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WO2024219430A1 - Latent curing agent and one-pack epoxy resin composition - Google Patents

Latent curing agent and one-pack epoxy resin composition Download PDF

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Publication number
WO2024219430A1
WO2024219430A1 PCT/JP2024/015300 JP2024015300W WO2024219430A1 WO 2024219430 A1 WO2024219430 A1 WO 2024219430A1 JP 2024015300 W JP2024015300 W JP 2024015300W WO 2024219430 A1 WO2024219430 A1 WO 2024219430A1
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Prior art keywords
epoxy
epoxy resin
general formula
bonded
group
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PCT/JP2024/015300
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French (fr)
Japanese (ja)
Inventor
雄希 藤田
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株式会社T&K Toka
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Publication of WO2024219430A1 publication Critical patent/WO2024219430A1/en

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  • the present invention relates to a latent curing agent and a one-part epoxy resin composition. According to the present invention, it is possible to obtain a latent curing agent that exhibits excellent storage stability.
  • Amine compounds are widely used as curing agents for epoxy resins.
  • imidazole curing agents cure sufficiently by heat curing even when the amount mixed with the epoxy resin is small, resulting in a cured product with a high glass transition point.
  • an object of the present invention is to provide an imidazole-based hardener that exhibits high storage stability without encapsulation.
  • the present inventors conducted extensive research into imidazole-based curing agents exhibiting high storage stability, and as a result, surprisingly found that an imidazole-based curing agent exhibiting high storage stability can be obtained by adding an epoxy compound having a specific structure to an imidazole compound.
  • the present invention is based on these findings.
  • the present invention provides [1] General formula (1), (2), (3), (4), or (5):
  • X represents general formula (6), (7), or (8):
  • R2 is a hydrogen atom or an -OCH2 epoxy group
  • R3 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • Y is represented by the general formula (9):
  • R 4 is an —OCH 2 epoxy group
  • R 3 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • Z is represented by the general formula (10): (wherein the two bonds may be bonded to any carbon atom in the structure of general formula (10), or two bonds may be bonded to one carbon atom),
  • R 1 is a single bond or an alkylene group having 1 to 3 carbon atoms
  • R 1 bonded to X may be bonded to either of the two ring structures of X, n is 1 to 15, m is 0 to 15, one R 2 of X present at the terminal is an
  • the latent hardener of the present invention can exhibit excellent storage stability.
  • Latent Curing Agent The latent curing agent of the present invention is represented by the general formula (1), (2), (3), (4), or (5): and an imidazole compound are added.
  • Epoxy compounds The epoxy compound is not particularly limited as long as it has any one of the structures of general formulas (1) to (5). By having the above structure, the epoxy compound can form a rigid skeleton. By forming a rigid skeleton, it is possible to improve the softening point of the epoxy compound and improve the storage stability of the latent curing agent.
  • X of the epoxy compound is represented by the general formula (6), (7), or (8): It is a group represented by the following formula:
  • R2 is a hydrogen atom or an -OCH2 epoxy group.
  • X is present at the end of an epoxy compound, at least one R2 is an -OCH2 epoxy group.
  • the two R2s of X are -OCH2 epoxy groups.
  • R3 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. The alkyl group having 1 to 3 carbon atoms is specifically a methyl group, an ethyl group, or a propyl group.
  • R3 is preferably a hydrogen atom or a methyl group.
  • Y is represented by the general formula (9): It is a group represented by the following formula: R4 is an -OCH2 epoxy group, and R3 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • the alkyl group having 1 to 3 carbon atoms is specifically a methyl group, an ethyl group, or a propyl group.
  • R3 is preferably a hydrogen atom or a methyl group.
  • Z is represented by the general formula (10):
  • the two bonds can be bonded to any carbon atom in the above structure. Specifically, they may be bonded to carbon atoms of two benzene rings. They may also be bonded to carbon atoms forming a cyclopentane ring, or two bonds may be bonded to one carbon atom.
  • R 1 is a single bond or an alkylene group having 1 to 3 carbon atoms.
  • the alkylene group having 1 to 3 carbon atoms is specifically a methylene group, an ethylene group, or a propyl group.
  • R 1 is preferably a single bond or a methylene group.
  • R 1 bonded to X may be bonded to either of the two ring structures of X.
  • n is 1 to 15, preferably 1 to 10, more preferably 1 to 8, even more preferably 1 to 5, even more preferably 1 to 3, even more preferably 1 or 2, and most preferably 1.
  • the epoxy compound represented by general formula (1) is a polymer, and may be a polymer having a single number of n, or a mixture of polymers having a number of n of 1 to 15. In the case of a mixture, n in general formula (1) means the average number of repetitions. In the case of a single polymer, n is an integer.
  • m is 0 to 15, preferably 0 to 10, more preferably 0 to 8, even more preferably 0 to 5, even more preferably 0 to 3, even more preferably 0 to 2, and even more preferably 0 or 1.
  • the epoxy compound represented by general formula (2) is a polymer, and may be a single polymer having m, or may be a mixture of polymers having m of 0 to 15. In the case of a mixture, m in general formula (1) means the average number of repetitions. In the case of a single polymer, m is an integer.
  • R2 of the X present at the terminal is an -OCH2 epoxy group.
  • a hydrogen atom is bonded to the bond on the terminal side of the X and Y present at the terminal.
  • the X and Y at the terminal are monovalent groups, not divalent groups.
  • the number of epoxy groups in the epoxy compound is not particularly limited as long as the effects of the present invention can be obtained, but for example, the upper limit is 5 or less, preferably 4 or less, and more preferably 3 or less.
  • the lower limit is not particularly limited as long as the effects of the present invention can be obtained, but is preferably 2 or more.
  • the number of -OCH2 epoxy groups in the repeating unit in general formula (1) or (2) is 1 or 2.
  • the epoxy compound represented by general formula (1) or (2) is a polymer, and as described above, it may be a mixture of polymers in which n is 1 to 15, or a mixture of polymers in which m is 0 to 15.
  • the average number of epoxy groups contained in the epoxy compound represented by general formula (1) or (2) is, for example, 5 or less in the upper limit, preferably 4 or less, and more preferably 3 or less.
  • the lower limit is not particularly limited as long as the effects of the present invention can be obtained, but is preferably 2 or more.
  • the epoxy compound used in the present invention is not limited, but specific examples thereof include compounds represented by the following formula:
  • m is 0 to 15 and l is 1 to 15.
  • m is 0 to 15, preferably 0 to 10, more preferably 0 to 8, even more preferably 0 to 5, even more preferably 0 to 3, even more preferably 0 to 2, and even more preferably 0 or 1.
  • the epoxy compound represented by the above formula is a polymer, and may be a single polymer with m as a number, or a mixture of polymers with m as a number from 0 to 15. In the case of a mixture, m in the above formula means the average number of repetitions. In the case of a single polymer, m is an integer.
  • l is 1 to 15, preferably 1 to 10, more preferably 1 to 8, even more preferably 1 to 5, even more preferably 1 to 3, even more preferably 1 or 2, and most preferably 1.
  • the epoxy compound represented by the above formula is a polymer, and may be a single polymer with l as a number, or a mixture of polymers with l as a number from 1 to 15. In the case of a mixture, l in the above formula means the average number of repetitions. In the case of a single polymer, l is an integer.
  • the imidazole compound is not limited to, but may be, for example, a compound represented by the general formula (11): (wherein R 13 and R 14 each independently represent a hydrogen atom, or a linear or branched alkyl group or aromatic group having 1 to 17 carbon atoms) can be used.
  • imidazole 4-cyanomethylimidazole, 4-ethylimidazole, 4,5-bis(hydroxymethyl)imidazole, 2-phenylimidazole, 4-phenylimidazole, 4-hydroxymethyl-5-methylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-propylimidazole, 2-butylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2,4-dimethylimidazole, 2-methyl-4-ethylimidazole, 2-methyl-4-propylimidazole
  • the imidazole include 2-methyl-4-butylimidazole, 2-ethyl-4-methylimidazole, 2,4-diethylimidazole, 2-ethyl-4-propylimidazole, 2-ethyl-4-butylimidazole, 2-propyl-4-methylimidazole, 2-propyl-4-methylimi
  • Preferred examples include 2-methylimidazole, 2-ethylimidazole, 2,4-dimethylimidazole, 2-methyl-4-ethylimidazole, 2-ethyl-4-methylimidazole, and 2,4-diethylimidazole.
  • Preferred are imidazole, 2-methylimidazole, and 2-ethyl-4-methylimidazole.
  • the contents of the imidazole compound and epoxy compound contained in the latent curing agent of the present invention are not particularly limited, but the epoxy compound is 0.5 to 2.0 equivalents per mole of the imidazole compound, more preferably 0.8 to 1.7 equivalents, and even more preferably 1.0 to 1.5 equivalents.
  • One-component epoxy resin composition contains the latent curing agent and an epoxy resin.
  • the epoxy resin contained in the one-component epoxy resin composition of the present invention is an epoxy resin having an average of one or more epoxy groups in one molecule, and preferably an epoxy resin having an average of more than one epoxy group.
  • the number of epoxy groups is not particularly limited as long as it is an average of one or more, but is preferably two or more.
  • the upper limit of the epoxy groups is not particularly limited when the effect of the epoxy resin in the epoxy resin composition is taken into consideration.
  • the "average” means the average number of epoxy groups in one molecule when two or more types of epoxy resins are mixed.
  • epoxy resins include epoxy compounds (polyglycidyl ethers) of mononuclear polyhydric phenol compounds, epoxy compounds (polyglycidyl ethers) of polynuclear polyhydric phenol compounds, epoxy compounds (polyglycidyl ethers) of polyhydric alcohols, epoxy compounds (polyglycidyl ether esters) of hydroxycarboxylic acids, epoxy compounds (polyglycidyl esters) of aliphatic, aromatic or alicyclic polybasic acids, epoxy compounds (glycidyl ether esters) of hydroxycarboxylic acids, epoxy compounds (glycidyl esters) of polyvalent carboxylic acids, epoxy compounds (glycidyl aminoglycidyl ethers) of aminophenols, epoxy compounds (glycidyl aminoglycidyl ethers) of polyvalent amines, and other epoxy compounds.
  • mononuclear polyhydric phenol compounds include catechol, resorcinol, hydroquinone, and halogen (e.g., chlorine, bromine) derivatives of these compounds.
  • polynuclear polyhydric phenol compound examples include bisphenol F, bisphenol A, bisphenol S, bisphenol AD, tetramethylbisphenol F, tetramethylbisphenol A, or halogen derivatives thereof; naphthol, biphenol, bixylenol, bisresorcinol, trihydroxybiphenyl, tetrahydroxyphenylethane, phenol novolac, cresol novolac, terpene phenol, phenolized dicyclopentadiene, or halogen derivatives thereof.
  • polyhydric alcohols include glycerin, neopentyl glycol, ethylene glycol, propylene glycol, butylene glycol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol, thiodiglycol, trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol, and bisphenol A-ethylene oxide or propylene oxide adducts.
  • hydroxycarboxylic acids include p-hydroxybenzoic acid and ⁇ -hydroxynaphthoic acid.
  • polyvalent carboxylic acids include phthalic acid, methylphthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, decanedioic acid, dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and polymerized fatty acids.
  • aminophenols include p-aminophenol and p-aminoalkylphenol.
  • polyamines include aniline, o-toluidine, tribromoaniline, m-xylylenediamine, 1,2-diaminocyclohexane, 1,3-bisaminomethylcyclohexane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodicyclohexylmethane, 2,2'-dimethyl-4,4'-4,4'-diaminodicyclohexylmethane, and diaminodiphenylsulfone.
  • the other epoxy compounds include epoxidized polyolefins, epoxidized polybutadiene, epoxidized soybean oil, glycidyl hydantoin, di- or triglycidyl isocyanurate, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, and 3,4-epoxycyclohexyl-3,4-epoxycyclohexane carboxylate.
  • epoxy resins exemplified above it is particularly preferable to use bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, naphthol type epoxy resin, or diaminodiphenylmethane type epoxy resin, because the cured product obtained by curing the epoxy resin composition of the present invention has excellent heat resistance, electrical properties such as insulation, and adhesive properties.
  • the above epoxy resins can be used alone or in combination of two or more types.
  • monofunctional epoxy compounds can be used in combination within the scope of not impairing the effects of the present invention.
