JP2021031617A - Curing agent for epoxy resin, epoxy resin composition and cured product thereof - Google Patents

Abstract

To provide a curing agent for epoxy resin that achieves a good balance between storage stability at room temperature to about 40°C and curability during heating, and can be suitably used as a curing agent for a one-liquid type epoxy resin composition, an epoxy resin composition and a cured product thereof.SOLUTION: A curing agent for epoxy resin contains an imidazole compound (A), and at least one compound (B) selected from the group consisting of a fatty acid metal salt (B1), a fatty acid boric acid metal salt (B2) and an aluminum chelate compound (B3).SELECTED DRAWING: None

Description

The present invention relates to an epoxy resin curing agent that can be used as a latent curing agent for an epoxy resin, an epoxy resin composition containing the same, and a cured product thereof.

Epoxy resins have excellent performance in terms of mechanical properties, electrical properties, thermal properties, chemical resistance, adhesiveness, etc., and therefore paints, insulating materials for electrical and electronic use, adhesives, etc. It is used for a wide range of purposes. As the epoxy resin composition, for example, a two-component type in which a main agent containing an epoxy resin as a main component and a curing agent containing a curing agent such as an amine compound or an acid anhydride as a main component are mixed and used immediately before use. A one-component epoxy resin composition is known in which an epoxy resin composition and dicyandiamide or the like as a latent curing agent are mixed with an epoxy resin in advance, stored as a composition, and cured by heating or the like at the time of use. There is.

In general, the drawbacks of the two-component epoxy resin composition include poor curing due to a weighing error during compounding and a short pot life after compounding. Further, when a polyamide amine, an aliphatic amine or the like is used as a curing agent, there is a problem that the heat resistance of the cured product is low and it is difficult to use it as a sealing material or the like that requires heat resistance. Similarly, when an acid anhydride is used, there is a drawback that the curing temperature must be raised. Therefore, recently, there has been a demand for a one-component liquid epoxy resin composition having low material loss and high productivity.

On the other hand, the one-component epoxy resin composition has little material loss and does not need to be mixed at the time of use, so that it is widely used as a sealing material for small electronic parts or electric parts whose manufacturing process is being automated. However, with the miniaturization, weight reduction and high density of electronic and electrical parts, the gaps between the adhesive parts and sealing parts of various parts tend to become very narrow, and such electronic and electric parts are sealed. When a one-component epoxy resin composition is used as a stop, a problem may occur in which the liquid epoxy resin and the curing agent are separated and curing failure occurs in a fine portion.

As one of the means for solving the above-mentioned problems, a latent curing agent composition liquid at room temperature, which is a mixture of an imidazole compound and a phosphorous acid compound having one or more hydroxyl groups, has been proposed (for example, a patent). Reference 1). It has also been proposed to use a salt formed by premixing 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) and benzoic acid as a latent curing agent (for example, patent). Reference 2). However, it is difficult to balance the demand for sophistication, particularly the storage stability at room temperature to about 40 ° C. and the curing rate at the time of heating, and improvement is required.

Japanese Unexamined Patent Publication No. 2010-168516 Japanese Unexamined Patent Publication No. 2008-019350

Therefore, the problem to be solved by the present invention is that it has an excellent balance between storage stability at room temperature to about 40 ° C. and curability when heated, and can be suitably used as a curing agent for a one-component epoxy resin composition. It is an object of the present invention to provide a curing agent for an epoxy resin, an epoxy resin composition, and a cured product thereof.

As a result of diligent studies to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by using an imidazole compound and a metal soap or the like in combination as a curing agent for an epoxy resin composition, and complete the present invention. I came to do it.

That is, the present invention comprises an imidazole compound (A) and one or more compounds (B) selected from the group consisting of a fatty acid metal salt (B1), a fatty acid borate metal salt (B2) and an aluminum chelate compound (B3). The present invention provides a curing agent for an epoxy resin, which comprises the above, an epoxy resin composition containing the curing agent, and a cured product thereof.

According to the present invention, an epoxy resin curing agent, an epoxy resin composition, and curing thereof, which have a good balance of storage stability at room temperature and curability under heating and can be suitably used as a latent curing agent. Can provide things.

The curing agent for epoxy resin of the present invention is one or more compounds selected from the group consisting of an imidazole compound (A), a fatty acid metal salt (B1), a fatty acid borate metal salt (B2), and an aluminum chelate compound (B3). It is characterized by containing (B) and.

The imidazole compound (A) used in the present invention is not particularly limited, and is, for example, imidazole, 1-methylimidazole, 2-methylimidazole, 3-methylimidazole, 4-methylimidazole, 5-methylimidazole, 1-. Ethylimidazole, 2-ethylimidazole, 3-ethylimidazole, 4-ethylimidazole, 5-ethylimidazole, 1-n-propylimidazole, 2-n-propylimidazole, 1-isopropylimidazole, 2-isopropylimidazole, 1-n -Butyl imidazole, 2-n-butyl imidazole, 1-isobutyl imidazole, 2-isobutyl imidazole, 2-undecyl-1H-imidazole, 2-heptadecyl-1H-imidazole, 1,2-dimethyl imidazole, 1,3-dimethyl imidazole , 2,4-Dimethylimidazole, 2-ethyl-4-methylimidazole, 1-phenylimidazole, 2-phenyl-1H-imidazole, 4-methyl-2-phenyl-1H-imidazole, 2-phenyl-4-methylimidazole , 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole , 1-Cyanoethyl-2-phenylimidazole, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5- Hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-4,5-di (2-cyanoethoxy) methylimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 1-benzyl-2-phenylimidazole hydrochloride Examples include salts, and only one type may be used, or two or more types may be used in combination.

Among these, it has good curability when heated, and when mixed with a fatty acid metal salt (B1), a fatty acid borate metal salt (B2), and an aluminum chelate compound (B3), which will be described later, it becomes a liquid curing agent. 1-Methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-isobutyl-2-methylimidazole, 1-vinylimidazole, N- (3-aminopropyl) ) It is preferable to use imidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole or 1-cyanoethyl-2-ethyl-4-methylimidazole.

The fatty acid metal salt (B1) used in the present invention may be a commercially available product or a prepared product. Examples of fatty acids include carboxylic acids such as octyl acid, neodecanoic acid, and naphthenic acid, and metals such as manganese, cobalt, calcium, nickel, magnesium, iron, zinc, zirconium, copper, strontium, barium, potassium, cerium, and rare earth. Salt (hereinafter, may be referred to as "metal soap") is mentioned, and only one kind may be used, or two or more kinds may be used in combination.

