JP2007091900A - Curing agent for rapidly curable epoxy resin and epoxy resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an excellent one pack-type epoxy resin composition having both of extremely high rapid curability and storage stability at normal temperature; to provide a latent curing agent for obtaining the composition; and to provide an anisotropic electroconductive material, an electroconductive adhesive material, an insulation adhesive material, an encapsulant or the like providing high reliability of connection and high sealing properties even under a curing condition of a low temperature or a short time. <P>SOLUTION: The microcapsule-type curing agent for an epoxy resin is obtained by microencapsulating a curing agent for the epoxy resin characterized by >1 and ≤7 molecular weight distribution defined by the ratio of the weight average molecular weight to the number average molecular weight of an amine adduct, >1 and ≤10 pts.mass content of a low-molecular weight amine compound (B) based on 100 pts.mass of the amine adduct (A), and a melt viscosity of from 0.1 mPa s to 30 Pa s of the curing agent for the epoxy resin at 140°C. The epoxy resin composition contains the curing agent. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a novel curing agent for epoxy resins and an epoxy resin composition. More specifically, it is an epoxy resin composition that is an epoxy resin curing agent with excellent low-temperature rapid curing properties, is easy to mix with epoxy resins, has good latent curing properties, and has excellent storage stability at room temperature. And an epoxy resin material using the same.

Epoxy resin has excellent performance in terms of mechanical properties, electrical properties, thermal properties, chemical resistance, adhesiveness, etc., and it can be used for paints, insulating materials for electrical and electronic materials, adhesives, etc. It is used for a wide range of applications. The epoxy resin composition generally used at present is a so-called two-component composition in which two components of an epoxy resin and a curing agent are mixed at the time of use.
The two-part epoxy resin composition can be cured at room temperature, but it is necessary to store the epoxy resin and the curing agent separately and weigh and mix them as necessary. It is.
In addition, since the usable time is limited, it cannot be mixed in a large amount in advance, the blending frequency increases, and a reduction in efficiency is inevitable.
In order to solve the problem of such a two-component epoxy resin compounded product, several one-component epoxy resin compositions have been proposed so far. For example, there is an epoxy resin blended with a latent curing agent such as dicyandiamide, BF ₃ -amine complex, amine salt, or modified imidazole compound.

  However, these latent curing agents, which are excellent in storage stability, have low curability and require high temperature or long time for curing, while those having high curability have low storage stability, for example It is necessary to store at a low temperature such as -20 ° C. For example, the storage stability of dicyandiamide is 6 months or more when stored at room temperature, but a curing temperature of 170 ° C. or higher is required. In order to lower this curing temperature, a curing accelerator is used in combination. Then, for example, curing at 130 ° C. is possible, but on the other hand, storage stability at room temperature is insufficient, storage at low temperature is unavoidable, and high curability and excellent storage stability can be achieved at the same time. There was a strong demand for things. In addition, when obtaining a film-like molded product or a product in which a base material is impregnated with an epoxy resin, it is often a compounded product containing a solvent, a reactive diluent, etc., and the conventional latent curing agent is cured with such a compounded product. When used as an agent, the storage stability is drastically lowered, and it is necessary to make it substantially two-component.

Numerous studies have been made to meet this requirement. For example, Patent Document 1 discloses a curing agent for epoxy resin whose surface is coated with a reaction product of an isocyanate compound.
However, in recent years, especially in the field of electronic equipment, to cope with higher circuit density and higher connection reliability, to use materials with low heat resistance as lighter mobile devices, or to greatly improve productivity. Therefore, the one-part epoxy resin composition used as one of the connection materials is strongly required to further improve the curability without impairing the storage stability, which is difficult to achieve with the conventional technology. there were.

JP-A-1-70523

The present invention is an epoxy resin curing agent and an epoxy resin composition that have extremely high fast curing properties and storage stability at room temperature, and high storage stability, even under low temperature or short time curing conditions. The purpose is to provide adhesive materials, conductive materials, insulating materials, sealing materials, coating materials, coating compositions, prepregs, structural adhesives, heat conductive materials, etc. that can provide high connection reliability and high sealing performance. And

  As a result of intensive studies to solve the above problems, the present inventors have found that a curing agent for an epoxy resin containing a low molecular weight amine compound in a specific ratio in an amine adduct having a specific molecular weight distribution and / or a curing agent thereof. By containing a curing agent in which a curing agent is microencapsulated and / or a masterbatch type curing agent in which the microencapsulated curing agent is blended with an epoxy resin, preferably a cyclic borate compound. The present inventors have found that the above problems can be solved, and have made the present invention.

That is, the present invention is as follows.
1) A curing agent for an epoxy resin mainly composed of an amine adduct (A) and a low molecular weight amine compound (B), the molecular weight distribution defined as the ratio of the weight average molecular weight and the number average molecular weight of the amine adduct (A) Is more than 1 and 7 or less, and the content of the low-molecular amine compound (B) is more than 1 part by mass and 10 parts by mass with respect to 100 parts by mass of the amine duct (A). An epoxy resin curing agent, wherein the resin curing agent has a melt viscosity at 140 ° C. of from 0.1 mPa · s to 30 Pa · s.
2) The epoxy resin curing agent as described in 1) above, which is solid at 25 ° C.

3) The curing agent for epoxy resin according to 1) or 2) above, wherein the amine adduct (A) is obtained by a reaction between the epoxy resin (a1) and the amine compound (b1).
4) The curing agent for epoxy resin according to any one of 1) to 3) above, wherein the low molecular amine compound (B) is an imidazole.
5) The surface of the core composed of at least one epoxy resin curing agent (C) selected from the group consisting of the epoxy resin curing agents of 1) to 4) above is formed by a shell composed of a synthetic resin and / or an inorganic oxide. A microcapsule type epoxy resin curing agent characterized by having a coated structure.

6) The microcapsule type epoxy resin curing agent (D) has a core composed of at least one epoxy resin curing agent (C) selected from the group consisting of the epoxy resin curing agents 1) to 4) above. From the film (c1) obtained by the reaction of the isocyanate compound (G) and the active hydrogen compound (H) and / or the film (c2) obtained from the reaction of the epoxy resin curing agent (C) and the epoxy resin (N). And a bonding group (x) that absorbs infrared rays having a wave number of 1630 to 1680 cm ⁻¹ and a bonding group (y) that absorbs infrared rays having a wave number of 1680 to 1725 cm ⁻¹ , which are coated with a shell of Hardener for capsule type epoxy resin.
7) The microcapsule type epoxy resin curing agent as described in 6) above, wherein the total chlorine content of the epoxy resin (N) is 2500 ppm or less.

8) The epoxy resin curing agent (C) according to any one of 1) to 4) above and / or the microcapsule type according to any one of 5) to 7) above in 10 to 50000 parts by weight of the epoxy resin (E). A curing agent composition for a masterbatch type epoxy resin, comprising 100 parts by weight of the curing agent for epoxy resin (D) as the curing agent for epoxy resin (C) and / or (D).
9) The masterbatch type epoxy resin curing agent composition according to 8) above, wherein the total chlorine content of the masterbatch type epoxy resin curing agent composition (F) is 2500 ppm or less.
10) The hardener composition for a masterbatch type epoxy resin according to 8) or 9) above, wherein the total chlorine content of the epoxy resin (E) is 2500 ppm or less.

11) The diol terminal impure component of the epoxy resin (E) is 0.001 to 30% by mass of the basic structural component of the epoxy resin (E), according to any one of 8) to 10) above Hardener composition for masterbatch type epoxy resin.
12) The curing agent composition for a masterbatch type epoxy resin according to any one of 8) to 11), further comprising a cyclic borate ester compound (L).
13) The master batch type epoxy resin according to 12) above, wherein the cyclic borate compound (L) is 2,2′-oxybis (5,5′-dimethyl-1,3,2-oxaborinane). Hardener composition.

14) The masterbatch type epoxy according to 12) or 13) above, wherein the amount of the cyclic borate compound (L) is 0.001 to 10 parts by mass with respect to 100 parts by mass of the epoxy resin (E). Hardener composition for resin.
15) The epoxy resin curing agent according to any one of 1) to 14), the microcapsule type epoxy resin curing agent, and the masterbatch type epoxy resin curing agent composition with respect to 100 parts by mass of the epoxy resin (J). An epoxy resin composition comprising 0.1 to 1000 parts by mass of at least one selected from products and containing them as a main component.
16) 1 to 200 parts by mass of at least one curing agent (K) selected from the group consisting of acid anhydrides, phenols, hydrazides, and guanidines with respect to 100 parts by mass of the epoxy resin (J). And at least one selected from the curing agent for epoxy resins, the curing agent for microcapsule type epoxy resins, and the curing agent composition for masterbatch type epoxy resins according to any one of 1) to 11) above, The epoxy resin composition which contains 200 mass parts and has them as a main component.

17) The epoxy resin composition as described in 15) or 16) above, which further contains a cyclic borate ester compound (L).
18) In the above 15) or 16), the cyclic borate compound (L) is 2,2′-oxybis (5,5′-dimethyl-1,3,2-oxaborinane). The epoxy resin composition as described.
19) The amount of the cyclic borate compound (L) is 0.001 to 10 parts by mass with respect to 100 parts by mass of the epoxy resin (E). Epoxy resin composition.
20) A paste-like composition comprising the epoxy resin composition according to any one of 8) to 19).
21) A film-like composition comprising the epoxy resin composition according to any one of 8) to 19).

22) An adhesive comprising the epoxy resin composition according to any one of 15) to 19).
23) A bonding paste comprising the epoxy resin composition according to any one of 15) to 19).
24) A bonding film comprising the epoxy resin composition according to any one of 15) to 19).
25) A conductive material comprising the epoxy resin composition according to any one of 15) to 19).
26) An anisotropic conductive material comprising the epoxy resin composition according to any one of 15) to 19).
27) An anisotropic conductive film comprising the epoxy resin composition according to any one of 15) to 19).

28) An insulating material comprising the epoxy resin composition according to any one of 15) to 19).
29) A sealing material comprising the epoxy resin composition according to any one of 15) to 19).
30) A coating material comprising the epoxy resin composition according to any one of 15) to 19).
31) A coating composition comprising the epoxy resin composition according to any one of 15) to 19).
32) A prepreg comprising the epoxy resin composition according to any one of 15) to 19).
33) A thermally conductive material comprising the epoxy resin composition according to any one of 15) to 19).

  The curing agent for epoxy resin and the epoxy resin composition of the present invention are effective in achieving both extremely high rapid curing properties and storage stability at room temperature, and the cured product has excellent reliability, water resistance, and electrical characteristics. Express the characteristics.

The present invention will be specifically described below.
The present invention relates to a microcapsule type epoxy in which the surface of a core made of an epoxy resin curing agent (C) containing an amine adduct (A) as a main component and containing a low molecular amine compound (B) in a specific ratio is coated with a shell. The curing agent for resin (D) and the curing agent for epoxy resin of microcapsule type (D) are dispersed in the epoxy resin (E) to obtain a curing agent for masterbatch type epoxy resin.

The amine adduct (A) will be described.
The amine adduct (A) is obtained by reacting at least one compound selected from the group consisting of a carboxylic acid compound, a sulfonic acid compound, an isocyanate compound, a urea compound and an epoxy resin (a1) with the amine compound (b1). It is a compound having an amino group. The carboxylic acid compound, sulfonic acid compound, isocyanate compound, urea compound and epoxy resin (a1) used as the raw material for the amine adduct (A) are shown below.
Examples of the carboxylic acid compound include succinic acid, adipic acid, sebacic acid, phthalic acid, and dimer acid.
Examples of the sulfonic acid compound include ethanesulfonic acid and p-toluenesulfonic acid.

Examples of the isocyanate compound include aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, aliphatic triisocyanate, and polyisocyanate. Examples of the aliphatic diisocyanate include ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate. Examples of alicyclic diisocyanates include isophorone diisocyanate, 4-4′-dicyclohexylmethane diisocyanate, norbornane diisocyanate, 1,4-isocyanatocyclohexane, 1,3-bis (isocyanatomethyl) -cyclohexane, 1,3-bis. (2-isocyanatopropyl-2-yl) -cyclohexane and the like can be mentioned. Examples of the aromatic diisocyanate include tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylene diisocyanate, 1,5-naphthalene diisocyanate, and the like. Examples of the aliphatic triisocyanate include 1,3,6-triisocyanate methylhexane, 2,6-diisocyanatohexanoic acid-2-isocyanatoethyl and the like. Examples of the polyisocyanate include polymethylene polyphenyl polyisocyanate and polyisocyanate derived from the diisocyanate compound. Examples of the polyisocyanate derived from the diisocyanate include isocyanurate type polyisocyanate, burette type polyisocyanate, urethane type polyisocyanate, allophanate type polyisocyanate, and carbodiimide type polyisocyanate.
Examples of the urea compound include urea, methylurea, dimethylurea, ethylurea, t-butylurea and the like.