  • examples include butyl glycidyl ether, phenyl glycidyl ether, higher alcohol glycidyl ether, benzoic acid glycidyl ester, branched fatty acid glycidyl ester (Cardura E; manufactured by Momentive Performance Materials), styrene oxide, etc.
  • these monofunctional epoxy compounds have low viscosity, which is advantageous in terms of handling the epoxy resin composition in particular, but since they may reduce the mechanical properties and heat resistance (glass transition temperature) of the final epoxy resin cured product, their amount should be kept as small as possible.
  • the monofunctional epoxy resins can be used alone or in combination of two or more types.
  • ⁇ Other Components in Epoxy Resin Composition> To the epoxy resin composition of the present invention, various additives may be added as necessary within the range in which the effects of the present invention can be obtained, for example, surfactants, flow improvers, thixotropy imparting agents, extender pigments and the like, coloring pigments or dyes for coloring, rust-preventive pigments or rust inhibitors, other resin powders, waxes, etc.
  • solvents for lowering the viscosity of the epoxy resin composition may be added, for example, aromatic solvents such as toluene and xylene, ketone solvents such as dimethyl ketone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ester solvents such as ethyl acetate and butyl acetate, alcohol solvents such as methanol, ethanol and isopropyl alcohol, glycol or glycol ester solvents such as methoxypropanol and methoxypropyl acetate, etc.
  • aromatic solvents such as toluene and xylene
  • ketone solvents such as dimethyl ketone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone
  • ester solvents such as ethyl acetate and butyl acetate
  • alcohol solvents such as methanol, ethanol and isoprop
  • the weight ratio or molar ratio of the latent curing agent to the epoxy resin is not particularly limited as long as the one-component epoxy resin composition can be cured to an arbitrary gelation degree. That is, the curable epoxy resin composition is used for various applications such as adhesives, paints, coatings, sealing, impregnation, etc., and the desired curing state, curing time, use conditions, etc. differ depending on the application, so the weight ratio or molar ratio of the latent curing agent to the epoxy resin having more than one epoxy group on average in the molecule in the one-component epoxy resin composition can be appropriately selected.
  • the content of the epoxy resin and the latent curing agent in the one-component epoxy resin composition of the present invention is preferably 2 to 50 parts by weight, more preferably 4 to 40 parts by weight, and most preferably 5 to 30 parts by weight, of the latent curing agent relative to 100 parts by weight of the epoxide compound.
  • the one-part curable epoxy resin composition of the present invention is a thermosetting epoxy resin composition that does not cure at room temperature (e.g., 0°C to 40°C), but cures rapidly when heated (e.g., 80°C to 200°C), and can be used as an adhesive, paint, coating, sealant, or impregnator.
  • the epoxy resin cured product of the present invention can be obtained by heating the one-part epoxy resin composition.
  • Specific examples of the cured product include adhesives, painted surfaces, coatings, sealing materials, and impregnated materials.
  • the method for producing the latent curing agent of the present invention comprises adding (1), (2), (3), (4), or (5) to an imidazole compound:
  • X represents general formula (6), (7), or (8):
  • R2 is a hydrogen atom or an -OCH2 epoxy group, and R3 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • Y is represented by the general formula (9):
  • R 4 is an —OCH 2 epoxy group, and R 3 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • Z is represented by the general formula (10): (wherein the two bonds may be bonded to any carbon atom in the structure of general formula (10), and two bonds may be bonded to one carbon atom),
  • R 1 is a single bond or an alkylene group having 1 to 3 carbon atoms, and R 1 bonded to X may be bonded to either of the two ring structures of X;
  • the "imidazole compound” and “epoxy compound” in the method for producing the latent curing agent of the present invention can be any of those described above for the "latent curing agent” without any limitation.
  • the weight ratio or molar ratio of the epoxy compound to the imidazole compound in the addition step is not limited, but the epoxy compound is used in an amount of 0.5 to 2.0 equivalents, more preferably 0.8 to 1.7 equivalents, and even more preferably 1.0 to 1.5 equivalents, relative to 1 mole of the imidazole compound.
  • the reaction temperature is not particularly limited, but is, for example, 60 to 150°C, and preferably 80 to 120°C.
  • the mechanism by which the storage stability of the latent curing agent of the present invention is improved has not been analyzed in detail, but can be assumed as follows. However, the present invention is not limited to the following assumption.
  • the imidazole compound used in the latent curing agent has a rigid structure. It is believed that this improves the softening point of the latent curing agent of the present invention and increases the glass transition point of the latent curing agent resin. It is presumed that the increase in Tg of the curing agent resin reduces low molecular weight components that dissolve from the surface of the curing agent particles into the epoxy resin in the epoxy resin formulation, resulting in improved storage stability.
  • Example 1 In this example, 2-methylimidazole was used as the imidazole compound, and XD-1000 (dicyclopentadiene-phenol type epoxy resin, epoxy equivalent: 250 g/eq, manufactured by Nippon Kayaku Co., Ltd.) was used as the epoxy compound to prepare a latent curing agent. Specifically, 82 parts of 2-methylimidazole and 82 parts of a 1:1 (weight ratio) mixed solvent of xylene and 2-propanol were added to a 1 L four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was heated to 80°C while stirring under a nitrogen stream.
  • XD-1000 dicyclopentadiene-phenol type epoxy resin, epoxy equivalent: 250 g/eq, manufactured by Nippon Kayaku Co., Ltd.
  • the obtained latent curing agent 10 parts were mixed with 100 parts of an epoxy resin (jER828 (Mitsubishi Chemical Corporation, bisphenol A type epoxy resin, epoxy equivalent: 190 g/eq)), and the storage stability and Tg of the cured product were measured.
  • an epoxy resin jER828 (Mitsubishi Chemical Corporation, bisphenol A type epoxy resin, epoxy equivalent: 190 g/eq)
  • the storage stability and Tg of the cured product were measured.
  • the curing agent of the present invention exhibited a high softening point, and the one-part epoxy resin composition exhibited excellent storage stability.
  • the obtained cured product exhibited a Tg of 150° C. or more.
  • Example 2 In this example, the procedure of Example 1 was repeated, except that the amount of XD-1000 was changed to the amount shown in Table 1. As shown in Table 1, the curing agent of the present invention exhibited a high softening point, and the one-part epoxy resin composition exhibited excellent storage stability. In addition, the obtained cured product exhibited a Tg of 150° C. or more.
  • Example 3 In this example, the procedure of Example 1 was repeated, except that 2-ethyl-4-methylimidazole was used instead of 2-methylimidazole.
  • the composition is shown in Table 1.
  • the curing agent of the present invention exhibited a high softening point, and the one-part epoxy resin composition exhibited excellent storage stability.
  • the obtained cured product exhibited a Tg of 150° C. or more.
  • Example 4 In this example, the procedure of Example 1 was repeated, except that imidazole was used instead of 2-methylimidazole.
  • the composition is shown in Table 1.
  • Table 1 the curing agent of the present invention exhibited a high softening point, and the one-part epoxy resin composition exhibited excellent storage stability.
  • the obtained cured product exhibited a Tg of 150° C. or more.
  • Example 5 In this example, the procedure of Example 1 was repeated, except that NC-7000L (naphthol-cresol novolac type epoxy resin, epoxy equivalent: 230 g/eq, manufactured by Nippon Kayaku Co., Ltd.) was used instead of XD-1000.
  • NC-7000L naphthol-cresol novolac type epoxy resin, epoxy equivalent: 230 g/eq, manufactured by Nippon Kayaku Co., Ltd.
  • the composition is shown in Table 1.
  • Table 1 the curing agent of the present invention exhibited a high softening point, and the one-part epoxy resin composition exhibited excellent storage stability.
  • the obtained cured product exhibited a Tg of 150° C. or more.
  • Example 6 In this example, the procedure of Example 1 was repeated, except that NC-3000H (biphenyl-novolac type epoxy resin, epoxy equivalent: 290 g/eq, manufactured by Nippon Kayaku Co., Ltd.) was used instead of XD-1000.
  • NC-3000H biphenyl-novolac type epoxy resin, epoxy equivalent: 290 g/eq, manufactured by Nippon Kayaku Co., Ltd.
  • the composition is shown in Table 1.
  • Table 1 the curing agent of the present invention exhibited a high softening point, and the one-part epoxy resin composition exhibited excellent storage stability.
  • the obtained cured product exhibited a Tg of 150° C. or more.
  • Example 7 In this example, the procedure of Example 1 was repeated, except that HP-4032D (manufactured by DIC Corporation, naphthalene-type epoxy resin, epoxy equivalent: 136 g/eq) was used instead of XD-1000.
  • the composition is shown in Table 1.
  • Table 1 the one-part epoxy resin composition containing the curing agent of the present invention exhibited excellent storage stability.
  • the obtained cured product exhibited a Tg of 150° C. or more.
  • Example 8 In this example, the procedure of Example 1 was repeated, except that HP-4700 (manufactured by DIC Corporation, naphthalene-type epoxy resin, epoxy equivalent: 165 g/eq) and jER828 were used instead of XD-1000.
  • the composition is shown in Table 1.
  • Table 1 the curing agent of the present invention exhibited a high softening point, and the one-part epoxy resin composition exhibited excellent storage stability.
  • the obtained cured product exhibited a Tg of 150° C. or more.
  • Example 9 In this example, the procedure of Example 1 was repeated, except that HP-4032D and HP-4700 were used instead of XD-1000.
  • the composition is shown in Table 1.
  • the curing agent of the present invention exhibited a high softening point, and the one-part epoxy resin composition exhibited excellent storage stability.
  • the obtained cured product exhibited a Tg of 150° C. or more.
  • Example 10 In this example, the procedure of Example 1 was repeated, except that HP-4770 (manufactured by DIC Corporation, naphthalene-type epoxy resin, epoxy equivalent: 204 g/eq) was used instead of XD-1000.
  • the composition is shown in Table 1.
  • Table 1 the curing agent of the present invention exhibited a high softening point, and the one-part epoxy resin composition exhibited excellent storage stability.
  • the obtained cured product exhibited a Tg of 150° C. or more.
  • Example 11 In this example, the procedure of Example 1 was repeated, except that OGSOL PG-100 (fluorene type epoxy resin, epoxy equivalent: 254 g/eq, manufactured by Osaka Gas Chemicals Co., Ltd.) was used instead of XD-1000.
  • the composition is shown in Table 1.
  • Table 1 the curing agent of the present invention exhibited a high softening point, and the one-part epoxy resin composition exhibited excellent storage stability.
  • the obtained cured product exhibited a Tg of 150° C. or more.
  • Comparative Example 1 In this comparative example, the procedure of Example 1 was repeated except that jER828 was used instead of XD-1000.
  • the composition is shown in Table 1. As shown in Table 1, the obtained curing agent and the one-component epoxy resin composition were poor in storage stability.
  • Comparative Example 2 In this example, the procedure of Example 3 was repeated, except that jER828 was used instead of XD-1000.
  • the composition is shown in Table 1. As shown in Table 1, the obtained curing agent and the one-component epoxy resin composition were poor in storage stability.
  • Comparative Example 3 In this example, the procedure of Example 1 was repeated, except that jER1001 (Mitsubishi Chemical Corporation, bisphenol A type epoxy resin, epoxy equivalent: 475 g/eq) was used instead of XD-1000.
  • the composition is shown in Table 1.
  • the one-component epoxy resin composition of the present invention had poor storage stability, and the Tg of the resulting cured product was 100 to 150°C.
  • Comparative Example 4 In this example, the procedure of Example 3 was repeated, except that jER1001 was used instead of XD-1000.
  • the composition is shown in Table 1.
  • the one-component epoxy resin composition of the present invention had poor storage stability, and the Tg of the resulting cured product was 100 to 150°C.
  • the latent curing agent of the present invention can be used in a one-part epoxy resin composition.
  • the one-part epoxy resin composition of the present invention can also be used as a thermosetting epoxy resin composition in adhesives, paints, etc.

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Abstract

The purpose of the present invention is to provide an imidazole-based curing agent which exhibits high storage stability without encapsulation.　The problem can be solved by a latent curing agent to which an imidazole compound and any epoxy compound having a specific structure represented by general formula (1), (2), (3), (4) or (5) in the present invention are added.

Description

潜在性硬化剤及び一液性エポキシ樹脂組成物Latent curing agent and one-component epoxy resin composition
　本発明は、潜在性硬化剤及び一液性エポキシ樹脂組成物に関する。本発明によれば、優れた保存安定性を示す潜在性硬化剤を得ることができる。 The present invention relates to a latent curing agent and a one-part epoxy resin composition. According to the present invention, it is possible to obtain a latent curing agent that exhibits excellent storage stability.