The fatty acid boric acid metal salt (B2) used in the present invention may be a commercially available product or a prepared product, and examples thereof include those represented by the following general formula (1). Only two or more may be used in combination.

（式中、Ｍはマンガン、コバルト、カルシウム、ニッケル、マグネシウム、鉄、亜鉛、ジルコニウム、銅、ストロンチウム、バリウム、カリウム、セリウム、レアアース等の金属原子を表し、Ｒ^１〜Ｒ^３はそれぞれ独立にオクチル酸、ネオデカン酸、ナフテン酸等のカルボン酸基を表す。なお、前記カルボン酸基は、カルボン酸が有するカルボキシル基の水素原子を除いた残基を意味する。）

(In the formula, M represents a metal atom such as manganese, cobalt, calcium, nickel, magnesium, iron, zinc, zirconium, copper, strontium, barium, potassium, cerium, rare earth, etc., and R ^{1 to} R ³ are octyl independently. Represents a carboxylic acid group such as an acid, neodecanoic acid, or naphthenic acid. The carboxylic acid group means a residue of the carboxyl group of the carboxylic acid excluding the hydrogen atom.)

The method for producing the fatty acid boric acid metal salt (B2) is not particularly limited, but is produced by the method described in, for example, Japanese Patent Publication No. 63-63551 from the viewpoint that the desired metal salt can be efficiently obtained. It is preferable to do so.

Among these, the fatty acid metal salt (B1) and the fatty acid hoe are considered to have good curability when heated and can be easily used as a liquid curing agent when mixed with the imidazole compound (A1). The metal in the acid metal salt (B2) is vanadium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, bismuth or rare earth, and the fatty acids are 2-ethylhexanoic acid, isononanoic acid, neodecanoic acid or It is preferably naphthenic acid.

As the aluminum chelate compound (B3) used in the present invention, it may be a commercially available product or a prepared product, or only one type may be used, or two or more types may be used in combination.

Examples of the aluminum chelate compound (B3) include a complex compound in which three β-ketoenolate anions represented by the following general formula (2) are coordinated to aluminum.

ここで、Ｒ^４、Ｒ^５、Ｒ^６は、それぞれ独立的にアルキル基又はアルコキシル基である。アルキル基としては、メチル基、エチル基等が挙げられ、アルコキシル基としては、メトキシ基、エトキシ基、オレイルオキシ基等が挙げられる。

Here, R ⁴ , R ⁵ , and R ⁶ are independently alkyl groups or alkoxyl groups, respectively. Examples of the alkyl group include a methyl group and an ethyl group, and examples of the alkoxyl group include a methoxy group, an ethoxy group and an oleyloxy group.

Specific examples of the aluminum chelate compound (B3) represented by the general formula (2) include aluminum tris (acetylacetonate), aluminumtris (ethylacetacetate), aluminum monoacetylacetonatebis (ethylacetacetate), and the like. Examples thereof include aluminum monoacetylacetate bisoleyl acetoacetate, ethyl acetoacetate aluminum diisopropirate, alkyl acetoacetate aluminum diisopropirate, etc., which have good curability when heated and are mixed with the imidazole compound (A1). In this case, diisopropoxyaluminum ethylacetoacetate or bis [ethyl-3- (oxo-κO) butanoato-κO'] (2-propanolato) aluminum can be used from the viewpoint that it can be easily used as a liquid curing agent. preferable.

As the aluminum chelate compound (B3), it may be used as it is, or a porous microencapsulated compound may be used, but it is possible to suppress curing defects when used in a smaller space. From the viewpoint of ease of handling and the like, it is preferably liquid.

As described above, the curing agent for epoxy resin of the present invention contains the imidazole compound (A), the fatty acid metal salt (B1), and the fatty acid borate metal from the viewpoint of achieving both potential (storage stability) and curability. It is used in combination with one or more compounds (B) selected from the group consisting of a salt (B2) and an aluminum chelate compound (B3), but in terms of ease of handling, uniformity of curing reaction, and microspace. From the viewpoint of curability and the like, the viscosity at 25 ° C. is preferably 3,000 Pa · s or less, and particularly preferably 500 Pa · s or less.

Examples of the method for liquefying the curing agent for epoxy resin include a method using a compound which is liquid at room temperature such as neodecanoic acid, 2-ethylhexaneic acid, and naphthenic acid as a fatty acid, and 1-methylimidazole as an imidazole compound. , 2-Dimethylimidazole, 2-ethyl-4-methylimidazole, 1-isobutyl-2-methylimidazole, 1-vinylimidazole, N- (3-aminopropyl) imidazole, 1-benzyl-2-methylimidazole, 1- Depending on the desired viscosity and the method of use, such as a method using a compound liquid at room temperature such as benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole or 1-cyanoethyl-2-ethyl-4-methylimidazole, as appropriate. It is possible to select.

In the curing agent for epoxy resin in the present invention, as described above, from the viewpoint of achieving both potential (storage stability) and curability, the imidazole compound (A), the fatty acid metal salt (B1), and the fatty acid hoe It is used in combination with one or more compounds (B) selected from the group consisting of an acid metal salt (B2) and an aluminum chelate compound (B3), but from the viewpoint of better balance, the imidazole compound (A). ) And the fatty acid metal salt (B1) or the fatty acid borate metal salt (B2) are the metals in the fatty acid metal salt (B1) or the fatty acid borate metal salt (B2) with respect to 1 mol of the imidazole compound. The number of moles of the compound is preferably in the range of 0.01 to 3.00, particularly preferably in the range of 0.02 to 1.0.

Similarly, the ratio of the imidazole compound (A) to the aluminum chelate compound (B3) used is 0.01 to 3.00 in the number of moles of aluminum of the aluminum chelate compound (B3) with respect to 1 mol of the imidazole compound. It is preferably in the range, particularly preferably in the range of 0.02 to 1.0.

The curing agent for epoxy resin of the present invention is mixed with various epoxy resins (C) and used as an epoxy resin composition, and can be particularly preferably used as a one-component epoxy resin composition. Further, in the curing agent for epoxy resin of the present invention, when this is mixed with an epoxy resin and heated, the imidazole compound (A), the fatty acid metal salt (B1), the fatty acid borate metal salt (B2) and the aluminum chelate compound ( B3) and B3) are separated in the composition, and the curing reaction of the epoxy resin by the imidazole compound as conventionally known is promoted, and the separated metal salt particularly contributes to the improvement of the adhesion to the substrate. Therefore, when it is used as a paint, an adhesive, a sealing material, a composite material, etc., it is preferably used from the viewpoint of improving its adhesion (adhesiveness) as compared with the case where the imidazole compound is used alone. Can be done.

