Latent curing agent and one-pack epoxy resin composition

Abstract

A purpose of the present invention is to provide an aliphatic amine curing agent or an alicyclic amine curing agent that exhibits high storage stability.　The purpose of the present invention can be achieved by a latent curing agent obtained by adding an epoxy compound represented by any one of general formulas (1), (2), (3), (4), and (5) to an aliphatic amine compound or an alicyclic amine compound.

Description

Latent curing agent and one-component epoxy resin composition

[0001] The present invention relates to a latent curing agent and a one-component epoxy resin composition. According to the present invention, a latent curing agent exhibiting excellent storage stability can be obtained.

[0002] Amine compounds are widely used as curing agents and curing catalysts for epoxy resins. Conventional amine curing agents are primarily liquid, and two-component systems, in which epoxy resin and curing agent are mixed, are the norm. Amine curing agents are broadly classified into aliphatic amines, aromatic amines, tertiary amines, imidazoles, and the like. Aliphatic amines and alicyclic amines, in particular, contain active hydrogen and are known to be able to cure at low temperatures when formulated with epoxy resins. However, many conventional aliphatic amines and alicyclic amines are liquid, and their formulations with epoxy resins have a short pot life, solidifying within a few hours at room temperature. Therefore, aliphatic amines and alicyclic amines that can be formulated as one-component systems are desirable.

[0003] Special Publication No. 7-5708

[0004] For example, epoxy adduct modification of aliphatic amines or alicyclic amines has been widely carried out, and modification with bisphenol A epoxy resin has been particularly widely used (Patent Document 1). However, modification with bisphenol A epoxy resin alone does not increase the softening point of the resulting resin, and even if the resulting resin is pulverized, it often re-aggregates at room temperature. Therefore, an object of the present invention is to provide an aliphatic amine curing agent or alicyclic amine curing agent that exhibits high storage stability.

[0005] The present inventors have conducted extensive research into aliphatic amine curing agents or alicyclic amine curing agents that exhibit high storage stability, and have surprisingly found that by adding an epoxy compound having a specific structure to an aliphatic amine compound or alicyclic amine compound, an aliphatic amine curing agent or alicyclic amine curing agent that exhibits high storage stability can be obtained. The present invention is based on this finding. Therefore, the present invention relates to a compound represented by the following general formula: [1] (1), (2), (3), (4), or (5): (wherein X represents general formula (6), (7), or (8): (In the formula, R ２ is a hydrogen atom or —OCH ２ is an epoxy group, and R ３ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), and Y is a group represented by general formula (9): (In the formula R ４ is -OCH ２ is an epoxy group, and R ３ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), and Z is a group represented by 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 may be bonded to either of the two ring structures of X, n is 1 to 15, m is 0 to 15, and one R of X present at the terminal ２ Ha-OCH ２ The epoxy group is a group having a hydrogen atom bonded to the terminal bond of X and Y, and the two R ２ Ha-OCH ２ is an epoxy group, and —OCH ２ the number of epoxy groups is 1 or 2) and an aliphatic amine compound or an alicyclic amine compound are added to each other. [2] The latent compound according to [1], wherein the epoxy compound is selected from the group consisting of epoxy compounds represented by the following formulas: (wherein, o is 0 to 14, 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] A cured epoxy resin product obtained by heating the one-component epoxy resin composition according to [3]; and [5] A compound comprising an aliphatic amine compound or an alicyclic amine compound and (1), (2), (3), (4), or (5): (wherein X represents general formula (6), (7), or (8): (In the formula, R ２ is a hydrogen atom or —OCH ２ is an epoxy group, and R ３ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), and Y is a group represented by general formula (9): (In the formula R ４ is -OCH ２ is an epoxy group, and R ３ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), and Z is a group represented by 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 may be bonded to either of the two ring structures of X, n is 1 to 15, m is 0 to 15, and one R of X present at the terminal ２ Ha-OCH ２ The epoxy group is a group having a hydrogen atom bonded to the terminal bond of X and Y, and the two R ２ Ha-OCH ２ is an epoxy group, and —OCH ２ wherein the number of epoxy groups is 1 or 2.

[0006] The latent curing agent of the present invention can exhibit excellent storage stability.

[0007] [1] 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 aliphatic amine compound or an alicyclic amine compound.