　エポキシ樹脂の硬化剤としてアミン系化合物が広く用いられている。特に、イミダゾール系の硬化剤はエポキシ樹脂に対する配合量が少ない場合も、加熱硬化により十分に硬化し、高いガラス転移点を有する硬化物が得られる。 Amine compounds are widely used as curing agents for epoxy resins. In particular, imidazole curing agents cure sufficiently by heat curing even when the amount mixed with the epoxy resin is small, resulting in a cured product with a high glass transition point.
特公平７－５７０８号公報Special Publication No. 7-5708
　しかしながら、通常のイミダゾール化合物は、エポキシ樹脂に処方した場合、ポットライフが短く、常温でも翌日には硬化して使用できなくなってしまう。従って、二液性で用いられており、一液化処方できるイミダゾール系硬化剤が望まれている。この課題を解決するため、イミダゾール化合物に対してビスフェノールＡ型エポキシ樹脂をアダクトした、旭化成イーマテリアルズのノバキュアが上市されている（特許文献１）。しかしながら、この硬化剤の保存安定性は十分でないため、前記ノバキュアは、カプセル化処理を行うことによって保存安定性を高めている。
　従って、本発明の目的は、カプセル化なしで高い保存安定性を示すイミダゾール系硬化剤を提供することである。 However, when a normal imidazole compound is formulated into an epoxy resin, it has a short pot life and hardens the next day even at room temperature, making it unusable. Therefore, it is used in a two-part system, and an imidazole-based curing agent that can be formulated as a one-part system is desired. To solve this problem, Asahi Kasei E-Materials' Novacure, which is an adduct of an imidazole compound and a bisphenol A-type epoxy resin, has been put on the market (Patent Document 1). However, since the storage stability of this curing agent is not sufficient, the Novacure is encapsulated to improve its storage stability.
Accordingly, an object of the present invention is to provide an imidazole-based hardener that exhibits high storage stability without encapsulation.
　本発明者は、高い保存安定性を示すイミダゾール系硬化剤について、鋭意研究した結果、驚くべきことに、特定の構造を有するエポキシ化合物をイミダゾール化合物に付加することのより、高い保存安定性を示すイミダゾール系硬化剤が得られることを見出した。
　本発明は、こうした知見に基づくものである。
　従って、本発明は、
［１］一般式（１）、（２）、（３）、（４）、又は（５）：
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000026
 （式中、Ｘは一般式（６）、（７）、又は（８）：
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000029
 （式中、Ｒ２は、水素原子又は－ＯＣＨ２エポキシ基であり、Ｒ３は、水素原子又は炭素数１～３のアルキル基である）で表される基であり、
Ｙは、一般式（９）：
Figure JPOXMLDOC01-appb-C000030
 （式中Ｒ４は、－ＯＣＨ２エポキシ基であり、Ｒ３は、水素原子又は炭素数１～３のアルキル基である）で表される基であり、
Ｚは、一般式（１０）：
Figure JPOXMLDOC01-appb-C000031
 （式中、２つの結合手は、一般式（１０）の構造の任意の炭素原子に結合してよく、１つの炭素原子に２つの結合手が結合してもよい）で表される基であり、Ｒ１は単結合であるか、又は炭素数１～３のアルキレン基であり、Ｘに結合するＲ１は、Ｘの２つの環構造のいずれに結合してもよく、ｎは１～１５であり、ｍは０～１５であり、末端に存在するＸの１つのＲ２は－ＯＣＨ２エポキシ基であり、末端に存在するＸ及びＹの末端の結合手には水素原子が結合しており、一般式（４）のＸの２つのＲ２は－ＯＣＨ２エポキシ基であり、そして繰り返し単位中の－ＯＣＨ２エポキシ基の数は、１又は２である）で表されるいずれかのエポキシ化合物と、イミダゾール化合物とが付加された、潜在性硬化剤、
［２］前記エポキシ化合物が、下記式で表されるエポキシ化合物からなる群から選択される、［１］に記載の潜在性化合物。
Figure JPOXMLDOC01-appb-C000032
 （式中、ｍは０～１５であり、ｌは１～１５である。）、
［３］［１］又は［２］に記載の潜在性硬化剤、及びエポキシ樹脂を含む一液性エポキシ樹脂組成物、
［４］［３］に記載の一液性エポキシ樹脂組成物を加熱することによって得られるエポキシ樹脂硬化物、及び
［５］イミダゾール化合物に、（１）、（２）、（３）、（４）、又は（５）：
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000037
 （式中、Ｘは一般式（６）、（７）、又は（８）：
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000040
 （式中、Ｒ２は、水素原子又は－ＯＣＨ２エポキシ基であり、Ｒ３は、水素原子又は炭素数１～３のアルキル基である）で表される基であり、
Ｙは、一般式（９）：
Figure JPOXMLDOC01-appb-C000041
 （式中Ｒ４は、－ＯＣＨ２エポキシ基であり、Ｒ３は、水素原子又は炭素数１～３のアルキル基である）で表される基であり、
Ｚは、一般式（１０）：
Figure JPOXMLDOC01-appb-C000042
 （式中、２つの結合手は、一般式（１０）の構造の任意の炭素原子に結合してよく、１つの炭素原子に２つの結合手が結合してもよい）で表される基であり、Ｒ１は単結合であるか、又は炭素数１～３のアルキレン基であり、Ｘに結合するＲ１は、Ｘの２つの環構造のいずれに結合してもよくｎは１～１５であり、ｍは０～１５であり、末端に存在するＸの１つのＲ２は－ＯＣＨ２エポキシ基であり、末端に存在するＸ及びＹの末端の結合手には水素原子が結合しており、一般式（４）のＸの２つのＲ２は－ＯＣＨ２エポキシ基であり、そして繰り返し単位中の－ＯＣＨ２エポキシ基の数は、１又は２である）
で表されるいずれかのエポキシ化合物を付加する工程を含む、潜在性硬化剤の製造方法、
に関する。 The present inventors conducted extensive research into imidazole-based curing agents exhibiting high storage stability, and as a result, surprisingly found that an imidazole-based curing agent exhibiting high storage stability can be obtained by adding an epoxy compound having a specific structure to an imidazole compound.
The present invention is based on these findings.
Thus, the present invention provides
[1] General formula (1), (2), (3), (4), or (5):
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000026
 (In the formula, X represents general formula (6), (7), or (8):
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000029
 (wherein R2 is a hydrogen atom or an -OCH2 epoxy group, and R3 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms),
Y is represented by the general formula (9):
Figure JPOXMLDOC01-appb-C000030
 (wherein R 4 is an —OCH 2 epoxy group, and R 3 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms),
Z is represented by the general formula (10):
Figure JPOXMLDOC01-appb-C000031
 (wherein the two bonds may be bonded to any carbon atom in the structure of general formula (10), or two bonds may be bonded to one carbon atom), R 1 is a single bond or an alkylene group having 1 to 3 carbon atoms, R 1 bonded to X may be bonded to either of the two ring structures of X, n is 1 to 15, m is 0 to 15, one R 2 of X present at the terminal is an -OCH 2 epoxy group, hydrogen atoms are bonded to the bonds at the terminals of X and Y present at the terminals, two R 2 of X in general formula (4) are -OCH 2 epoxy groups, and the number of -OCH 2 epoxy groups in the repeating unit is 1 or 2),
[2] The latent compound according to [1], wherein the epoxy compound is selected from the group consisting of epoxy compounds represented by the following formula:
Figure JPOXMLDOC01-appb-C000032
 (In the formula, m is 0 to 15, and l is 1 to 15.)
[3] A one-component epoxy resin composition comprising the latent curing agent according to [1] or [2] and an epoxy resin.
[4] An epoxy resin cured product obtained by heating the one-component epoxy resin composition according to [3], and [5] an imidazole compound, comprising (1), (2), (3), (4), or (5):
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000037
 (In the formula, X represents general formula (6), (7), or (8):
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000040
 (wherein R2 is a hydrogen atom or an -OCH2 epoxy group, and R3 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms),
Y is represented by the general formula (9):
Figure JPOXMLDOC01-appb-C000041
 (wherein R 4 is an —OCH 2 epoxy group, and R 3 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms),
Z is represented by the general formula (10):
Figure JPOXMLDOC01-appb-C000042
 (wherein the two bonds may be bonded to any carbon atom in the structure of general formula (10), or two bonds may be bonded to one carbon atom), R 1 is a single bond or an alkylene group having 1 to 3 carbon atoms, R 1 bonded to X may be bonded to either of the two ring structures of X, n is 1 to 15, m is 0 to 15, one R 2 of X present at the terminal is an -OCH 2 epoxy group, hydrogen atoms are bonded to the bonds at the terminals of X and Y present at the terminals, two R 2 of X in general formula (4) are -OCH 2 epoxy groups, and the number of -OCH 2 epoxy groups in the repeating unit is 1 or 2)
A method for producing a latent curing agent, comprising the step of adding any one of the epoxy compounds represented by the following formula:
Regarding.
　本発明の潜在性硬化剤によれば、優れた保存安定性を示すことができる。 The latent hardener of the present invention can exhibit excellent storage stability.
［１］潜在性硬化剤
　本発明の潜在性硬化剤は、一般式（１）、（２）、（３）、（４）、又は（５）：
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000047
 で表されるエポキシ化合物とイミダゾール化合物とが付加されている。 [1] Latent Curing Agent The latent curing agent of the present invention is represented by the general formula (1), (2), (3), (4), or (5):
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000047
 and an imidazole compound are added.
　エポキシ化合物と、イミダゾール化合物との付加とは限定されるものではないが、イミダゾール化合物の＝ＮＨ基とエポキシ化合物のエポキシ基（ＣＨ２（Ｏ）ＣＨ－）とが反応し、＝Ｎ－ＣＨ２－ＣＨ（ＯＨ）－結合を形成することを意味する。 The addition of an epoxy compound to an imidazole compound means, but is not limited to, that the =NH group of the imidazole compound reacts with the epoxy group (CH 2 (O)CH-) of the epoxy compound to form a =N-CH 2 -CH(OH)- bond.
《エポキシ化合物》
　エポキシ化合物は、一般式（１）～（５）のいずれかの構造を有する限りにおいて、特に限定されるものではない。前記の構造を有することにより、エポキシ化合物は、剛直な骨格を形成することが可能である。剛直な骨格を形成することにより、エポキシ化合物の軟化点を向上させることが可能であり、潜在性硬化剤の保存安定性を向上させることができる。 Epoxy compounds
The epoxy compound is not particularly limited as long as it has any one of the structures of general formulas (1) to (5). By having the above structure, the epoxy compound can form a rigid skeleton. By forming a rigid skeleton, it is possible to improve the softening point of the epoxy compound and improve the storage stability of the latent curing agent.
　前記エポキシ化合物のＸは一般式（６）、（７）、又は（８）：
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000050
 で表される基である。 X of the epoxy compound is represented by the general formula (6), (7), or (8):
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000050
 It is a group represented by the following formula:
　Ｒ２は、水素原子又は－ＯＣＨ２エポキシ基である。Ｘがエポキシ化合物の末端に存在する場合は、少なくとも１つのＲ２は－ＯＣＨ２エポキシ基である。一般式（４）におけるＸの２つのＲ２は－ＯＣＨ２エポキシ基である。
　Ｒ３は、水素原子又は炭素数１～３のアルキル基である。炭素数１～３のアルキル基は、具体的にはメチル基、エチル基、又はプロピル基である。Ｒ３は、好ましくは水素原子又はメチル基である。 R2 is a hydrogen atom or an -OCH2 epoxy group. When X is present at the end of an epoxy compound, at least one R2 is an -OCH2 epoxy group. In general formula (4), the two R2s of X are -OCH2 epoxy groups.
R3 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. The alkyl group having 1 to 3 carbon atoms is specifically a methyl group, an ethyl group, or a propyl group. R3 is preferably a hydrogen atom or a methyl group.
