Latent curing agent and one-component epoxy resin composition

Abstract

The object of the present invention is to provide an aliphatic amine-based curing agent or an alicyclic amine curing agent that exhibits high storage stability. [Solution] The above problem can be solved by a latent curing agent to which an epoxy compound represented by any of the general formulas (1), (2), (3), (4), or (5) of the present invention is added to an aliphatic amine compound or an alicyclic amine compound.

Description

Technical Field

[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 showing excellent storage stability can be obtained.

Background Art

[0002] Amine compounds are widely used as curing agents and curing catalysts for epoxy resins. Ordinary amine curing agents mainly take a liquid form, and the two-component system in which the epoxy resin and the curing agent are mixed and used is the mainstream. Amine curing agents are roughly classified into aliphatic amines, aromatic amines, tertiary amines, or imidazoles. In particular, aliphatic amines or alicyclic amine types have active hydrogen, and it is known that formulations with epoxy resins can be cured at low temperatures. However, many ordinary aliphatic amines or alicyclic amines are liquid, and formulations with epoxy resins have a short pot life and solidify within about several hours at room temperature. Therefore, aliphatic amines or alicyclic amines that can be formulated into a one-component system are desired.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] For example, epoxy adduct modification is widely performed on aliphatic amines or alicyclic amines, and in particular, modification with bisphenol A type epoxy resin is widely used (Patent Document 1). However, with modification only by bisphenol A type epoxy resin, it is difficult for the softening point of the obtained resin to increase, and the obtained resin often re-aggregates at room temperature even when pulverized. Therefore, an object of the present invention is to provide an aliphatic amine-based curing agent or an alicyclic amine curing agent showing high storage stability.

Means for Solving the Problems

[0005] As a result of intensive research on aliphatic amine curing agents or alicyclic amine curing agents exhibiting high storage stability, the present inventor has surprisingly found that by adding an epoxy compound having a specific structure to an aliphatic amine compound or an alicyclic amine compound, an aliphatic amine curing agent or an alicyclic amine curing agent exhibiting high storage stability can be obtained. The present invention is based on such findings. Therefore, the present invention provides [1] General formula (1), (2), (3), (4), or (5): [[ID=1x]]

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0006] The latent curing agent of the present invention exhibits excellent storage stability. [Modes for carrying out the invention]

[0007] [1] Latent curing agent The latent curing agent of the present invention is a general formula (1), (2), (3), (4), or (5): [ka] [ka] [ka] [ka] [ka] An epoxy compound represented by [formula] is added to an aliphatic amine compound or an alicyclic amine compound.

[0008] The addition of an epoxy compound to an aliphatic amine compound or alicyclic amine compound is not limited to this, but may involve the addition of the -NH2 group or =NH group of the aliphatic amine compound or alicyclic amine compound to the epoxy group (CH) of the epoxy compound. 2 (O)CH-) reacts with -NH-CH 2 -CH(OH)- or =N-CH 2 This means forming a -CH(OH)- bond.

[0009] Epoxy compounds The epoxy compound is not particularly limited as long as it has one of the structures of general formulas (1) to (5). By having the above structures, the epoxy compound can form a rigid skeleton. By forming a rigid skeleton, it is possible to improve the softening point of aliphatic amine compounds or alicyclic amine compounds, and improve the storage stability of latent curing agents.

[0010] The epoxy compound X is of general formula (6), (7), or (8): [ka] [ka] [ka] It is a base represented by .

[0011] R 2 is a hydrogen atom or -OCH 2 It is an epoxy group. If X is at the end of the epoxy compound, then at least one R 2 ha-OCH 2 It is an epoxy group. The two R's of X in general formula (4) 2 ha-OCH 2 It is an epoxy group. R 3R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Specifically, alkyl groups having 1 to 3 carbon atoms are methyl, ethyl, or propyl groups. 3 This is preferably a hydrogen atom or a methyl group.

[0012] Y is given by the general formula (9): [ka] It is a base represented by . R 4 is, -OCH 2 It is an epoxy group, R 3 R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Specifically, alkyl groups having 1 to 3 carbon atoms are methyl, ethyl, or propyl groups. 3 This is preferably a hydrogen atom or a methyl group.

[0013] Z is given by the general formula (10): [ka] This is a group represented by . 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. Alternatively, they may be bonded to carbon atoms forming a cyclopentane ring, or both bonds may be bonded to a single carbon atom.

