JP4942937B2 - Epoxy resin composition - Google Patents

Description

  The present invention relates to an epoxy resin composition using an inclusion compound containing a curing agent and / or a curing accelerator as a guest compound.

  Epoxy resins are characterized by excellent chemical resistance, corrosion resistance, mechanical properties, thermal properties, excellent adhesion to various substrates, electrical properties, workability that does not matter for the environment, adhesives, paints, Widely used in electrical metal materials and composite materials. The epoxy group in the epoxy resin is a functional group with high distortion and reacts with either acid or base, and the epoxy resin is cured using this high reactivity to make it three-dimensional. The epoxy resin composition is composed of a combination of an epoxy prepolymer having two or more epoxy groups in one molecule and a curing agent, and a curing accelerator, a modifier, a filler, etc. may be added depending on the application. Many. It is known that the properties of the cured resin are greatly influenced by the curing agent, and various curing agents have been used for industrial applications. Epoxy resin compositions can be broadly classified into one-pack type and two-pack type depending on the method of use, and the former one-pack type can be cured by heating, pressing, or leaving the composition itself. It can be done. On the other hand, in the two-component type, the main agent and the curing agent or curing accelerator are mixed at the time of use, and then the mixture can be cured by heating, pressurizing, or leaving it to stand. The epoxy resin composition is usually a two-part type, and this two-part type is troublesome and inefficient when viewed from the work surface, but is excellent in the strength, thermal characteristics, electrical characteristics, etc. of the cured product. Therefore, it is widely used in the field of electrical parts, automobiles and aircraft. However, in the two-component type, (1) the pot life, that is, the time for maintaining the composition prepared for curing is short, a partial reaction starts by the preparation, and the viscosity of the system increases. There is a problem that workability is lowered, and (2) physical properties are lowered due to mixing mistakes and incomplete preparation, and one-pack type latent curing agents and curing accelerators are desired. The latent curing agent and the curing accelerator are those in which the curing agent and the curing accelerator blended in the resin are stable at room temperature and cause a curing reaction by an action such as heat. The initiation of the curing reaction can be effected by heat, light, pressure, etc., but heat is often used. Microcapsules are used to stabilize the curing agent and curing accelerator, but there are problems in terms of stability, such as lack of mechanical strength and inability to withstand blends for adjusting the resin composition.

  The curing agent includes (1) an addition-type curing agent in which a curing agent molecule is always incorporated into a cured resin by reacting with an epoxy group, and (2) a curing agent molecule is not incorporated into the resin. There are polymerization-type curing agents that catalyze the ring opening of epoxy groups and cause polymerization addition reaction between oligomers, and (3) photoinitiated type curing agents that cause curing by ultraviolet irradiation. Whichever method is used, it is most important for obtaining a stable cured product that the polymerization addition reaction is performed more uniformly and rapidly under a certain condition. However, with these existing curing agents alone, (1) the curing reaction stops halfway along with an increase in resin viscosity, (2) there are many obstacles to the curing reaction, and (3) it is harsh to complete the curing reaction. (4) There is a problem that a large amount of curing agent is required to perform the curing reaction uniformly, and it is possible to perform the polymerization addition reaction uniformly and quickly under mild conditions. There is a need for a cure accelerator that can be leveled. The curing accelerator is for advancing the curing speed of the curing agent that cures the epoxy resin, and for facilitating the curing reaction quickly. Addition-type curing agents such as primary and secondary amines use alcohols or phenols as curing accelerators that accelerate the polymerization addition reaction, but polymerization-type curing agents such as imidazole proceed between oligomers. There was a problem in versatility such as anionic polymerization being inhibited.

  In view of the above problems, the present inventors have greatly improved the thermal stability, which is extremely important in controlling the curing reaction, by inclusion of a curing agent or a curing accelerator with a tetrakisphenol-based compound. It was reported that it became possible (see Patent Document 1). However, when the third component is added at the time of use, there are problems such as a decrease in the curing start temperature and coloring when the resin composition is cured.