As the epoxy resin (a1), a monoepoxy compound, a polyvalent epoxy compound, or a mixture thereof is used. Monoepoxy compounds include butyl glycidyl ether, hexyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, para-tert-butylphenyl glycidyl ether, ethylene oxide, propylene oxide, paraxyl glycidyl ether, glycidyl acetate, glycidyl butyrate, glycidyl Examples include hexoate and glycidyl benzoate. Examples of the polyvalent epoxy compound include bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol AD, tetramethyl bisphenol S, tetrabromobisphenol A, and tetrachlorobisphenol A. Bisphenol-type epoxy resin obtained by glycidylation of bisphenols such as tetrafluorobisphenol A; epoxy resin obtained by glycidylation of other dihydric phenols such as biphenol, dihydroxynaphthalene and 9,9-bis (4-hydroxyphenyl) fluorene; 1,1,1-tris (4-hydroxyphenyl) methane, 4,4- (1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) pheny ) Ethylidene) Epoxy resin obtained by glycidylation of trisphenol such as bisphenol; Epoxy resin obtained by glycidylation of tetrakisphenol such as 1,1,2,2, -tetrakis (4-hydroxyphenyl) ethane; Phenol novolak, Cresol novolak , Novolak-type epoxy resins obtained by glycidylating novolaks such as bisphenol A novolak, brominated phenol novolak, brominated bisphenol A novolak, etc .; epoxy resins obtained by glycidylating polyhydric phenols, polyhydric alcohols such as glycerin and polyethylene glycol Glycidylated aliphatic ether type epoxy resin; ether ester type epoxy resin obtained by glycidylation of hydroxycarboxylic acid such as p-oxybenzoic acid and β-oxynaphthoic acid; phthalic acid, Ester-type epoxy resin obtained by glycidylation of polycarboxylic acid such as terephthalic acid; Glycidyl type such as amine-type epoxy resin such as glycidylated products of amine compounds such as 4,4-diaminodiphenylmethane and m-aminophenol and triglycidyl isocyanurate Examples include epoxy resins and alicyclic epoxides such as 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate.
Of the carboxylic acid compound, sulfonic acid compound, isocyanate compound, urea compound, and epoxy resin (a1) used as a raw material for the amine adduct (A), the epoxy resin (a1) has high curability and storage stability. preferable.

  As an epoxy resin (a1), since the storage stability of an epoxy resin composition can be improved, a polyvalent epoxy compound is preferable. As polyvalent epoxy compounds, amine compounds are overwhelmingly high in productivity, so glycidyl-type epoxy resins are preferable, and more preferably, epoxy having glycidylated polyhydric phenols because of excellent adhesion and heat resistance of cured products. Resin, more preferably bisphenol type epoxy resin. An epoxy resin obtained by glycidylating bisphenol A and an epoxy resin obtained by glycidylating bisphenol F are more preferable. An epoxy resin obtained by glycidylating bisphenol A is even more preferable. These epoxy resins may be used alone or in combination.

The total chlorine content of the epoxy resin (a1) is preferably 2500 ppm or less in order to obtain an epoxy resin composition having a balance between curability and storage stability.
More preferably, it is 2000 ppm or less, More preferably, it is 1500 ppm or less, More preferably, it is 800 ppm or less, More preferably, it is 400 ppm or less, More preferably, it is 180 ppm or less, More preferably, it is 100 ppm or less, More preferably Is 80 ppm or less, more preferably 50 ppm or less.

  In the present invention, the total chlorine amount is the total amount of organic chlorine and inorganic chlorine contained in the compound, and is a value based on the mass of the compound. The total chlorine amount is obtained by measuring by the following method. The epoxy resin composition is repeatedly washed and filtered with xylene until the epoxy resin is exhausted. Next, the filtrate is distilled off under reduced pressure at 100 ° C. or lower to obtain an epoxy resin. The obtained epoxy resin samples 1 to 10 g were precisely weighed so that the titration amount was 3 to 7 ml, dissolved in 25 ml of ethylene glycol monobutyl ether, added with 25 ml of 1N KOH propylene glycol solution and boiled for 20 minutes. After that, it is obtained by calculation from titration titrated with an aqueous silver nitrate solution.

By using an epoxy resin (a1) having a total chlorine content of 2500 ppm or less, a curing agent having high curing reactivity can be obtained.
Further, in order to facilitate control of the shell formation reaction, the total chlorine amount is preferably 0.01 ppm or more. More preferably, it is 0.02 ppm or more, More preferably, it is 0.05 ppm or more, More preferably, it is 0.1 ppm or more, More preferably, it is 0.2 ppm or more, More preferably, it is 0.5 ppm or more. When the total chlorine amount is 0.1 ppm or more, the shell forming reaction is efficiently performed on the surface of the curing agent, and a shell having excellent storage stability can be obtained. For example, a preferable range of the total amount of chlorine in the curing agent is 0.1 ppm to 200 ppm, a more preferable range is 0.2 ppm to 80 ppm, and a more preferable range is 0.5 ppm to 50 ppm.

Among the total chlorine, chlorine contained in the 1,2-chlorohydrin group is generally referred to as hydrolyzable chlorine, and the amount of hydrolyzable chlorine in the epoxy resin used as a raw material for the amine adduct is preferably 50 ppm or less. More preferably, it is 0.01 to 20 ppm, and still more preferably 0.05 to 10 ppm. Hydrolyzable chlorine is obtained by measurement by the following method. 3 g of a sample is dissolved in 50 ml of toluene, 20 ml of a 0.1 N KOH methanol solution is added thereto, and the mixture is boiled for 15 minutes, and then calculated by titration titrated with an aqueous silver nitrate solution.
A hydrolyzable chlorine content of 50 ppm or less is advantageous for achieving both high curability and storage stability, and exhibits excellent electrical properties.
These epoxy resins may be used alone or in combination.

The amine compound (b1) includes at least one primary amino group and / or secondary amino group but no tertiary amino group, at least one tertiary amino group and at least one activity. Examples thereof include compounds having a hydrogen group.
Examples of the compound having at least one primary amino group and / or secondary amino group but not having a tertiary amino group include, for example, methylamine, ethylamine, propylamine, butylamine, ethylenediamine, propylenediamine, hexamethylenediamine, Primary amines having no tertiary amino group such as diethylenetriamine, triethylenetetramine, ethanolamine, propanolamine, cyclohexylamine, isophoronediamine, aniline, toluidine, diaminodiphenylmethane, diaminodiphenylsulfone, such as dimethylamine, diethylamine, Dipropylamine, dibutylamine, dipentylamine, dihexylamine, dimethanolamine, diethanolamine, dipropanolamine, dicyclohexylamine, Perijin, piperidone, diphenylamine, phenylmethylamine, mention may be made of secondary amines having no tertiary amino group such as phenylethylamine.
In the compound having at least one tertiary amino group and at least one active hydrogen group, examples of the active hydrogen group include a primary amino group, a secondary amino group, a hydroxyl group, a thiol group, a carboxylic acid, and a hydrazide group.

Examples of the compound having at least one tertiary amino group and at least one active hydrogen group include 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol. Amino alcohols such as 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, methyldiethanolamine, triethanolamine, N-β-hydroxyethylmorpholine; 2- (dimethylaminomethyl) phenol, 2,4, Aminophenols such as 6-tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-amino Ethyl-2-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-ethyl-4-methylimidazole, 1- ( Imidazoles such as 2-hydroxy-3-butoxypropyl) -2-methylimidazole and 1- (2-hydroxy-3-butoxypropyl) -2-ethyl-4-methylimidazole; 1- (2-hydroxy-3- Phenoxypropyl) -2-phenylimidazoline, 1- (2-hydroxy-3-butoxypropyl) -2-methylimidazoline, 2-methylimidazoline, 2,4-dimethylimidazoline, 2-ethylimidazoline, 2-ethyl-4- Methyl imidazoline, 2-benzyl imidazoline, 2-phenyl imidazoline 2- (o-tolyl) -imidazoline, tetramethylene-bis-imidazoline, 1,1,3-trimethyl-1,4-tetramethylene-bis-imidazoline, 1,3,3-trimethyl-1,4-tetra Methylene-bis-imidazoline, 1,1,3-trimethyl-1,4-tetramethylene-bis-4-methylimidazoline, 1,3,3-trimethyl-1,4-tetramethylene-bis-4-methylimidazoline, Imidazolines such as 1,2-phenylene-bis-imidazoline, 1,3-phenylene-bis-imidazoline, 1,4-phenylene-bis-imidazoline, 1,4-phenylene-bis-4-methylimidazoline, dimethylaminopropyl Amine, diethylaminopropylamine, dipropylaminopropylamine, dibutylaminopropyl Tertiary aminoamines such as amine, dimethylaminoethylamine, diethylaminoethylamine, dipropylaminoethylamine, dibutylaminoethylamine, N-methylpiperazine, N-aminoethylpiperazine, diethylaminoethylpiperazine; 2-dimethylaminoethanethiol, 2-mercapto Aminomercaptans such as benzimidazole, 2-mercaptobenzothiazole, 2-mercaptopyridine, 4-mercaptopyridine; N, N-dimethylaminobenzoic acid, N, N-dimethylglycine, nicotinic acid, isonicotinic acid, picolinic acid, etc. And amino hydrazides such as N, N-dimethylglycine hydrazide, nicotinic acid hydrazide and isonicotinic acid hydrazide.
The amine compound (b1) is preferably a compound having at least one tertiary amino group and at least one active hydrogen group, more preferably an imidazole, since it has an excellent balance between storage stability and curability. 2-methylimidazole and 2-ethyl-4-methylimidazole are more preferable.

In the present invention, by exhibiting the molecular weight distribution of the amine adduct (A) within a specific range, it exhibits high fast curability as a curing agent for epoxy resins without impairing the storage stability of the one-component epoxy resin composition. be able to.
That is, the molecular weight distribution of the amine adduct (A) used in the present invention is more than 1 and 7 or less. Here, the molecular weight distribution is defined as the ratio of the weight average molecular weight to the number average molecular weight, and is calculated from the molecular weight determined in terms of polystyrene using a gel permeation chromatography (hereinafter referred to as GPC) method. The molecular weight distribution of the amine adduct (A) is preferably from 1.01 to 6.50, more preferably from 1.20 to 5.75, and even more preferably from 1.30 to 5.00. By setting the molecular weight distribution of the amine adduct (A) from 1 to 7, an epoxy resin composition having high curability and excellent storage stability can be obtained.

  The amine adduct (A) used in the present invention comprises, for example, an epoxy resin (a1) and an amine compound (b1) in an active hydrogen group in the amine compound (b1) with respect to 1 equivalent of the epoxy group of the epoxy resin (a1). Is preferably in the range of 0.8 equivalents to 10 equivalents (more preferably 0.9 equivalents to 5 equivalents, more preferably 0.95 equivalents to 4 equivalents), for example, 50 to It is obtained by reacting at a temperature of 250 ° C. for 0.1 to 10 hours. When the equivalent ratio of active hydrogen groups to epoxy groups is 0.8 or more, it is advantageous to obtain an amine adduct (A) having a molecular weight distribution of 7 or less, and the equivalent ratio is 10 or less, for the epoxy resin of the present invention. The recovery of the unreacted amine compound (b1), which is carried out in order to bring the content of the low molecular amine compound (B) contained in the curing agent to a desired value, is advantageous because it is economical.

  In the reaction for obtaining the amine adduct (A) from the epoxy resin (a1) and the amine compound (b1), the solvent used as necessary is not particularly limited. For example, benzene, toluene, xylene, cyclohexane , Hydrocarbons such as mineral spirits, naphtha, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, esters such as ethyl acetate, n-butyl acetate, propylene glycol monomethyl ether acetate, methanol, isopropanol, n-butanol, Examples thereof include alcohols such as butyl cellosolve and butyl carbitol, water, and the like, and these solvents may be used in combination. The solvent used is preferably removed by distillation or the like.

Examples of the low molecular amine compound (B) used in the present invention include compounds having primary, secondary and / or tertiary amino groups. These can be used in combination.
Examples of the compound having a primary amino group include methylamine, ethylamine, propylamine, butylamine, ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, ethanolamine, propanolamine, cyclohexylamine, isophoronediamine, aniline, Toluidine, diaminodiphenylmethane, diaminodiphenylsulfone and the like can be mentioned.
Examples of the compound having a secondary amino group include dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, dimethanolamine, diethanolamine, dipropanolamine, dicyclohexylamine, piperidine, piperidone, diphenylamine, phenyl Examples thereof include methylamine and phenylethylamine.

Examples of the compound having a tertiary amino group include trimethylamine, triethylamine, benzyldimethylamine, N, N′-dimethylpiperazine, triethylenediamine, 1,8-diazabicyclo (5,4,0) -undecene-7, Tertiary amines such as 1,5-diazabicyclo (4,3,0) -nonene-5; 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, Amino alcohols such as 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, methyldiethanolamine, triethanolamine, N-β-hydroxyethylmorpholine; 2- (dimethylaminomethyl) phenol, 2,4,6 -Tris (dimethylaminomethyl) Aminophenols such as phenol; 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-aminoethyl-2-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-ethyl-4-methylimidazole, 1- (2-hydroxy-3-butoxypropyl) Imidazoles such as 2-methylimidazole and 1- (2-hydroxy-3-butoxypropyl) -2-ethyl-4-methylimidazole; 1- (2-hydroxy-3-phenoxypropyl) -2-phenylimidazoline, 1- (2-hydroxy-3-butoxypropyl)- -Methylimidazoline, 2-methylimidazoline, 2,4-dimethylimidazoline, 2-ethylimidazoline, 2-ethyl-4-methylimidazoline, 2-benzylimidazoline, 2-phenylimidazoline, 2- (o-tolyl) -imidazoline, Tetramethylene-bis-imidazoline, 1,1,3-trimethyl 1,4-tetramethylene bis-imidazoline, 1,3,3 trimethyl 1,4-tetramethylene bis-imidazoline, 1,1,3 trimethyl 1,4-tetramethylene Bis 4 methyl imidazoline, 1,3,3 trimethyl 1,4-tetramethylene bis 4 methyl imidazoline, 1,2 phenylene bis imidazoline, 1,3 phenylene bis imidazoline, 1,4 phenylene bis imidazoline, 1,4 phenylene bis 4 methyl Imidazoline etc. Dazolines, dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, dipropylaminoethylamine, dibutylaminoethylamine, N-methylpiperazine, N-aminoethylpiperazine, Tertiary aminoamines such as diethylaminoethylpiperazine; aminomercaptans such as 2-dimethylaminoethanethiol, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptopyridine, 4-mercaptopyridine; N, N-dimethyl Aminocarboxylic acids such as aminobenzoic acid, N, N-dimethylglycine, nicotinic acid, isonicotinic acid and picolinic acid; N, N-dimethylglycy And aminohydrazides such as hydrazide, nicotinic acid hydrazide and isonicotinic acid hydrazide.
As the low molecular amine compound (B), an epoxy resin composition having excellent storage stability is obtained, and therefore a compound having a tertiary amino group is preferable, imidazoles are more preferable, 2-methylimidazole, 2-ethyl- 4-methylimidazole is more preferred.