A wide variety of compounds can be used as the epoxy resin (C) without particular limitation. Further, one type of epoxy resin (C) may be used alone, or two or more types may be used in combination. Specific examples of the epoxy resin (C) include, for example, diglycidyloxybenzene, diglycidyloxynaphthalene, aliphatic epoxy resin, biphenol type epoxy resin, bisphenol type epoxy resin, novolak type epoxy resin, and triphenol methane type. Epoxy resin, tetraphenol ethane type epoxy resin, phenol or naphthol aralkyl type epoxy resin, phenylene or naphthylene ether type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenolic hydroxyl group-containing compound-alkoxy group-containing aromatic Examples thereof include compound cocondensation type epoxy resin, glycidylamine type epoxy resin, and naphthalene skeleton-containing epoxy resin other than these.

Examples of the aliphatic epoxy resin include glycidyl etherified products of various aliphatic polyol compounds. The aliphatic polyol compound is, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 2-methylpropanediol, 1,2,2-trimethyl-1,3-propanediol, 2,2-dimethyl-3. -Isopropyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 3-methyl1,5-pentane Aliphatic diol compounds such as diol, neopentyl glycol, 1,6-hexanediol, 1,4-bis (hydroxymethyl) cyclohesane, 2,2,4-trimethyl-1,3-pentanediol; trimethylolethane, tri Examples thereof include trifunctional or higher functional aliphatic polyol compounds such as methylolpropane, glycerin, hexanetriol, pentaerythritol, ditrimethylolpropane, and dipentaerythritol. Among them, the glycidyl etherified product of the aliphatic diol compound is preferable because the composition is more excellent in mechanical strength in the cured product.

Examples of the biphenol type epoxy resin include those obtained by polyglycidyl etherifying one or more kinds of biphenol compounds such as biphenol and tetramethylbiphenol with epihalohydrin. Of these, those having an epoxy equivalent in the range of 150 to 200 g / eq are preferable.

Examples of the bisphenol type epoxy resin include those obtained by polyglycidyl etherification of one or more bisphenol compounds such as bisphenol A, bisphenol F, and bisphenol S with epihalohydrin. Of these, those having an epoxy equivalent in the range of 158 to 200 g / eq are preferable.

The novolak type epoxy resin is obtained by polyglycidyl etherification of a novolak resin composed of one or more kinds of various phenol compounds such as phenol, dihydroxybenzene, cresol, xylenol, naphthol, dihydroxynaphthalene, bisphenol, and biphenol with epihalohydrin. Can be mentioned.

Examples of the triphenol methane type epoxy resin include those having a structural portion represented by the following structural formula (3) as a repeating structural unit.

［式中Ｒ^７、Ｒ^８はそれぞれ独立に水素原子又は構造式（３）で表される構造部位と＊印が付されたメチン基を介して連結する結合点の何れかである。ｎは１以上の整数である。］

[In the formula, R ⁷ and R ⁸ are either hydrogen atoms or structural sites represented by the structural formula (3) and bonding points linked via a methine group marked with *, respectively. n is an integer of 1 or more. ]

In the phenol or naphthol aralkyl type epoxy resin, for example, the glycidyloxybenzene or glycidyloxynaphthalene structure is knotted at a structural site represented by any of the following structural formulas (4-1) to (4-3). Those having a molecular structure can be mentioned.

（式中Ｘは炭素原子数２〜６のアルキレン基、エーテル結合、カルボニル基、カルボニルオキシ基、スルフィド基、スルホン基の何れかである。］

(X in the formula is any of an alkylene group having 2 to 6 carbon atoms, an ether bond, a carbonyl group, a carbonyloxy group, a sulfide group, and a sulfone group.]

The glycidylamine type epoxy resin is, for example, N, N-diglycidylaniline, 4,4'-methylenebis [N, N-diglycidylaniline], triglycidylaminophenol, N, N, N', N'-tetra. Examples thereof include glycidylxylylenediamine.

Examples of the naphthalene skeleton-containing epoxy resin include bis (hydroxynaphthalene) type epoxy resins represented by any of the following structural formulas (5-1) to (5-3).

Among the epoxy resins (C), from the viewpoint of further exhibiting the effects of the present invention, it is preferable to use a liquid epoxy resin having a viscosity at 25 ° C. of 500 Pa · s or less, preferably 50 Pa · s or less. From the viewpoint of excellent balance between heat resistance and mechanical strength in the cured product, an aliphatic epoxy resin, a bisphenol type epoxy resin, a triphenol methane type epoxy resin, a glycidylamine type epoxy resin, and the structural formula (5-1). It is preferable to use any of the bis (hydroxynaphthalene) type epoxy resins represented by any of (5-3).

As for the ratio of the curing agent for epoxy resin of the present invention to be used, the curing for epoxy resin of the present invention is cured with respect to 100 parts by mass of the epoxy resin (C) from the viewpoint of good curability and superior characteristics of the obtained cured product. It is preferable to add 0.5 to 20 parts by mass of the agent, and it is preferable to add 0.5 to 2 parts by mass of the imidazole amount.

The curing agent for epoxy resin of the present invention is used as a curing agent or curing accelerator for the epoxy resin (C), but a conventional curing agent for epoxy resin may be used in combination depending on the intended use and performance. You may. In this case, the function as a latent curing agent is impaired, but the curing property is good, or as described above, the base material and filling when used as a paint, an adhesive, a sealing material, a composite material, etc. It is preferable because it improves the adhesion with the material and the fiber reinforced material.

Examples of conventional curing agents for epoxy resins include amine compounds, for example, ethylenediamine, N, N, N', N'-tetramethylethylenediamine, propylenediamine, N, N, N', N'-tetramethylpropylene. Diamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropylamine, diethylenetriamine, N, N, N', N'', N''-pentamethyldiethylenetriamine, triethylenetetramine, tetraethylenepentamine, 3,3' -Diaminodipropylamine, butanediamine, pentanediamine, hexanediamine, trimethylhexanediamine, N, N, N', N'-tetramethylhexanediamine, bis (2-dimethylaminoethyl) ether, dimethylaminoethoxyethoxyethanol, Aliphatic amine compounds such as triethanolamine, dimethylaminohexanol, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxyspiro (5,5) undecane adduct;

Amine compounds having a polyoxyalkylene structure in the molecular structure, such as polyoxyethylenediamine and polyoxypropylenediamine;

Alicyclic amine compounds such as cyclohexylamine, dimethylaminocyclohexane, mensendiamine, isophoronediamine, norbornenediamine, bis (aminomethyl) cyclohexane, diaminodicyclohexylmethane, methylenebis (methylcyclohexaneamine);