  In addition, the present applicant reports that a molecular compound comprising a tetrakiscarboxylic acid derivative, a curing agent for a paint, a resin, an adhesive, and a curing accelerator as a component compound is useful as a catalyst for a curing agent for an epoxy resin. (See Patent Document 2). However, Patent Document 2 does not specifically include a case where a curing agent or a curing accelerator is included, and there is no example where it is combined with an epoxy resin.

JP-A-11-71449 JP 2001-172225 A

  The problem of the present invention is that when a curing agent and / or a curing accelerator is mixed with an epoxy resin, the thermal stability, which is extremely important in controlling the curing reaction, is greatly improved, and the pot life (epoxy resin and curing agent, etc.) It is an object of the present invention to provide an epoxy resin composition in which a one-component stability when mixed is extended, a stable cured product is obtained even under mild conditions, and the degree of coloring of the cured product can be suppressed.

  In order to solve the above-mentioned problems, the present inventors have included a curing agent and / or a curing accelerator for epoxy resin with a specific carboxylic acid derivative, and compared with a case where a specific tetrakisphenol-based compound is included. Thus, it has been found that an excellent epoxy resin composition can be obtained and the degree of coloring of the cured product can be suppressed, and the present invention has been completed.

That is, the present invention
(1) Epoxy resin and formula (I) or formula (II)

[In the formulas (I) and (II), X represents (CH ₂ ) n (n represents an integer of 0 to 3) or a phenylene group which may have a substituent, and R ₁ to R ₈ and R ₁₃ to R ₂₀ are each independently a hydrogen atom, an alkyl group of C1 -C6, alkenyl group of C2 -C6, which may have a substituent phenyl group, a halogen atom, or a C1 an alkoxy group -C6, R ₉ to R ₁₂ and R ₂₁ to R ₂₄ are each independently a hydrogen atom, an alkyl group of C1 -C6, alkenyl group of C2 -C6, aralkyl groups of C7 to C12, Or represents an alkali metal. An inclusion compound (a) having a carboxylic acid derivative represented by formula (I) as a host compound and a curing agent as a guest compound,
(2) The said inclusion compound (a) is 0.001-1.0 mol with respect to 1 mol of epoxy rings of an epoxy resin, It is related with the epoxy resin composition as described in (1) characterized by the above-mentioned.

The present invention also provides:
(3) Epoxy resin and formula (I) or formula (II)

[In the formulas (I) and (II), X represents (CH ₂ ) n (n represents an integer of 0 to 3) or a phenylene group which may have a substituent, and R ₁ to R ₈ and R ₁₃ to R ₂₀ are each independently a hydrogen atom, an alkyl group of C1 -C6, alkenyl group of C2 -C6, which may have a substituent phenyl group, a halogen atom, or a C1 an alkoxy group -C6, R ₉ to R ₁₂ and R ₂₁ to R ₂₄ are each independently a hydrogen atom, an alkyl group of C1 -C6, alkenyl group of C2 -C6, aralkyl groups of C7 to C12, Or represents an alkali metal. And an inclusion compound (b) having a curing accelerator as a guest compound and a carboxylic acid derivative represented by the following formula:

(4) The clathrate compound (b) is contained in an amount of 0.001 to 1.0 mol per mol of the epoxy ring of the epoxy resin, and relates to the epoxy resin composition according to (3).

  The epoxy resin composition of the present invention has excellent one-component stability in a state where an epoxy resin and a curing agent coexist, can be cured at a predetermined temperature, and can suppress the degree of coloring of the cured product. Is.

Hereinafter, the epoxy resin of the present invention will be described in detail.
The epoxy resin of the present invention comprises (1) an epoxy resin, (2) an inclusion compound (a) having a carboxylic acid derivative represented by the formula (I) or formula (II) as a host compound and a curing agent as a guest compound (a ). The epoxy resin composition of the present invention comprises (1) an epoxy resin, (2) a carboxylic acid derivative represented by the above formula (I) or formula (II) as a host compound, and a curing accelerator as a guest compound. The inclusion compound (b) is contained.

  The epoxy resin used in the epoxy resin composition of the present invention is not particularly limited as long as it has at least one epoxy group in one molecule. For example, bisphenol A-epichlorohydrin resin, polyfunctional epoxy resin, alicyclic epoxy resin, brominated epoxy resin, novolac type epoxy resin, acrylic epoxy resin and the like can be mentioned. These epoxy resins can be used alone or in combination of two or more.