In the present invention, it was found that an epoxy resin composition having high storage stability can be obtained by containing a specific amount of a low molecular amine compound in the amine adduct (A).
That is, in the present invention, the amount of the low molecular weight amine compound (B) with respect to 100 parts by mass of the amine adduct (A) exceeds 10 parts by mass to obtain an epoxy resin composition having high storage stability at room temperature. Part or less. Preferably, it is 1.01 to 8 parts by mass, more preferably 1.2 to 6 parts by mass, and even more preferably 1.8 to 5 parts by mass.

When the content of the low-molecular amine compound (B) exceeds 1 part by mass, a curing agent for epoxy resin (C) that realizes high rapid curability can be obtained.
If the content of the low molecular amine compound (B) is more than 10 parts by mass, the amount of elution through the capsule membrane at room temperature increases, and the potential is impaired.
The low molecular amine compound (B) may be mixed with the amine adduct (A) after the production of the amine adduct (A), or may be mixed before and / or during the production of the amine adduct (A). . Moreover, you may use the unreacted substance of the amine compound (b1) which is a raw material of an amine adduct (A) as a low molecular amine compound (B).

The melt viscosity at 140 ° C. of the epoxy resin curing agent (C) is preferably from 0.1 mPa · s to 30 Pa · s. More preferably, it is 20 Pa.s or less, More preferably, it is 12 Pa.s or less, More preferably, it is 8 Pa.s or less, More preferably, it is 5 Pa.s or less. By setting the melt viscosity at 140 ° C. of the epoxy resin curing agent to 30 Pa · s or less, an epoxy resin curing agent having excellent curability in a short time can be obtained. Further, in order to obtain a microcapsule type epoxy resin curing agent having high storage stability, the melt viscosity at 140 ° C. is preferably 0.1 mPa · s or less.
As a form of the hardening | curing agent for epoxy resins (C), it is preferable that it is solid at 25 degreeC, ie, a softening point exceeds 25 degreeC. More preferably, the softening point is 40 ° C. or higher, more preferably the softening point is 60 ° C. or higher. By using the epoxy resin curing agent (C) which is solid at 25 ° C., an epoxy resin composition having high storage stability can be obtained.

  Examples of the solid curing agent for epoxy resin (C) further include a lump, granule, powder, and the like, preferably a granule or powder, and more preferably a powder. In the present invention, the powder form is not particularly limited, but an average particle diameter of 0.1 to 50 μm is preferable, and an average particle diameter of 0.5 to 10 μm is more preferable. By setting the thickness to 50 μm or less, a homogeneous cured product can be obtained. The particle size referred to in the present invention refers to the Stokes diameter measured by the light scattering method. Moreover, an average particle diameter refers to a median diameter. The shape thereof is not particularly limited, and may be either spherical or indeterminate, and spherical is preferable for reducing the viscosity of the one-component epoxy resin composition. Here, the term “spherical” includes not only a true sphere but also a shape in which an irregular corner is rounded.

  The total amount of chlorine in the epoxy resin curing agent (C) of the present invention is preferably 2500 ppm or less. More preferably, it is 2000 ppm or less, More preferably, it is 1500 ppm or less, More preferably, it is 800 ppm or less, More preferably, it is 400 ppm or less, More preferably, it is 180 ppm or less, More preferably, it is 100 ppm or less, More preferably Is 80 ppm or less, more preferably 50 ppm or less. An epoxy resin composition having a high balance between curability and storage stability with a total chlorine content of 2500 ppm or less can be obtained.

In order to facilitate the control of the shell formation reaction, the total chlorine content of the epoxy resin curing agent (C) is preferably 0.01 ppm or more. More preferably, it is 0.02 ppm or more, More preferably, it is 0.05 ppm or more, More preferably, it is 0.1 ppm or more, More preferably, it is 0.2 ppm or more, More preferably, it is 0.5 ppm or more. When the total chlorine amount is 0.1 ppm or more, the shell forming reaction is efficiently performed on the surface of the curing agent, and a shell having excellent storage stability can be obtained.
The microcapsule type epoxy resin curing agent (D) according to the present invention has a structure in which the surface of the core made of the epoxy resin curing agent (C) is covered with a shell made of a synthetic resin or an inorganic oxide. Is. Among these, a synthetic resin is preferable from the viewpoints of film stability, ease of destruction during heating, and uniformity of a cured product.

Synthetic resins include epoxy resins, polyester resins, polyethylene resins, nylon resins, polystyrene resins, urethane resins, and the like. Urethane resins that are addition products of mono- or polyhydric alcohols and mono- or polyisocyanates, amine-based resins A reaction product of a curing agent and an epoxy resin and a phenol resin are desirable, and among them, a reaction product of an amine curing agent and an epoxy resin is preferable from the viewpoint of film stability and ease of destruction during heating.
Examples of the inorganic substance include boron compounds such as boron oxide and boric acid ester, silicon dioxide, and calcium oxide. Boron oxide is preferable from the viewpoint of film stability and ease of destruction during heating.

In the case of using an epoxy resin curing agent (C) of the present invention as the core absorbs bonded group that absorbs infrared wave number 1630～1680Cm ^-1 (x) and the infrared wave number 1680～1725Cm ^-1 bond What has group (y) on the surface at least is preferable from a viewpoint of the balance of storage stability and reactivity.
The bonding group (x) and the bonding group (y) can be measured using a Fourier transform infrared spectrophotometer (referred to as FT-IR). Moreover, it can be measured using microscopic FT-IR that the bonding group (x) and / or the bonding group (y) has at least the surface of the curing agent for epoxy resin (C).
Among the bonding groups (x), urea bonds can be mentioned as particularly useful. Among the linking groups (y), buret bonds can be mentioned as particularly useful.

  What has this urea bond and burette bond is a reaction product produced | generated by reaction of an isocyanate compound (G) and an active hydrogen compound (H). As an isocyanate compound (G) used to generate a urea bond that is representative of the linking group (x) and a burette bond that is representative of the linking group (y), one or more isocyanate groups are present in one molecule. However, it is preferable to use a compound having two or more isocyanate groups in one molecule, and preferred isocyanates include aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, low molecular weight triisins. An isocyanate and a polyisocyanate can be mentioned. Examples of the aliphatic diisocyanate include ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate. Examples of alicyclic diisocyanates include isophorone diisocyanate, 4-4′-dicyclohexylmethane diisocyanate, norbornane diisocyanate, 1,4-isocyanatocyclohexane, 1,3-bis (isocyanatomethyl) -cyclohexane, 1,3-bis. (2-isocyanatopropyl-2-yl) -cyclohexane and the like can be mentioned. Examples of the aromatic diisocyanate include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylene diisocyanate, 1,5-naphthalene diisocyanate, and the like. Examples of low molecular weight triisocyanates include 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, 2,6-diisocyanatohexane Aliphatic triisocyanate compounds such as acid-2-isocyanatoethyl and 2,6-diisocyanatohexanoic acid-1-methyl-2-isocyanatoethyl, alicyclic triisocyanates such as tricyclohexylmethane triisocyanate and bicycloheptane triisocyanate Examples thereof include aromatic triisocyanate compounds such as isocyanate compounds, triphenylmethane triisocyanate, and tris (isocyanatephenyl) thiophosphate. Examples of the polyisocyanate include polymethylene polyphenyl polyisocyanate, polyisocyanate derived from the above diisocyanate, and low molecular triisocyanate. Examples of the polyisocyanate derived from the diisocyanate and triisocyanate include isocyanurate type polyisocyanate, burette type polyisocyanate, urethane type polyisocyanate, allophanate type polyisocyanate, carbodiimide type polyisocyanate and the like. These isocyanate compounds (G) can be used in combination.

The active hydrogen compound (H) for generating a urea bond or a burette bond, which is representative of the bonding groups (x) and (y), includes water, one or more primary and / or secondary amino groups in one molecule. And a compound having one or more hydroxyl groups in one molecule. These can be used in combination. Water and a compound having one or more hydroxyl groups in one molecule are preferable. As the compound having one or more primary and / or secondary amino groups in one molecule, aliphatic amines, alicyclic amines, and aromatic amines can be used. Examples of the aliphatic amine include alkylamines such as methylamine, ethylamine, propylamine, butylamine, and dibutylamine. Alkylene diamines such as ethylene diamine, propylene diamine, butylene diamine and hexamethylene diamine; Examples include polyalkylene polyamines such as diethylenetriamine, triethylenetetramine, and tetraethylenepentamine, and polyoxyalkylene polyamines such as polyoxypropylene diamine and polyoxyethylene diamine. Examples of the alicyclic amine include cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, and isophoronediamine. Examples of the aromatic amine include aniline, toluidine, benzylamine, naphthylamine, diaminodiphenylmethane, diaminodiphenylsulfone and the like.

  Examples of the compound having one or more hydroxyl groups in one molecule used as the active hydrogen compound (H) include alcohol compounds and phenol compounds. Examples of alcohol compounds include methyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, dodecyl alcohol, stearyl alcohol, eicosyl alcohol, Monoalcohols such as allyl alcohol, crotyl alcohol, propargyl alcohol, cyclopentanol, cyclohexanol, benzyl alcohol, cinnamyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol monobutyl , Ethylene glycol, polyethylene glycol, propylene Recall, polypropylene glycol, 1,3-butanediol, 1,4-butanediol, hydrogenated bisphenol A, neopentyl glycol, glycerin, trimethylol propane, may be mentioned polyhydric alcohols such as pentaerythritol. A secondary compound obtained by a reaction between a compound having one or more epoxy groups in one molecule and a compound having one or more hydroxyl groups, carboxyl groups, primary or secondary amino groups, or mercapto groups in one molecule. Compounds having two or more hydroxyl groups in one molecule are also exemplified as polyhydric alcohols. These alcohol compounds may be any of primary, secondary, or tertiary alcohols. Examples of the phenol compound include monophenols such as carboxylic acid, cresol, xylenol, carvacrol, motil, and naphthol, and polyhydric phenols such as catechol, resorcin, hydroquinone, bisphenol A, bisphenol F, pyrogallol, and phloroglucin. As the compound having one or more hydroxyl groups in one molecule, polyhydric alcohols and polyhydric phenols are preferable. Polyhydric alcohols are more preferred.

  On the surface of the core made of the epoxy resin curing agent (C), the bonding group (x) and the bonding group (y) have a concentration in the range of 1 to 1000 meq / kg and 1 to 1000 meq / kg, respectively. Is preferred. The density | concentration said here is a value with respect to the hardening | curing agent (C) for epoxy resins. It is advantageous to obtain a capsule-type curing agent having a bonding group (x) concentration of 1 meq / kg or more and high resistance to mechanical shearing force. Moreover, it is advantageous for obtaining high curability at 1000 meq / kg or less. A more preferable concentration range of the linking group (x) is 10 to 300 meq / kg.

It is advantageous to obtain a capsule-type curing agent having a bonding group (y) concentration of 1 meq / kg or more and high resistance to mechanical shearing force. Moreover, it is advantageous for obtaining high curability at 1000 meq / kg or less. A more preferable range of the linking group (y) is 10 to 200 meq / kg.
In addition to the bonding group (x) and the bonding group (y), the surface of the core made of the epoxy resin curing agent (C) mainly composed of the amine adduct (A) and the low molecular amine compound (B) It preferably has a bonding group (z) that absorbs infrared rays having a wave number of 1730 to 1755 cm ⁻¹ . The bonding group (z) can also be measured using a Fourier transform infrared spectrophotometer (FT-IR). Moreover, it can be measured using microscopic FT-IR that the bonding group (z) has at least the surface of the curing agent for epoxy resin (C).
Of these linking groups (z), a particularly useful one is a urethane bond. This urethane bond is generated by a reaction between the isocyanate compound (G) and a compound having one or more hydroxyl groups in one molecule. As an isocyanate compound (G) used here, the isocyanate compound (G) used in order to produce | generate a urea bond and a burette bond can be used.