　Ｙは、一般式（９）：
Figure JPOXMLDOC01-appb-C000051
 で表される基である。
　Ｒ４は、－ＯＣＨ２エポキシ基であり、Ｒ３は、水素原子又は炭素数１～３のアルキル基である。炭素数１～３のアルキル基は、具体的にはメチル基、エチル基、又はプロピル基である。Ｒ３は、好ましくは水素原子又はメチル基である。 Y is represented by the general formula (9):
Figure JPOXMLDOC01-appb-C000051
 It is a group represented by the following formula:
R4 is an -OCH2 epoxy group, and R3 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. The alkyl group having 1 to 3 carbon atoms is specifically a methyl group, an ethyl group, or a propyl group. R3 is preferably a hydrogen atom or a methyl group.
　Ｚは、一般式（１０）：
Figure JPOXMLDOC01-appb-C000052
 で表される基である。２つの結合手は、前記の構造の任意の炭素原子に結合することができる。具体的には２つのベンゼン環の炭素原子に結合してもよい。また、シクロペンタンの環を形成する炭素原子に結合してもよく、１つの炭素原子に２つの結合手が結合してもよい。 Z is represented by the general formula (10):
Figure JPOXMLDOC01-appb-C000052
 The two bonds can be bonded to any carbon atom in the above structure. Specifically, they may be bonded to carbon atoms of two benzene rings. They may also be bonded to carbon atoms forming a cyclopentane ring, or two bonds may be bonded to one carbon atom.
　Ｒ１は単結合であるか、又は炭素数１～３のアルキレン基である。炭素数１～３のアルキレン基は、具体的にはメチレン基、エチレン基、又はプロピル基である。Ｒ１は、好ましくは単結合、又はメチレン基である。Ｘに結合するＲ１は、Ｘの２つの環構造のいずれに結合してもよい。 R 1 is a single bond or an alkylene group having 1 to 3 carbon atoms. The alkylene group having 1 to 3 carbon atoms is specifically a methylene group, an ethylene group, or a propyl group. R 1 is preferably a single bond or a methylene group. R 1 bonded to X may be bonded to either of the two ring structures of X.
　ｎは１～１５であり、好ましくは１～１０であり、より好ましくは１～８であり、更に好ましくは１～５であり、更に好ましくは、１～３であり、更に好ましくは１又は２であり、最も好ましくは１である。なお、一般式（１）で表されるエポキシ化合物はポリマーであり、ｎの数が単一のポリマーでもよいが、ｎの数が１～１５のポリマーの混合物でもよい。混合物の場合、一般式（１）のｎは繰り返し数の平均を意味する。なお、単一のポリマーの場合、ｎは整数である。
　ｍは０～１５であり、好ましくは０～１０であり、より好ましくは０～８であり、更に好ましくは０～５であり、更に好ましくは、０～３であり、更に好ましくは０～２であり、更に好ましくは０又は１である。なお、一般式（２）で表されるエポキシ化合物はポリマーであり、ｍの数が単一のポリマーでもよいが、ｍの数が０～１５のポリマーの混合物でもよい。混合物の場合、一般式（１）のｍは繰り返し数の平均を意味する。なお、単一のポリマーの場合、ｍは整数である。 n is 1 to 15, preferably 1 to 10, more preferably 1 to 8, even more preferably 1 to 5, even more preferably 1 to 3, even more preferably 1 or 2, and most preferably 1. The epoxy compound represented by general formula (1) is a polymer, and may be a polymer having a single number of n, or a mixture of polymers having a number of n of 1 to 15. In the case of a mixture, n in general formula (1) means the average number of repetitions. In the case of a single polymer, n is an integer.
m is 0 to 15, preferably 0 to 10, more preferably 0 to 8, even more preferably 0 to 5, even more preferably 0 to 3, even more preferably 0 to 2, and even more preferably 0 or 1. The epoxy compound represented by general formula (2) is a polymer, and may be a single polymer having m, or may be a mixture of polymers having m of 0 to 15. In the case of a mixture, m in general formula (1) means the average number of repetitions. In the case of a single polymer, m is an integer.
（末端）
　末端に存在するＸの１つのＲ２は－ＯＣＨ２エポキシ基である。末端に存在するＸ及びＹの末端側の結合手には水素原子が結合している。すなわち、末端のＸ及びＹは、２価の基ではなく、１価の基である。 (End)
One R2 of the X present at the terminal is an -OCH2 epoxy group. A hydrogen atom is bonded to the bond on the terminal side of the X and Y present at the terminal. In other words, the X and Y at the terminal are monovalent groups, not divalent groups.
（エポキシ基）
　前記エポキシ化合物のエポキシ基の数は、本発明の効果が得られる限りにおいて、特に限定されるものではないが、例えば上限は５以下であり、好ましくは４以下であり、更に好ましくは３以下である。下限は本発明の効果が得られる限りにおいて特に限定されるものではないが、好ましくは２以上である。前記範囲であることにより、イミダゾール－エポキシ付加物合成時のゲル化を防ぎ、良好なエポキシ樹脂硬化物を得ることができる。 (epoxy group)
The number of epoxy groups in the epoxy compound is not particularly limited as long as the effects of the present invention can be obtained, but for example, the upper limit is 5 or less, preferably 4 or less, and more preferably 3 or less. The lower limit is not particularly limited as long as the effects of the present invention can be obtained, but is preferably 2 or more. By keeping the number in the above range, gelation during synthesis of the imidazole-epoxy adduct can be prevented, and a good epoxy resin cured product can be obtained.
（繰り返し単位）
　一般式（１）又は（２）における繰り返し単位中の－ＯＣＨ２エポキシ基の数は、１又は２である。 (Repeating Unit)
The number of -OCH2 epoxy groups in the repeating unit in general formula (1) or (2) is 1 or 2.
（平均エポキシ基数）
　一般式（１）又は（２）で表されるエポキシ化合物はポリマーであるが、前記の通り、ｎの数が１～１５のポリマーの混合物、又はｍの数が０～１５のポリマーの混合物でもよい。混合物の場合、一般式（１）又は（２）で表されるエポキシ化合物に含まれる平均エポキシ基数は、例えば上限は５以下であり、好ましくは４以下であり、更に好ましくは３以下である。下限は本発明の効果が得られる限りにおいて特に限定されるものではないが、好ましくは２以上である。前記範囲であることによって、エポキシ樹脂硬化物のゲル化を防ぎ、良好なエポキシ樹脂硬化物を得ることができる。 (Average number of epoxy groups)
The epoxy compound represented by general formula (1) or (2) is a polymer, and as described above, it may be a mixture of polymers in which n is 1 to 15, or a mixture of polymers in which m is 0 to 15. In the case of a mixture, the average number of epoxy groups contained in the epoxy compound represented by general formula (1) or (2) is, for example, 5 or less in the upper limit, preferably 4 or less, and more preferably 3 or less. The lower limit is not particularly limited as long as the effects of the present invention can be obtained, but is preferably 2 or more. By being in the above range, gelation of the epoxy resin cured product can be prevented, and a good epoxy resin cured product can be obtained.
　本発明に用いるエポキシ化合物として、限定されるものではないが、具体的には、下記式で表される化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000053
 　式中、ｍは０～１５であり、ｌは１～１５である。
　ｍは０～１５であり、好ましくは０～１０であり、より好ましくは０～８であり、更に好ましくは０～５であり、更に好ましくは、０～３であり、更に好ましくは０～２であり、更に好ましくは０又は１である。なお、前記式で表されるエポキシ化合物はポリマーであり、ｍの数が単一のポリマーでもよいが、ｍの数が０～１５のポリマーの混合物でもよい。混合物の場合、前記式のｍは繰り返し数の平均を意味する。なお、単一のポリマーの場合、ｍは整数である。
　ｌは１～１５であり、好ましくは１～１０であり、より好ましくは１～８であり、更に好ましくは１～５であり、更に好ましくは、１～３であり、更に好ましくは１又は２であり、最も好ましくは１である。なお、前記式で表されるエポキシ化合物はポリマーであり、ｌの数が単一のポリマーでもよいが、ｌの数が１～１５のポリマーの混合物でもよい。混合物の場合、前記式のｌは繰り返し数の平均を意味する。なお、単一のポリマーの場合、ｌは整数である。 The epoxy compound used in the present invention is not limited, but specific examples thereof include compounds represented by the following formula:
Figure JPOXMLDOC01-appb-C000053
 In the formula, m is 0 to 15 and l is 1 to 15.
m is 0 to 15, preferably 0 to 10, more preferably 0 to 8, even more preferably 0 to 5, even more preferably 0 to 3, even more preferably 0 to 2, and even more preferably 0 or 1. The epoxy compound represented by the above formula is a polymer, and may be a single polymer with m as a number, or a mixture of polymers with m as a number from 0 to 15. In the case of a mixture, m in the above formula means the average number of repetitions. In the case of a single polymer, m is an integer.
l is 1 to 15, preferably 1 to 10, more preferably 1 to 8, even more preferably 1 to 5, even more preferably 1 to 3, even more preferably 1 or 2, and most preferably 1. The epoxy compound represented by the above formula is a polymer, and may be a single polymer with l as a number, or a mixture of polymers with l as a number from 1 to 15. In the case of a mixture, l in the above formula means the average number of repetitions. In the case of a single polymer, l is an integer.
《イミダゾール化合物》
　イミダゾール化合物は、限定されるものではないが、例えば一般式（１１）：
Figure JPOXMLDOC01-appb-C000054
 （式中、Ｒ１３及びＲ１４はそれぞれ独立して、水素原子、又は炭素数１～１７の直鎖又は分岐したアルキル基又は芳香族基である）で表されるイミダゾールを用いることができる。
　具体的には、イミダゾール、４－シアノメチルイミダゾール、４－エチルイミダゾール、４，５－ビス（ヒドロキシメチル）イミダゾール、２－フェニルイミダゾール、４－フェニルイミダゾール、４－ヒドロキシメチル－５－メチルイミダゾール、２－メチルイミダゾール、２－エチルイミダゾール、２－プロピルイミダゾール、２－ブチルイミダゾール、２－ウンデシルイミダゾール、２－ヘプタデシルイミダゾール、２，４－ジメチルイミダゾール、２－メチル－４－エチルイミダゾール、２－メチル－４－プロピルイミダゾール、２－メチル－４－ブチルイミダゾール、２－エチル－４－メチルイミダゾール、２，４－ジエチルイミダゾール、２－エチル－４－プロピルイミダゾール、２－エチル－４－ブチルイミダゾール、２－プロピル－４－メチルイミダゾール、２－プロピル－４－エチルイミダゾール、２，４－ジプロピルイミダゾール、２－プロピル－４－ブチルイミダゾール、２－ブチル－４－メチルイミダゾール、２－ブチル－４－エチルイミダゾール、２－ブチル－４－プロピルイミダゾール、２，４－ジブチルイミダゾール等が挙げられる。好ましくは、２－メチルイミダゾール、２－エチルイミダゾール、２，４－ジメチルイミダゾール、２－メチル－４－エチルイミダゾール、２－エチル－４－メチルイミダゾール、２，４－ジエチルイミダゾールが挙げられる。好ましくはイミダゾール、２－メチルイミダゾール、２－エチル－４－メチルイミダゾールである。 <Imidazole compounds>
The imidazole compound is not limited to, but may be, for example, a compound represented by the general formula (11):
Figure JPOXMLDOC01-appb-C000054
 (wherein R 13 and R 14 each independently represent a hydrogen atom, or a linear or branched alkyl group or aromatic group having 1 to 17 carbon atoms) can be used.
Specifically, imidazole, 4-cyanomethylimidazole, 4-ethylimidazole, 4,5-bis(hydroxymethyl)imidazole, 2-phenylimidazole, 4-phenylimidazole, 4-hydroxymethyl-5-methylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-propylimidazole, 2-butylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2,4-dimethylimidazole, 2-methyl-4-ethylimidazole, 2-methyl-4-propylimidazole Examples of the imidazole include 2-methyl-4-butylimidazole, 2-ethyl-4-methylimidazole, 2,4-diethylimidazole, 2-ethyl-4-propylimidazole, 2-ethyl-4-butylimidazole, 2-propyl-4-methylimidazole, 2-propyl-4-ethylimidazole, 2,4-dipropylimidazole, 2-propyl-4-butylimidazole, 2-butyl-4-methylimidazole, 2-butyl-4-ethylimidazole, 2-butyl-4-propylimidazole, 2,4-dibutylimidazole, etc. Preferred examples include 2-methylimidazole, 2-ethylimidazole, 2,4-dimethylimidazole, 2-methyl-4-ethylimidazole, 2-ethyl-4-methylimidazole, and 2,4-diethylimidazole. Preferred are imidazole, 2-methylimidazole, and 2-ethyl-4-methylimidazole.