[0008] The addition of an epoxy compound to an aliphatic amine compound or an alicyclic amine compound is not limited, but may be carried out by the addition of an —NH ２ group or ═NH group and the epoxy group (CH ２ (O)CH-) reacts to form -NH-CH ２ -CH(OH)- or =N-CH ２ This means forming a —CH(OH)— bond.

[0009] <Epoxy Compound> The epoxy compound is not particularly limited as long as it has a structure represented by any one of general formulas (1) to (5). By having the structure, the epoxy compound can form a rigid skeleton. By forming a rigid skeleton, it is possible to increase the softening point of the aliphatic amine compound or alicyclic amine compound, and to improve the storage stability of the latent curing agent.

[0010] X of the epoxy compound is represented by the general formula (6), (7), or (8): It is a group represented by the following formula:

[0011] R ２ is a hydrogen atom or —OCH ２ When X is present at the terminal of the epoxy compound, at least one R ２ Ha-OCH ２ The two R of X in general formula (4) are epoxy groups. ２ Ha-OCH ２ It is an epoxy group. ３is 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. R ３ is preferably a hydrogen atom or a methyl group.

[0012] Y is a group represented by the general formula (9): R is a group represented by the formula: ４ is -OCH ２ is an epoxy group, and R ３ 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. R ３ is preferably a hydrogen atom or a methyl group.

[0013] Z is a group 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.

[0014] 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. １ may be attached to either of the two ring structures of X.

[0015] 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 single polymer or a mixture of polymers where n is 1 to 15. In the case of a mixture, n in general formula (1) represents the average number of repeating units. 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 or a mixture of polymers where m is 0 to 15. In the case of a mixture, m in general formula (1) represents the average number of repeating units. In the case of a single polymer, m is an integer.

[0016] (Terminal) One R of X present at the terminal ２ Ha-OCH ２ It is an epoxy group. A hydrogen atom is bonded to the bond on the terminal side of X and Y present at the terminal. In other words, X and Y at the terminal are monovalent groups, not divalent groups.

[0017] (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. When the number is within the above range, gelation during synthesis of the aliphatic amine or alicyclic amine-epoxy adduct can be prevented, and a good epoxy resin curing agent can be obtained.

[0018] (Repeating unit) —OCH in the repeating unit of general formula (1) or (2) ２ The number of epoxy groups is one or two.

[0019] (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 upper limit of the average number of epoxy groups contained in the epoxy compound represented by general formula (1) or (2) is, for example, 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 within the above range, gelation of the epoxy resin adduct can be prevented and a good epoxy resin curing agent can be obtained.

[0020] The epoxy compound used in the present invention is not limited, but specific examples include compounds represented by the following formula: In the formula, o is 0 to 14, and l is 1 to 15. o is 0 to 14, 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 formula is a polymer, and the number of o may be a single polymer, or a mixture of polymers where the number of o is 0 to 14. In the case of a mixture, o in the formula represents the average number of repeats. In the case of a single polymer, o 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 formula is a polymer, and the number of o may be a single polymer, or a mixture of polymers where the number of o is 1 to 15. In the case of a mixture, l in the formula represents the average number of repeats. In the case of a single polymer, l is an integer.

[0021] Aliphatic Amine Compound The aliphatic amine compound is not particularly limited as long as the effects of the present invention can be obtained. Examples of the aliphatic amine compound include ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, diethylenetriamine, dipropylenetriamine, triethylenetetramine (TETA), tripropylenetetramine, tetraethylenepentamine, hexamethylenediamine, iminobispropylamine, and bis(hexamethylene)triamine. , 1,3,6-trisaminomethylhexane, trimethylhexamethylenediamine, polyether diamine, diethylaminopropylamine, metaxylylenediamine (MXDA), 1,3-bisaminomethylcyclohexane (1,3-BAC), 1,4-bisaminomethylcyclohexane, bis(aminomethyl)norbornane, N-aminoethylpiperazine, or 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro(5.5)undecane.

[0022] <<Alicyclic Amine Compound>> The alicyclic amine compound is not particularly limited as long as the effects of the present invention can be obtained, and examples thereof include menthene diamine, 1,4-cyclohexane diamine, isophorone diamine, bis(4-aminocyclohexyl)methane, 2,2′-dimethyl-4,4′-methylenebis(cyclohexylamine), and 1,2-diaminocyclohexane.