  Examples of the compound having one or more hydroxyl groups in one molecule used to form a urethane bond that is representative of the bonding group (z) include aliphatic saturated alcohols, aliphatic unsaturated alcohols, aliphatic alcohols, and aromatics. Alcohol compounds such as alcohol and phenol compounds can be used. Aliphatic alcohols include methyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, dodecyl alcohol, stearyl alcohol, eicosyl alcohol Monoalcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoalkyl ethers such as ethylene glycol monohexyl ether; ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1, Divalent, such as 3-butanediol and neopentyl glycol Alcohols like; it may be mentioned tetravalent alcohols such as pentaerythritol; glycerol, trimethylol, trihydric alcohols such as propane. Examples of the aliphatic unsaturated alcohol include allyl alcohol, crotyl alcohol, propargyl alcohol and the like. Examples of the alicyclic alcohol include cyclopentanol, cyclohexanol, and cyclohexanedimethanol. Examples of the aromatic alcohol include monoalcohols such as benzyl alcohol and cinnamyl alcohol. These alcohols may be primary, secondary, or tertiary alcohols. Also obtained by reaction of a compound having one or more epoxy groups in one molecule with a compound having one or more hydroxyl groups, carboxyl groups, primary or secondary amino groups, or mercapto groups in one molecule. A compound having one or more secondary hydroxyl groups in one molecule can also be used as the alcohol compound. Examples of phenolic compounds include monohydric phenols such as carboxylic acid, cresol, xylenol, carvacrol, motile, naphthol, dihydric phenols such as catechol, resorcin, hydroquinone, bisphenol A, bisphenol F, and trivalent phenols such as pyrogallol and phloroglucin. be able to. A compound having one or more hydroxyl groups in one molecule is preferably an alcohol compound or a phenol compound having a divalent or higher hydroxyl group.

A preferable concentration range of the bonding group (z) on the surface of the core made of the epoxy resin curing agent (C) is 1 to 200 meq / kg. The density | concentration said here is a value with respect to the hardening | curing agent (C) for epoxy resins. When the concentration of the linking group (z) is 1 meq / kg or more, it is advantageous for forming a shell having high resistance to mechanical shearing force, and when it is 200 meq / kg or less, it is advantageous for obtaining high curability. is there. A more preferable concentration range of the linking group (z) is 5 to 100 meq / kg. The quantification of the concentration of the linking group (x), the linking group (y), and the linking group (z) can be performed by the method disclosed in Patent Document 1.
The total thickness of the bonding groups (x), bonding groups (y), and bonding groups (z) existing on the surface of the core made of the epoxy resin curing agent (C) is preferably 5 to 1000 nm in terms of the average layer thickness. Storage stability is obtained at 5 nm or more, and practical curability is obtained at 1000 nm or less. The thickness of a layer here can be measured with a transmission electron microscope. The total thickness of the bonding groups on the core surface made of a particularly preferable epoxy resin curing agent (C) is 10 to 100 nm in average layer thickness.

The ratio of the bonding group on the surface to the core made of the epoxy resin curing agent (C) is 100/1 to 100/100 in terms of mass ratio. Within this range, storage stability and curability are compatible. Preferably it is 100 / 2-100 / 80, More preferably, it is 100 / 5-100 / 60, More preferably, it is 100 / 10-100 / 50.
As a method for causing a bonding group to exist on the surface of the core made of the epoxy resin curing agent (C), the bonding group component is dissolved in a dispersion medium in which the epoxy resin curing agent (C) is dispersed. A method of lowering the solubility of the components of the epoxy resin and precipitating it on the surface of the curing agent for epoxy resin (C), and forming a bonding group in a dispersion medium in which the curing agent for epoxy resin (C) is dispersed, Examples include a method in which a bonding group is precipitated on the surface of the curing agent (C), or the surface of the curing agent (C) for the epoxy resin is used as a reaction field to generate a bonding group there. The latter method is preferable because the reaction and the coating can be performed simultaneously.

Here, examples of the dispersion medium include a solvent, a plasticizer, and resins. Moreover, an epoxy resin can also be used as a dispersion medium.
Examples of the solvent include hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirit, and naphtha; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ethyl acetate, n-butyl acetate, propylene glycol monomethyl ethyl ether Examples include esters such as acetate; alcohols such as methanol, isopropanol, n-butanol, butyl cellosolve, and butyl carbitol; water, and the like. Plasticizers include dibutyl phthalate, di (2-ethylhexyl) phthalate diesters, aliphatic dibasic acid esters such as di (2-ethylhexyl) adipate, and tricresyl phosphate triphosphates. Examples include ester series and glycol ester series such as polyethylene glycol ester. Examples of the resins include silicone resins, epoxy resins, phenol resins and the like.

  Examples of the epoxy resin that can be used as a dispersion medium in the method of coating the epoxy resin curing agent (C) with a bonding group include bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, Bisphenol type epoxy resin obtained by glycidylation of bisphenols such as tetramethylbisphenol AD, tetramethylbisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A, tetrafluorobisphenol A; biphenol, dihydroxynaphthalene, dihydroxybenzene, 9,9-bis Epoxy resin obtained by glycidylation of other dihydric phenols such as (4-hydroxyphenyl) fluorene; 1,1,1-tris (4-hydroxyphenyl) Nyl) methane, epoxy resin obtained by glycidylation of trisphenols such as 4,4- (1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) bisphenol; Epoxy resins obtained by glycidylating tetrakisphenols such as 2,2, -tetrakis (4-hydroxyphenyl) ethane; novolaks such as phenol novolak, cresol novolak, bisphenol A novolak, brominated phenol novolak, brominated bisphenol A novolak Glycidylated novolac epoxy resin, etc .; epoxy resin obtained by glycidylation of polyhydric phenols, aliphatic ether type epoxy resin obtained by glycidylation of polyhydric alcohols such as glycerin and polyethylene glycol; p-oxybenzoic acid, β-oxy Ether ester type epoxy resin obtained by glycidylation of hydroxycarboxylic acid such as naphthoic acid; ester type epoxy resin obtained by glycidylation of polycarboxylic acid such as phthalic acid and terephthalic acid; 4,4-diaminodiphenylmethane, m-aminophenol, etc. Glycidyl-type epoxy resins such as amine-type epoxy resins such as glycidylated amine compounds and triglycidyl isocyanurate, and alicyclic epoxides such as 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate Illustrated.

Among them, the glycidyl type epoxy resin is preferable because the storage stability of the epoxy resin composition is high. Yes, more preferably a bisphenol type epoxy resin. An epoxy resin obtained by glycidylating bisphenol A and an epoxy resin obtained by glycidylating bisphenol F are more preferable. An epoxy resin obtained by glycidylating bisphenol A is even more preferable.

In the method in which the surface of the epoxy resin curing agent (C) is used as a reaction field and a bonding group is generated there, the reaction between the isocyanate compound (G) and the active hydrogen compound (H) is usually at a temperature of -10 ° C to 150 ° C. In the range of 10 minutes to 12 hours of reaction time.
The amount ratio of the isocyanate compound (G) and the active hydrogen compound (H) is not particularly limited, but usually the equivalent ratio of the isocyanate group in the isocyanate compound (G) and the active hydrogen in the active hydrogen compound (H) is It is used in the range of 1: 0.1 to 1: 1000.

  As the shell of the microcapsule type epoxy resin curing agent (D) according to the present invention, the reaction in the case of using a reaction product comprising a reaction product of the epoxy resin curing agent (C) and the epoxy resin (N) is as follows: The reaction is usually performed at a temperature range of 0 ° C. to 150 ° C., preferably 10 ° C. to 100 ° C., for a reaction time of 1 to 168 hours, preferably 2 hours to 72 hours, and can also be performed in a dispersion medium. Examples of the dispersion medium include a solvent and a plasticizer. Moreover, epoxy resin (N) itself can also be used as a dispersion medium. In this case, the epoxy resin (E) in the masterbatch type epoxy resin curing agent composition (F) and the epoxy resin (N) used in the shell forming reaction may be the same epoxy resin.

Examples of the solvent include hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirit, and naphtha; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ethyl acetate, n-butyl acetate, propylene glycol monomethyl ethyl ether Examples include esters such as acetate; alcohols such as methanol, isopropanol, n-butanol, butyl cellosolve, and butyl carbitol; water, and the like. Plasticizers include dibutyl phthalate, di (2-ethylhexyl) phthalate diesters, aliphatic dibasic acid esters such as di (2-ethylhexyl) adipate, and tricresyl phosphate triphosphates. Examples include ester series and glycol ester series such as polyethylene glycol ester.
The mass ratio when the epoxy resin curing agent (C) and the epoxy resin (N) are reacted is not particularly limited, but is usually in the range of 1: 0.001 to 1: 1000, preferably 1: 0.01. Used in the range of ˜1: 100.

As a method of covering the core with a shell made of a reaction product of the epoxy resin curing agent (C) and the epoxy resin (N), the shell component is dissolved and the epoxy resin curing agent (C) is dispersed. The method of lowering the solubility of the shell component in the medium to deposit the shell on the surface of the curing agent for epoxy resin (C), the formation reaction of the shell in the dispersion medium in which the curing agent for epoxy resin (C) is dispersed And a method of depositing a shell on the surface of the curing agent for epoxy resin (C), or a method of generating a shell there by using the surface of the core made of the curing agent for epoxy resin (C) as a reaction field. . The latter two methods are preferable because the reaction and the coating can be performed simultaneously.
In the latter case, the curing agent for epoxy resin of the present invention may use the amine compound in the core or may be added separately.

The average thickness of the shell covering the surface of the epoxy resin curing agent (C) of the present invention is preferably 5 to 1000 nm. Storage stability is obtained at 5 nm or more, and practical curability is obtained at 1000 nm or less. The thickness of the layer here is observed with a transmission electron microscope. A particularly preferable shell thickness is 50 to 700 nm as an average layer thickness.
The epoxy resin (N) of the present invention is not particularly limited as long as the effects intended by the present invention are not impaired. An example of such an epoxy resin (N) is, for example, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol A.
D, bisphenol type epoxy resin obtained by glycidylation of bisphenols such as tetramethylbisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A, tetrafluorobisphenol A; biphenol, 9,9-bis (4-hydroxyphenyl) fluorene, etc. Epoxy resin obtained by glycidylation of other dihydric phenols; 1,1,1-tris (4-hydroxyphenyl) methane, 4,4- (1- (4- (1- (4-hydroxyphenyl) -1- Epoxy resin obtained by glycidylation of trisphenols such as methylethyl) phenyl) ethylidene) bisphenol; epoxy resin obtained by glycidylation of tetrakisphenols such as 1,1,2,2, -tetrakis (4-hydroxyphenyl) ethane; phenol Novolac Novolak type epoxy resin obtained by glycidylation of novolaks such as cresol novolak, bisphenol A novolak, brominated phenol novolak, brominated bisphenol A novolak, etc .; Aliphatic ether type epoxy resin obtained by glycidylation of alcohol; ether ester type epoxy resin obtained by glycidylation of hydroxycarboxylic acid such as p-oxybenzoic acid and β-oxynaphthoic acid; polycarboxylic acid such as phthalic acid and terephthalic acid Glycidylated ester-type epoxy resins; glycidylated amine compounds such as 4,4-diaminodiphenylmethane and m-aminophenol, and amine-type epoxy resins such as triglycidyl isocyanurate Examples thereof include glycidyl type epoxy resins and alicyclic epoxides such as 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate.
These epoxy resins may be used alone or in combination.

  The total chlorine content of the epoxy resin (N) of the present invention is preferably 2500 ppm or less. More preferably, it is 2000 ppm or less, More preferably, it is 1500 ppm or less, More preferably, it is 800 ppm or less, More preferably, it is 400 ppm or less, More preferably, it is 180 ppm or less, More preferably, it is 100 ppm or less, More preferably Is 80 ppm or less, more preferably 50 ppm or less. An epoxy resin composition having a high balance between curability and storage stability with a total chlorine content of 2500 ppm or less can be obtained.

  In order to facilitate control of the shell formation reaction, the total chlorine content of the epoxy resin (N) is preferably 0.01 ppm or more. More preferably, it is 0.02 ppm or more, More preferably, it is 0.05 ppm or more, More preferably, it is 0.1 ppm or more, More preferably, it is 0.2 ppm or more, More preferably, it is 0.5 ppm or more. When the total chlorine amount is 0.1 ppm or more, the shell forming reaction is efficiently performed on the surface of the curing agent, and a shell having excellent storage stability can be obtained.

  The masterbatch type epoxy resin curing agent composition (F) of the present invention comprises 10 to 50000 parts by weight of epoxy resin (E), epoxy resin curing agent (C) and / or microcapsule type epoxy resin curing agent ( 100 weight part was mix | blended considering D) as a hardening | curing agent for epoxy resins (C), It is characterized by the above-mentioned. When the amount of the epoxy resin (E) is more than 50000 parts by weight, the curability is lowered, and when it is less than 10 parts by weight, the viscosity of the curing agent composition for the masterbatch type epoxy resin is increased and workability is lowered. From such a viewpoint, the amount of the epoxy resin (E) is preferably 100 to 5000 with respect to 100 parts by weight of the curing agent for epoxy resin (C) and / or the curing agent for microcapsule type epoxy resin (D). Yes, more preferably 120 to 1000, and particularly preferably 150 to 400.

The total chlorine content of the masterbatch type epoxy resin curing agent composition (F) of the present invention is desirably 2500 ppm or less in order to achieve both high curability and storage stability.
More preferably, it is 1500 ppm or less, More preferably, it is 800 ppm or less, More preferably, it is 400 ppm or less, More preferably, it is 200 ppm or less, More preferably, it is 100 ppm or less, More preferably, it is 80 ppm or less, More preferably Is 50 ppm or less.
The total chlorine content of the epoxy resin (E) is desirably 2500 ppm or less in order to achieve both high curability and storage stability.
More preferably, it is 1500 ppm or less, More preferably, it is 800 ppm or less, More preferably, it is 400 ppm or less, More preferably, it is 200 ppm or less, More preferably, it is 100 ppm or less, More preferably, it is 80 ppm or less, More preferably Is 50 ppm or less.