  The clathrate compound (a) used in the epoxy resin composition of the present invention is a clathrate compound having the carboxylic acid derivative represented by the formula (I) or formula (II) as a host compound and a curing agent as a guest compound. is there. In addition, the inclusion compound (b) used in the epoxy resin composition of the present invention includes a carboxylic acid derivative represented by the formula (I) or (II) as a host compound and a curing accelerator as a guest compound. It is a contact compound.

In the formulas (I) and (II), X is (CH ₂ ) n (n represents an integer of 0 to 3), or may have a substituent (p-phenylene group, m-phenylene group, phenylene group such as o-phenylene group). Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; C1-C6 such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and t-butyl group. Alkyl group; vinyl group, allyl group, isopropenyl group, 1-propenyl group, 2-butenyl group, 3-butenyl group, 1,3-butadienyl group and the like C2-C6 alkenyl group; methoxy group, ethoxy group, n -C1-C6 alkoxy groups, such as a propoxy group, an isopropoxy group, n-butoxy group, t-butoxy group, can be mentioned.

R _{1 to} R ₈ and R _{13 to} R ₂₀ are each independently a hydrogen atom; C _{1 to} C _{6 such as} methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, etc. An alkyl group; a C2-C6 alkenyl group such as a vinyl group, an allyl group, an isopropenyl group, a 1-propenyl group, a 2-butenyl group, a 3-butenyl group, or a 1,3-butadienyl group; A phenyl group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; or C1 to C1 such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, or a t-butoxy group A C6 alkoxy group; Examples of the substituent of the phenyl group which may have a substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; methyl group, ethyl group, n-propyl group, isopropyl group, n- C1 to C6 alkyl groups such as butyl group and t-butyl group; C2 such as vinyl group, allyl group, isopropenyl group, 1-propenyl group, 2-butenyl group, 3-butenyl group and 1,3-butadienyl group C6 alkenyl group; C1-C6 alkoxy groups such as methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group and t-butoxy group can be exemplified.

R _{9 to} R ₁₂ and R _{21 to} R ₂₄ are each independently a hydrogen atom; C 1 to C _{6 such as} methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, etc. Alkyl group; C2-C6 alkenyl group such as vinyl group, allyl group, isopropenyl group, 1-propenyl group, 2-butenyl group, 3-butenyl group, 1,3-butadienyl group; benzyl group, phenethyl group, etc. C7-C12 aralkyl group; or an alkali metal such as sodium or potassium.
These carboxylic acid derivatives represented by the above formulas (I) and (II) can be used singly or in combination of two or more.

  Among these, a compound in which X is a single bond is particularly preferable from the viewpoints of chemical stabilization, non-volatility, sustained release, pulverization and the like of the curing agent or curing accelerator.

  Examples of the carboxylic acid derivative represented by the formula (I) or the formula (II) include tetrakis (4-carboxyphenyl) ethane, tetrakis (4-carboxyphenyl) ethanetetramethyl ester, and tetrakis (4-carboxyphenyl). Ethane tetraethyl ester, tetrakis (4-carboxyphenyl) ethane tetra-n-propyl ester, tetrakis (4-carboxyphenyl) ethane tetrabenzyl ester, tetrakis (3,5-dimethyl-4-carboxyphenyl) ethane, tetrakis (3,5 -Dimethyl-4-carboxyphenyl) ethane tetramethyl ester, tetrakis (3,5-dimethyl-4-carboxyphenyl) ethane tetraethyl ester, tetrakis (3,5-dimethyl-4-carboxyphenyl) ethane La-n-propyl ester, tetrakis (3,5-dimethyl-4-carboxyphenyl) ethanetetrabenzyl ester, tetrakis (4-carboxyphenyl) ethanetetrasodium salt, tetrakis (4-carboxyphenyl) ethanetetrapotassium salt, tetrakis (3-carboxyphenyl) ethane, tetrakis (3-carboxyphenyl) ethanetetramethyl ester, tetrakis (3-carboxy-4,5-dimethylphenyl) ethane, tetrakis (3-carboxyphenyl) ethanetetraethyl ester, tetrakis (3- Carboxyphenyl) ethanetetra-n-propyl ester, tetrakis (3-carboxyphenyl) ethanetetrabenzyl ester, tetrakis (3-carboxy-4,5-dimethylphenyl) ethane, Tetrakis (3-carboxy-4,5-dimethylphenyl) ethanetetramethyl ester, tetrakis (3-carboxy-4,5-dimethylphenyl) ethanetetraethyl ester, tetrakis (3-carboxy-4,5-dimethylphenyl) ethanetetra- n-propyl ester, tetrakis (3,5-dimethyl-4-carboxyphenyl) ethanetetrabenzyl ester, tetrakis (3-carboxyphenyl) ethanetetrasodium salt, tetrakis (3-carboxyphenyl) ethanetetrapotassium salt, etc. Can do.