Pyrridine, piperidine, piperazine, N, N'-dimethylpiperazine, morpholine, methylmorpholine, ethylmorpholine, quinuclidine (1-azabicyclo [2.2.2] octane), triethylenediamine (1,4-diazabicyclo [2.2. 2] Octane), pyrrol, pyrazole, pyridine, hexahydro-1,3,5-tris (3-dimethylaminopropyl) -1,3,5-triazine, 1,8-diazabicyclo- [5.4.0]- Heterocyclic amine compounds such as 7-undecene;

Phenylene diamine, diaminodiphenylmethane, diaminodiphenylsulfone, N-methylbenzylamine, N, N-dimethylbenzylamine, diethyltoluenediamine, xylylenediamine, α-methylbenzylmethylamine, 2,4,6-tris (dimethylaminomethyl) ) Aromatic ring-containing amine compounds such as phenol;

Examples thereof include imidazoline compounds such as 2-methylimidazoline and 2-phenylimidazoline.

Further, as other curing agents or curing accelerators, for example, phthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylendoethylenetetrahydrophthalic anhydride, trialkyltetrahydrochloride Acid anhydrides such as phthalic acid, phthalic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and maleic anhydride;

The amine compound (B) is reacted with dicyandiamide, an aliphatic dicarboxylic acid such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, or azelaic acid, or a carboxylic acid compound such as fatty acid or dimeric acid. The resulting amide compound;

Phenol, dihydroxybenzene, trihydroxybenzene, naphthol, dihydroxynaphthalene, trihydroxynaphthalene, anthracenol, dihydroxyanthracene, trihydroxyanthracene, biphenol, bisphenol, methyl group, ethyl group, vinyl group, propyl group on these aromatic nuclei , Butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group and other aliphatic hydrocarbon groups; methoxy group, ethoxy group, propyloxy group, butoxy group and other alkoxy groups; fluorine Halogen atoms such as atoms, chlorine atoms and bromine atoms; phenyl group, naphthyl group, anthryl group, and aryl group in which the aliphatic hydrocarbon group, alkoxy group, halogen atom and the like are substituted on these aromatic nuclei; phenylmethyl group. , Phenylethyl group, naphthylmethyl group, naphthylethyl group, and phenolic group having one or more substituents such as an aliphatic hydrocarbon group, an alkoxy group, an aralkyl group substituted with a halogen atom, etc. on these aromatic nuclei. Hydroxyl group-containing compound;

Novolak type phenol resin, triphenol methane type phenol resin, tetraphenol ethane type phenol resin, phenol or naphthol aralkyl type phenol resin, phenylene or naphthylene ether type phenol resin resin, which are composed of one or more of the phenolic hydroxyl group-containing compounds. Phenolic resins such as dicyclopentadiene-phenol addition reaction type phenolic resin, phenolic hydroxyl group-containing compound-alkoxy group-containing aromatic compound cocondensation type phenolic resin;

p-chlorophenyl-N, N-dimethylurea, 3-phenyl-1,1-dimethylurea, 3- (3,4-dichlorophenyl) -N, N-dimethylurea, N- (3-chloro-4-methylurea) ) -N', N'-urea compounds such as dimethylurea;

Phosphorus compounds; organic acid metal salts; Lewis acids; amine complex salts and the like may be used depending on the purpose.

The epoxy resin composition of the present invention may contain other components depending on the intended use and performance. Examples of other components include acid-modified polybutadiene, polyether sulfone resin, polycarbonate resin, polyphenylene ether resin, and acrylic resin.

The acid-modified polybutadiene is a component having reactivity with the epoxy resin (C), and when the acid-modified polybutadiene is used in combination, excellent mechanical strength, heat resistance, and moist heat resistance are exhibited in the obtained cured product. Can be done.

Examples of the acid-modified polybutadiene include those having a skeleton derived from 1,3-butadiene or 2-methyl-1,3-butadiene in a butadiene skeleton. Those derived from 1,3-butadiene include those having a structure of 1,2-vinyl type, 1,4-trans type, or 1,4-cis type, and those having two or more of these structures. Can be mentioned. Those derived from 2-methyl-1,3-butadiene have any of 1,2-vinyl type, 3,4-vinyl type, 1,4-cis type, and 1,4-trans type structures. Or, those having two or more of these structures can be mentioned.

The acid-modifying component of the acid-modified polybutadiene is not particularly limited, and examples thereof include unsaturated carboxylic acids. As the unsaturated carboxylic acid, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, and itaconic anhydride are preferable, and itaconic anhydride and maleic anhydride are preferable from the viewpoint of reactivity, and maleic anhydride is more preferable. ..

The content of the unsaturated carboxylic acid in the acid-modified polybutadiene is, when the acid-modified polybutadiene is composed of one derived from 1,3-butadiene, from the viewpoint of reactivity with the epoxy resin (C). The acid value is preferably 5 mgKOH / g to 400 mgKOH / g, more preferably 20 mgKOH / g to 300 mgKOH / g, and even more preferably 50 mgKOH / g to 200 mgKOH / g. Further, the unsaturated carboxylic acid component may be copolymerized in acid-modified polybutadiene, and its form is not limited. For example, random copolymerization, block copolymerization, graft copolymerization (graft modification) and the like can be mentioned. The weight average molecular weight (Mw) of the acid-modified polybutadiene is preferably in the range of 1,000 to 100,000.

The acid-modified polybutadiene is obtained by modifying polybutadiene with an unsaturated carboxylic acid, but a commercially available product may be used as it is. As commercially available products, for example, maleic anhydride-modified liquid polybutadiene manufactured by Evonik Degussa (polyvest MA75, Polyvest EP MA120, etc.), maleic anhydride-modified polyisoprene manufactured by Kuraray (LIR-403, LIR-410), etc. are used. can do.

The content of the acid-modified polybutadiene in the composition is 1 mass by mass when the total mass of the resin components of the composition is 100 parts by mass from the viewpoint that the obtained cured product has good elongation, heat resistance, and moisture heat resistance. It is preferably contained in a proportion of parts to 40 parts by mass, and more preferably contained in a ratio of 3 parts by mass to 30 parts by mass.

The polyether sulfone resin is a thermoplastic resin and is not included in the cross-linking network in the curing reaction of the composition, but is further excellent in the cured product obtained by the excellent modifier effect having a high Tg. It is possible to develop mechanical strength and heat resistance.