  When the epoxy resin (E) and the epoxy resin (N) are the same, the total chlorine content of the epoxy resin (E) is preferably 0.01 ppm or more in order to facilitate control of the shell formation reaction. More preferably, it is 0.02 ppm or more, More preferably, it is 0.05 ppm or more, More preferably, it is 0.1 ppm or more, More preferably, it is 0.2 ppm or more, More preferably, it is 0.5 ppm or more. For example, the preferable range of the total chlorine amount is 0.1 ppm to 200 ppm, the more preferable range is 0.2 ppm to 80 ppm, and the more preferable range is 0.5 ppm to 50 ppm.

As a method for producing the masterbatch type epoxy resin curing agent composition (F) of the present invention, the epoxy resin curing agent (C) and / or the microcapsule type epoxy resin curing agent (D) produced previously is used. For example, a method of dispersing in an epoxy resin (E) using a three-roll or the like, or a coating reaction of an epoxy resin curing agent (C) in the epoxy resin (E) to obtain a curing agent The method etc. which obtain the hardening agent (F) for masterbatch type epoxy resins are illustrated. The latter is preferable because of high productivity.
Moreover, it is desirable that the diol terminal impurity component of the epoxy resin (E) of the present invention is 0.001 to 30% by mass of the basic structural component of the epoxy resin (E).

In the present invention, the basic structural component of the epoxy resin (E) refers to a structure in which an epoxy group is present at all terminals. The diol terminal impure component of the epoxy resin (E) is such that at least one epoxy group of the terminal epoxy groups has a structure of α-glycol terminal. As a reference document, mention is made of “Review Epoxy Resin Vol. 1 Basic I” published by the Epoxy Resin Technology Association.
For the analysis method of the basic structural component and the diol terminal impurity component of the epoxy resin (E), refer to the method described in the literature cited in “Review: Epoxy Resin Vol. Perform an analysis.

  When the ratio of the epoxy resin (E) diol terminal impurity component to the epoxy resin (E) basic structure component is larger than 30% by mass, the water resistance of the cured product may be lowered, and may be less than 0.001% by mass. When small, the sclerosis | hardenability of an epoxy resin composition may fall. From such a viewpoint, the ratio of the epoxy resin (E) to the basic structural component of the diol terminal impure component of the epoxy resin (E) is preferably 0.01 to 25% by mass, more preferably 0.1 to 20%. % By weight, particularly preferably 0.5 to 18% by weight, particularly preferably 1.2 to 15% by weight.

The ratio of the epoxy resin (E) to the basic structural component of the epoxy resin (E) with respect to the diol terminal impure component of the epoxy resin (E) of the present invention can be determined by the method described in the Examples section.
The masterbatch type epoxy resin curing agent composition (F) preferably has a total chlorine content of 2500 ppm or less. The lower the total chlorine content, the higher the reactivity, and when the epoxy resin composition is used as an electronic material, it is desirable from the viewpoint of high reliability, more preferably 1500 ppm, more preferably 1000 ppm or less, and more preferably. Is 800 ppm or less, more preferably 500 ppm, more preferably 300 ppm or less, more preferably 200 ppm or less, more preferably 100 ppm or less, and even more preferably 50 ppm or less. In the present invention, the total chlorine amount is the total amount of organic chlorine and inorganic chlorine contained in the compound, and is a value based on the mass of the compound.

The epoxy resin composition of the present invention is preferably in the form of a paste that is liquid at room temperature or has a viscosity at 25 ° C. of 10 million mPa · s or less. The lower the viscosity, the higher the workability, and the lower the amount of adhesion to the container, which can reduce waste, which is preferable.
The epoxy resin composition of the present invention contains an epoxy resin curing agent (C) and / or a microcapsule type epoxy resin curing agent (D), an epoxy resin (E), and a cyclic borate ester compound (L). It is desirable.
Thereby, the storage stability of an epoxy resin composition, especially the storage stability at the time of high temperature can be improved.

The cyclic borate ester compound (L) is a compound in which boron obtained from boric acid and an aliphatic or aromatic diol is contained in a cyclic structure. Examples of such cyclic borate compounds include tris-o-phenylene bisborate, bis-dimethyltrimethylene boroborate, bis-dimethylethylene boroborate, and bis-diethylethylene boroborate. In particular, 2,2′-oxybis (5,5′-dimethyl-1,3,2-oxaborinane) is preferable.
As content of the said cyclic borate ester compound (L), 0.001-10 mass parts with respect to 100 mass parts of epoxy resins (E), Preferably it is 0.01-2 mass parts, More preferably, it is 0.05. It is -0.9 mass part. By using in this range, the composition is cured with excellent storage stability at high temperatures, and an excellent cured product that does not impair the original short-time curability, heat resistance, adhesiveness, and connection reliability is obtained. be able to.

The masterbatch type epoxy resin curing agent composition (F) of the present invention comprises an epoxy resin curing agent (C) and / or a microcapsule type epoxy resin curing agent (D) and an epoxy resin (E). However, it can contain other components as long as the function is not deteriorated. The content of other components is preferably less than 30% by mass.
One or more selected from the epoxy resin curing agent (C), the microcapsule type epoxy resin curing agent (D), and the masterbatch type epoxy resin curing agent composition (F) for the epoxy resin (J). Are mixed to obtain a one-component epoxy resin composition.

The epoxy resin (J) used for the epoxy resin composition of this invention should just have an average of two or more epoxy groups per molecule, and may be the same as an epoxy resin (E). For example, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A, tetrafluorobisphenol A, etc. Bisphenol type epoxy resin obtained by glycidylation of bisphenols; Epoxy resin obtained by glycidylation of other dihydric phenols such as biphenol, dihydroxynaphthalene and 9,9-bis (4-hydroxyphenyl) fluorene; 1,1,1-tris (4-Hydroxyphenyl) methane, 4,4- (1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) bisphenol Epoxy resin obtained by glycidylation of trisphenol such as 1, epoxy resin obtained by glycidylation of tetrakisphenol such as 1,1,2,2, -tetrakis (4-hydroxyphenyl) ethane; phenol novolak, cresol novolak, bisphenol A novolak , Novolak epoxy resins obtained by glycidylation of novolaks such as brominated phenol novolak and brominated bisphenol A novolac; epoxy resins obtained by glycidylation of polyhydric phenols; polyhydric alcohols such as glycerin and polyethylene glycol were glycidylated Aliphatic ether type epoxy resins; ether ester type epoxy resins obtained by glycidylation of hydroxycarboxylic acids such as p-oxybenzoic acid and β-oxynaphthoic acid; such as phthalic acid and terephthalic acid Ester-type epoxy resin obtained by glycidylation of polycarboxylic acid; amine-type epoxy resin such as glycidylated product of amine compounds such as 4,4-diaminodiphenylmethane and m-aminophenol, triglycidyl isocyanurate, and 3,4-epoxycyclohexylmethyl Examples include alicyclic epoxides such as -3 ′, 4′-epoxycyclohexanecarboxylate.

One or more selected from the curing agent for epoxy resin (C), the curing agent for microcapsule type epoxy resin (D), and the curing agent composition for masterbatch type epoxy resin (F) of the present invention, and the epoxy resin (J) The mixing ratio is determined from the viewpoints of curability and properties of the cured product, but preferably 100 parts by mass of the epoxy resin (J), the curing agent for epoxy resin (C) of the present invention, micro What is necessary is just to use 1 or more types chosen from the hardening | curing agent for capsule type epoxy resins (D) and the hardening | curing agent composition for masterbatch type epoxy resins (F) in the quantity used as 0.1-1000 mass parts. More preferably, it is 0.2-200 mass parts, More preferably, it is 0.5-30 mass parts. Curing performance that is practically satisfactory at 0.1 parts by mass or more can be obtained, and a curing agent having well-balanced curing performance at 100 parts by mass or less without uneven distribution of the epoxy resin composition of the present invention. give.
Further, the masterbatch type epoxy resin curing agent composition (F) used in the present invention can be mixed with a high molecular weight epoxy resin and a resin generally called a phenoxy resin having a self-film forming property. .

One or more selected from the curing agent for epoxy resin (C), the curing agent for microcapsule type epoxy resin (D), and the curing agent composition for masterbatch type epoxy resin (F) used in the present invention are an acid anhydride. At least one curing agent (K) selected from the group consisting of phenols, phenols, hydrazides, and guanidines can be used in combination.
Examples of acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, -3-chlorophthalic anhydride, -4-chlorophthalic anhydride, and benzophenone anhydride. Tetracarboxylic acid, succinic anhydride, methyl succinic anhydride, dimethyl succinic anhydride, dichlor succinic anhydride, methyl nadic acid, dodecyl succinic anhydride, chlorendec succinic anhydride, maleic anhydride, etc .; phenols include, for example, phenol novolac, cresol Examples of hydrazines include succinic acid dihydrazide, adipic acid dihydrazide, phthalic acid dihydrazide, isophthalic acid dihydrazide terephthalic acid dihydrazide, p-oxybenzoic acid hydrazide, Luric acid hydrazide, phenylaminopropionic acid hydrazide, maleic acid dihydrazide, etc .; Examples of guanidines include dicyandiamide, methylguanidine, ethylguanidine, propylguanidine, butylguanidine, dimethylguanidine, trimethylguanidine, phenylguanidine, diphenylguanidine, toluylguanidine Etc. are exemplified.

Of the curing agents (K), guanidines and acid anhydrides are preferred. More preferred are dicyandiamide, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylnadic anhydride.
When using a hardening | curing agent (K), the hardening | curing agent (K) for epoxy resin of this invention and / or the hardening | curing agent for microcapsule type epoxy resins (D) of this invention with respect to 1-200 mass parts of hardening | curing agents (K). And / or the masterbatch type epoxy resin curing agent composition (F) is preferably used in an amount of 0.1 to 200 parts by mass.
By using in this range, a composition excellent in curability and storage stability can be obtained, and a cured product excellent in heat resistance and water resistance can be obtained.

For the masterbatch type epoxy resin curing agent composition (F) used in the present invention, a filler, a reinforcing material, a filler, conductive fine particles, a pigment, an organic solvent, a reactive diluent, a non-reactive dilution, if desired. Agents, resins, crystalline alcohols, coupling agents and the like can be added. Examples of the filler include, for example, coal tar, glass fiber, asbestos fiber, boron fiber, carbon fiber, cellulose, polyethylene powder, polypropylene powder, quartz powder, mineral silicate, mica, asbestos powder, slate powder, Kaolin, aluminum oxide trihydrate, aluminum hydroxide, chalk powder, gypsum, calcium carbonate, antimony trioxide, penton, silica, aerosol, lithopone, barite, titanium dioxide, carbon black, graphite, carbon nanotube, fullerene, iron oxide , Gold, silver, aluminum powder, iron powder, nano-sized metal crystals, intermetallic compounds, and the like, all of which can be used effectively depending on the application. Examples of the organic solvent include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate and the like. Examples of the reactive diluent include butyl glycidyl ether, N, N′-glycidyl-o-toluidine, phenyl glycidyl ether, styrene oxide, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and 1,6-hexanediol diester. Examples thereof include glycidyl ether. Examples of non-reactive diluents include dioctyl phthalate, dibutyl phthalate, dioctyl adipate, and petroleum solvents. Examples of the resins include polyester resins, polyurethane resins, acrylic resins, polyether resins, melamine resins, urethane-modified epoxy resins, rubber-modified epoxy resins, alkyd-modified epoxy resins, and other modified epoxy resins. Examples of the crystalline alcohol include 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, pentaerythritol, sorbitol, sucrose, and trimethylolpropane.

The epoxy resin composition used in the present invention comprises an epoxy resin curing agent (C) and / or a microcapsule type epoxy resin curing agent (D) and an epoxy resin (E), and if necessary, an epoxy resin (J). And a hardening | curing agent (K) is a main component. The epoxy resin composition of the present invention exhibits desired performance when cured by heating, but the main component mentioned here means a component that forms the main component of the curing reaction by heating, and is cured by heating. It is preferable that it is 60% or more of the sex component. More preferably, it is 70% or more.
Among the one-part epoxy resin compositions, examples of components that do not participate in curing include extenders, reinforcing materials, fillers, conductive materials, pigments, organic solvents, resins, and the like. It is preferably used in the range of 0 to 90% by mass with respect to the entire liquid epoxy resin composition.

The epoxy resin composition of the present invention includes a conductive material, an anisotropic conductive material, an insulating material, a sealing material, a coating material, a coating composition, a prepreg, a heat, in addition to an adhesive and / or a bonding paste and a bonding film. It is useful as a conductive material.
The adhesive and / or bonding paste and bonding film are useful as liquid adhesives, film adhesives, die bonding materials, and the like. Examples of the method for producing the film adhesive include methods described in JP-A-62-141083 and JP-A-05-295329. More specifically, a solution is prepared by dissolving, mixing, and dispersing solid epoxy resin, liquid epoxy resin, and solid urethane resin in toluene so as to be 50% by weight. A varnish is prepared by adding and dispersing 30% by weight of the curing agent composition for masterbatch type epoxy resin (F) of the present invention to the solution. This solution, for example, is applied to a polyethylene terephthalate substrate for peeling having a thickness of 50 μm so that the toluene has a thickness of 30 μm after drying. By drying toluene, it is possible to obtain a bonding film that is inactive at normal temperature and exhibits adhesiveness by the action of the latent curing agent when heated.

