measurement results of the time and temperature on the horizontal axis are shown in Fig. 1D. The epoxy resin-forming composition A containing the crystal cage compound A has a higher rising temperature of the exothermic peak accompanying the epoxy hardening than the composition for forming an epoxy-curable resin containing only 2E4MZ, thereby confirming the crystal cage-based Increased thermal stability (Figure 1D). [Example 3] (Preparation of crystal cage compound) In Example 1, 2E4MZ was changed to 2.06 g of 1-methylimidazole (hereinafter referred to as 1 MZ), and the solvent alkane-ethyl acetate mixed solvent was changed to itself. The alkane was prepared in the same manner as above to obtain 5.86 g of a product. According to the XRD, TG-DSC and ¹ H-NMR measurement of the obtained product, it was confirmed that 9,9-bis(4-hydroxyphenyl)fluorene and 1 MZ were crystallized at a molar ratio of 1:2. Crystal cage compound B. The measurement results are shown in Figs. 2A to 2C. (XRD measurement) The diffraction pattern of 9,9-bis(4-hydroxyphenyl)fluorene as a raw material disappeared, and a novel diffraction pattern was observed, so that crystal cage formation was confirmed (Fig. 2A). (Measured by TG-DSC). 1 MZ is a liquid, and the onset temperature of the endothermic peak accompanying decomposition is 117 ° C. On the other hand, the endothermic peak accompanying the crystal melting of the cage compound is 122 ° C. Further, regarding the initial temperature at the time of weight reduction, 1 MZ was observed from the vicinity of room temperature, whereas the weight loss of the crystal cage compound derived from 1 MZ was 113 ° C, and it was moved to the high temperature side, and it was found that the crystal cage was formed. Increased thermal stability (Figure 2B). ⁽¹ H-NMR measurement), and the peak integration value according fluorenyl attributed to 9,9-bis (4-hydroxyphenyl) 1MZ, the known 9,9-bis (4-hydroxyphenyl) fluorene, and 2-to-one 1MZ The form is caged (Fig. 2C). [Example 4] (Preparation of a composition for forming an epoxy-curable resin) The preparation of the composition for forming an epoxy-curable resin of Example 2 was carried out by changing the crystal cage compound A to the crystal cage compound B, and the same. The preparation was carried out to obtain a composition B for forming an epoxy resin. (Measurement by DSC of the epoxy resin-forming composition) The DSC measurement of the epoxy resin-forming composition of Example 2 was carried out, and the epoxy resin-forming composition A was changed to the epoxy resin-forming composition. B. Measurement was performed in the same manner as above, and heat generation by the curing reaction was measured. The measurement results of the time and temperature on the horizontal axis are shown in Fig. 2D. Compared with the composition for forming an epoxy-curable resin containing only 1 MZ, the epoxy resin-forming composition B containing the crystal cage compound B has a relatively slow rise temperature of the exothermic peak accompanying epoxy hardening, thereby confirming the crystal cage-based Improved thermal stability (Figure 2D). [Example 5] (Preparation of crystal cage compound) In Example 1, 2E4MZ was changed to 2.06 g of 2-methylimidazole (hereinafter referred to as 2MZ), and the solvent-hexane-ethyl acetate mixed solvent was changed to toluene. The preparation was carried out in the same manner as above, and 5.96 g of a product was obtained. The obtained product was confirmed to be a 1:2 crystal of 9,9-bis(4-hydroxyphenyl)fluorene and 2 MZ molar ratio by XRD, TG-DSC and ¹ H-NMR measurement. Cage compound C. The measurement results are shown in Figs. 3A to 3C. (XRD measurement) The diffraction pattern of 9,9-bis(4-hydroxyphenyl)fluorene and 2MZ as a raw material disappeared, and a novel diffraction pattern was observed, thereby confirming the crystal cage (Fig. 3A). (Measured by TG-DSC). Regarding the onset temperature of the endothermic peak accompanying the melting, 2 MZ was 141 ° C, whereas in the case of the cage compound, it was 169 ° C. Further, regarding the initial temperature at the time of weight reduction, 2 MZ is 162 ° C. On the other hand, the weight loss of the crystal cage compound derived from 2 MZ is 169 ° C, and the temperature is shifted to the high temperature side, so that thermal stability due to crystal cage formation is known. Improve (Figure 3B). ⁽¹ H-NMR measurement), and the peak integration value according fluorenyl attributed to 9,9-bis (4-hydroxyphenyl) 2MZ, the known 9,9-bis (4-hydroxyphenyl) fluorene, and 2-to-one 2MZ The form is caged (Fig. 3C). [Example 6] (Preparation of a composition for forming an epoxy resin) The preparation of the epoxy resin-forming composition of Example 2 was carried out by changing the crystal cage compound A to the crystal cage compound