[0023] The contents of the aliphatic amine compound or alicyclic amine compound and the epoxy compound contained in the latent curing agent of the present invention are not particularly limited, but the amount of the epoxy compound relative to 1 mole of the aliphatic amine compound or alicyclic amine compound is 0.5 to 2.0 equivalents, more preferably 0.8 to 1.7 equivalents, and even more preferably 1.0 to 1.5 equivalents.

[0024] (Softening Point) The composition in which an epoxy compound is added to the aliphatic amine compound or alicyclic amine compound is a solid composition. The softening point of the solid composition is not particularly limited as long as the solid composition can be pulverized into powder, but the upper limit is, for example, 150°C or lower, in one embodiment 140°C or lower, and in one embodiment 135°C or lower. The lower limit is, for example, 90°C or higher, in one embodiment 95°C or higher, and in one embodiment 100°C or higher. The upper and lower limits can be combined as appropriate.

[0025] [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.

[0026] <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 per molecule, 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, taking into account the effect of the epoxy resin in the epoxy resin composition. Note that "average" refers to the average number of epoxy groups per molecule when two or more 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 polycarboxylic acids, epoxy compounds (glycidyl aminoglycidyl ethers) of aminophenols, epoxy compounds (glycidyl aminoglycidyl ethers) of polyamines, and other epoxy compounds.

[0027] More specific examples of the mononuclear polyhydric phenol compound include catechol, resorcinol, hydroquinone, and halogen (for example, chlorine, bromine) derivatives thereof.

[0028] More 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.

[0029] More 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.

[0030] More specific examples of the hydroxycarboxylic acids include p-hydroxybenzoic acid and β-hydroxynaphthoic acid.

[0031] More specific examples of the polycarboxylic 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.

[0032] More specific examples of the aminophenols include p-aminophenol and p-aminoalkylphenol.

[0033] More specific examples of the polyvalent amines 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 diaminodiphenyl sulfone.

[0034] More specific examples of the other epoxy compounds include epoxidized polyolefin, epoxidized polybutadiene, epoxidized soybean oil, glycidyl hydantoin, di- or triglycidyl isocyanurate, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide, and 3,4-epoxycyclohexyl-3,4-epoxycyclohexane carboxylate.

[0035] Among the epoxy resins exemplified above, it is particularly preferable to use bisphenol A epoxy resins, bisphenol F epoxy resins, phenol novolac epoxy resins, cresol novolac epoxy resins, biphenyl epoxy resins, naphthol epoxy resins, or diaminodiphenylmethane epoxy resins, because when the epoxy resin composition of the present invention is cured, the cured product has excellent heat resistance, electrical properties such as insulating properties, adhesiveness, etc. The above epoxy resins can be used alone or in combination of two or more.

[0036] As the epoxy resin in the epoxy resin composition of the present invention, monofunctional epoxy compounds can be used in combination, provided that the effects of the present invention are not impaired. 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), and styrene oxide. Generally, these monofunctional epoxy compounds have low viscosity, which is advantageous, particularly in terms of handling the epoxy resin composition. However, they can also reduce the mechanical properties and heat resistance (glass transition temperature) of the final epoxy resin cured product, so their use amount should be kept as small as possible. Furthermore, the monofunctional epoxy resins can be used alone or in combination of two or more types.

[0037] <Other Components in Epoxy Resin Composition> To the epoxy resin composition of the present invention, various additives may be added as needed, within the scope of obtaining the effects of the present invention, such as surfactants, flow improvers, thixotropy-imparting agents, extender pigments and other extender agents, coloring pigments or dyes for coloring, anti-rust pigments or anti-rust agents, other resin powders, waxes, etc. In addition, solvents for reducing the viscosity of the epoxy resin composition may be added, such as 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.

[0038] The weight or molar ratio of the latent curing agent to the epoxy resin in the one-component epoxy resin composition of the present invention is not particularly limited, as long as it can cure the one-component epoxy resin composition to a desired gelation degree. In other words, curable epoxy resin compositions are used for a variety of applications, such as adhesives, paints, coatings, encapsulants, and impregnation. Since the desired cure state, cure time, and use conditions vary depending on the application, the weight or molar ratio of the latent curing agent to the epoxy resin having an average of more than one epoxy group per molecule in the one-component epoxy resin composition can be appropriately selected. However, the content of the epoxy resin and the latent curing agent contained in the one-component epoxy resin composition of the present invention is preferably 2 to 70 parts by weight, more preferably 4 to 60 parts by weight, and most preferably 5 to 50 parts by weight, of the latent curing agent per 100 parts by weight of the epoxide compound.