Examples of the conductive material include a conductive film and a conductive paste. Examples of anisotropic conductive materials include anisotropic conductive films and anisotropic conductive pastes. As the manufacturing method, for example, there is a method described in JP-A-01-113480. More specifically, for example, in the production of the bonding film described above, the conductive material and the anisotropic conductive material are mixed and dispersed during the preparation of the varnish,
It can manufacture by drying after apply | coating to the base material for peeling. Conductive particles include solder particles, nickel particles, nano-sized metal crystals, metal particles coated with other metals, metal particles such as copper and silver inclined particles, and styrene resins, urethane resins, melamine resins, etc. Particles obtained by coating resin particles such as epoxy resin, acrylic resin, phenol resin, and styrene-butadiene resin with a conductive thin film such as gold, nickel, silver, copper, and solder are used. In general, the conductive particles are spherical fine particles of about 1 to 20 μm. As a base material in the case of forming a film, for example, there is a method of drying a solvent after coating on a base material such as polyester, polyethylene, polyimide, polytetrafluoroethylene and the like.

Examples of the insulating material include an insulating adhesive film and an insulating adhesive paste. By using the bonding film described above, an insulating adhesive film that is an insulating material can be obtained. In addition to using a sealing material, an insulating adhesive paste can be obtained by blending an insulating filler among the aforementioned fillers.
As a sealing material, it is useful as a solid sealing material, a liquid sealing material, a film-like sealing material, etc., and as a liquid sealing material, it is useful as an underfill material, a potting material, a dam material, or the like. As a method for producing a sealing material, for example, in JP-A-5-43661 and JP-A-2002-226675, there is a description as a molding material for sealing / impregnating electric / electronic parts. More specifically, a bisphenol A type epoxy resin, methylhexahydrophthalic anhydride as an acid anhydride curing agent as a curing agent, and spherical fused silica powder are added and mixed uniformly, and the master obtained in the present invention is mixed. The curing agent composition for batch type epoxy resin (F) can be added and mixed uniformly to obtain a sealing material.

  Examples of the coating material include an electronic material coating material, an overcoat material for a printed wiring board cover, and a resin composition for interlayer insulation of a printed board. Examples of the method for producing the coating material include various methods described in JP-B-4-6116, JP-A-7-304931, JP-A-8-64960, and JP-A-2003-246838. More specifically, silica or the like is selected from the filler, and as a filler, phenoxy resin, rubber-modified epoxy resin, etc. are blended in addition to bisphenol A type epoxy resin, and further the masterbatch type epoxy resin curing agent composition of the present invention. Compound (F) is prepared and a 50% solution is prepared with MEK. This is coated on a polyimide film with a thickness of 50 μm, and a copper foil is overlaid, laminated at 60 to 150 ° C., and the laminate is heated and cured at 180 to 200 ° C. to coat the interlayer with an epoxy resin composition. A laminated sheet can be obtained.

  Examples of the method for producing the coating composition include the methods described in JP-A Nos. 11-323247 and 2005-113103. More specifically, titanium dioxide, talc, and the like are blended with a bisphenol A type epoxy resin, and a 1: 1 mixed solvent of MIBK / xylene is added as a mixed solvent, stirred, and mixed to obtain a main agent. An epoxy coating composition can be obtained by adding and uniformly dispersing the curing agent composition (F) for masterbatch type epoxy resin of the present invention.

  As a method for producing the prepreg, for example, as in the methods described in JP-A Nos. 09-71633 and WO98 / 44017, the reinforcing base material can be impregnated into a reinforcing substrate and heated. Examples of the varnish solvent to be impregnated include methyl ethyl ketone, acetone, ethyl cellosolve, methanol, ethanol, isopropyl alcohol, and the like. It is preferable that these solvents do not remain in the prepreg. In addition, although the kind of reinforcement base material is not specifically limited, For example, paper, a glass cloth, a glass nonwoven fabric, an aramid cloth, a liquid crystal polymer etc. are mention | raise | lifted as an example. The ratio of the resin composition and the reinforcing substrate is not particularly limited, but it is usually preferable that the resin component in the prepreg is prepared at 20 to 80% by weight.

  Examples of the method for producing the heat conductive material include Japanese Patent Laid-Open Nos. 06-136244, 10-237410, and 2000-3987. More specifically, an epoxy resin as a thermosetting resin, a phenol novolac curing agent as a curing agent, and graphite powder as a heat conductive filler are blended and uniformly kneaded. The masterbatch type epoxy resin curing agent composition (F) of the present invention can be blended into this to obtain a heat conductive resin paste.

The present invention will be described in more detail based on examples, but the technical scope and embodiments of the present invention are not limited thereto. “Part” or “%” in Examples and Comparative Examples is based on mass unless otherwise specified.
The physical property evaluation test of the resin and its cured product according to this example and the comparative example was performed by the method described below.
(1) Epoxy equivalent It is the mass (g) of the epoxy resin containing 1 equivalent of an epoxy group, and was determined based on JIS K-7236.

(2) Total chlorine amount 1 g of a sample was dissolved in 25 ml of ethylene glycol monobutyl ether, 25 ml of a 1N KOH propylene glycol solution was added thereto and boiled for 20 minutes, and then titrated with an aqueous silver nitrate solution.
(3) Total chlorine content of epoxy resin (N) / (E) and masterbatch type epoxy resin curing agent composition (F) Wash the epoxy resin or epoxy resin composition with xylene until the epoxy resin is gone Repeat filtration. Next, the filtrate is distilled off under reduced pressure at 100 ° C. or lower to obtain an epoxy resin. 1-10 g of the obtained epoxy resin sample was precisely weighed so that the titration amount was 3-7 ml, dissolved in 25 ml of ethylene glycol monobutyl ether, added with 25 ml of 1N KOH propylene glycol solution and boiled for 20 minutes. After that, it was titrated with an aqueous silver nitrate solution.

(4) Hydrolyzable chlorine amount 3 g of a sample was dissolved in 50 ml of toluene, 20 ml of a 0.1 N KOH methanol solution was added thereto and boiled for 15 minutes, and then titrated with an aqueous silver nitrate solution.
(5) Viscosity The viscosity was measured at 25 ° C. using a BM viscometer.
(6) Melt viscosity Using RE-550H type viscometer (rotor R-H HH4) manufactured by Toki Sangyo Co., Ltd., the viscosity was measured under the conditions of a rotation speed of 20 rpm and a measurement temperature of 140 ° C.
(7) Softening point Conforms to JIS K-7234 (ring and ball method).

(8) FT-IR measurement Absorbance was measured using FT / IR-410 manufactured by JASCO Corporation.
(9) Molecular weight distribution Using Tosoh Co., Ltd. HLC8220GPC (detector: RI), two columns: PLgel 3 μMIXED-E (Polymer Laboratories), eluent: dimethylformamide 1% lithium bromide solution, calibration curve: polystyrene Gel permeation chromatography was performed under the conditions, and the molecular weight distribution was shown by the value obtained by dividing the weight average molecular weight by the number average molecular weight.
(10) Gel time measurement A curast meter type V manufactured by TS Engineering Co., Ltd. was used, and the gel time was measured according to JIS K6300.

(11) Determination of basic structural components of epoxy resin (E) The epoxy resin composition is repeatedly washed and filtered using xylene until the epoxy resin is eliminated. Next, the filtrate is distilled off under reduced pressure at 100 ° C. or lower to obtain an epoxy resin.
The obtained epoxy resin is analyzed and quantified by the following method. Tosoh high performance liquid chromatography (AS-8021, detector UV-8020, hereinafter HPLC), the column uses Novapack C-18 manufactured by Millipore. The mobile phase is gradient from water / acetonitrile = 70/30 to 0/100. The detection wavelength was 254 nm. The separation conditions based on the difference in both terminal structures are selected by HPLC analysis, and the separation liquid is fractionated using a switching valve. The separated separated liquid is distilled off under reduced pressure for each fraction, and the residue is analyzed by MS. According to the MS spectrum, those having a difference of 18 in the mass number of the reference peak are recognized as basic structural components having a smaller value. About this basic structural component, basic structural component content of an epoxy resin (E) is calculated | required by the area ratio from the peak intensity on a HPLC analysis chart.

(12) Quantification of the diol terminal impurity component of the epoxy resin (E) The separation liquid is analyzed by MS in the same manner as the quantification of the basic structural component of the epoxy resin (E). According to the MS spectrum, those having a difference of 18 in the mass number of the reference peak are recognized as those having a larger value of 18 as a diol terminal impurity component. The content of the diol terminal impure component with respect to the basic structural component in the epoxy resin (E) is determined by the area ratio of the area indicating the intensity of the diol terminal impure component peak on the HPLC analysis chart and the peak intensity indicating the basic structural component. The detection wavelength was 254 nm.
As used herein, the structure of the diol terminal impurity component refers to a structure in which one or both terminal epoxy groups are ring-opened to form 1,2-glycol.

(13) Separation of the microcapsule type epoxy resin curing agent (D) from the masterbatch type epoxy resin curing agent (F) The masterbatch type epoxy resin curing agent (F) was prepared by using xylene. Repeat washing and filtering until no longer present. Next, washing and filtration with cyclohexane are repeated until the xylene disappears. Cyclohexane is filtered off, and the cyclohexane is completely removed and dried at a temperature of 50 ° C. or lower.
(14) Separation of capsule membrane from microcapsule-type epoxy resin curing agent (D) Wash and filter microcapsule-type epoxy resin curing agent (D) with methanol until the epoxy resin curing agent disappears. Repeatedly, methanol is completely removed and dried at a temperature of 50 ° C. or lower.

(15) Curability of one-part epoxy resin composition 30 parts of the masterbatch type epoxy resin curing agent (F) produced in the examples or comparative examples was replaced with bisphenol A type epoxy resin (epoxy equivalent 189 g / equivalent, total chlorine). Amount 1200 ppm: hereinafter referred to as epoxy resin (M)) 100 parts, mixed to produce a one-part epoxy resin composition and measure the gel time. When the temperature at which the gel time is less than 20 minutes is less than 90 ° C., When it exceeded 90 degreeC and less than 100 degreeC, it was set as (circle), when exceeding 100 degreeC and less than 110 degreeC, (triangle | delta), when exceeding 110 degreeC and less than 120 degreeC, it was set as x.

(16) Storage stability of a one-part epoxy resin composition 30 parts of a masterbatch type epoxy resin curing agent (F) produced in the examples or comparative examples is mixed with 100 parts of an epoxy resin (M) to produce a one-part epoxy. A resin composition was produced, stored at 30 ° C. for 1 week, and the storage stability was evaluated by a value obtained by dividing the viscosity after storage by the viscosity before storage (hereinafter referred to as viscosity magnification). The viscosity ratio was less than 1.5 times, ◎, less than 2 times, ◯, 2 times or more and less than 3 times, Δ, 3 times or more, x, and gelation during storage as xx.

[Production Example 1]
(Production of amine adduct (A-1))
Bisphenol A type epoxy resin (epoxy equivalent 185 g / equivalent, total chlorine amount 1900 ppm: hereinafter referred to as epoxy resin a1-1) 1.5 equivalent, 2-methylimidazole 1 equivalent (in terms of active hydrogen), n-butanol and toluene In a 1/1 mixed solvent (resin content: 50%). Thereafter, the solvent was distilled off together with the solvent under reduced pressure until the content of 2-methylimidazole was less than 10 ppm, and solid amine adduct A-1 was obtained at 25 ° C. The resulting amine adduct had a molecular weight distribution of 3.7.

[Production Example 2]
(Production of amine adduct (A-2))
Hereinafter, 2 equivalents of epoxy resin a1-1, 1 equivalent of bisphenol A type epoxy resin (epoxy equivalent 470 g / equivalent, total chlorine amount 1300 ppm: hereinafter referred to as epoxy resin a1-2), 2 equivalents of triethylenetetramine and 2-propanol The reaction was carried out at 80 ° C. in a 1/2 mixed solvent of xylene (resin content: 50%). Thereafter, the solvent and the unreacted low molecular amine compound were distilled off under reduced pressure, and when the triethylenetetramine was 2.3% (based on the resin content of 100%), the distillation was terminated and solid at 25 ° C. The amine adduct A-2 was obtained. The molecular weight distribution of the obtained amine adduct was 4.3. The melt viscosity was 14.2 Pa · s.

[Production Example 3]
(Production of amine adduct (A-3))
1.5 equivalents of epoxy resin a1-2, 1 equivalent of cresol novalak type epoxy resin (epoxy equivalent 215 g / equivalent, total chlorine amount 1500 ppm: hereinafter referred to as epoxy resin a1-3), and 1.5 equivalents of N-methylpiperazine The reaction was carried out in the same manner as in Production Example 2 except that the product was distilled off to obtain a solid amine adduct A-3 at 25 ° C. N-methylpiperazine contained in the resulting amine adduct was 3.8% (relative to 100% resin content), and the molecular weight distribution was 4.9. The melt viscosity was 13.8 Pa · s.

[Production Example 4]
(Production of amine adduct (A-4))
Epoxy resin a1-1 was changed to 1 equivalent and 2-methylimidazole 0.9 equivalent, and the reaction was carried out in the same manner as in Production Example 2 except that the solvent was the same as in Production Example 1, followed by distillation at 25 ° C. Solid amine adduct A-4 was obtained. The 2-methylimidazole contained in the obtained amine adduct was 2.5% (based on 100% resin content), and the molecular weight distribution was 1.5. The melt viscosity was 8.9 Pa · s.