The content of the polyether sulfone resin in the composition is 1 mass when the total mass of the resin components of the composition is 100 parts by mass from the viewpoint of improving the mechanical strength and heat resistance of the obtained cured product. It is preferably contained in a proportion of parts to 30 parts by mass, and more preferably contained in a ratio of 3 parts by mass to 20 parts by mass.

Examples of the polycarbonate resin include a polycondensate of divalent or bifunctional phenol and carbonyl halide, or a polymer obtained by polymerizing divalent or bifunctional phenol and carbonic acid diester by a transesterification method. Be done.

The divalent or bifunctional phenol is, for example, 4,4'-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4). -Hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 1,1-bis (4-) Hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ketone, Examples thereof include hydroquinone, resorcin, and catechol. Among these divalent phenols, bis (hydroxyphenyl) alkanes are preferable, and those using 2,2-bis (4-hydroxyphenyl) propane as a main raw material are particularly preferable.

On the other hand, carbonyl halides or carbonate diesters that react with divalent or bifunctional phenols include, for example, phosgene; dihaloformates of divalent phenols, diphenyl carbonates, ditolyl carbonates, bis (chlorophenyl) carbonates, m-cresyl carbonates and the like. Diaryl carbonate; examples thereof include aliphatic carbonate compounds such as dimethyl carbonate, diethyl carbonate, diisopropyl carbonate, dibutyl carbonate, diamyl carbonate, and dioctyl carbonate.

Further, the polycarbonate resin may have a branched structure in addition to the one in which the molecular structure of the polymer chain is a linear structure. Such a branched structure has 1,1,1-tris (4-hydroxyphenyl) ethane, α, α', α ”-tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene as raw material components. , Fluoroglucin, trimellitic acid, isatinbis (o-cresol) and the like.

The polyphenylene ether resin is, for example, poly (2,6-dimethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-14-phenylene) ether, poly (2,6-diethyl-1,1, 4-phenylene) ether, poly (2-ethyl-6-n-propyl-1,4-phenylene) ether, poly (2,6-di-n-propyl-1,4-phenylene) ether, poly (2-) Methyl-6-n-butyl-1,4-phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-phenylene) ether, poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ) Ether and the like can be mentioned.

Of these, poly (2,6-dimethyl-1,4-phenylene) ether is preferable, and 2- (dialkylaminomethyl) -6-methylphenylene ether unit and 2- (N-alkyl-N-phenylaminomethyl)- It may be a polyphenylene ether containing a 6-methylphenylene ether unit or the like as a partial structure.

The resin is a modified polyphenylene in which a reactive functional group such as a carboxyl group, an epoxy group, an amino group, a mercapto group, a silyl group, a hydroxyl group or a dicarboxyl anhydride group is introduced into the resin structure by some method such as a graft reaction or a copolymerization. The ether resin can also be used as long as the object of the present invention is not impaired.

The acrylic resin can be added for the purpose of improving the mechanical strength of the cured product, particularly the fracture toughness.

The constituent monomer of the acrylic resin, the polymerization method, and the like are appropriately selected depending on the desired performance. Specific examples of the constituent monomers include (meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; (Meta) acrylic acid ester having an alicyclic structure such as cyclohexyl (meth) acrylic acid and cyclohexyl methacrylate; (meth) acrylic acid ester having an aromatic ring such as benzyl (meth) acrylic acid; (meth) acrylic acid 2- (Meta) acrylic acid (fluoro) alkyl ester such as trifluoroethyl; acid group-containing monomer such as (meth) acrylic acid, (anhydrous) maleic acid, maleic anhydride; hydroxyethyl (meth) acrylic acid, (meth) acrylic Hydroxyl group-containing monomers such as hydroxypropyl acid and hydroxybutyl (meth) acrylate; epoxy group-containing monomers such as glycidyl (meth) acrylate and 3,4-epoxycyclohexylmethylmethacrylate; aromatic vinyl compounds such as styrene; butadiene, isoprene And the like diene compounds and the like. Among them, an acrylic resin containing (meth) acrylic acid alkyl ester as a main component is preferable because the composition is more excellent in mechanical strength in the cured product.

The acrylic resin is preferably a block copolymer in which a plurality of block polymers having different monomer configurations are copolymerized. Examples of the block copolymer include AB type diblock type, ABA type and ABC type triblock type. Above all, it is preferable to have both a block containing methyl (meth) acrylate as a main component and a block containing butyl (meth) acrylate as a main component, because the composition is more excellent in mechanical strength in the cured product. .. More specifically, a triblock acrylic resin composed of polymethylmethacrylate block-polybutylacrylate block-polymethylmethacrylate block and a diblock acrylic resin composed of polymethylmethacrylate block-polybutylacrylate block are preferable, and a diblock type acrylic resin is preferable. Acrylic resin is particularly preferable. The weight average molecular weight (Mw) of the acrylic resin is preferably in the range of 1,000 to 500,000.

The content of the acrylic resin in the composition is not particularly limited, and is appropriately adjusted according to the desired cured product performance and the like. Above all, since the composition is more excellent in mechanical strength in the cured product, it is preferably in the range of 0.1 to 20 parts by mass when the total mass of the resin components of the composition is 100 parts by mass. More preferably, it is in the range of 5 to 10 parts by mass.

The composition of the present invention can contain a flame retardant / flame retardant aid, a filler, an additive, an organic solvent and the like within a range that does not impair the effects of the present invention. The blending order when producing the composition is not particularly limited as long as the effect of the present invention can be achieved. That is, all the components may be mixed in advance and used, or may be mixed and used in an appropriate order. Further, the blending method can be produced by kneading using, for example, a kneader such as an extruder, a heating roll, a kneader, a roller mixer, or a Banbury mixer. Hereinafter, various members that can be contained in the composition of the present invention will be described.

-Flame Retardant / Flame Retardant Aid The composition of the present invention may contain a non-halogen flame retardant that does not substantially contain a halogen atom in order to exhibit flame retardancy.

Examples of the non-halogen flame retardant include phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, organic metal salt flame retardants, and the like, and their use is also restricted. However, they may be used alone, a plurality of flame retardants of the same system may be used, or different flame retardants may be used in combination.

As the phosphorus-based flame retardant, either an inorganic type or an organic type can be used. Examples of the inorganic compound include ammonium phosphates such as red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate and ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as phosphate amide. ..

The red phosphorus is preferably surface-treated for the purpose of preventing hydrolysis and the like, and examples of the surface treatment method include (i) magnesium hydroxide, aluminum hydroxide, zinc hydroxide, and water. A method of coating with an inorganic compound such as titanium oxide, bismuth oxide, bismuth hydroxide, bismuth nitrate or a mixture thereof, (ii) inorganic compounds such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide and titanium hydroxide, and Method of coating with a mixture of thermosetting resins such as phenol resin, (iii) Thermocurability of phenol resin or the like on a film of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide Examples thereof include a method of double coating with a resin.