　本発明の潜在性硬化剤に含まれるイミダゾール化合物及びエポキシ化合物の含有量は、特に限定されるものではないが、イミダゾール化合物１モルに対して、エポキシ化合物は０．５～２．０当量であり、より好ましくは０．８～１．７当量であり、更に好ましくは１．０～１．５当量である。 The contents of the imidazole compound and epoxy compound contained in the latent curing agent of the present invention are not particularly limited, but the epoxy compound is 0.5 to 2.0 equivalents per mole of the imidazole compound, more preferably 0.8 to 1.7 equivalents, and even more preferably 1.0 to 1.5 equivalents.
［２］一液性エポキシ樹脂組成物
　本発明の一液性エポキシ樹脂組成物は、前記潜在性硬化剤、及びエポキシ樹脂を含む。 [2] One-component epoxy resin composition The one-component epoxy resin composition of the present invention contains the latent curing agent and an epoxy resin.
《エポキシ樹脂》
　本発明一液性エポキシ樹脂組成物に含まれるエポキシ樹脂は、１分子中に平均１個以上のエポキシ基を有するエポキシ樹脂であり、好ましくは平均１個を超えるエポキシ基を有するエポキシ樹脂である。エポキシ基の数は、平均１個以上であれば、特に限定されるものではないが、好ましくは２個以上である。エポキシ基の上限は、エポキシ樹脂組成物におけるエポキシ樹脂の効果を考慮した場合、特に限定されるものではない。なお、「平均」とは、２種類以上のエポキシ樹脂を混合した場合の１分子中の平均のエポキシ基の数を意味する。具体的にはエポキシ樹脂として、例えば単核多価フェノール化合物のエポキシ化合物（ポリグリシジルエーテル）、多核多価フェノール化合物のエポキシ化合物（ポリグリシジルエーテル）、多価アルコール類のエポキシ化合物（ポリグリシジルエーテル）、ヒドロキシカルボン酸のエポキシ化合物（ポリグリシジルエーテルエステル）、脂肪族、芳香族又は脂環族多塩基酸のエポキシ化合物（ポリグリシジルエステル）、ヒドロキシカルボン酸類のエポキシ化合物（グリシジルエーテルエステル）、多価カルボン酸類のエポキシ化合物（グリシジルエステル）、アミノフェノール類のエポキシ化合物（グリシジルアミノグリシジルエーテル）、多価アミン類のエポキシ化合物（グリシジルアミン）、又はその他のエポキシ化合物を挙げることができる。 《Epoxy resin》
The epoxy resin contained in the one-component epoxy resin composition of the present invention is an epoxy resin having an average of one or more epoxy groups in one molecule, and preferably an epoxy resin having an average of more than one epoxy group. The number of epoxy groups is not particularly limited as long as it is an average of one or more, but is preferably two or more. The upper limit of the epoxy groups is not particularly limited when the effect of the epoxy resin in the epoxy resin composition is taken into consideration. The "average" means the average number of epoxy groups in one molecule when two or more types of epoxy resins are mixed. Specific examples of epoxy resins include epoxy compounds (polyglycidyl ethers) of mononuclear polyhydric phenol compounds, epoxy compounds (polyglycidyl ethers) of polynuclear polyhydric phenol compounds, epoxy compounds (polyglycidyl ethers) of polyhydric alcohols, epoxy compounds (polyglycidyl ether esters) of hydroxycarboxylic acids, epoxy compounds (polyglycidyl esters) of aliphatic, aromatic or alicyclic polybasic acids, epoxy compounds (glycidyl ether esters) of hydroxycarboxylic acids, epoxy compounds (glycidyl esters) of polyvalent carboxylic acids, epoxy compounds (glycidyl aminoglycidyl ethers) of aminophenols, epoxy compounds (glycidyl aminoglycidyl ethers) of polyvalent amines, and other epoxy compounds.
　前記単核多価フェノール化合物としてより詳しくは、例えば、カテコール、レゾルシン、ヒドロキノン、又はこれらのハロゲン（例えば、塩素、臭素）誘導体等が挙げられる。 Specific examples of the mononuclear polyhydric phenol compounds include catechol, resorcinol, hydroquinone, and halogen (e.g., chlorine, bromine) derivatives of these compounds.
　前記多核多価フェノール化合物としてより詳しくは、例えば、ビスフェノールＦ、ビスフェノールＡ、ビスフェノールＳ、ビスフェノールＡＤ、テトラメチルビスフェノールＦ、テトラメチルビスフェノールＡ、又はこれらのハロゲン誘導体；ナフトール、ビフェノール、ビキシレノール、ビスレゾルシノール、トリヒドロキシビフェニル、テトラヒドロキシフェニルエタン、フェノールノボラック、クレゾールノボラック、テルペンフェノール、フェノール化ジシクロペンタジエン、又はこれらのハロゲン誘導体等が挙げられる。 Specific examples of the polynuclear polyhydric phenol compound include bisphenol F, bisphenol A, bisphenol S, bisphenol AD, tetramethylbisphenol F, tetramethylbisphenol A, or halogen derivatives thereof; naphthol, biphenol, bixylenol, bisresorcinol, trihydroxybiphenyl, tetrahydroxyphenylethane, phenol novolac, cresol novolac, terpene phenol, phenolized dicyclopentadiene, or halogen derivatives thereof.
　前記多価アルコール類としてより詳しくは、例えば、グリセリン、ネオペンチルグリコール、エチレングリコール、プロピレングリコール、ブチレングリコール、１，６－ヘキサンジオール、ポリエチレングリコール、ポリプロピレングリコール、チオジグリコール、トリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、ソルビトール、ビスフェノールＡ－エチレンオキサイド又はプロピレンオキサイド付加物等が挙げられる。 Specific examples of the polyhydric alcohols include glycerin, neopentyl glycol, ethylene glycol, propylene glycol, butylene glycol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol, thiodiglycol, trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol, and bisphenol A-ethylene oxide or propylene oxide adducts.
　前記ヒドロキシカルボン酸類としてより詳しくは、例えば、ｐ－オキシ安息香酸、又はβ－オキシナフトエ酸等が挙げられる。 Specific examples of the hydroxycarboxylic acids include p-hydroxybenzoic acid and β-hydroxynaphthoic acid.
　前記多価カルボン酸類としてより詳しくは、例えば、フタル酸、メチルフタル酸、イソフタル酸、テレフタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、エンドメチレンテトラヒドロフタル酸、トリメリット酸、トリメシン酸、ピロメリット酸、マレイン酸、フマル酸、イタコン酸、コハク酸、グルタル酸、アジピン酸、アゼライン酸、セバシン酸、デカン二酸、ドデカン二酸、テトラデカン二酸、オクタデカン二酸、又は重合脂肪酸等が挙げられる。 Specific examples of the polyvalent carboxylic acids include phthalic acid, methylphthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, decanedioic acid, dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and polymerized fatty acids.
　前記アミノフェノール類としてより詳しくは、例えば、ｐ－アミノフェノール、又はｐ－アミノアルキルフェノール等が挙げられる。 Specific examples of the aminophenols include p-aminophenol and p-aminoalkylphenol.
　前記多価アミン類としてより詳しくは、例えば、アニリン、ｏ－トルイジン、トリブロモアニリン、ｍ－キシリレンジアミン、１，２－ジアミノシクロヘキサン、１，３－ビスアミノメチルシクロヘキサン、４，４′－ジアミノジフェニルメタン、４，４′－ジアミノジシクロヘキシルメタン、２，２′－ジメチル－４，４′－４，４′－ジアミノジシクロヘキシルメタン、又はジアミノジフェニルスルホン等が挙げられる。 Specific examples of the polyamines include aniline, o-toluidine, tribromoaniline, m-xylylenediamine, 1,2-diaminocyclohexane, 1,3-bisaminomethylcyclohexane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodicyclohexylmethane, 2,2'-dimethyl-4,4'-4,4'-diaminodicyclohexylmethane, and diaminodiphenylsulfone.
　前記その他のエポキシ化合物としてより詳しくは、例えば、エポキシ化ポリオレフィン、エポキシ化ポリブタジエン、エポキシ化大豆油、グリシジルヒダントイン、ジ又はトリグリシジルイソシアヌレート、ビニルシクロヘキセンジエポキシド、ジシクロペンタジエンジエポキシド、又は３，４－エポキシシクロヘキシル－３，４－エポキシシクロヘキサンカルボキシレート等が挙げられる。 Specific examples of the other epoxy compounds include epoxidized polyolefins, epoxidized polybutadiene, epoxidized soybean oil, glycidyl hydantoin, di- or triglycidyl isocyanurate, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, and 3,4-epoxycyclohexyl-3,4-epoxycyclohexane carboxylate.
　前記例示したエポキシ樹脂において、中でも、本発明のエポキシ樹脂組成物を硬化させたときの硬化物の耐熱性、絶縁性等の電気特性、接着性等に優れることから、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂、ナフトール型エポキシ樹脂、又はジアミノジフェニルメタン型エポキシ樹脂を用いることが特に好ましい。前記エポキシ樹脂は、１種類又は２種類以上を混合して使用することができる。 Among the epoxy resins exemplified above, it is particularly preferable to use bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, naphthol type epoxy resin, or diaminodiphenylmethane type epoxy resin, because the cured product obtained by curing the epoxy resin composition of the present invention has excellent heat resistance, electrical properties such as insulation, and adhesive properties. The above epoxy resins can be used alone or in combination of two or more types.
　本発明に係わるエポキシ樹脂組成物におけるエポキシ樹脂として、本発明の効果を損なわない範囲で、１官能のエポキシ化合物を併用することができる。例示するならば、ブチルグリシジルエーテル、フェニルグリシジルエーテル、高級アルコールグリシジルエーテル、安息香酸グリシジルエステル、分岐脂肪酸グリシジルエステル（カージュラＥ；モメンティブパフォーマンスマテリアルズ社製）、スチレンオキサイド等が挙げられる。一般に、これら１官能エポキシ化合物は粘度が低いため、特に、エポキシ樹脂組成物の取り扱いの面では有利ではあるが、最終的なエポキシ樹脂硬化物の機械的特性や耐熱性（ガラス転移温度）を低下させることがあるため、その使用量は可能な限り少なくするべきである。また、前記１官能エポキシ樹脂は１種類又は２種類以上を併用して使用することができる。 As the epoxy resin in the epoxy resin composition of the present invention, monofunctional epoxy compounds can be used in combination within the scope of not impairing the effects of the present invention. Examples include butyl glycidyl ether, phenyl glycidyl ether, higher alcohol glycidyl ether, benzoic acid glycidyl ester, branched fatty acid glycidyl ester (Cardura E; manufactured by Momentive Performance Materials), styrene oxide, etc. In general, these monofunctional epoxy compounds have low viscosity, which is advantageous in terms of handling the epoxy resin composition in particular, but since they may reduce the mechanical properties and heat resistance (glass transition temperature) of the final epoxy resin cured product, their amount should be kept as small as possible. In addition, the monofunctional epoxy resins can be used alone or in combination of two or more types.
＜エポキシ樹脂組成物におけるその他の成分＞
　本発明のエポキシ樹脂組成物には、本発明の効果が得られる範囲で、必要に応じて各種添加剤、例えば、界面活性剤、流動性改良剤、チクソ性付与剤、体質顔料等の増量剤、カラーリングのための着色顔料又は染料、防錆顔料又は防錆剤、他の樹脂粉末、ワックス等を添加することもできる。また、エポキシ樹脂組成物の粘度を下げるための溶剤、例えば、トルエン、キシレン等の芳香族系溶剤；ジメチルケトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶剤；酢酸エチル、酢酸ブチル等のエステル系溶剤；メタノール、エタノール、イソプロピルアルコール等のアルコール系溶剤；メトキシプロパノール、メトキシプロピルアセテート等のグリコール又はグリコールエステル系溶剤等を添加することもできる。 <Other Components in Epoxy Resin Composition>
To the epoxy resin composition of the present invention, various additives may be added as necessary within the range in which the effects of the present invention can be obtained, for example, surfactants, flow improvers, thixotropy imparting agents, extender pigments and the like, coloring pigments or dyes for coloring, rust-preventive pigments or rust inhibitors, other resin powders, waxes, etc. In addition, solvents for lowering the viscosity of the epoxy resin composition may be added, for example, aromatic solvents such as toluene and xylene, ketone solvents such as dimethyl ketone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ester solvents such as ethyl acetate and butyl acetate, alcohol solvents such as methanol, ethanol and isopropyl alcohol, glycol or glycol ester solvents such as methoxypropanol and methoxypropyl acetate, etc.