[Production Example 5]
(Production of amine adduct (A-5))
After reacting 1 equivalent of bisphenol F type epoxy resin (epoxy equivalent 165 g / equivalent, total chlorine amount 300 ppm: hereinafter referred to as epoxy resin a14) and 1 equivalent of 2 methylimidazole in the same manner as in Production Example 4, it was distilled off. Thus, a solid amine adduct A-5 was obtained at 25 ° C. The 2-methylimidazole contained in the obtained amine adduct was 6.0% (based on the resin content of 100%), and the molecular weight distribution was 2.2. The melt viscosity was 5.3 Pa · s.

[Production Example 6]
(Production of amine adduct (A-6))
2 equivalents of epoxy resin a1-1 and 1 equivalent of 2-methylimidazole were reacted in the same manner as in Production Example 4 and then distilled off to obtain a solid amine adduct A-6 at 25 ° C. The 2-methylimidazole contained in the obtained amine adduct was 2.1% (based on the resin content of 100%), and the molecular weight distribution was 6.1. The melt viscosity was 21.5 Pa · s.

[Production Example 7]
(Production of amine adduct (A-7))
5 equivalents of epoxy resin a1-1 and 1 equivalent of 2-methylimidazole were reacted in the same manner as in Production Example 4, and then distilled off to obtain a solid amine adduct A-7 at 25 ° C. The 2-methylimidazole contained in the obtained amine adduct was 0.1% (relative to 100% resin content), and the molecular weight distribution was 9.5. The melt viscosity was 42.0 Pa · s.

[Production Example 8]
(Production of amine adduct (A-8))
1 equivalent of epoxy resin a1-1 and 2.5 equivalent of 2-methylimidazole were reacted in the same manner as in Production Example 4 and then distilled off to obtain a solid amine adduct A-8 at 25 ° C. . The 2-methylimidazole contained in the obtained amine adduct was 12% (based on the resin content of 100%), and the molecular weight distribution was 1.5. The melt viscosity was 2.9 Pa · s.

[Example 1]
100 parts by mass of the amine adduct A-1 obtained in Production Example 1 was melted, 2.5 parts by mass of 2-ethyl-4-methylimidazole was uniformly mixed therein, cooled to room temperature, and pulverized. An epoxy resin curing agent C-1 having a solid average particle diameter of 2.5 μm at a temperature of 0 ° C. was obtained. The melt viscosity was 12.5 Pa · s. Add 100 parts by weight of epoxy resin curing agent C-1, 1 part by weight of water and 8 parts by weight of tolylene diisocyanate to 200 parts by weight of epoxy resin E-1, and continue the reaction for 3 hours while stirring at 40 ° C. It was. Then, shell formation reaction was performed at 50 degreeC for 6 hours, and the hardening agent F-1 for masterbatch type epoxy resins was obtained.

Separating microcapsule type epoxy resin curing agent from masterbatch type epoxy resin curing agent F-1 using xylene and confirming that it has bonding groups (x), (y) and (z) by FTIR measurement. It was done.
Furthermore, the curability and storage stability of the one-part epoxy resin composition were evaluated when 30 parts of the obtained masterbatch type epoxy resin curing agent F-1 was blended with 100 parts of the epoxy resin (M). . The obtained results are shown in Table-1.

[Examples 2 to 6]
The amine adducts A-2 to A-6 obtained in Production Examples 2 to 6 were pulverized to obtain epoxy resin curing agents C-2 to C-6 described in Table 1. The properties of the resulting epoxy resin curing agent are shown in Table 1.
Furthermore, masterbatch type epoxy resin curing agents F-2 to 6 were obtained in the same manner as in Example 1 with the formulation shown in Table-1. Each was confirmed to have bonding groups (x), (y), (z) in the same manner as in Example 1, and the masterbatch type epoxy resin curing agents F-2 to 6 were added in the same manner as in Example 1. The curability and storage stability of the one-part epoxy resin composition when used as a curing agent were evaluated. The evaluation results are shown in Table-1.

[Example 7]
The amine adduct A-4 obtained in Production Example 4 was pulverized to obtain an epoxy resin curing agent C-4 having an average particle size of 2.4 μm at 25 ° C. 100 parts by mass of the resulting epoxy resin curing agent C-4, 2.5 parts by mass of water, and 10 parts by mass of MR-200 were added, and the reaction was continued for 3 hours while stirring at 40 ° C. Thereafter, 0.17 part of a cyclic borate ester compound (L) was added, and a shell formation reaction was further performed at 50 ° C. for 6 hours to obtain a masterbatch type epoxy resin curing agent F-7. In the same manner as in Example 1, it was confirmed that it had bonding groups (x), (y), and (z). The curability and storage stability of the resin composition were evaluated. The evaluation results are shown in Table-1.

[Comparative Example 1]
The amine adduct A-8 obtained in Production Example 8 was pulverized to obtain a curing agent C-7 for epoxy resin described in Table-1. The properties of the resulting epoxy resin curing agent are shown in Table 1.
Further, a masterbatch type epoxy resin curing agent F-8 was obtained in the same manner as in Example 1 with the formulation shown in Table-1. In the same manner as in Example 1, the curability and storage stability of the one-part epoxy resin composition when the curing agent F-8 for masterbatch type epoxy resin was used as a curing agent were evaluated. The evaluation results are shown in Table-1.

[Comparative Example 2]
Using the epoxy resin curing agent C-7 shown in Table-1 obtained by pulverizing the amine adduct A-8 obtained in Production Example 8, and using the same formulation as shown in Table-1, as in Example 7. Thus, a masterbatch type epoxy resin curing agent F-9 was obtained. In the same manner as in Example 1, the curability and storage stability of the one-part epoxy resin composition when the curing agent F-9 for masterbatch type epoxy resin was used as a curing agent were evaluated. The evaluation results are shown in Table-1.

[Comparative Example 3]
The amine adduct A-7 obtained in Production Example 7 was pulverized to obtain a curing agent C-8 for epoxy resin described in Table-1. The properties of the resulting epoxy resin curing agent are shown in Table 1.
Further, a masterbatch type epoxy resin curing agent F-10 was obtained in the same manner as in Example 1 with the formulation shown in Table-1. In the same manner as in Example 1, the curability and storage stability of the one-pack epoxy resin composition when the curing agent F-10 for masterbatch type epoxy resin was used as a curing agent were evaluated. The evaluation results are shown in Table-1.

[Comparative Example 4]
Production Example 7 100 parts by mass of the amine adduct A-7 obtained was melted, and 3.9 parts by mass of 2-methylimidazole was uniformly mixed therein, so that the content of 2-methylimidazole was 4.0 parts in total. And cooled to room temperature and pulverized to obtain a curing agent C-9 for epoxy resin having an average particle size of 3.5 μm and a solid state at 25 ° C. The melt viscosity was 24.5 Pa · s. Add 100 parts by mass of epoxy resin curing agent C-9, 2 parts by mass of water, and 7 parts by mass of MR-200 to 200 parts by mass of epoxy resin E-1, and react for 3 hours while stirring at 40 ° C. Continued. Then, shell formation reaction was performed at 50 degreeC for 6 hours, and the hardening agent F-11 for masterbatch type epoxy resins was obtained.

The microcapsule type curing agent for epoxy resin is separated from the masterbatch type curing agent for epoxy resin F-11 using xylene, and has bonding groups (x), (y), (z) by FT-IR measurement. Was confirmed.
Furthermore, the curability and storage stability of the one-part epoxy resin composition were evaluated when 30 parts of the obtained masterbatch type epoxy resin curing agent F-11 was blended with 100 parts of the epoxy resin (M). . The obtained results are shown in Table-2.

[Comparative Example 5]
When producing the masterbatch type epoxy resin curing agent F-12 using the same epoxy resin curing agent C-9 as in Comparative Example 4, the cyclic borate ester compound (L) was changed to 0 as in Example 7. In addition, 1 part was added and a shell forming reaction was further performed at 50 ° C. for 6 hours to obtain a masterbatch type epoxy resin curing agent F-12. Furthermore, the curability and storage stability of the one-part epoxy resin composition were evaluated when 30 parts of the obtained masterbatch type epoxy resin curing agent F-12 was blended with 100 parts of the epoxy resin (M). . The obtained results are shown in Table-2.

[Comparative Example 6]
The amine adduct A-1 obtained in Production Example 1 was pulverized as it was to obtain a curing agent C-10 for epoxy resin listed in Table-2. The properties of the resulting epoxy resin curing agent are shown in Table 2. Further, a masterbatch type epoxy resin curing agent F-13 was obtained in the same manner as in Example 1 with the formulation shown in Table-2. Furthermore, the curability and storage stability of the one-part epoxy resin composition were evaluated when 30 parts of the obtained masterbatch type epoxy resin curing agent F-13 was blended with 100 parts of the epoxy resin (M). . The obtained results are shown in Table-2.

[Example of production of conductive film]
15 parts of bisphenol A type epoxy resin (AER-2603 manufactured by Asahi Kasei Chemicals), 6 parts of phenol novolac resin (trade name “BRG-558” manufactured by Showa Polymer Co., Ltd.), synthetic rubber (trade name “Nipol 1072” manufactured by ZEON Corporation) 4 parts of a weight average molecular weight of 300,000) was dissolved in 20 parts of a 1: 1 (weight ratio) mixed solvent of methyl ethyl ketone and butyl cellosolve acetate. This solution was mixed with 74 parts of silver powder and further kneaded with a three-roll. To this, 30 parts of the masterbatch type epoxy resin curing agent F-2 obtained in Example 2 was further added and mixed uniformly to obtain a conductive adhesive. Using the obtained conductive adhesive, it was cast on a polypropylene film having a thickness of 40 μm and dried and semi-cured at 80 ° C. for 60 minutes to obtain a conductive film having a conductive adhesive layer having a thickness of 35 μm. . Using this conductive film, the conductive film was transferred onto the back surface of the silicon wafer on the heat block at 80 ° C. Furthermore, when the silicon wafer was fully diced and the semiconductor chip with a conductive adhesive was bonded and cured on the lead frame on the heat block at 200 ° C. for 2 minutes, there was no problem with the conductivity of the chip.

[Example of production of conductive paste]
100 parts of epoxy resin (M), 30 parts of the masterbatch type epoxy resin curing agent F-1 obtained in Example 1, scaly silver powder having an average particle diameter of 14 μm and an aspect ratio of 11 (Tokuroku Chemical) 150 g of Research Laboratory Co., Ltd.) and 60 g of scaly nickel powder having an average particle size of 10 μm and an aspect ratio of 9 (trade name “NI110104”, manufactured by High Purity Chemical Co., Ltd.) are added and stirred until uniform. The conductive paste was uniformly dispersed with three rolls. The obtained conductive paste was screen-printed on a polyimide film substrate having a thickness of 1.4 mm and then cured by heating at 200 ° C. for 1 hour. As a result of measuring the conductivity of the obtained wiring board, it was useful as a conductive paste.

[Example of production of anisotropic conductive film]
40 parts by weight of bisphenol A type epoxy resin (AER6097 manufactured by Asahi Kasei Chemicals, epoxy equivalent 42500 g / eq) and 30 parts by weight of phenoxy resin (manufactured by Toto Kasei, YP-50) were dissolved in 30 parts of ethyl acetate. 30 parts of the obtained masterbatch type epoxy resin curing agent F-2 is added to 5 parts of conductive particles (cross-linked polystyrene plated with gold) with a particle size of 8 μm and mixed uniformly to obtain a one-part epoxy resin composition. Got. This was applied onto a polyester film, and ethyl acetate was removed by drying at 70 ° C. to obtain an anisotropic conductive film.
The obtained anisotropic conductive film was sandwiched between the IC chip and the electrode and subjected to thermocompression bonding on a hot plate at 200 ° C. for 30 seconds at 30 kg / cm 2. It was useful as a sex material.

[Example of production of anisotropic conductive paste]
50 parts by weight of bisphenol A type epoxy resin (AER6091 manufactured by Asahi Kasei Chemicals, epoxy equivalent 480 g / eq), 50 parts by weight of bisphenol A type epoxy resin (AER2603 manufactured by Asahi Kasei Chemicals) and micropearl Au-205 (manufactured by Sekisui Chemical, specific gravity) 2.67) After mixing 5 parts by weight, 30 parts of the masterbatch type epoxy resin curing agent F-2 obtained in Example 2 was added and mixed uniformly to obtain an anisotropic conductive paste. . The obtained anisotropic conductive paste was applied on a low alkali glass having an ITO electrode. Using a 230 ° C. ceramic tool, the test TAB (Tape Automated Bonding) film was pressed and bonded for 30 seconds at a pressure of 2 MPa. When the resistance value between adjacent ITO electrodes was measured, it was useful as an anisotropic conductive paste.

[Example of production of insulating paste]
100 parts by weight of bisphenol F type epoxy resin (trade name “YL983U” manufactured by Yuka Shell Epoxy Co., Ltd.), 4 parts by weight of dicyandiamide, 100 parts by weight of silica powder, 10 parts by weight of phenylglycidyl ether as a diluent, and organic phosphoric acid After fully mixing 1 part by weight of an ester (manufactured by Nippon Kayaku Co., Ltd., trade name “PM-2”), the mixture is further kneaded with three rolls. Further, 30 parts of the masterbatch type epoxy resin curing agent F-2 obtained in Example 2 was added thereto, and further uniformly mixed, and subjected to vacuum defoaming and centrifugal defoaming treatment. Manufactured. Using the obtained insulating paste, a semiconductor chip is placed on a resin substrate at 200 ° C.
When it was heated and cured for a period of time, it was useful as an insulating paste.