Examples of the organic phosphorus compound include general-purpose organic phosphorus compounds such as phosphoric acid ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphoran compounds, and organic nitrogen-containing phosphorus compounds, as well as 9,10-. Dihydro-9-oxa-10-phosphaphenanthrene = 10-oxide, 10- (2,5-dihydrooxyphenyl) -10H-9-oxa-10-phosphaphenanthrene = 10-oxide, 10- (2,7) Examples thereof include cyclic organic phosphorus compounds such as −dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene = 10-oxide.

When the phosphorus-based flame retardant is used, hydrotalcite, magnesium hydroxide, boring compound, zirconium oxide, black dye, calcium carbonate, zeolite, zinc molybdate, activated charcoal, etc. may be used in combination with the phosphorus-based flame retardant. Good.

Examples of the nitrogen-based flame retardant include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, and phenothiazine, and triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds are preferable.

Examples of the triazine compound include melamine, acetoguanamine, benzoguanamine, melon, melamine, succinoguanamine, ethylenedimelamine, polyphosphate melamine, triguanamine and the like, and for example, guanyl melamine sulfate, melem sulfate, melam sulfate and the like. Examples thereof include an aminotriazine sulfate compound, the aminotriazine-modified phenol resin, and a product obtained by further modifying the aminotriazine-modified phenol resin with tung oil, isomerized linseed oil, or the like.

Specific examples of the cyanuric acid compound include cyanuric acid and melamine cyanuric acid.

The blending amount of the nitrogen-based flame retardant is appropriately selected depending on the type of the nitrogen-based flame retardant, other components of the composition, and the desired degree of flame retardancy. For example, the resin component of the composition. It is preferably blended in the range of 0.05 parts by mass to 10 parts by mass, and particularly preferably in the range of 0.1 parts by mass to 5 parts by mass with respect to 100 parts by mass in total.

When using the nitrogen-based flame retardant, a metal hydroxide, a molybdenum compound, or the like may be used in combination.

The silicone-based flame retardant can be used without particular limitation as long as it is an organic compound containing a silicon atom, and examples thereof include silicone oil, silicone rubber, and silicone resin.

The blending amount of the silicone-based flame retardant is appropriately selected depending on the type of the silicone-based flame retardant, other components of the composition, and the desired degree of flame retardancy. For example, the resin component of the composition. It is preferable to mix in the range of 0.05 parts by mass to 20 parts by mass with respect to 100 parts by mass in total. Further, when using the silicone flame retardant, a molybdenum compound, alumina or the like may be used in combination.

Examples of the inorganic flame retardant include metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low melting point glass.

Specific examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, zirconium hydride and the like.

Specific examples of the metal oxide include zinc molybdenum, molybdenum trioxide, zinc tinate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, and cobalt oxide. , Vismus oxide, chromium oxide, nickel oxide, copper oxide, tungsten oxide and the like.

Specific examples of the metal carbonate compound include zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, titanium carbonate and the like.

Specific examples of the metal powder include aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, tin and the like.

Specific examples of the boron compound include zinc borate, zinc metaborate, barium metaborate, boric acid, borax and the like.

Specific examples of the low melting point glass include Shipley (Boxy Brown Co., Ltd.), hydrated glass SiO ₂ -MgO-H ₂ O, PbO-B ₂ O ₃ system, ZnO-P ₂ O _5- MgO system, and the like. P ₂ O _5- B ₂ O _3- PbO-MgO system, P-Sn-OF system, PbO-V ₂ O _5- TeO ₂ system, Al ₂ O _3- H ₂ O system, lead borosilicate, etc. Glassy compounds of.

The blending amount of the inorganic flame retardant is appropriately selected depending on the type of the inorganic flame retardant, other components of the composition, and the desired degree of flame retardancy. For example, the resin component of the composition. It is preferable to mix in the range of 0.05 parts by mass to 20 parts by mass, and particularly preferably in the range of 0.5 parts by mass to 15 parts by mass with respect to 100 parts by mass in total.

Examples of the organometallic salt-based flame retardant include ferrocene, an acetylacetonate metal complex, an organometallic carbonyl compound, an organocobalt salt compound, an organosulfonic acid metal salt, a metal atom and an aromatic compound, or a heterocyclic compound. Examples thereof include a coordinate-bonded compound.

The blending amount of the organometallic salt-based flame retardant is appropriately selected depending on the type of the organometallic salt-based flame retardant, other components of the composition, and the desired degree of flame retardancy. For example, the composition. It is preferable to blend in the range of 0.005 part by mass to 10 parts by mass with respect to 100 parts by mass of the total resin component of.

-Filler The composition of the present invention may contain a filler. When the composition of the present invention contains a filler, excellent mechanical properties can be exhibited in the obtained cured product.

Fillers include, for example, titanium oxide, glass beads, glass flakes, glass fibers, calcium carbonate, barium carbonate, calcium sulfate, barium sulfate, potassium titanate, aluminum borate, magnesium borate, molten silica, crystalline silica, alumina, nitride. Examples thereof include fibrous reinforcing agents such as silicon, aluminum hydroxide, Kenaf fiber, carbon fiber, alumina fiber, and quartz fiber, and non-fibrous reinforcing agent. These may be used alone or in combination of two or more. Further, these may be coated with an organic substance, an inorganic substance or the like.

When glass fiber is used as the filler, it can be selected from long fiber type roving, short fiber type chopped strand, milled fiber and the like. As the glass fiber, it is preferable to use a surface-treated material for the resin to be used. By blending the filler, the strength of the non-combustible layer (or carbonized layer) generated during combustion can be further improved. The non-combustible layer (or carbonized layer) once formed during combustion is less likely to be damaged, and a stable heat insulating capacity can be exhibited, so that a larger flame-retardant effect can be obtained. Furthermore, high rigidity can be imparted to the material.

-Additives The composition of the present invention may contain additives. When the composition of the present invention contains an additive, other properties such as rigidity and dimensional stability are improved in the obtained cured product. Examples of the additive include a plastic agent, an antioxidant, an ultraviolet absorber, a stabilizer such as a light stabilizer, an antistatic agent, a conductivity-imparting agent, a stress relieving agent, a mold release agent, a crystallization accelerator, and a hydrolysis inhibitor. Agents, lubricants, impact-imparting agents, slidability improvers, defoamers, nucleating agents, strengthening agents, reinforcing agents, flow conditioners, dyes, sensitizers, coloring pigments, rubber polymers, thickeners , Anti-settling agent, anti-sagging agent, defoaming agent, coupling agent, rust preventive, antibacterial / antifungal agent, antifouling agent, conductive polymer and the like can also be added.