  The curing agent is not particularly limited as long as it is a compound that reacts with an epoxy group in the epoxy resin to cure the epoxy resin. The curing accelerator is not particularly limited as long as it is a compound that reacts with an epoxy group in the epoxy resin to accelerate the curing rate of the compound that cures the epoxy resin. As such a curing agent and a curing accelerator, any one selected from conventional epoxy resin curing agents and those conventionally used as curing accelerators can be selected and used. For example, amine compounds, imidazole compounds, imidazoline compounds, amide compounds, ester compounds, phenol compounds, alcohol compounds, thiol compounds, ether compounds, thioether compounds, urea compounds, thiourea compounds Lewis acid compounds, phosphorus compounds, acid anhydride compounds, onium salt compounds, active silicon compounds-aluminum complexes, and the like.

Examples of amine compounds include aliphatic amines, alicyclic and heterocyclic amines, aromatic amines, and modified amines.
Examples of the aliphatic amines include ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenediamine, dimethylaminopropylamine, diethylaminopropylamine, trimethylhexamethylene. Diamine, pentanediamine, bis (2-dimethylaminoethyl) ether, pentamethyldiethylenetriamine, alkyl-t-monoamine, 1,4-diazabicyclo (2,2,2) octane (triethylenediamine), N, N, N ′, N′-tetramethylhexamethylenediamine, N, N, N ′, N′-tetramethylpropylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N-dimethylsilane B hexylamine, dimethylaminoethoxy ethoxyethanol, dimethylamino hexanol, and the like.

  Examples of alicyclic and heterocyclic amines include piperidine, piperazine, menthanediamine, isophoronediamine, methylmorpholine, ethylmorpholine, N, N ′, N ″ -tris (dimethylaminopropyl) hexahydro-s-triazine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxyspiro (5,5) undecane adduct, N-aminoethylpiperazine, trimethylaminoethylpiperazine, bis (4-aminocyclohexyl) methane N, N′-dimethylpiperazine, 1,8-diazabicyclo (4,5,0) undecene-7, and the like.

Examples of aromatic amines include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, benzylmethylamine, dimethylbenzylamine, m-xylenediamine, pyridine, and picoline. It is done.
Examples of the modified amines include epoxy compound-added polyamine, Michael addition polyamine, Mannich addition polyamine, thiourea addition polyamine, ketone-capped polyamine, dicyandiamide, guanidine, organic acid hydrazide, diaminomaleonitrile, amine imide, boron trifluoride-piperidine. Complex, boron trifluoride-monoethylamine complex, etc. are mentioned.

  Examples of the imidazole compound include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-n-propylimidazole, 2-undecyl-1H-imidazole, 2-heptadecyl-1H-imidazole, 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-1H-imidazole, 4-methyl-2-phenyl-1H-imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Imidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl 4-methylimidazolium trimellitate, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2'- Methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- (2′-undecylimidazolyl-)-ethyl-s-triazine, 2,4-diamino-6- [2 ′ -Ethyl-4-imidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethyl ester Dazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-4,5-di (2-cyanoethoxy) methylimidazole, 1-dodecyl-2-methyl-3-benzylimidazo Examples include lithium chloride, 1-benzyl-2-phenylimidazole hydrochloride, 1-benzyl-2-phenylimidazolium trimellitate, and the like.