[0039] The one-component 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 for adhesives, paints, coatings, sealing, and impregnation.

[0040] <<Cured Epoxy Resin Product>> The cured epoxy resin product of the present invention can be obtained by heating the one-component epoxy resin composition. Specific examples of the cured product include an adherend (adhesive), a painted surface, a coated material, a sealed material, and an impregnated material.

[0041] [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 aliphatic amine compound or an alicyclic amine compound: (wherein X represents general formula (6), (7), or (8): (In the formula, R ２ is a hydrogen atom or —OCH ２ is an epoxy group, and R ３is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), and Y is a group represented by general formula (9): (In the formula R ４ is -OCH ２ is an epoxy group, and R ３ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), and Z is a group represented by 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 may be bonded to either of the two ring structures of X, n is 1 to 15, m is 0 to 15, and one R of X present at the terminal ２ Ha-OCH ２ The epoxy group is a group having a hydrogen atom bonded to the terminal bond of X and Y, and the two R ２ Ha-OCH ２ is an epoxy group, and —OCH ２ The number of epoxy groups is 1 or 2).

[0042] In the method for producing a latent curing agent of the present invention, the "aliphatic amine compound or alicyclic amine compound" and "epoxy compound" can be any of those described above under "latent curing agents" without any limitation. The weight ratio or molar ratio of the epoxy compound to the aliphatic amine compound or alicyclic amine 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 per mole of the aliphatic amine compound or alicyclic amine compound.

[0043] The addition reaction is not particularly limited, but may be carried out by reacting an aliphatic amine compound or an alicyclic amine compound with —NH ２ group or ═NH group and the epoxy group (CH ２ (O)CH-) reacts to form -NH-CH ２-CH(OH)- or =N-CH ２ It means forming a —CH(OH)— bond. —NH of an aliphatic amine compound or an alicyclic amine compound ２ group or ═NH group and the epoxy group (CH ２ Although it is not necessary for all groups to react with (O)CH-), 1.0 to 1.5 equivalents of epoxy are usually used per mole of amino groups. Therefore, basically, all epoxy groups are consumed by the addition reaction.

[0044] The reaction temperature is not particularly limited, but is, for example, 60 to 150°C, preferably 80 to 120°C.

[0045] <<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 presumed as follows. However, the present invention is not limited by the following presumption. The epoxy compound used in the latent curing agent has a rigid structure. This is thought to improve the softening point of the latent curing agent of the present invention, and increase the glass transition temperature of the latent curing agent resin. It is presumed that increasing the Tg of the curing agent resin can reduce low-molecular-weight components that dissolve from the surface of curing agent particles into the epoxy resin in the epoxy resin formulation, resulting in improved storage stability.

[0046] The present invention will be specifically described below with reference to examples, but these examples are not intended to limit the scope of the present invention.

[0047] Example 1 In this example, a latent curing agent was prepared using ethylenediamine (EDA) as the aliphatic amine and XD-1000 (a dicyclopentadiene-phenol type epoxy resin, epoxy equivalent: 250 g / eq, manufactured by Nippon Kayaku Co., Ltd.) as the epoxy compound. Specifically, 90 parts by weight of EDA and 90 parts of a 1:1 (by weight) 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 prepared by dissolving 250 parts of XD-1000 in 250 parts of a xylene and 2-propanol mixed solvent was added dropwise over 2 hours. After completion of the dropwise addition, 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, yielding a brown solid compound. This was then finely pulverized using a jet mill to obtain a latent curing agent with a particle size of approximately 5 μm. 20 parts of the obtained latent curing agent were mixed with 100 parts of an epoxy resin (jER828 (bisphenol A-type epoxy resin manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 190 g / eq)), and the storage stability and gel time were measured. As shown in Table 1, the one-component epoxy resin composition using the curing agent of the present invention exhibited excellent curability at 80°C and excellent storage stability at 40°C.

[0048] (Measurement of Softening Point) The softening point of the obtained solid compound was measured in accordance with JIS K 7234.

[0049] (Evaluation of pulverization) The pulverized powder was stored overnight at room temperature, and the state of aggregation was checked the next day. Evaluation was performed according to the following criteria: ◯: No change in state ×: Aggregated and unusable

[0050] (Evaluation of curability) The gel time of the obtained one-component epoxy resin composition was measured using a Yasuda gel timer. Specifically, 2.0 g of the epoxy resin composition was placed in a test tube as a sample and maintained at a predetermined temperature in an oil bath. A glass rod was inserted into the sample and stirred by rotating it, and the time when stirring became impossible was taken as the gel time. The evaluation was made according to the following criteria: ◎: Gelation occurred within 5 minutes; ○: Gelation occurred within 6 minutes; ×: No gelation occurred within 6 minutes.