[0014] R 1 It is either a single bond or an alkylene group having 1 to 3 carbon atoms. Specifically, the alkylene group having 1 to 3 carbon atoms is a methylene group, an ethylene group, or a propyl group. 1 R is preferably a single bond or a methylene group. 1 It may be bonded 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 n may be a single polymer or a mixture of polymers with n ranging from 1 to 15. In the case of a mixture, n in general formula (1) represents the average number of repeats. 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 the number of m may be a single polymer or a mixture of polymers with m values ​​from 0 to 15. In the case of a mixture, m in general formula (1) represents the average number of repeats. In the case of a single polymer, m is an integer.

[0016] (end) One R of X located at the end 2 ha-OCH 2 It is an epoxy group. Hydrogen atoms are bonded to the terminal bonds of X and Y at the ends. In other words, the terminal X and Y 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 are 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 are obtained, but preferably 2 or more. By being within this range, gelation during the synthesis of aliphatic amines or alicyclic amine-epoxy adducts can be prevented, and a good epoxy resin curing agent can be obtained.

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

[0019] (Average number of epoxy groups) The epoxy compound represented by general formula (1) or (2) is a polymer, but as described above, it may be a mixture of polymers where n is 1 to 15, or a mixture of polymers where 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 as 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 are obtained, but is preferably 2 or more. By being within this range, gelation of the epoxy resin adduct is prevented, and a good epoxy resin curing agent can be obtained.

[0020] The epoxy compounds used in the present invention are not limited to those described above, but specifically include compounds represented by the following formula. [ka] In the formula, m ranges from 0 to 15, and l ranges from 1 to 15. m is between 0 and 15, preferably between 0 and 10, more preferably between 0 and 8, even more preferably between 0 and 5, even more preferably between 0 and 3, even more preferably between 0 and 2, and even more preferably between 0 or 1. The epoxy compound represented by the above formula is a polymer, and the number of m may be a single polymer or a mixture of polymers with m between 0 and 15. In the case of a mixture, m in the above formula represents 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 the number of l may be a single polymer or a mixture of polymers with l values ​​from 1 to 15. In the case of a mixture, l in the above formula represents the average number of repetitions. In the case of a single polymer, l is an integer.

[0021] Aliphatic amine compounds Aliphatic amine compounds are not particularly limited as long as the effects of the present invention are obtained, but examples include ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, diethylenetriamine, dipropylenetriamine, triethylenetetramine (TETA), tripylenetetramine, tetraethylenepentamine, hexamethylenediamine, iminobispropylamine, bis(hexamethylene)triamine, 1,3,6-trisaminomethylhexane, trimethylhexamethylenediamine, polyetherdiamine, 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 compounds The alicyclic amine compounds are not particularly limited as long as the effects of the present invention are obtained, but examples include mensendiamine, 1,4-cyclohexanediamine, isophoronediamine, bis(4-aminocyclohexyl)methane, 2,2'-dimethyl-4,4'-methylenebis(cyclohexylamine), or 1,2-diaminocyclohexane.

[0023] The content of the aliphatic amine compound or alicyclic amine compound and the epoxy compound in the latent curing agent of the present invention is not particularly limited, but the epoxy compound is 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.

[0024] (softening point) The composition obtained by adding an epoxy compound 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 a powder, but the upper limit is, for example, 150°C or less, in some embodiments 140°C or less, and in other embodiments 135°C or less. The lower limit is, for example, 90°C or higher, in some embodiments 95°C or higher, and in other embodiments 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 comprises the latent curing agent and the 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, 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 epoxy groups is not particularly limited when considering the effect of the epoxy resin in the epoxy resin composition. Note that "average" means the average number of epoxy groups in one molecule when two or more types of epoxy resins are mixed. Specifically, examples of epoxy resins include, for example, epoxy compounds of mononuclear polyvalent phenol compounds (polyglycidyl ethers), epoxy compounds of polynuclear polyvalent phenol compounds (polyglycidyl ethers), epoxy compounds of polyhydric alcohols (polyglycidyl ethers), epoxy compounds of hydroxycarboxylic acids (polyglycidyl ether esters), epoxy compounds of aliphatic, aromatic, or alicyclic polybasic acids (polyglycidyl esters), epoxy compounds of hydroxycarboxylic acids (glycidyl ether esters), epoxy compounds of polyhydric carboxylic acids (glycidyl esters), epoxy compounds of aminophenols (glycidylaminoglycidyl ethers), epoxy compounds of polyhydric amines (glycidylamines), or other epoxy compounds.