Examples of the imidazoline-based compound include 2-methylimidazoline, 2-phenylimidazoline, and the like.
Examples of the amide compound include polyamide obtained by condensation of dimer acid and polyamine.
Examples of the ester compounds include active carbonyl compounds such as aryl and thioaryl esters of carboxylic acids.

Examples of the phenol compound, alcohol compound, thiol compound, ether compound, and thioether compound include phenol novolak, cresol novolak, polyol, polymercaptan, polysulfide, 2- (dimethylaminomethylphenol), 2,4. , 6-tris (dimethylaminomethyl) phenol, tri-2-ethylhexyl hydrochloride of 2,4,6-tris (dimethylaminomethyl) phenol, and the like.
Examples of the urea compound, thiourea compound, and Lewis acid compound include butylated urea, butylated melamine, butylated thiourea, boron trifluoride, and the like.

  Examples of phosphorus compounds include organic phosphine compounds, for example, alkylphosphine such as ethylphosphine and butylphosphine, first phosphine such as phenylphosphine, dialkylphosphine such as dimethylphosphine and dipropylphosphine, diphenylphosphine such as diphenylphosphine, and methylethylphosphine. 2 phosphine; a third phosphine such as trimethylphosphine and triethylphosphine;

  Examples of acid anhydride compounds include phthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, maleic anhydride , Tetramethylene maleic anhydride, trimellitic anhydride, chlorendic anhydride, pyromellitic anhydride, dodecenyl succinic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis (anhydrotrimellitate), methylcyclohexene tetracarboxylic anhydride And polyazeline acid anhydride.

  Examples of onium salt compounds and active silicon compounds-aluminum complexes include aryldiazonium salts, diaryliodonium salts, triarylsulfonium salts, triphenylsilanol-aluminum complexes, triphenylmethoxysilane-aluminum complexes, and silyl peroxides. An aluminum complex, a triphenylsilanol-tris (salicylide aldehyde) aluminum complex, etc. are mentioned.

  The clathrate compound (a) used in the epoxy resin composition of the present invention and the method for producing the clathrate compound (b) include a carboxylic acid derivative represented by the formula (I) or the formula (II), a curing agent, It can be obtained by directly mixing with a curing accelerator or by mixing in a solvent. In the case of a substance having a low boiling point or a substance having a high vapor pressure, the target clathrate compound is obtained by allowing the vapor of these substances to act on the carboxylic acid derivative represented by the above formula (I) or formula (II). Can be obtained. In addition, by reacting the carboxylic acid derivative represented by the formula (I) or the formula (II) with two or more kinds of curing agents and / or curing accelerators, a package comprising three or more components. A contact compound can also be obtained. Further, an inclusion compound of the carboxylic acid derivative represented by the formula (I) or the formula (II) and a certain curing agent or curing accelerator is first generated, and this inclusion compound is combined with another curing agent or curing agent. The target clathrate compound can be obtained by reacting the accelerator with the above-described method.

The structure of the clathrate compound obtained can be confirmed by thermal analysis (TG and DTA), infrared absorption spectrum (IR), X-ray diffraction pattern, solid NMR spectrum, and the like. The composition of the clathrate compound can be confirmed by thermal analysis, ¹ H-NMR spectrum, high performance liquid chromatography (HPLC), elemental analysis or the like.

The 50% volume average particle diameter of the clathrate compound used in the epoxy resin composition of the present invention is not particularly limited, but is usually about 0.01 to 80 μm, preferably about 0.01 to 10 μm, more preferably about 0.1. The range is ˜4 μm. It is not preferable to produce an inclusion compound having a volume average particle diameter of less than about 0.01 μm because the productivity of the compound itself deteriorates. On the other hand, those having a volume average particle diameter exceeding about 80 μm are not preferable because the low-temperature curability and the appearance of the coating film are deteriorated.
The 50% volume average particle diameter represents the particle diameter μm at which the cumulative curve is 50% when the cumulative curve is obtained with the volume of the powder group as 100%.