　本発明の一液性エポキシ樹脂組成物における、エポキシ樹脂に対する潜在性硬化剤の重量比又はモル比は、一液性エポキシ樹脂組成物を任意のゲル化度まで硬化させることができる限り、特に限定されるものではない。すなわち、硬化性エポキシ樹脂組成物は、接着剤用、塗装用、コーティング用、封止用、含浸用などの様々な用途に用いるものであり、その用途により所望の硬化状態、硬化時間、使用条件等が異なるため、一液性エポキシ樹脂組成物中の分子内に平均１個より多くのエポキシ基を有するエポキシ樹脂に対する重量比又はモル比は、適宜選択することができる。
　しかしながら、本発明の一液性エポキシ樹脂組成物に含まれる、エポキシ樹脂及び前記潜在性硬化剤の含有量としては、好ましくは潜在性硬化剤がエポキシド化合物１００重量部に対して２～５０重量部であり、より好ましくは４～４０重量部であり、最も好ましくは５～３０重量部である。 In the one-component epoxy resin composition of the present invention, the weight ratio or molar ratio of the latent curing agent to the epoxy resin is not particularly limited as long as the one-component epoxy resin composition can be cured to an arbitrary gelation degree. That is, the curable epoxy resin composition is used for various applications such as adhesives, paints, coatings, sealing, impregnation, etc., and the desired curing state, curing time, use conditions, etc. differ depending on the application, so the weight ratio or molar ratio of the latent curing agent to the epoxy resin having more than one epoxy group on average in the molecule in the one-component epoxy resin composition can be appropriately selected.
However, the content of the epoxy resin and the latent curing agent in the one-component epoxy resin composition of the present invention is preferably 2 to 50 parts by weight, more preferably 4 to 40 parts by weight, and most preferably 5 to 30 parts by weight, of the latent curing agent relative to 100 parts by weight of the epoxide compound.
　本発明の一液性硬化性エポキシ樹脂組成物は、熱硬化性のエポキシ樹脂組成物であり、常温（例えば、０℃～４０℃）では硬化しないが、加熱（例えば、８０℃～２００℃）により急激に硬化し、接着剤用、塗装用、コーティング用、封止用、含浸用として用いることが可能である。 The one-part curable epoxy resin composition of the present invention is a thermosetting epoxy resin composition that does not cure at room temperature (e.g., 0°C to 40°C), but cures rapidly when heated (e.g., 80°C to 200°C), and can be used as an adhesive, paint, coating, sealant, or impregnator.
《エポキシ樹脂硬化物》
　本発明のエポキシ樹脂硬化物は、前記一液性エポキシ樹脂組成物を加熱することによって得られる。具体的な硬化物は、接着物（接着剤）、塗装面、コーティング物、封止物、又は含侵物などである。 <<Cured epoxy resin>>
The epoxy resin cured product of the present invention can be obtained by heating the one-part epoxy resin composition. Specific examples of the cured product include adhesives, painted surfaces, coatings, sealing materials, and impregnated materials.
［３］潜在性硬化剤の製造方法
　本発明の潜在性硬化剤の製造方法は、イミダゾール化合物に、（１）、（２）、（３）、（４）、又は（５）：
Figure JPOXMLDOC01-appb-C000055
Figure JPOXMLDOC01-appb-C000056
Figure JPOXMLDOC01-appb-C000057
Figure JPOXMLDOC01-appb-C000058
Figure JPOXMLDOC01-appb-C000059
 （式中、Ｘは一般式（６）、（７）、又は（８）：
Figure JPOXMLDOC01-appb-C000060
Figure JPOXMLDOC01-appb-C000061
Figure JPOXMLDOC01-appb-C000062
 （式中、Ｒ２は、水素原子又は－ＯＣＨ２エポキシ基であり、Ｒ３は、水素原子又は炭素数１～３のアルキル基である）で表される基であり、
Ｙは、一般式（９）：
Figure JPOXMLDOC01-appb-C000063
 （式中Ｒ４は、－ＯＣＨ２エポキシ基であり、Ｒ３は、水素原子又は炭素数１～３のアルキル基である）で表される基であり、
Ｚは、一般式（１０）：
Figure JPOXMLDOC01-appb-C000064
 （式中、２つの結合手は、一般式（１０）の構造の任意の炭素原子に結合してよく、１つの炭素原子に２つの結合手が結合してもよい）で表される基であり、
Ｒ１は単結合であるか、又は炭素数１～３のアルキレン基であり、Ｘに結合するＲ１は、Ｘの２つの環構造のいずれに結合してもよく、
ｎは１～１５であり、ｍは０～１５であり、
末端に存在するＸの１つのＲ２は－ＯＣＨ２エポキシ基であり、末端に存在するＸ及びＹの末端の結合手には水素原子が結合しており、一般式（４）のＸの２つのＲ２は－ＯＣＨ２エポキシ基であり、そして
繰り返し単位中の－ＯＣＨ２エポキシ基の数は、１又は２である）
で表されるいずれかのエポキシ化合物を付加する工程を含む。 [3] Method for Producing Latent Curing Agent The method for producing the latent curing agent of the present invention comprises adding (1), (2), (3), (4), or (5) to an imidazole compound:
Figure JPOXMLDOC01-appb-C000055
Figure JPOXMLDOC01-appb-C000056
Figure JPOXMLDOC01-appb-C000057
Figure JPOXMLDOC01-appb-C000058
Figure JPOXMLDOC01-appb-C000059
 (In the formula, X represents general formula (6), (7), or (8):
Figure JPOXMLDOC01-appb-C000060
Figure JPOXMLDOC01-appb-C000061
Figure JPOXMLDOC01-appb-C000062
 (wherein R2 is a hydrogen atom or an -OCH2 epoxy group, and R3 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms),
Y is represented by the general formula (9):
Figure JPOXMLDOC01-appb-C000063
 (wherein R 4 is an —OCH 2 epoxy group, and R 3 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms),
Z is represented by the general formula (10):
Figure JPOXMLDOC01-appb-C000064
 (wherein the two bonds may be bonded to any carbon atom in the structure of general formula (10), and two bonds may be bonded to one carbon atom),
R 1 is a single bond or an alkylene group having 1 to 3 carbon atoms, and R 1 bonded to X may be bonded to either of the two ring structures of X;
n is 1 to 15, m is 0 to 15,
One R2 of X at the terminal is an -OCH2 epoxy group, hydrogen atoms are bonded to the bonds at the terminals of X and Y at the terminals, two R2 of X in general formula (4) are -OCH2 epoxy groups, and the number of -OCH2 epoxy groups in the repeating unit is 1 or 2.
The method includes the step of adding any one of the epoxy compounds represented by the following formula:
　本発明の潜在性硬化剤の製造方法における「イミダゾール化合物」及び「エポキシ化合物」は前記「潜在性硬化剤」に記載のものを限定することなく用いることができる。
　前記付加工程におけるイミダゾール化合物に対するエポキシ化合物の重量比又はモル比は限定されるものではないが、イミダゾール化合物１モルに対して、エポキシ化合物は０．５～２．０当量であり、より好ましくは０．８～１．７当量であり、更に好ましくは１．０～１．５当量である。 The "imidazole compound" and "epoxy compound" in the method for producing the latent curing agent of the present invention can be any of those described above for the "latent curing agent" without any limitation.
The weight ratio or molar ratio of the epoxy compound to the imidazole compound in the addition step is not limited, but the epoxy compound is used in an amount of 0.5 to 2.0 equivalents, more preferably 0.8 to 1.7 equivalents, and even more preferably 1.0 to 1.5 equivalents, relative to 1 mole of the imidazole compound.
　付加反応は、特に限定されるものではないが、イミダゾール化合物の＝ＮＨ基とエポキシ化合物のエポキシ基（ＣＨ２（Ｏ）ＣＨ－）とが反応し、＝Ｎ－ＣＨ２－ＣＨ（ＯＨ）－結合を形成することを意味する。
　イミダゾール化合物の＝ＮＨ基とエポキシ化合物のエポキシ基（ＣＨ２（Ｏ）ＣＨ－）とは、すべての基が反応していなくてもよいが、通常イミダゾール１モルに対して、エポキシを１．０～１．５当量使用する。従って、基本的にはエポキシ基は、前記の付加反応によってすべて消費される。 The addition reaction is not particularly limited, but means that the =NH group of an imidazole compound reacts with the epoxy group (CH 2 (O)CH-) of an epoxy compound to form a =N-CH 2 -CH(OH)- bond.
It is not necessary for all =NH groups of the imidazole compound and the epoxy groups (CH 2 (O)CH-) of the epoxy compound to react, but usually 1.0 to 1.5 equivalents of epoxy are used per mole of imidazole. Therefore, basically, all of the epoxy groups are consumed by the addition reaction.
　反応温度も特に限定されるものではないが、例えば６０～１５０℃であり、好ましくは８０～１２０℃である。 The reaction temperature is not particularly limited, but is, for example, 60 to 150°C, and preferably 80 to 120°C.
《作用》
　本発明の潜在性硬化剤において、保存安定性が向上する機構は、詳細に解析されているわけではないが、以下のように推定することができる。しかしながら、本発明は以下の推定によって、限定されるものではない。
　潜在性硬化剤において用いるイミダゾール化合物は、剛直な構造を有している。それによって、本発明の潜在性硬化剤の軟化点が向上し、潜在性硬化剤樹脂のガラス転移点が高くなっていると考えられる。硬化剤樹脂のＴｇが高くなることで、エポキシ樹脂処方物中で硬化剤粒子表面からエポキシ樹脂へ溶解する低分子成分を減らすことができ、その結果、保存安定性が向上するものと推定される。 Action
The mechanism by which the storage stability of the latent curing agent of the present invention is improved has not been analyzed in detail, but can be assumed as follows. However, the present invention is not limited to the following assumption.
The imidazole compound used in the latent curing agent has a rigid structure. It is believed that this improves the softening point of the latent curing agent of the present invention and increases the glass transition point of the latent curing agent resin. It is presumed that the increase in Tg of the curing agent resin reduces low molecular weight components that dissolve from the surface of the curing agent particles into the epoxy resin in the epoxy resin formulation, resulting in improved storage stability.
　以下、実施例によって本発明を具体的に説明するが、これらは本発明の範囲を限定するものではない。 The present invention will be explained in detail below with reference to examples, but these are not intended to limit the scope of the present invention.
《実施例１》
　本実施例では、イミダゾール化合物として、２－メチルイミダゾールを用い、エポキシ化合物としてＸＤ－１０００（日本化薬(株)製　ジシクロペンタジエン－フェノール型エポキシ樹脂　エポキシ当量：２５０ｇ／ｅｑ）を用いて、潜在性硬化剤を作製した。具体的には、撹拌機、窒素導入管を取り付けた１Ｌの４つ口フラスコに対して、２－メチルイミダゾールを８２部、キシレン、２－プロパノールの１：１（重量比）の混合溶媒を８２部加え、窒素気流下攪拌しながら８０℃まで昇温した。内温が８０℃に到達後、ＸＤ－１０００　３００部をキシレン、２－プロパノール混合溶媒３００部に溶解させたエポキシ溶液を２時間かけて滴下した。滴下終了後、８０℃３０分間温度を保持したまま攪拌し、その後２００℃まで昇温させ、さらに減圧して脱溶剤を行うことで、褐色の固体状化合物を得た。これをジェットミルにより微粉砕化を行うことで、粒径が約５μｍの潜在硬化剤を得た。エポキシ樹脂（ｊＥＲ８２８（三菱ケミカル(株)製　ビスフェノールＡ型エポキシ樹脂　エポキシ当量：１９０ｇ／ｅｑ））１００部に対して、得られた潜在性硬化剤１０部を混合して、保存安定性及び硬化物のＴｇを測定した。
　表１に示したように、本発明の硬化剤は、高い軟化点を示し、一液性エポキシ樹脂組成物は優れた保存安定性を示した。また、得られた硬化物は、１５０℃以上のＴｇを示した。 Example 1
In this example, 2-methylimidazole was used as the imidazole compound, and XD-1000 (dicyclopentadiene-phenol type epoxy resin, epoxy equivalent: 250 g/eq, manufactured by Nippon Kayaku Co., Ltd.) was used as the epoxy compound to prepare a latent curing agent. Specifically, 82 parts of 2-methylimidazole and 82 parts of a 1:1 (weight ratio) mixed solvent of xylene and 2-propanol were added to a 1 L four-neck flask equipped with a stirrer and a nitrogen inlet tube, and the mixture was heated to 80°C while stirring under a nitrogen stream. After the internal temperature reached 80°C, an epoxy solution in which 300 parts of XD-1000 was dissolved in 300 parts of a mixed solvent of xylene and 2-propanol was added dropwise over 2 hours. After the dropwise addition was completed, the mixture was stirred while maintaining the temperature at 80°C for 30 minutes, then heated to 200°C, and further reduced pressure was applied to remove the solvent, thereby obtaining a brown solid compound. The mixture was pulverized in a jet mill to obtain a latent curing agent having a particle size of about 5 μm. 10 parts of the obtained latent curing agent were mixed with 100 parts of an epoxy resin (jER828 (Mitsubishi Chemical Corporation, bisphenol A type epoxy resin, epoxy equivalent: 190 g/eq)), and the storage stability and Tg of the cured product were measured.