-Organic solvent The composition of the present invention may contain an organic solvent when a fiber-reinforced resin molded product is produced by a filament winding method. Examples of the organic solvent that can be used here include methyl ethyl ketone acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate, and the like. Can be appropriately selected depending on the application.

The composition of the present invention has a high curing rate and is excellent in heat resistance and mechanical strength in the cured product, and can be used for various purposes such as paints, electric / electronic materials, adhesives, and molded products. The composition of the present invention can be suitably used not only for applications in which it is cured and used, but also for fiber-reinforced composite materials, fiber-reinforced resin molded products, and the like. These will be described below.

-Cured product of composition As a method of obtaining a cured product from the composition of the present invention, a general curing method of an epoxy resin composition may be followed. For example, the heating temperature condition may be appropriately selected depending on the application or the like. Good. For example, a method of heating the composition in a temperature range of about 120 to 250 ° C. can be mentioned. As a molding method or the like, a general method of the composition can be used, and in particular, conditions specific to the composition of the present invention are not required.

-Fiber-reinforced composite material A fiber-reinforced composite material is a material in a state before curing after impregnating a reinforcing fiber with a composition. Here, the reinforcing fiber may be any of twisted yarn, untwisted yarn, untwisted yarn and the like, but the untwisted yarn and the untwisted yarn are preferable because they have excellent moldability in the fiber-reinforced composite material. Further, as the form of the reinforcing fiber, one in which the fiber directions are aligned in one direction or a woven fabric can be used. For woven fabrics, plain weaves, satin weaves, and the like can be freely selected according to the part to be used and the intended use. Specific examples thereof include carbon fiber, glass fiber, aramid fiber, boron fiber, alumina fiber, and silicon carbide fiber because of their excellent mechanical strength and durability, and two or more of these can be used in combination. .. Among these, carbon fibers are particularly preferable from the viewpoint of improving the strength of the molded product, and various carbon fibers such as polyacrylonitrile-based, pitch-based, and rayon-based can be used.

The method for obtaining the fiber-reinforced composite material from the composition of the present invention is not particularly limited, but for example, each component constituting the composition is uniformly mixed to produce a varnish, and then the varnish obtained above is used. A method of immersing the unidirectional reinforcing fibers in which the reinforcing fibers are aligned in one direction (state before curing by the pull-fusion method or the filament winding method), or a method of stacking the reinforcing fiber fabrics and setting them in a concave shape, and then a convex shape. Examples thereof include a method of injecting a resin after sealing with a varnish and impregnating with pressure (state before curing by the RTM method).

The fiber-reinforced composite material does not necessarily have to be impregnated to the inside of the fiber bundle, and the composition may be localized near the surface of the fiber.

Further, the fiber-reinforced composite material preferably has a volume content of the reinforcing fibers of 40% to 85% with respect to the total volume of the fiber-reinforced composite material, and further preferably in the range of 50% to 70% from the viewpoint of strength. preferable. When the volume content is less than 40%, the content of the composition is too high and the flame retardancy of the obtained cured product is insufficient, or various requirements for a fiber-reinforced composite material having excellent specific elastic modulus and specific strength. It may not be possible to meet the characteristics. On the other hand, if the volume content exceeds 85%, the adhesiveness between the reinforcing fiber and the resin composition may decrease.

-Fiber-reinforced resin molded product A fiber-reinforced resin molded product is a molded product having a reinforcing fiber and a cured product of a composition, and is obtained by thermosetting a fiber-reinforced composite material. As the fiber-reinforced resin molded product, specifically, the volume content of the reinforcing fiber in the fiber-reinforced molded product is preferably in the range of 40% to 85%, and is in the range of 50% to 70% from the viewpoint of strength. Is particularly preferable. Examples of such fiber-reinforced resin molded products include automobile parts such as front subframes, rear subframes, front pillars, center pillars, side members, cross members, side sills, roof rails, and propeller shafts, and core members of electric wire cables. Examples include pipe materials for subframe oil fields, roll pipe materials for printing machines, robot fork materials, primary structural materials for aircraft, and secondary structural materials.

The method for obtaining the fiber-reinforced molded product from the composition of the present invention is not particularly limited, but it is preferable to use a pultrusion molding method (plutrusion method), a filament winding method, an RTM method, or the like. The pultrusion method is a method of molding a fiber-reinforced resin molded product by introducing a fiber-reinforced composite material into a mold, heat-curing it, and then drawing it out with a drawing device. Is a method in which a fiber-reinforced composite material (including one-way fiber) is wound around an aluminum liner, a plastic liner, etc. while rotating, and then heat-cured to form a fiber-reinforced resin molded product. Is a method of using two types of molds, a concave mold and a convex mold, in which a fiber-reinforced composite material is heat-cured in the mold to form a fiber-reinforced resin molded product. When molding a large-sized product or a fiber-reinforced resin molded product having a complicated shape, it is preferable to use the RTM method.

As the molding conditions for the fiber-reinforced resin molded product, it is preferable to mold the fiber-reinforced composite material by thermosetting in a temperature range of 50 ° C. to 250 ° C., and more preferably to mold in a temperature range of 70 ° C. to 220 ° C. .. This is because if the molding temperature is too low, sufficient rapid curing may not be obtained, and if it is too high, warpage due to thermal strain may easily occur. Other molding conditions include pre-curing the fiber-reinforced composite material at 50 ° C. to 100 ° C. to form a tack-free cured product, and then further treating the fiber-reinforced composite material at a temperature condition of 120 ° C. to 200 ° C. in two steps. Examples include a method of curing.

Other methods for obtaining a fiber-reinforced molded product from the composition of the present invention include a hand lay-up method, a spray-up method, and a male mold in which a fiber aggregate is laid on a mold and the varnish and the fiber aggregate are laminated in multiple layers. -Use one of the female molds, stack the base material made of reinforcing fibers while impregnating it with varnish, mold it, cover it with a flexible mold that can apply pressure to the molded product, and vacuum (depressurize) the one that is airtightly sealed. ) The vacuum bag method for molding, the SMC press method in which a varnish containing reinforcing fibers is previously formed into a sheet and compression molded with a mold can be mentioned.

Next, the present invention will be specifically described with reference to Examples and Comparative Examples. In the following, "parts" and "%" are based on mass unless otherwise specified.