  The method for producing the epoxy resin composition of the present invention includes the epoxy resin, the inclusion compound (a) and / or the inclusion compound (b), and optionally a curing agent and / or a curing accelerator, and other additives. Produced by melting, kneading, cooling, pulverizing, and applying to a classifier, using a kneader, an extruder, etc. can do.

  The amount of the clathrate compound to be used may be the same amount as that of a usual curing agent or curing accelerator such as amine-based or imidazole-based clathrate, and depends on the curing method. In the case of an addition type curing agent in which a curing agent molecule is always incorporated into a cured resin by reacting with an epoxy group, depending on the properties of the required resin, it is usually included in 1 mol of an epoxy group. The clathrate compound is used so that the curing agent is about 0.3 to 1.0 mol. In addition, in the case of a polymerization type curing agent or a photoinitiated type curing agent that induces a polymerization addition reaction between oligomers without causing the curing agent molecule to be incorporated into the resin, it is also a curing accelerator. In the case of using as a clathrate, 1.0 mol or less of an inclusion compound is sufficient for 1 mol of an epoxy group. In particular, in the present invention, by using an inclusion compound using the carboxylic acid derivative represented by the above formula (I) or formula (II), even a trace amount is sufficient, 0.001 to 1.0 mol, and further 0 The amount used may be 0.001 to 0.1 mol. These clathrate compounds can be used alone or in combination of two or more.

The epoxy resin composition containing the epoxy resin of the present invention and the clathrate compound (a) may further contain a curing accelerator, and the epoxy resin of the present invention and the clathrate compound (b) In the epoxy resin composition containing, a curing agent may be further contained.
As the curing agent and the curing accelerator used here, the same ones listed as the curing agent and the curing accelerator can be used.

  If desired, other additives can be added to the epoxy resin composition of the present invention. Other additives include vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, and γ-methacryloxy. Propyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane Silane coupling agents such as N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane; Um, light calcium carbonate, natural silica, synthetic silica, kaolin, clay, titanium oxide, barium sulfate, zinc oxide, aluminum hydroxide, magnesium hydroxide, talc, mica, wollastonite, potassium titanate, aluminum borate, sepiolite, Fillers such as zonotolite; NBR, polybutadiene, chloroprene rubber, silicone, crosslinked NBR, crosslinked BR, acrylic, core shell acrylic, urethane rubber, polyester elastomer, functional group-containing liquid NBR, liquid polybutadiene, liquid polyester, liquid polysulfide, modified silicone Elastomer modifiers such as urethane prepolymers;

  Hexabromocyclodecane, bis (dibromopropyl) tetrabromobisphenol A, tris (dibromopropyl) isocyanurate, tris (tribromoneopentyl) phosphate, decabromodiphenyl oxide, bis (pentabromo) phenylethane, tris (tribromophenoxy) Triazine, ethylenebistetrabromophthalimide, polybromophenylindane, brominated polystyrene, tetrabromobisphenol A polycarbonate, brominated phenylene ethylene oxide, polypentabromobenzyl acrylate, triphenyl phosphate, trigresyl phosphate, trixinyl phosphate, cresyl diphenyl Phosphate, xylyldiphenyl phosphate, cresyl bis (di-2,6-xylenyl) phosphate Fate, 2-ethylhexyl diphenyl phosphate, resorcinol bis (diphenyl) phosphate, bisphenol A bis (diphenyl) phosphate, bisphenol A bis (dicresidyl) phosphate, resorcinol bis (di-2,6-xylenyl) phosphate, tris (chloroethyl) phosphate, Tris (chloropropyl) phosphate, tris (diclopropyl) phosphate, tris (tribromopropyl) phosphate, diethyl-N, N-bis (2-hydroxyethyl) aminomethylphosphonate, anionic oxalic acid treated aluminum hydroxide, nitrate treated Aluminum hydroxide, high-temperature hydrothermal treatment aluminum hydroxide, stannic acid surface treatment hydrated metal compound, nickel compound surface treatment magnesium hydroxide, silicone poly -Flame retardants such as surface treated magnesium hydroxide, procovite, multilayer surface treated hydrated metal compound, cationic polymer treated magnesium hydroxide; high density polyethylene, polypropylene, polystyrene, polymethyl methacrylate, polyvinyl chloride, nylon 6, 6, engineering plastics such as polyacetal, polyethersulfone, polyetherimide, polybutylene terephthalate, polyetheretherketone, polycarbonate, polysulfone; plasticizer; reactive diluent; extender; reinforcing agent; colorant; thickener A mold release agent; and the like. The blending amount of these additives is not particularly limited, and the blending amount can be appropriately determined within the limit that the effects of the present invention can be obtained.