As shown in Table 1, the curing agent of the present invention exhibited a high softening point, and the one-part epoxy resin composition exhibited excellent storage stability. In addition, the obtained cured product exhibited a Tg of 150° C. or more.
（軟化点の測定）
　得られた固体状化合物について、軟化点をＪＩＳ　Ｋ　７２３４に従い、測定した。 (Softening Point Measurement)
The softening point of the obtained solid compound was measured in accordance with JIS K 7234.
（Ｔｇの測定）
　エポキシ樹脂（ｊＥＲ８２８）１００部に対して、潜在性硬化剤１０部を混合した処方物を注型枠に注ぎ込み、１５０℃で１ｈ硬化させた。この硬化物を昇温速度２℃／ｍｉｎ、周波数１Ｈｚの動的粘弾性測定を行い、ガラス転移点の測定を行った。表１におけるＴｇの評価基準は以下のとおりである。
〇：１５０℃以上
△：１００～１５０℃
×：１００度未満 (Measurement of Tg)
A formulation in which 100 parts of epoxy resin (jER828) was mixed with 10 parts of latent curing agent was poured into a casting mold and cured at 150°C for 1 hour. The cured material was subjected to dynamic viscoelasticity measurement at a temperature increase rate of 2°C/min and a frequency of 1 Hz to measure the glass transition point. The evaluation criteria for Tg in Table 1 are as follows:
◯: 150℃ or higher △: 100 to 150℃
×: Less than 100 degrees
（保存安定性）
　エポキシ樹脂（ｊＥＲ８２８）１００部に対して、得られた潜在性硬化剤１０部を混合した処方物の初期粘度を測定。これを４０℃で保管し、経時での粘度変化を測定し、その比から増粘率を算出した。表１における保存安定性の評価基準は以下のとおりである。
◎：４０℃、１週間で増粘率の増加が２倍以下
〇：４０℃、１週間で増粘率の増加が２倍以上（１日で増粘率の増加が２倍未満）
△：４０℃、１日で増粘率の増加が２倍以上
×：４０℃、１日でゲル化した (Storage stability)
The initial viscosity of a formulation in which 10 parts of the obtained latent hardener were mixed with 100 parts of epoxy resin (jER828) was measured. This was stored at 40°C, and the change in viscosity over time was measured, and the viscosity increase rate was calculated from the ratio. The evaluation criteria for storage stability in Table 1 are as follows.
◎: At 40°C, the increase in viscosity rate is less than doubled in one week. 〇: At 40°C, the increase in viscosity rate is more than doubled in one week (the increase in viscosity rate is less than doubled in one day).
△: Viscosity increase rate increased by more than double in one day at 40°C. ×: Gelled in one day at 40°C.
《実施例２》
　本実施例では、ＸＤ－１０００の量を表１に示した量に変更したことを除いて、実施例１の操作を繰り返した。
　表１に示したように、本発明の硬化剤は、高い軟化点を示し、一液性エポキシ樹脂組成物は優れた保存安定性を示した。また、得られた硬化物は、１５０℃以上のＴｇを示した。 Example 2
In this example, the procedure of Example 1 was repeated, except that the amount of XD-1000 was changed to the amount shown in Table 1.
As shown in Table 1, the curing agent of the present invention exhibited a high softening point, and the one-part epoxy resin composition exhibited excellent storage stability. In addition, the obtained cured product exhibited a Tg of 150° C. or more.
《実施例３》
　本実施例では、２－メチルイミダゾールに代えて、２－エチル－４－メチルイミダゾールを用いたことを除いては、実施例１の操作を繰り返した。組成は、表１に示した。
　表１に示したように、本発明の硬化剤は、高い軟化点を示し、一液性エポキシ樹脂組成物は優れた保存安定性を示した。また、得られた硬化物は、１５０℃以上のＴｇを示した。 Example 3
In this example, the procedure of Example 1 was repeated, except that 2-ethyl-4-methylimidazole was used instead of 2-methylimidazole. The composition is shown in Table 1.
As shown in Table 1, the curing agent of the present invention exhibited a high softening point, and the one-part epoxy resin composition exhibited excellent storage stability. In addition, the obtained cured product exhibited a Tg of 150° C. or more.
《実施例４》
　本実施例では、２－メチルイミダゾールに代えて、イミダゾールを用いたことを除いては、実施例１の操作を繰り返した。組成は、表１に示した。
　表１に示したように、本発明の硬化剤は、高い軟化点を示し、一液性エポキシ樹脂組成物は優れた保存安定性を示した。また、得られた硬化物は、１５０℃以上のＴｇを示した。 Example 4
In this example, the procedure of Example 1 was repeated, except that imidazole was used instead of 2-methylimidazole. The composition is shown in Table 1.
As shown in Table 1, the curing agent of the present invention exhibited a high softening point, and the one-part epoxy resin composition exhibited excellent storage stability. In addition, the obtained cured product exhibited a Tg of 150° C. or more.
《実施例５》
　本実施例では、ＸＤ－１０００に代えて、ＮＣ－７０００Ｌ（日本化薬(株)製　ナフトール－クレゾールノボラック型エポキシ樹脂　エポキシ当量：２３０ｇ／ｅｑ）を用いたことを除いては、実施例１の操作を繰り返した。組成は、表１に示した。
　表１に示したように、本発明の硬化剤は、高い軟化点を示し、一液性エポキシ樹脂組成物は優れた保存安定性を示した。また、得られた硬化物は、１５０℃以上のＴｇを示した。 Example 5
In this example, the procedure of Example 1 was repeated, except that NC-7000L (naphthol-cresol novolac type epoxy resin, epoxy equivalent: 230 g/eq, manufactured by Nippon Kayaku Co., Ltd.) was used instead of XD-1000. The composition is shown in Table 1.
As shown in Table 1, the curing agent of the present invention exhibited a high softening point, and the one-part epoxy resin composition exhibited excellent storage stability. In addition, the obtained cured product exhibited a Tg of 150° C. or more.
《実施例６》
　本実施例では、ＸＤ－１０００に代えて、ＮＣ－３０００Ｈ（日本化薬(株)製　ビフェニル－ノボラック型エポキシ樹脂　エポキシ当量：２９０ｇ／ｅｑ）を用いたことを除いては、実施例１の操作を繰り返した。組成は、表１に示した。
　表１に示したように、本発明の硬化剤は、高い軟化点を示し、一液性エポキシ樹脂組成物は優れた保存安定性を示した。また、得られた硬化物は、１５０℃以上のＴｇを示した。 Example 6
In this example, the procedure of Example 1 was repeated, except that NC-3000H (biphenyl-novolac type epoxy resin, epoxy equivalent: 290 g/eq, manufactured by Nippon Kayaku Co., Ltd.) was used instead of XD-1000. The composition is shown in Table 1.
As shown in Table 1, the curing agent of the present invention exhibited a high softening point, and the one-part epoxy resin composition exhibited excellent storage stability. In addition, the obtained cured product exhibited a Tg of 150° C. or more.
《実施例７》
　本実施例では、ＸＤ－１０００に代えて、ＨＰ－４０３２Ｄ（ＤＩＣ(株)製　ナフタレン型エポキシ樹脂　エポキシ当量：１３６ｇ／ｅｑ）を用いたことを除いては、実施例１の操作を繰り返した。組成は、表１に示した。
　表１に示したように、本発明の硬化剤は、一液性エポキシ樹脂組成物は優れた保存安定性を示した。また、得られた硬化物は、１５０℃以上のＴｇを示した。 Example 7
In this example, the procedure of Example 1 was repeated, except that HP-4032D (manufactured by DIC Corporation, naphthalene-type epoxy resin, epoxy equivalent: 136 g/eq) was used instead of XD-1000. The composition is shown in Table 1.
As shown in Table 1, the one-part epoxy resin composition containing the curing agent of the present invention exhibited excellent storage stability. In addition, the obtained cured product exhibited a Tg of 150° C. or more.
《実施例８》
　本実施例では、ＸＤ－１０００に代えて、ＨＰ－４７００（ＤＩＣ(株)製　ナフタレン型エポキシ樹脂　エポキシ当量：１６５ｇ／ｅｑ）およびｊＥＲ８２８を用いたことを除いては、実施例１の操作を繰り返した。組成は、表１に示した。
　表１に示したように、本発明の硬化剤は、高い軟化点を示し、一液性エポキシ樹脂組成物は優れた保存安定性を示した。また、得られた硬化物は、１５０℃以上のＴｇを示した。 Example 8
In this example, the procedure of Example 1 was repeated, except that HP-4700 (manufactured by DIC Corporation, naphthalene-type epoxy resin, epoxy equivalent: 165 g/eq) and jER828 were used instead of XD-1000. The composition is shown in Table 1.
As shown in Table 1, the curing agent of the present invention exhibited a high softening point, and the one-part epoxy resin composition exhibited excellent storage stability. In addition, the obtained cured product exhibited a Tg of 150° C. or more.
《実施例９》
　本実施例では、ＸＤ－１０００に代えて、ＨＰ－４０３２ＤおよびＨＰ－４７００を用いたことを除いては、実施例１の操作を繰り返した。組成は、表１に示した。
　表１に示したように、本発明の硬化剤は、高い軟化点を示し、一液性エポキシ樹脂組成物は優れた保存安定性を示した。また、得られた硬化物は、１５０℃以上のＴｇを示した。 Example 9
In this example, the procedure of Example 1 was repeated, except that HP-4032D and HP-4700 were used instead of XD-1000. The composition is shown in Table 1.
As shown in Table 1, the curing agent of the present invention exhibited a high softening point, and the one-part epoxy resin composition exhibited excellent storage stability. In addition, the obtained cured product exhibited a Tg of 150° C. or more.
《実施例１０》
　本実施例では、ＸＤ－１０００に代えて、ＨＰ－４７７０（ＤＩＣ(株)製　ナフタレン型エポキシ樹脂　エポキシ当量：２０４ｇ／ｅｑ）を用いたことを除いては、実施例１の操作を繰り返した。組成は、表１に示した。
　表１に示したように、本発明の硬化剤は、高い軟化点を示し、一液性エポキシ樹脂組成物は優れた保存安定性を示した。また、得られた硬化物は、１５０℃以上のＴｇを示した。 Example 10
In this example, the procedure of Example 1 was repeated, except that HP-4770 (manufactured by DIC Corporation, naphthalene-type epoxy resin, epoxy equivalent: 204 g/eq) was used instead of XD-1000. The composition is shown in Table 1.
As shown in Table 1, the curing agent of the present invention exhibited a high softening point, and the one-part epoxy resin composition exhibited excellent storage stability. In addition, the obtained cured product exhibited a Tg of 150° C. or more.
《実施例１１》
　本実施例では、ＸＤ－１０００に代えて、オグソールＰＧ－１００（大阪ガスケミカル(株)製　フルオレン型エポキシ樹脂　エポキシ当量：２５４ｇ／ｅｑ）を用いたことを除いては、実施例１の操作を繰り返した。組成は、表１に示した。
　表１に示したように、本発明の硬化剤は、高い軟化点を示し、一液性エポキシ樹脂組成物は優れた保存安定性を示した。また、得られた硬化物は、１５０℃以上のＴｇを示した。 Example 11
In this example, the procedure of Example 1 was repeated, except that OGSOL PG-100 (fluorene type epoxy resin, epoxy equivalent: 254 g/eq, manufactured by Osaka Gas Chemicals Co., Ltd.) was used instead of XD-1000. The composition is shown in Table 1.