[0027] More specifically, examples of the mononuclear polyvalent phenol compound include catechol, resorcinol, hydroquinone, or halogen (e.g., chlorine, bromine) derivatives thereof.

[0028] More specifically, the aforementioned polynuclear polyvalent phenolic compounds include, for example, 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 specifically, examples of the aforementioned polyhydric alcohols include glycerin, neopentyl glycol, ethylene glycol, propylene glycol, butylene glycol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol, thiodiglycol, trimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol, bisphenol A-ethylene oxide, or propylene oxide adducts.

[0030] More specifically, examples of the hydroxycarboxylic acids include p-oxybenzoic acid or β-oxynaphthoic acid.

[0031] More specifically, examples of the aforementioned 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, decandiolic acid, dodecandiolic acid, tetradecandiolic acid, octadecandiolic acid, or polymerized fatty acids.

[0032] More specifically, examples of the aforementioned aminophenols include p-aminophenol or p-aminoalkylphenol.

[0033] More specifically, examples of the aforementioned polyhydric 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, or diaminodiphenylsulfone.

[0034] More specifically, other epoxy compounds include, for example, epoxidized polyolefins, epoxidized polybutadienes, epoxidized soybean oil, glycidyl hydantoin, di or triglycidyl isocyanurates, vinylcyclohexene diepoxides, dicyclopentadiene diepoxides, or 3,4-epoxycyclohexyl-3,4-epoxycyclohexanecarboxylate.

[0035] 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, as these exhibit excellent heat resistance, electrical properties such as insulation, and adhesive properties when the epoxy resin composition of the present invention is cured. The epoxy resin can be used individually or in mixtures of two or more types.

[0036] In the epoxy resin composition according to the present invention, monofunctional epoxy compounds can be used in combination as the epoxy resin, as long as they do not impair the effects of the present invention. Examples include butyl glycidyl ether, phenyl glycidyl ether, higher alcohol glycidyl ether, glycidyl benzoate 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 in terms of handling the epoxy resin composition, but they may reduce the mechanical properties and heat resistance (glass transition temperature) of the final epoxy resin cured product, so their use should be kept to a minimum. Furthermore, one or more of the above monofunctional epoxy resins can be used in combination.

[0037] <Other components in epoxy resin compositions> The epoxy resin composition of the present invention may optionally contain various additives, such as surfactants, fluidity improvers, thixotropic agents, extender pigments and other fillers, coloring pigments or dyes for coloring, rust-inhibiting pigments or rust inhibitors, other resin powders, waxes, etc., to the extent that the effects of the present invention are obtained. In addition, solvents to reduce 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; and glycol or glycol ester solvents such as methoxypropanol and methoxypropyl acetate.

[0038] 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 any desired degree of gelation. That is, curable epoxy resin compositions are used for various applications such as adhesives, coatings, sealants, and impregnations, and the desired curing state, curing time, and usage conditions differ depending on the application. Therefore, the weight ratio or molar ratio of the epoxy resin having an average of more than one epoxy group in its 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 70 parts by weight of the latent curing agent per 100 parts by weight of the epoxide compound, more preferably 4 to 60 parts by weight, and most preferably 5 to 50 parts by weight.

[0039] The one-component curable epoxy resin composition of the present invention is a thermosetting epoxy resin composition that does not harden at room temperature (e.g., 0°C to 40°C), but hardens rapidly when heated (e.g., 80°C to 200°C), and can be used as an adhesive, paint, coating, sealing, and impregnation agent.

[0040] 《Epoxy resin cured product》 The epoxy resin cured product of the present invention is obtained by heating the one-component epoxy resin composition. Specific cured products include adhesives, painted surfaces, coatings, sealants, or impregnated materials.

[0041] [3] Method for manufacturing latent curing agent The method for producing the latent curing agent of the present invention involves adding (1), (2), (3), (4), or (5) to an aliphatic amine compound or an alicyclic amine compound: [ka] [ka] [ka] [ka] [ka] (wherein X is general formula (6), (7), or (8): [ka] [ka] [ka] (In the formula, R 2 is a hydrogen atom or -OCH 2 It is an epoxy group, R 3 This is a group represented by a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Y is given by the general formula (9): [ka] (R in the formula 4 is, -OCH 2 It is an epoxy group, R 3 This is a group represented by a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Z is given by the general formula (10): [ka] (In the formula, the two bonds may be bonded to any carbon atom of the structure of general formula (10), and two bonds may be bonded to one carbon atom) is the group represented by R 1 R is either a single bond or an alkylene group having 1 to 3 carbon atoms, and is bonded to X. 1 It may bond to either of the two ring structures of X, n is between 1 and 15, and m is between 0 and 15. One R of X located at the end 2 ha-OCH 2It is an epoxy group, and hydrogen atoms are bonded to the terminal bonds of X and Y at the ends, and the two R of X in general formula (4) 2 ha-OCH 2 It is an epoxy group, and -OCH in repeating units 2 The number of epoxy groups is 1 or 2. The process includes adding one of the epoxy compounds represented by [the formula].