C, and the same manner. The preparation was carried out to obtain a composition C for forming an epoxy resin. (Measurement by DSC of the epoxy resin-forming composition) The DSC measurement of the epoxy resin-forming composition of Example 2 was carried out, and the epoxy resin-forming composition A was changed to the epoxy resin-forming composition. C, except that the measurement was performed in the same manner, and the heat generation by the hardening reaction was measured. The measurement results of the time and temperature on the horizontal axis are shown in Fig. 3D. The rise temperature of the exothermic peak accompanying epoxy hardening of the epoxy resin-forming composition C was slower than that of 2 MZ, and the improvement in thermal stability by crystal cage formation was confirmed (FIG. 2D). [Example 7] In the same manner as in Example 1, except that the amount of 2E4MZ was changed from 2.76 g to 2.08 g, the preparation was carried out in the same manner to obtain a product of 6.27 g. It was confirmed by XRD, TG-DSC and ¹ H-NMR measurement of the obtained product that it was crystallized in the form of 2,3-bis(4-hydroxyphenyl)fluorene and 2E4MZ in the form of 2 to 3. Cage Compound D. The measurement results are shown in Figs. 4A to 4C. (XRD measurement) In the same manner as in Example 1, the diffraction pattern derived from the raw material disappeared, and a novel diffraction pattern was observed, so that the crystal cage was confirmed (Fig. 4A). (Measured by TG-DSC). In the same manner as in the first embodiment, the endothermic peak at the time of melting of the crystal and the initial temperature at the time of weight reduction were shifted to the high temperature side as compared with 2E4MZ alone, and the thermal stability of 2E4MZ was improved by the crystal cage. (Fig. 4B). ⁽¹ H-NMR measurement) in the same manner as in Example 1, the peak integration value, known 9,9-bis (4-hydroxyphenyl) fluorene and 2E4MZ 2 is in the form of clathrate of the 3 (FIG. 4C). [Example 8] (Preparation of a composition for forming an epoxy-curable resin) The preparation of the composition for forming an epoxy-curable resin of Example 2 was carried out by changing the crystal cage compound A to the crystal cage compound D, and the same. The preparation was carried out to obtain a composition B for forming an epoxy resin. (Measurement by DSC of the epoxy resin-forming composition) The DSC measurement of the epoxy resin-forming composition of Example 2 was carried out, and the epoxy resin-forming composition A was changed to the epoxy resin-forming composition. D, except that the measurement was performed in the same manner, and DSC measurement was performed. The measurement results of the time and temperature on the horizontal axis are shown in Fig. 4D. In the same manner as in the case of the second embodiment, the epoxy resin cured composition-forming composition D containing the crystal cage compound D has a higher rising temperature of the exothermic peak accompanying the epoxy curing, and the thermal stability of the resin is improved by the crystal cage (Fig. 4D).

Fig. 1A is a graph showing the results of XRD measurement of the cage compound A obtained in Example 1. Fig. 1B is a graph showing the results of TG-DSC measurement of the crystal cage compound A obtained in Example 1. Fig. 1C is a view showing the ¹ H-NMR spectrum of the cage compound A obtained in Example 1. Fig. 1D is a view showing the results of DSC measurement of the composition A for forming an epoxy resin which is obtained in Example 2. Fig. 2A is a graph showing the results of XRD measurement of the cage compound B obtained in Example 3. Fig. 2B is a graph showing the results of TG-DSC measurement of the cage compound B obtained in Example 3. FIG. 2C are diagrams FIGS H-NMR spectrum of the clathrate obtained in Example 3 of the embodiment ^B-1 compound. 2D is a view showing the results of DSC measurement of the epoxy resin-forming composition obtained in Example 4. Fig. 3A is a graph showing the results of XRD measurement of the cage compound C obtained in Example 5. Fig. 3B is a graph showing the results of TG-DSC measurement of the cage compound C obtained in Example 5. Fig. 3C is a view showing the ¹ H-NMR spectrum of the cage compound C obtained in Example 5. Fig. 3D is a graph showing the results of DSC measurement of the epoxy resin-forming composition obtained in Example 6. Fig. 4A is a graph showing the results of XRD measurement of the cage compound D obtained in Example 7. Fig. 4B is a graph showing the results of TG-DSC measurement of the cage compound D obtained in Example 7. Fig. 4C is a view showing the ¹ H-NMR spectrum of the cage compound D obtained in Example 7. 4D is a view showing the results of DSC measurement of the epoxy resin-forming composition obtained in Example 8.