[Example of production of insulating film]
180 parts by weight of phenoxy resin (trade name “YP-50” manufactured by Toto Kasei Co., Ltd.), 40 cresol novolac type epoxy resin (epoxy equivalent 200 g / eq, trade name “EOCN-1020-80” manufactured by Nippon Kayaku Co., Ltd.) Part by weight, spherical silica (average particle size: 2 μm, manufactured by Admatech Co., Ltd., trade name SE-5101) and 200 parts by weight of methyl ethyl ketone were prepared and uniformly dispersed, and then the master obtained in Example 1 was prepared. 250 parts by weight of the curing agent F-1 for batch type epoxy resin is added and further stirred and mixed to obtain a solution containing the epoxy resin composition. The obtained solution is applied onto polyethylene terephthalate that has been subjected to mold release treatment so that the thickness after drying is 50 μm, and is dried by heating in a hot-air circulating dryer to provide insulating properties for semiconductor adhesion. A film was obtained. The obtained insulating film for adhering semiconductors is cut together with the supporting substrate larger than the wafer size of 5 inches, and the resin film is aligned with the electrode part side of the wafer with bump electrodes. Next, a support substrate with a release treatment is sandwiched between them, and heat-pressed in vacuum at 70 ° C., 1 MPa, and a pressurization time of 10 seconds to obtain a wafer with an adhesive resin. Subsequently, it was observed that the resin element of the semiconductor element with the adhesive film was cut and separated using a dicing saw (DAD-2H6M manufactured by DISCO) at a spindle rotation speed of 30,000 rpm and a cutting speed of 20 mm / sec. The obtained film was useful as an insulating film.

[Example of production of sealing material]
50 parts by weight of bisphenol A type epoxy resin (AER6091 manufactured by Asahi Kasei Chemicals, epoxy equivalent 480 g / eq), 50 parts by weight of bisphenol A type epoxy resin (AER2603 manufactured by Asahi Kasei Chemicals), HN-2200 mainly composed of phthalic anhydride as a curing agent 40 parts by weight (manufactured by Hitachi Chemical Co., Ltd.) and 80 parts by weight of spherical fused silica having an average particle diameter of 16 μm are uniformly dispersed and blended. 5 parts by weight of the masterbatch type epoxy resin curing agent F-1 obtained in Example 1 is added thereto to obtain an epoxy resin composition. The obtained epoxy resin composition was applied to a printed wiring board in a 1 cm square so as to have a thickness of 60 μm, and was semi-cured by heating in an oven at 110 ° C. for 10 minutes. Thereafter, the silicon chip having a thickness of 370 μm and a 1 cm square silicon chip is placed on the semi-cured epoxy resin composition, and a full curing process is performed at 220 ° C. for 1 hour while applying and applying a load to contact and hold the bump and the chip electrode. went. The obtained sealing material composed of the epoxy resin composition was useful without any problem in appearance and chip conduction.

[Example of production of coating material]
30 parts of epoxy resin (M), 30 parts of YP-50 as a phenoxy resin (manufactured by Tohto Kasei), methyl ethyl ketone solution of methoxy group-containing silane-modified epoxy resin (Arakawa Chemical Industries, Ltd., trade name "COMPOCERAN E103") 50 parts of this, 30 parts of the masterbatch type epoxy resin curing agent F-1 obtained in Example 1 was added thereto, and a solution diluted to 50% by weight with methyl ethyl ketone was prepared. The prepared solution was applied onto a release PET (polyethylene terephthalate) film (SG-1 manufactured by Panac Co., Ltd.) using a roll coater, dried and cured at 150 ° C. for 15 minutes, and a semi-cured resin with a release film (Dry film) A film thickness of 100 μm was prepared. These dry films were thermocompression bonded at 120 ° C. for 10 minutes at 6 MPa on the above copper-clad laminate, then returned to room temperature to remove the release film and cured at 200 ° C. for 2 hours. A useful coating material was obtained.

[Example of preparation of coating composition]
30 parts by weight of titanium dioxide and 70 parts by weight of talc are blended with 50 parts by weight of bisphenol A type epoxy resin (AER6091, manufactured by Asahi Kasei Chemicals, epoxy equivalent of 480 g / eq), and a 1: 1 mixed solvent of MIBK / xylene as a mixed solvent is 140 weights. Add part, stir and mix to make main ingredient. By adding 30 parts by weight of the curing agent F-1 for masterbatch type epoxy resin obtained in Example 1 to this and dispersing it uniformly, a useful epoxy coating composition was obtained.

[Examples of prepreg production]
Example of prepreg In a flask in an oil bath at 130 ° C., 15 parts of a novolac type epoxy resin (EPICLON N-740 manufactured by Dainippon Ink and Chemicals) and 40 parts of bisphenol F type epoxy resin (Epicoat 4005 manufactured by JER) Then, 30 parts of bisphenol A type liquid epoxy resin (AER2603 manufactured by Asahi Kasei Chemicals) is dissolved and mixed and cooled to 80 ° C. Further, 15 parts of the masterbatch type epoxy resin curing agent composition F-1 obtained in Example 1 is added, and sufficiently stirred and mixed. The resin composition cooled to room temperature was applied onto a release paper with a resin basis weight of 162 g / m 2 using a doctor knife to obtain a resin film. Next, a CF cloth made by Mitsubishi Rayon (model number: TR3110, weight per unit area: 200 g / m2) obtained by plain weaving of carbon fiber having an elastic modulus of 24 ton / mm2 at 12.5 pieces / inch is layered on the resin film, and the resin composition is carbon fiber. After impregnating the cloth, a polypropylene film was overlaid and passed between a pair of rolls having a surface temperature of 90 ° C. to prepare a cloth prepreg. The resin content was 45% by weight. The obtained prepreg is further laminated with the fiber direction aligned, and can be molded under curing conditions of 150 ° C. for 1 hour to obtain an FRP molded body using carbon fiber as a reinforcing fiber. The produced prepreg is useful. Met.

[Example of production of thermally conductive epoxy resin composition]
100 parts of bisphenol A type epoxy resin (AER2603 manufactured by Asahi Kasei Chemicals), 40 parts by weight of 50% methyl ethyl ketone solution of phenol novolac resin (trade name “Tamanol 759” manufactured by Arakawa Chemical Industries, Ltd.) as a curing agent for epoxy resin, scaly 15 parts by weight of graphite powder (trade name HOPG manufactured by Union Carbide Corporation) was stirred until uniform and dispersed uniformly with three rolls. Further, 15 parts of the curing agent composition F-1 for masterbatch type epoxy resin obtained in Example 1 is added and sufficiently stirred and mixed. The obtained conductive paste was used to mount a semiconductor chip (1.5 mm square, thickness 0.8 mm) on a Cu lead frame, and heat cured at 150 ° C. for 30 minutes to obtain an evaluation sample. The thermal conductivity of the obtained sample is measured by a laser flash method. That is, when the thermal conductivity K was determined from the measured thermal diffusivity α, specific heat Cp, and density σ using the following equation, K = α × Cp × σ, K was 5 × 10 ⁻³ Cal / cm · sec · It was higher than ° C. and was useful as a heat conductive paste.

  According to the present invention, it is possible to obtain an epoxy resin composition that provides a cured product having both low temperature curability and storage stability, and also having properties such as electrical properties, mechanical strength, heat resistance, and moisture resistance in a well-balanced manner. The epoxy resin composition using the capsule-type curing agent of the present invention includes an adhesive, a sealing material, a filler, an insulating material, a conductive material, a prepreg, a film adhesive, an anisotropic conductive film, and an anisotropic conductive paste. Excellent performance as insulating adhesive film, insulating adhesive paste, underfill material, potting material, die bonding material, conductive paste, solder resist, etc.

Claims (33)

  A curing agent for an epoxy resin mainly composed of an amine adduct (A) and a low molecular weight amine compound (B), wherein the molecular weight distribution defined as a ratio of the weight average molecular weight and the number average molecular weight of the amine adduct (A) is 1 And the content of the low-molecular amine compound (B) is more than 1 part by weight and 10 parts by weight with respect to 100 parts by weight of the amine duct (A), for epoxy resin A curing agent for epoxy resin, wherein the curing viscosity of the curing agent at 140 ° C. is from 0.1 mPa · s to 30 Pa · s.   The curing agent for epoxy resin according to claim 1, which is solid at 25 ° C.   The curing agent for epoxy resins according to claim 1 or 2, wherein the amine adduct (A) is obtained by a reaction between the epoxy resin (a1) and the amine compound (b1).   The curing agent for an epoxy resin according to any one of claims 1 to 3, wherein the low molecular amine compound (B) is an imidazole.   The surface of the core consisting of at least one epoxy resin curing agent (C) selected from the group consisting of epoxy resin curing agents according to claims 1 to 4 is covered with a synthetic resin and / or inorganic oxide shell. A microcapsule type epoxy resin curing agent characterized by having a structure as described above. The microcapsule-type epoxy resin curing agent (D) comprises at least one epoxy resin curing agent (C) selected from the group consisting of epoxy resin curing agents according to claims 1 to 4 with an isocyanate compound ( G) a shell (c1) obtained by the reaction of the active hydrogen compound (H) and / or a shell (c2) obtained by the reaction of the epoxy resin curing agent (C) and the epoxy resin (N). coated, micro-capsule epoxy, characterized in that it comprises at least on the surface of the bonding group (y) absorbing bonded group that absorbs infrared wave number 1630～1680Cm ^-1 (x) and the infrared wave number 1680～1725Cm ^-1 Curing agent for resin.   The hardener for a microcapsule type epoxy resin according to claim 6, wherein the total chlorine content of the epoxy resin (N) is 2500 ppm or less.   The epoxy resin curing agent (C) according to any one of claims 1 to 4 and / or the microcapsule type according to any one of claims 5 to 7 in 10 to 50000 parts by weight of the epoxy resin (E). A hardener composition for a masterbatch type epoxy resin, comprising 100 parts by weight of the epoxy resin curing agent (D) as the epoxy resin curing agent (C) and / or (D).   The masterbatch type epoxy resin curing agent composition (F) according to claim 8, wherein the total chlorine content is 2500 ppm or less.   10. The curing agent composition for a masterbatch type epoxy resin according to claim 8, wherein the total chlorine content of the epoxy resin (E) is 2500 ppm or less.   The diol terminal impurity component of an epoxy resin (E) is 0.001-30 mass% of the basic structural component of an epoxy resin (E), The master of any one of Claims 8-10 characterized by the above-mentioned. Curing agent composition for batch type epoxy resin.   Furthermore, the cyclic borate ester compound (L) is contained, The hardening | curing agent composition for masterbatch type epoxy resins of any one of Claims 8-11 characterized by the above-mentioned.   The curing agent for a masterbatch type epoxy resin according to claim 12, wherein the cyclic borate ester compound (L) is 2,2'-oxybis (5,5'-dimethyl-1,3,2-oxaborinane). Composition.   The amount of the cyclic borate ester compound (L) is 0.001 to 10 parts by mass with respect to 100 parts by mass of the epoxy resin (E). Agent composition.   Curing agent for epoxy resin, curing agent for microcapsule type epoxy resin, curing agent composition for masterbatch type epoxy resin according to any one of claims 1 to 14, with respect to 100 parts by mass of epoxy resin (J) An epoxy resin composition comprising 0.1 to 1000 parts by mass of at least one selected from the group consisting mainly of these.   1 to 200 parts by mass of at least one curing agent (K) selected from the group consisting of acid anhydrides, phenols, hydrazides, and guanidines with respect to 100 parts by mass of the epoxy resin (J), The at least 1 sort (s) chosen from the hardening | curing agent for epoxy resins of any one of claim | item 1-11, the hardening | curing agent for microcapsule type | mold epoxy resins, the hardening | curing agent composition for masterbatch type epoxy resins is 0.1-200. An epoxy resin composition containing parts by mass and containing them as a main component.   The epoxy resin composition according to claim 15 or 16, further comprising a cyclic borate ester compound (L).   The epoxy according to claim 15 or 16, wherein the cyclic borate compound (L) is 2,2'-oxybis (5,5'-dimethyl-1,3,2-oxaborinane). Resin composition.   The compounding quantity of the said cyclic borate ester compound (L) is 0.001-10 mass parts with respect to 100 mass parts of epoxy resins (E), The epoxy resin of Claim 15 or 16 characterized by the above-mentioned. Composition.   A paste-like composition comprising the epoxy resin curing agent composition or epoxy resin composition according to any one of claims 8 to 19.   A film-like composition comprising the epoxy resin curing agent composition or epoxy resin composition according to any one of claims 8 to 19.   An adhesive comprising the epoxy resin composition according to any one of claims 15 to 19.   A bonding paste comprising the epoxy resin composition according to any one of claims 15 to 19.   A bonding film comprising the epoxy resin composition according to any one of claims 15 to 19. A conductive material comprising the epoxy resin composition according to any one of claims 15 to 19.   An anisotropic conductive material comprising the epoxy resin composition according to any one of claims 15 to 19.   An anisotropic conductive film comprising the epoxy resin composition according to any one of claims 15 to 19.   An insulating material comprising the epoxy resin composition according to any one of claims 15 to 19.   A sealing material comprising the epoxy resin composition according to any one of claims 15 to 19.   A coating material comprising the epoxy resin composition according to any one of claims 15 to 19.   A coating composition comprising the epoxy resin composition according to any one of claims 15 to 19.   A prepreg comprising the epoxy resin composition according to any one of claims 15 to 19.   A heat conductive material comprising the epoxy resin composition according to any one of claims 15 to 19.