[0042] In the method for producing the latent curing agent of the present invention, the "aliphatic amine compound or alicyclic amine compound" and the "epoxy compound" can be used without being limited to those described in the "latent curing agent" section above. 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 is 0.5 to 2.0 equivalents of the epoxy compound per mole of the aliphatic amine compound or alicyclic amine compound, more preferably 0.8 to 1.7 equivalents, and even more preferably 1.0 to 1.5 equivalents.

[0043] The addition reaction is not particularly limited, but may involve the -NH2 or =NH group of an aliphatic amine compound or alicyclic amine compound and the epoxy group (CH) of an epoxy compound. 2 (O)CH-) reacts with -NH-CH 2 -CH(OH)- or =N-CH 2 This means forming a -CH(OH)- bond. -NH2 group or =NH group of an aliphatic amine compound or alicyclic amine compound and epoxy group (CH) of an epoxy compound 2 In the (O)CH-) reaction, not all groups need to react, but typically 1.0 to 1.5 equivalents of epoxy are used for every mole of amino groups. Therefore, the epoxy groups are essentially all consumed by the addition reaction described above.

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

[0045] 《Action》 Although the mechanism by which storage stability is improved in the latent curing agent of the present invention has not been analyzed in detail, it 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 raise the glass transition temperature of the latent curing agent resin. By increasing the Tg of the curing agent resin, it is possible to reduce the amount of low-molecular-weight components that dissolve from the surface of the curing agent particles into the epoxy resin in the epoxy resin formulation, and as a result, it is presumed that the storage stability is improved. [Examples]

[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, ethylenediamine (EDA) was used as the aliphatic amine, and XD-1000 (dicyclopentadiene-phenol type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 250 g / eq) was used as the epoxy compound to prepare a latent curing agent. Specifically, 90 parts by weight of EDA and 90 parts by weight of a 1:1 (by weight) mixed solvent of xylene and 2-propanol were added to a 1 L four-necked flask equipped with a stirrer and a nitrogen inlet tube, and the temperature was raised 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 the xylene-2-propanol mixed solvent was added dropwise over 2 hours. After the dropwise addition was complete, the temperature was maintained at 80°C for 30 minutes while stirring, then the temperature was raised to 200°C, and the solvent was removed by reducing the pressure to obtain a brown solid compound. This was then finely ground 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 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 grinding) The crushed powder was stored at room temperature overnight, and its aggregation state was checked the following day. The evaluation was performed according to the following criteria. ○: No change in state ×: Agglomerates and unusable.

[0050] (Evaluation of hardening properties) The gelation 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 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 at which stirring became impossible was defined as the gelation time. The evaluation was performed according to the following criteria. ◎: Gelates within 5 minutes ○: Gelates within 6 minutes ×: Did not gel in 6 minutes

[0051] (Storage stability) The initial viscosity of a formulation prepared by mixing 20 parts of the obtained latent curing agent with 100 parts of epoxy resin (jER828) was measured. This was stored at 40°C, and the change in viscosity over time was measured. The viscosity increase ratio was calculated from the ratio. The evaluation criteria for storage stability in Table 1 are as follows. ◎: At 40℃, the increase in viscosity is less than double in one week. ○: At 40℃, the increase in viscosity more than doubles in one week (the increase in viscosity is less than double in one day). △: At 40℃, the increase in viscosity more than doubles in one day. ×: Gel formed at 40°C in 1 day.

[0052] Example 2 In this example, the procedure of Example 1 was repeated, except that the aliphatic amine was changed from EDA to diethylenetriamine (DETA) in the amounts 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 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.

[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 in the amount shown in Table 1, instead of EDA. 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 the aliphatic amine was changed from EDA to metaxylylenediamine (MXDA) 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.

[0056] Example 6 In this example, the procedure of Example 1 was repeated, except that isophorone diamine (IPDA) was used as the alicyclic amine in the amounts shown in Table 1, instead of EDA. 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 type epoxy resin manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 230 g / eq) was used as the epoxy compound instead of XD-1000 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.