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Claims (11)

A crystal cage compound comprising the hydrazine compound represented by the formula (I) and the imidazole compound represented by the formula (II), [Chemical Formula 1] (wherein X ¹ each independently represents a halogeno group, an unsubstituted or substituted C1-6 alkyl group, a hydroxyl group, an unsubstituted or substituted C1-6 alkoxy group, an amine group, a nitro group Or cyano; m represents any integer from 0 to 4, n represents any integer from 0 to 4; X ² independently represents a halo group, an unsubstituted or substituted C1 to 6 alkyl group, a hydroxyl group , unsubstituted or substituted C 1 -6 alkoxy, amine, nitro, or cyano; p represents any integer from 0 to 4, q represents any integer from 0 to 4), [Chemical 2 ] (wherein R ¹ represents a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, or an unsubstituted or substituted C6-10 aryl group; and R ² to R ⁴ each independently represent a hydrogen atom; , halo, unsubstituted or substituted C1-6 alkyl, unsubstituted or substituted C6-10 aryl, nitro, or cyano). The cage compound of claim 1, wherein the hydrazine compound represented by the formula (I) is 9,9-bis(4-hydroxyphenyl)fluorene. A hardening catalyst for an epoxy resin comprising the crystal cage compound of claim 1 or 2. A composition for forming an epoxy resin comprising the following components (A) and (B): (A) an epoxy resin, (B) an anthracene compound represented by the formula (I), and a formula (II) The crystal cage compound represented by the imidazole compound as a main component, [Chemical 3] (wherein X ¹ each independently represents a halogeno group, an unsubstituted or substituted C1-6 alkyl group, a hydroxyl group, an unsubstituted or substituted C1-6 alkoxy group, an amine group, a nitro group , or cyano; m represents any integer of 0 to 4, n-represents any one of an integer from 0 to 4; X ² each independently represents halo, unsubstituted or substituted with C1 ~ 6 alkyl group, the hydroxy , unsubstituted or substituted C 1 -6 alkoxy, amine, nitro, or cyano; p represents any integer from 0 to 4, q represents any integer from 0 to 4), ] (wherein R ¹ represents a hydrogen atom, an unsubstituted or substituted C1-6 alkyl group, or an unsubstituted or substituted C6-10 aryl group; and R ² to R ⁴ each independently represent a hydrogen atom; , halo, unsubstituted or substituted C1-6 alkyl, unsubstituted or substituted C6-10 aryl, nitro, or cyano). The epoxy resin-forming composition according to claim 4, wherein the imidazole compound represented by the formula (II) in the component (B) is contained with respect to the epoxy ring 1 mol of the epoxy resin as the component (A). 0.01 to 1.0 m. The epoxy resin hardening resin-forming composition according to claim 4 or 5, wherein the hydrazine compound represented by the formula (I) is 9,9-bis(4-hydroxyphenyl)fluorene. A method for producing an epoxy resin, which is obtained by heat-treating a composition for forming an epoxy resin according to any one of claims 4 to 6, and curing the epoxy resin. An epoxy-hardening resin obtained by heat-treating the epoxy resin-forming composition according to any one of claims 4 to 6 and curing it. The epoxy resin-forming composition according to claim 4, which further comprises at least one selected from the group consisting of a cyclic hydrazine compound, an acid anhydride, a hydrazine compound, a tertiary amine compound, an aromatic amine compound, an imidazole compound, and an organic phosphine compound. The epoxy resin is used as a hardening catalyst. The epoxy resin-forming composition according to claim 4, which further contains a curing agent. The epoxy resin-forming composition according to claim 4, which further contains a filler.