  Furthermore, the epoxy resin composition of the present invention may contain other resins in addition to the epoxy resin. Examples of other resins include polyester resins, acrylic resins, silicone resins, polyurethane resins, and the like.

  The epoxy resin composition of the present invention includes powder coating, electrodeposition coating, anticorrosion coating, can coating, semiconductor sealant, semiconductor mount, electrical insulating resin, printed wiring board, high voltage film capacitor, resistor, choke coil , Epoxy adhesives, various electrical components (electronic components for automobiles, electronic components for motorcycles), civil engineering and construction (concrete adhesives, binders, lining agents, jointing agents, waterproofing agents), binders for paving, adhesives for paving, It can be used for steel structure adhesives, steel structure binders, steel structure lining materials and the like.

  EXAMPLES Next, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to the following Examples at all.

(Production Example 1) Production of Inclusion Compound A 1,1,2,2-Tetrakis (4-carboxyphenyl) ethane 1.28 g (2.5 mmol) was dissolved in 800 ml of ethyl alcohol with heating, and then 2-ethyl-4 -1.10 g (10 mmol) of methylimidazole mixed with 1.10 g of ethyl alcohol was added and left at room temperature for 24 hours. The precipitated crystals were collected by filtration, dried under reduced pressure using a rotary vacuum pump at 40 ° C. for 1 hour, and 1,1,2,2-tetrakis (4-carboxyphenyl) ethane and 2-ethyl-4-methylimidazole. The inclusion compound A having a composition ratio of 1: 3 (molar ratio) was obtained. The inclusion compound was confirmed by thermal analysis (TG / DTA), ¹ H-NMR and X-ray diffraction pattern. Further, it was confirmed from the X-ray diffraction pattern that it was clearly crystalline. Inclusion compound A released 2-ethyl-4-methylimidazole in the range of approximately 180 ° C to 300 ° C.

(Example 1) Production of epoxy resin composition A 100 parts by weight of epoxy resin (trade name: Epototo YD-128, manufactured by Toho Kasei Co., Ltd.), 4 parts by weight in terms of 2-ethyl-4-methylimidazole Compound A was added. Epoxy resin composition A was obtained by kneading at 25 ° C. for 10 minutes.

(Comparative example 1) Production of epoxy resin composition B From a composition ratio of 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane and 2-ethyl-4-methylimidazole 1: 2 (molar ratio) The resulting inclusion compound is referred to as inclusion compound B.
Except for using 4 parts by weight of clathrate compound B in terms of 2-ethyl-4-methylimidazole instead of 4 parts by weight of clathrate compound A in terms of 2-ethyl-4-methylimidazole in Example 1, In the same manner as in Example 1, an epoxy resin composition B was obtained.

(Comparative Example 2) Production of epoxy resin composition C In Example 1, instead of 4 parts by weight of inclusion compound A in terms of 2-ethyl-4-methylimidazole, 4 parts by weight of 2-ethyl-4-methylimidazole was used. Except having used, it carried out similarly to Example 1, and obtained the epoxy resin composition C.

(Comparative Example 3) Production of epoxy resin composition D In Example 1, instead of 4 parts by weight of inclusion compound A in terms of 2-ethyl-4-methylimidazole, 1,1,2,2-tetrakis (4- Epoxy resin composition D was obtained in the same manner as in Example 1 except that 6.3 parts by weight of carboxyphenyl) ethane and 4 parts by weight of 2-ethyl-4-methylimidazole were used.

(DSC measurement of epoxy resin compositions A to D)
A part of each of the epoxy resin compositions A to D obtained in Example 1 and Comparative Examples 1 to 3 was sampled, and a differential scanning calorimeter (DSC, manufactured by Rigaku Corporation, Thermoplus TG-8230) was used. Then, the heat generation based on the curing reaction of the epoxy resin composition was measured under the condition of a temperature rising rate of 10 ° C./min under a nitrogen stream of 30 ml / min.