[0051] (Storage Stability) 20 parts of the obtained latent curing agent was mixed with 100 parts of epoxy resin (jER828) to measure the initial viscosity of the formulation. 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: ◎: The viscosity increase rate increased by 2 times or less in one week at 40°C; ○: The viscosity increase rate increased by 2 times or more in one week at 40°C (the viscosity increase rate increased by less than 2 times in one day); △: The viscosity increase rate increased by 2 times or more in one day at 40°C; ×: Gelation occurred in one day at 40°C.

[0052] Example 2 In this example, the procedure of Example 1 was repeated, except that diethylenetriamine (DETA) was used as the aliphatic amine instead of EDA in the amount shown in Table 1. As shown in Table 1, the one-component epoxy resin composition using the curing agent of the present invention exhibited excellent curability at 80°C and excellent storage stability at 40°C.

[0053] Example 3 In this example, the procedure of Example 1 was repeated, except that N,N'-dimethylaminopropylamine (DMAPA) was used as the aliphatic amine instead of EDA in the amount shown in Table 1. The composition is shown in Table 1. As shown in Table 1, the one-component epoxy resin composition using the curing agent of the present invention exhibited excellent curability at 80°C and excellent storage stability at 40°C.

[0054] Example 4 In this example, the procedure of Example 1 was repeated, except that N-aminoethylpiperazine (N-AEP) was used as the aliphatic amine instead of EDA in the amount shown in Table 1. The composition is shown in Table 1. As shown in Table 1, the one-component epoxy resin composition using the curing agent of the present invention exhibited excellent curability at 80°C and excellent storage stability at 40°C.

[0055] Example 5 In this example, the procedure of Example 1 was repeated, except that metaxylylenediamine (MXDA) was used as the aliphatic amine instead of EDA in the amount shown in Table 1. The composition is shown in Table 1. As shown in Table 1, the one-component epoxy resin composition using the curing agent of the present invention exhibited excellent curability at 80°C and excellent storage stability at 40°C.

[0056] Example 6 In this example, the procedure of Example 1 was repeated, except that isophoronediamine (IPDA) was used as the alicyclic amine instead of EDA in the amount shown in Table 1. The composition is shown in Table 1. As shown in Table 1, the one-component epoxy resin composition using the curing agent of the present invention exhibited excellent curability at 80°C and excellent storage stability at 40°C.

[0057] Example 7 In this example, the procedure of Example 1 was repeated, except that EDA was used as the aliphatic amine and NC-7000L (naphthol-cresol novolac epoxy resin, epoxy equivalent: 230 g / eq, manufactured by Nippon Kayaku Co., Ltd.) was used as the epoxy compound instead of XD-1000, in the amounts shown in Table 1. The composition is shown in Table 1. As shown in Table 1, the one-component epoxy resin composition using the curing agent of the present invention exhibited excellent curability at 80°C and excellent storage stability at 40°C.

[0058] Example 8 In this example, the procedure of Example 1 was repeated, except that EDA was used as the aliphatic amine and NC-3000H (biphenyl-novolac type epoxy resin, epoxy equivalent: 290 g / eq, manufactured by Nippon Kayaku Co., Ltd.) was used as the epoxy compound instead of XD-1000, in the amounts shown in Table 1. The composition is shown in Table 1. As shown in Table 1, the one-component epoxy resin composition using the curing agent of the present invention exhibited excellent curability at 80°C and excellent storage stability at 40°C.

[0059] Example 9 In this example, the procedure of Example 1 was repeated, except that EDA was used as the aliphatic amine and HP-4700 (a naphthalene-type epoxy resin manufactured by DIC Corporation, epoxy equivalent: 165 g / eq) was used as the epoxy compound in the amounts shown in Table 1. The composition is shown in Table 1. As shown in Table 1, the one-component epoxy resin composition using the curing agent of the present invention exhibited excellent curability at 80°C and excellent storage stability at 40°C.