[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 manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 290 g / eq) was used as the epoxy compound instead of XD-1000 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.

[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 (Naphthalene-type epoxy resin, manufactured by DIC Corporation, epoxy equivalent: 165 g / eq) was used as the epoxy compound 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.

[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 (Naphthalene-type epoxy resin, manufactured by DIC Corporation, epoxy equivalent: 204 g / eq) was used as the epoxy compound 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.

[0061] Example 11 In this example, the procedure of Example 1 was repeated, except that EDA was used as the aliphatic amine and the amount of Ogusol PG-100 (fluorene-type epoxy resin manufactured by Osaka Gas Chemical Co., Ltd., epoxy equivalent: 254 g / eq) as the epoxy compound was changed to 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.

[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 for the curing agent resin, agglomerated at room temperature, and no powder was 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 for the curing agent resin, agglomerated at room temperature, and no powder was 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 for the curing agent resin, agglomerated at room temperature, and 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 for the curing agent resin, agglomerated at room temperature, and 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 an amine adduct type latent curing agent, and the procedure in Example 1 was repeated. As shown in Table 1, the one-component epoxy resin composition using this curing agent exhibited excellent storage stability, but poor curing performance at 80°C.

[0067] [Table 1] [Industrial applicability]

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

Claims

1. General formulas (1), (2), (3), (4), or (5): 【Chemistry 1】 【Chemistry 2】 【Transformation 3】 【Chemistry 4】 【Transformation 5】 (wherein X is general formula (6), (7), or (8): 【Transformation 6】 【Transformation 7】 【Transformation 8】 (In the formula, R ２ is a hydrogen atom or -OCH ２ It is an epoxy group, R ３ This is a group represented by a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Y is given by the general formula (9): 【Chemistry 9】 (In the formula R ４ is, -OCH ２ It is an epoxy group, R ３ This is a group represented by a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Z is given by general formula (10): 【Chemistry 10】 (In the formula, the two bonds may be bonded to any carbon atom of the structure of general formula (10), and the two bonds may be bonded to one carbon atom) is the group represented by R １ R is either a single bond or an alkylene group having 1 to 3 carbon atoms, and is bonded to X. １ It may bond to either of the two ring structures of X, n is between 1 and 15, and m is between 0 and 15. One R of X present at the end ２ is -OCH ２ is an epoxy group, and a hydrogen atom is bonded to the terminal bond hands of X and Y present at the end. Two Rs of X in the general formula (4) ２ is -OCH ２ is an epoxy group, and -OCH in repeating units ２ The number of epoxy groups is one or two. A latent curing agent comprising an epoxy compound represented by one of the following, to which an aliphatic amine compound or an alicyclic amine compound is added.

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. 【Chemistry 11】 (In the formula, m is between 0 and 15, and l is between 1 and 15.)

3. A one-component epoxy resin composition comprising a latent curing agent according to claim 1 or 2, and an epoxy resin.

4. An epoxy resin cured product obtained by heating the one-component epoxy resin composition described in claim 3.

5. Aliphatic amine compounds or alicyclic amine compounds containing (1), (2), (3), (4), or (5): 【Chemistry 12】 【Chemistry 13】 【Chemistry 14】 【Chemistry 15】 【Chemistry 16】 (wherein X is general formula (6), (7), or (8): 【Chemistry 17】 [Chemistry 18] 【Chemistry 19】 (In the formula, R ２ is a hydrogen atom or -OCH ２ It is an epoxy group, R ３ This is a group represented by a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Y is given by the general formula (9): 【Chemistry 20】 (In the formula R ４ is, -OCH ２ It is an epoxy group, R ３ This is a group represented by a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Z is given by general formula (10): 【Chemistry 21】 (In the formula, the two bonds may be bonded to any carbon atom of the structure of general formula (10), and the two bonds may be bonded to one carbon atom) is the group represented by R １ R is either a single bond or an alkylene group having 1 to 3 carbon atoms, and is bonded to X. １ It may bond to either of the two ring structures of X, n is between 1 and 15, and m is between 0 and 15. One R of X is located at the end ２ ha-OCH ２ It is an epoxy group, and hydrogen atoms are bonded to the terminal bonds of X and Y at the ends, and the two R of X in general formula (4) ２ ha-OCH ２ It is an epoxy group, and -OCH in repeating units ２ The number of epoxy groups is one or two. The process includes adding one of the epoxy compounds represented by A method for manufacturing a latent curing agent.

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