The respective DSC charts of the epoxy resin compositions A to D are shown in FIGS. In the figure, the horizontal axis represents the measured temperature (° C.), and the vertical axis represents the calorific value (Heat Flow / mW).
Table 1 shows the respective curing start temperatures, reaction heat peaks, cure end temperatures, and endothermic peak states of the epoxy resin compositions A to D.

  When the degree of coloring after curing of the epoxy resin compositions A and B was visually observed, it was confirmed that the epoxy resin composition B was colored.

It is a figure which shows the thermal-analysis (TG-DTA) chart of 1,1,2,2-tetrakis (4-carboxyphenyl) ethane. It is a figure which shows the thermal analysis (TG-DTA) chart of 2-ethyl-4-methylimidazole. It is a figure which shows the thermal analysis (TG-DTA) chart of the inclusion compound A. It is a figure which shows the powder X-ray-diffraction pattern of 1,1,2,2-tetrakis (4-carboxyphenyl) ethane. FIG. 3 is a diagram showing a powder X-ray diffraction pattern of inclusion compound A. ¹ is a diagram showing a ¹ H-NMR spectrum of an inclusion compound A. FIG. It is a figure which shows the DSC chart of the epoxy resin composition A. It is a figure which shows the DSC chart of the epoxy resin composition B. It is a figure which shows the DSC chart of the epoxy resin composition C. It is a figure which shows the DSC chart of the epoxy resin composition D.

Claims (4)

Epoxy resin and formula (I) or formula (II)

[In the formulas (I) and (II), X represents (CH ₂ ) n (n represents an integer of 0 to 3), or a halogen atom as a substituent , a C1-C6 alkyl group, C2-C6 's an alkenyl group, or a phenylene group which may have an alkoxy group of C1 -C6, R ₁ to R ₈ and R ₁₃ to R _20, each independently, a hydrogen atom, an alkyl group of C1 -C6, A C2- C6 alkenyl group, a halogen atom as a substituent , a C1-C6 alkyl group, a C2-C6 alkenyl group or a phenyl group optionally having a C1-C6 alkoxy group, a halogen atom, or C1-C6 R _{9 to} R ₁₂ and R _{21 to} R ₂₄ each independently represent a hydrogen atom, a C1 to C6 alkyl group, a C2 to C6 alkenyl group, a C7 to C12 aralkyl group, or an alkali. Represents a metal. An inclusion compound (a) having a carboxylic acid derivative represented by formula (I) as a host compound and a curing agent as a guest compound, and the inclusion compound (a) with respect to 1 mol of the epoxy ring of the epoxy resin 0.001-1.0 mol of epoxy resin composition characterized by the above-mentioned. Epoxy resin and formula (I) or formula (II)

[In the formulas (I) and (II), X represents (CH ₂ ) n (n represents an integer of 0 to 3), or a halogen atom as a substituent , a C1-C6 alkyl group, C2-C6 's an alkenyl group, or a phenylene group which may have an alkoxy group of C1 -C6, R ₁ to R ₈ and R ₁₃ to R _20, each independently, a hydrogen atom, an alkyl group of C1 -C6, A C2- C6 alkenyl group, a halogen atom as a substituent , a C1-C6 alkyl group, a C2-C6 alkenyl group or a phenyl group optionally having a C1-C6 alkoxy group, a halogen atom, or C1-C6 R _{9 to} R ₁₂ and R _{21 to} R ₂₄ each independently represent a hydrogen atom, a C1 to C6 alkyl group, a C2 to C6 alkenyl group, a C7 to C12 aralkyl group, or an alkali. Represents a metal. And a clathrate compound (b) having a curing accelerator as a guest compound and the clathrate compound (b) with respect to 1 mol of the epoxy ring of the epoxy resin. An epoxy resin composition containing 0.001 to 1.0 mol. The epoxy resin composition according to claim 1 or 2, wherein X is a single bond in formula (I) or formula (II). The epoxy resin composition according to any one of claims 1 to 3, wherein the guest compound is an imidazole compound.

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