As shown in Table 1, the curing agent of the present invention exhibited a high softening point, and the one-part epoxy resin composition exhibited excellent storage stability. In addition, the obtained cured product exhibited a Tg of 150° C. or more.
《比較例１》
　本比較例では、ＸＤ－１０００に代えて、ｊＥＲ８２８を用いたことを除いては、実施例１の操作を繰り返した。組成は、表１に示した。
　表１に示したように、得られた硬化剤は、一液性エポキシ樹脂組成物は保存安定性も劣っていた。 Comparative Example 1
In this comparative example, the procedure of Example 1 was repeated except that jER828 was used instead of XD-1000. The composition is shown in Table 1.
As shown in Table 1, the obtained curing agent and the one-component epoxy resin composition were poor in storage stability.
《比較例２》
　本実施例では、ＸＤ－１０００に代えて、ｊＥＲ８２８を用いたことを除いては、実施例３の操作を繰り返した。組成は、表１に示した。
　表１に示したように、得られた硬化剤は、一液性エポキシ樹脂組成物は保存安定性も劣っていた。 Comparative Example 2
In this example, the procedure of Example 3 was repeated, except that jER828 was used instead of XD-1000. The composition is shown in Table 1.
As shown in Table 1, the obtained curing agent and the one-component epoxy resin composition were poor in storage stability.
《比較例３》
　本実施例では、ＸＤ－１０００に代えて、ｊＥＲ１００１（三菱ケミカル(株)製　ビスフェノールＡ型エポキシ樹脂　エポキシ当量：４７５ｇ／ｅｑ）を用いたことを除いては、実施例１の操作を繰り返した。組成は、表１に示した。
　表１に示したように、本発明の一液性エポキシ樹脂組成物は保存安定性が劣っており、また、得られた硬化物のＴｇは、１００～１５０℃であった。 Comparative Example 3
In this example, the procedure of Example 1 was repeated, except that jER1001 (Mitsubishi Chemical Corporation, bisphenol A type epoxy resin, epoxy equivalent: 475 g/eq) was used instead of XD-1000. The composition is shown in Table 1.
As shown in Table 1, the one-component epoxy resin composition of the present invention had poor storage stability, and the Tg of the resulting cured product was 100 to 150°C.
《比較例４》
　本実施例では、ＸＤ－１０００に代えて、ｊＥＲ１００１を用いたことを除いては、実施例３の操作を繰り返した。組成は、表１に示した。
　表１に示したように、本発明の一液性エポキシ樹脂組成物は保存安定性が劣っており、また、得られた硬化物のＴｇは、１００～１５０℃であった。 Comparative Example 4
In this example, the procedure of Example 3 was repeated, except that jER1001 was used instead of XD-1000. The composition is shown in Table 1.
As shown in Table 1, the one-component epoxy resin composition of the present invention had poor storage stability, and the Tg of the resulting cured product was 100 to 150°C.
　本発明の潜在性硬化剤は、一液性エポキシ樹脂組成物に用いることができる。また本発明の一液性エポキシ樹脂組成物は熱硬化性のエポキシ樹脂組成物として、接着剤、塗料などに用いることができる。 The latent curing agent of the present invention can be used in a one-part epoxy resin composition. The one-part epoxy resin composition of the present invention can also be used as a thermosetting epoxy resin composition in adhesives, paints, etc.

Claims (5)

  1. 　一般式（１）、（２）、（３）、（４）、又は（５）：
    Figure JPOXMLDOC01-appb-C000001
    Figure JPOXMLDOC01-appb-C000002
    Figure JPOXMLDOC01-appb-C000003
    Figure JPOXMLDOC01-appb-C000004
    Figure JPOXMLDOC01-appb-C000005
     （式中、Ｘは一般式（６）、（７）、又は（８）：
    Figure JPOXMLDOC01-appb-C000006
    Figure JPOXMLDOC01-appb-C000007
    Figure JPOXMLDOC01-appb-C000008
     （式中、Ｒ２は、水素原子又は－ＯＣＨ２エポキシ基であり、Ｒ３は、水素原子又は炭素数１～３のアルキル基である）で表される基であり、
    Ｙは、一般式（９）：
    Figure JPOXMLDOC01-appb-C000009
     （式中Ｒ４は、－ＯＣＨ２エポキシ基であり、Ｒ３は、水素原子又は炭素数１～３のアルキル基である）で表される基であり、
    Ｚは、一般式（１０）：
    Figure JPOXMLDOC01-appb-C000010
     （式中、２つの結合手は、一般式（１０）の構造の任意の炭素原子に結合してよく、１つの炭素原子に２つの結合手が結合してもよい）で表される基であり、
    Ｒ１は単結合であるか、又は炭素数１～３のアルキレン基であり、Ｘに結合するＲ１は、Ｘの２つの環構造のいずれに結合してもよく、
    ｎは１～１５であり、ｍは０～１５であり、
    末端に存在するＸの１つのＲ２は－ＯＣＨ２エポキシ基であり、末端に存在するＸ及びＹの末端の結合手には水素原子が結合しており、一般式（４）のＸの２つのＲ２は－ＯＣＨ２エポキシ基であり、そして
    繰り返し単位中の－ＯＣＨ２エポキシ基の数は、１又は２である）
    で表されるいずれかのエポキシ化合物と、イミダゾール化合物とが付加された、潜在性硬化剤。     General formula (1), (2), (3), (4), or (5):
    Figure JPOXMLDOC01-appb-C000001
    Figure JPOXMLDOC01-appb-C000002
    Figure JPOXMLDOC01-appb-C000003
    Figure JPOXMLDOC01-appb-C000004
    Figure JPOXMLDOC01-appb-C000005
     (In the formula, X represents general formula (6), (7), or (8):
    Figure JPOXMLDOC01-appb-C000006
    Figure JPOXMLDOC01-appb-C000007
    Figure JPOXMLDOC01-appb-C000008
     (wherein R2 is a hydrogen atom or an -OCH2 epoxy group, and R3 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms),
    Y is represented by the general formula (9):
    Figure JPOXMLDOC01-appb-C000009
     (wherein R 4 is an —OCH 2 epoxy group, and R 3 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms),
    Z is represented by the general formula (10):
    Figure JPOXMLDOC01-appb-C000010
     (wherein the two bonds may be bonded to any carbon atom in the structure of general formula (10), and two bonds may be bonded to one carbon atom),
    R 1 is a single bond or an alkylene group having 1 to 3 carbon atoms, and R 1 bonded to X may be bonded to either of the two ring structures of X;
    n is 1 to 15, m is 0 to 15,
    One R2 of X at the terminal is an -OCH2 epoxy group, hydrogen atoms are bonded to the bonds at the terminals of X and Y at the terminals, two R2 of X in general formula (4) are -OCH2 epoxy groups, and the number of -OCH2 epoxy groups in the repeating unit is 1 or 2.
    and an imidazole compound are added to any one of the epoxy compounds represented by the following formula (1):
  2. 　前記エポキシ化合物が、下記式で表されるエポキシ化合物からなる群から選択される、請求項１に記載の潜在性化合物。
    Figure JPOXMLDOC01-appb-C000011
     （式中、ｍは０～１５であり、ｌは１～１５である。）     2. The latent compound according to claim 1, wherein the epoxy compound is selected from the group consisting of epoxy compounds represented by the following formula:
    Figure JPOXMLDOC01-appb-C000011
     (In the formula, m is 0 to 15, and l is 1 to 15.)
  3. 　請求項１又は２に記載の潜在性硬化剤、及びエポキシ樹脂を含む一液性エポキシ樹脂組成物。 A one-part epoxy resin composition comprising the latent curing agent according to claim 1 or 2 and an epoxy resin.
  4. 　請求項３に記載の一液性エポキシ樹脂組成物を加熱することによって得られるエポキシ樹脂硬化物。 An epoxy resin cured product obtained by heating the one-part epoxy resin composition described in claim 3.
  5. 　イミダゾール化合物に、（１）、（２）、（３）、（４）、又は（５）：
    Figure JPOXMLDOC01-appb-C000012
    Figure JPOXMLDOC01-appb-C000013
    Figure JPOXMLDOC01-appb-C000014
    Figure JPOXMLDOC01-appb-C000015
    Figure JPOXMLDOC01-appb-C000016
     （式中、Ｘは一般式（６）、（７）、又は（８）：
    Figure JPOXMLDOC01-appb-C000017
    Figure JPOXMLDOC01-appb-C000018
    Figure JPOXMLDOC01-appb-C000019
     （式中、Ｒ２は、水素原子又は－ＯＣＨ２エポキシ基であり、Ｒ３は、水素原子又は炭素数１～３のアルキル基である）で表される基であり、
    Ｙは、一般式（９）：
    Figure JPOXMLDOC01-appb-C000020
     （式中Ｒ４は、－ＯＣＨ２エポキシ基であり、Ｒ３は、水素原子又は炭素数１～３のアルキル基である）で表される基であり、
    Ｚは、一般式（１０）：
    Figure JPOXMLDOC01-appb-C000021
     （式中、２つの結合手は、一般式（１０）の構造の任意の炭素原子に結合してよく、１つの炭素原子に２つの結合手が結合してもよい）で表される基であり、
    Ｒ１は単結合であるか、又は炭素数１～３のアルキレン基であり、Ｘに結合するＲ１は、Ｘの２つの環構造のいずれに結合してもよく、
    ｎは１～１５であり、ｍは０～１５であり、
    末端に存在するＸの１つのＲ２は－ＯＣＨ２エポキシ基であり、末端に存在するＸ及びＹの末端の結合手には水素原子が結合しており、一般式（４）のＸの２つのＲ２は－ＯＣＨ２エポキシ基であり、そして
    繰り返し単位中の－ＯＣＨ２エポキシ基の数は、１又は２である）
    で表されるいずれかのエポキシ化合物を付加する工程を含む、
    潜在性硬化剤の製造方法。     The imidazole compound is (1), (2), (3), (4), or (5):
    Figure JPOXMLDOC01-appb-C000012
    Figure JPOXMLDOC01-appb-C000013
    Figure JPOXMLDOC01-appb-C000014
    Figure JPOXMLDOC01-appb-C000015
    Figure JPOXMLDOC01-appb-C000016
     (In the formula, X represents general formula (6), (7), or (8):
    Figure JPOXMLDOC01-appb-C000017
    Figure JPOXMLDOC01-appb-C000018
    Figure JPOXMLDOC01-appb-C000019
     (wherein R2 is a hydrogen atom or an -OCH2 epoxy group, and R3 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms),
    Y is represented by the general formula (9):
    Figure JPOXMLDOC01-appb-C000020
     (wherein R 4 is an —OCH 2 epoxy group, and R 3 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms),
    Z is represented by the general formula (10):
    Figure JPOXMLDOC01-appb-C000021
     (wherein the two bonds may be bonded to any carbon atom in the structure of general formula (10), and two bonds may be bonded to one carbon atom),
    R 1 is a single bond or an alkylene group having 1 to 3 carbon atoms, and R 1 bonded to X may be bonded to either of the two ring structures of X;
    n is 1 to 15, m is 0 to 15,
    One R2 of X at the terminal is an -OCH2 epoxy group, hydrogen atoms are bonded to the bonds at the terminals of X and Y at the terminals, two R2 of X in general formula (4) are -OCH2 epoxy groups, and the number of -OCH2 epoxy groups in the repeating unit is 1 or 2.
    The epoxy compound represented by the formula:
    A method for producing a latent hardener.
PCT/JP2024/015300 2023-04-17 2024-04-17 Latent curing agent and one-pack epoxy resin composition WO2024219430A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003171443A (en) * 2001-12-05 2003-06-20 Asahi Denka Kogyo Kk Curing agent composition for epoxy resin
JP2014136761A (en) * 2013-01-17 2014-07-28 Asahi Kasei E-Materials Corp Method of producing adduct-modified amine compound
JP2019123795A (en) * 2018-01-16 2019-07-25 大阪ガスケミカル株式会社 Amine adduct and use thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003171443A (en) * 2001-12-05 2003-06-20 Asahi Denka Kogyo Kk Curing agent composition for epoxy resin
JP2014136761A (en) * 2013-01-17 2014-07-28 Asahi Kasei E-Materials Corp Method of producing adduct-modified amine compound
JP2019123795A (en) * 2018-01-16 2019-07-25 大阪ガスケミカル株式会社 Amine adduct and use thereof

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