Example 1
7.4 g of DICNAME NBC-2 (cobalt neodecanoate manufactured by DIC Corporation) and 92.6 g of 1-methylimidazole were stirred and mixed at 80 ° C. to obtain a liquid curing agent 1 at 25 ° C.

Example 2
16.3 g of DICNAME 5000 (cobalt neodecanoate manufactured by DIC Corporation) and 83.7 g of 1-methylimidazole were stirred and mixed at 80 ° C. to obtain a liquid curing agent 2 at 25 ° C.

Example 3
DICNAME SG-160 (manganese neodecanoate manufactured by DIC Corporation) was used as it was. (1-Methylimidazole: 70%) Use as a curing agent 3.

Example 4
32.4 g of DICNAME Fe 5% (iron neodecanoate manufactured by DIC Corporation) and 67.6 g of 1-methylimidazole were stirred and mixed at 80 ° C. to obtain a liquid curing agent 4 at 25 ° C.

Example 5
87.1 g of DICSTATE 425 (bismuth 2-ethylhexanoate manufactured by DIC Corporation) and 12.9 g of 1-methylimidazole were stirred and mixed at 80 ° C. to obtain a liquid curing agent 5 at 25 ° C.

Example 6
24.7 g of DICNAME AL-500 (aluminum chelate manufactured by DIC Corporation) and 75.3 g of 1-methylimidazole were stirred and mixed at 80 ° C. to obtain a liquid curing agent 6 at 25 ° C.

Example 7
30.0 g of DICNAME 5000 (cobalt neodecanoate manufactured by DIC Corporation) and 70.0 g of 1-methylimidazole were stirred and mixed at 80 ° C. to obtain a liquid curing agent 7 at 25 ° C.

Example 8
44.6 g of DICNAME 5000 (cobalt neodecanoate manufactured by DIC Corporation) and 55.4 g of 1-methylimidazole were stirred and mixed at 80 ° C. to obtain a liquid curing agent 8 at 25 ° C.

Example 9
61.8 g of DICNAME 5000 (cobalt neodecanoate manufactured by DIC Corporation) and 38.2 g of 1-methylimidazole were stirred and mixed at 80 ° C. to obtain a liquid curing agent 9 at 25 ° C.

Example 10
13.7 g of Co-OCTOATE 12% (cobalt 2-ethylhexanoate manufactured by DIC Corporation) and 86.3 g of 2-ethyl-4-methylimidazole are stirred and mixed at 80 ° C., and a liquid curing agent 10 at 25 ° C. Got

Examples 11-20, Comparative Examples 1-2
Hardeners 1-10 and 1-methylimidazole (1MI) obtained in Examples 1 to 10 with respect to 100 g of epoxy resin (“EPICLON 850S” bisphenol A type epoxy resin manufactured by DIC Co., Ltd., epoxy equivalent 188 g / equivalent). , 2-Ethyl-4-methylimidazole (2E4MZ) was mixed using the masses shown in Tables 1 and 2, and the thickening rate and curability were evaluated according to the following.

<Thickness thickening rate>
The viscosity at 40 ° C. was measured using a Brookfield viscometer "DV2T" (manufactured by Eiko Seiki Co., Ltd.), and the viscosity after 5 hours with respect to the initial viscosity immediately after compounding was defined as the thickening rate.

<Curable>
0.15 g of the composition immediately after blending was placed on a hot plate heated to 150 ° C., and the time (seconds) until it became a gel was measured while stirring with a spatula. The same operation was repeated three times, and the average value was used for evaluation.

Examples 21 to 24, Comparative Example 3
Epoxy resin ("EPICLON 850S" manufactured by DIC Co., Ltd., bisphenol A type epoxy resin, epoxy equivalent 188 g / equivalent) 10.53 g and acid anhydride ("EPICLON B-570-H" manufactured by DIC Co., Ltd.) methyltetrahydrophthalic acid 9 A curing agent was added to 3 g in the mass shown in Table 3, and the thickening rate was measured.

Claims (12)

With imidazole compound (A)
Curing for epoxy resin, which comprises one or more compounds (B) selected from the group consisting of a fatty acid metal salt (B1), a fatty acid borate metal salt (B2), and an aluminum chelate compound (B3). Agent. The curing agent for an epoxy resin according to claim 1, which is a liquid having a viscosity at 25 ° C. of 3,000 Pa · s or less. The imidazole compound (A) is 1-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-isobutyl-2-methylimidazole, 1-vinylimidazole, N- (3-aminopropyl). ) Imidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole or 1-cyanoethyl-2-ethyl-4-methylimidazole according to claim 1 or 2. Hardener for epoxy resin. Any of claims 1 to 3, wherein the metal in the fatty acid metal salt (B1) and the fatty acid borate metal salt (B2) is vanadium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, bismuth or rare earth. The curing agent for epoxy resin according to item 1. The epoxy according to any one of claims 1 to 4, wherein the fatty acid in the fatty acid metal salt (B1) and the fatty acid borate metal salt (B2) is 2-ethylhexanoic acid, isononanoic acid, neodecanoic acid or naphthenic acid. Hardener for resin. Any one of claims 1 to 3, wherein the aluminum chelate compound (B3) is diisopropoxyaluminum ethylacetoacetate or bis [ethyl-3- (oxo-κO) butanoato-κO'] (2-propanolato) aluminum. The hardener for epoxy resin described. The ratio of the imidazole compound (A) to the fatty acid metal salt (B1) or the fatty acid borate metal salt (B2) to 1 mol of the imidazole compound is the fatty acid metal salt (B1) or the fatty acid borate metal salt (B1). The curing agent for an epoxy resin according to any one of claims 1 to 5, wherein the number of moles of the metal in B2) is in the range of 0.01 to 3.00. The ratio of the imidazole compound (A) to the aluminum chelate compound (B3) used is in the range of 0.01 to 3.00 in the number of moles of aluminum of the aluminum chelate compound (B3) with respect to 1 mol of the imidazole compound. The curing agent for an epoxy resin according to claim 1, 2, 3 or 6. An epoxy resin composition containing the epoxy resin curing agent according to any one of claims 1 to 8 and the epoxy resin (C). The epoxy resin composition according to claim 9, wherein the epoxy resin (C) is a liquid epoxy resin having a viscosity at 25 ° C. of 500 Pa · s or less. Claim 9 or 10 which comprises 0.5 to 20 parts by mass of the epoxy resin curing agent according to any one of claims 1 to 8 with respect to 100 parts by mass of the epoxy resin (C). The epoxy resin composition according to the above. A cured product of the epoxy resin composition according to any one of claims 9 to 11.