[0060] Example 10 In this example, the procedure of Example 1 was repeated, except that EDA was used as the aliphatic amine and HP-4770 (a naphthalene-type epoxy resin manufactured by DIC Corporation, epoxy equivalent: 204 g / eq) was used as the epoxy compound in the amounts shown in Table 1. The composition is shown in Table 1. As shown in Table 1, the one-component epoxy resin composition using the curing agent of the present invention exhibited excellent curability at 80°C and excellent storage stability at 40°C.

[0061] Example 11 In this example, the procedure of Example 1 was repeated, except that EDA was used as the aliphatic amine and OGSOL PG-100 (a fluorene-type epoxy resin, epoxy equivalent: 254 g / eq, manufactured by Osaka Gas Chemicals Co., Ltd.) was used as the epoxy compound in the amounts shown in Table 1. The composition is shown in Table 1. As shown in Table 1, the one-component epoxy resin composition using the curing agent of the present invention exhibited excellent curability at 80°C and excellent storage stability at 40°C.

[0062] Comparative Example 1 In this 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 had a low softening point of the curing agent resin, and aggregated at room temperature, so that no powder could be obtained.

[0063] Comparative Example 2 In this example, the procedure of Comparative Example 1 was repeated, except that DMAPA was used instead of EDA as the aliphatic amine. The composition is shown in Table 1. As shown in Table 1, the obtained curing agent had a low softening point of the curing agent resin, and aggregated at room temperature, so that no powder could be obtained.

[0064] Comparative Example 3 In this example, the procedure of Comparative Example 1 was repeated, except that MXDA was used instead of EDA as the aliphatic amine. The composition is shown in Table 1. As shown in Table 1, the obtained curing agent had a low softening point of the curing agent resin, and aggregated at room temperature, so no powder was obtained.

[0065] Comparative Example 4 In this example, the procedure of Comparative Example 1 was repeated, except that IPDA was used instead of EDA as the aliphatic amine. The composition is shown in Table 1. As shown in Table 1, the obtained curing agent had a low softening point of the curing agent resin, and aggregated at room temperature, so that no powder was obtained.

[0066] Comparative Example 5 In this example, a one-component epoxy resin composition was prepared using FXR-1020 manufactured by T&K TOKA Corporation as the amine adduct latent curing agent, and the procedure of Example 1 was repeated. As shown in Table 1, the one-component epoxy resin composition using this curing agent had excellent storage stability, but poor curing properties at 80°C.

[0067]

[0068] The latent curing agent of the present invention can be used in a one-component epoxy resin composition, and the one-component epoxy resin composition of the present invention can be used as a thermosetting epoxy resin composition for adhesives, paints, etc.

Claims

1. General formula (1), (2), (3), (4), or (5): (wherein X represents general formula (6), (7), or (8): (In the formula, R ２ is a hydrogen atom or —OCH ２ is an epoxy group, and R ３ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), and Y is a group represented by general formula (9): (In the formula R ４ is -OCH ２ is an epoxy group, and R ３ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), and Z is a group represented by 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 may be bonded to either of the two ring structures of X, n is 1 to 15, m is 0 to 15, and one R of X present at the terminal ２ Ha-OCH ２ The epoxy group is a group having a hydrogen atom bonded to the terminal bond of X and Y, and the two R ２ Ha-OCH ２ is an epoxy group, and —OCH ２ The number of epoxy groups is 1 or 2), and an aliphatic amine compound or an alicyclic amine compound are added to the epoxy compound represented by the following formula (1):

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: (wherein o is 0 to 14, and l is 1 to 15.) 3. A one-component epoxy resin composition comprising the latent curing agent according to claim 1 or 2 and an epoxy resin.

4. A cured epoxy resin product obtained by heating the one-component epoxy resin composition according to claim 3.

5. An aliphatic amine compound or an alicyclic amine compound containing (1), (2), (3), (4), or (5): (wherein X represents general formula (6), (7), or (8): (In the formula, R ２ is a hydrogen atom or —OCH ２ is an epoxy group, and R ３ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), and Y is a group represented by general formula (9): (In the formula R ４ is -OCH ２ is an epoxy group, and R ３ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), and Z is a group represented by 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 may be bonded to either of the two ring structures of X, n is 1 to 15, m is 0 to 15, and one R of X present at the terminal ２ Ha-OCH ２ The epoxy group is a group having a hydrogen atom bonded to the terminal bond of X and Y, and the two R ２ Ha-OCH ２ is an epoxy group, and —OCH ２ wherein the number of epoxy groups is 1 or 2.

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