JP6283568B2 - Curing agent for epoxy resin, curing agent for microcapsule type epoxy resin, curing agent composition for masterbatch type epoxy resin, one-part epoxy resin composition and processed product - Google Patents

Description

  The present invention relates to a curing agent for epoxy resin, a curing agent for microcapsule type epoxy resin, a curing agent composition for masterbatch type epoxy resin, a one-part epoxy resin composition, and a processed product.

  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 such problems of the two-part epoxy resin composition, several one-part 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 have low storage stability if they are excellent in storage stability and require high temperature or a 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, dicyandiamide has a storage stability of a blended product of 6 months or more when stored at room temperature, but a curing temperature of 170 ° C. or more is required. When a curing accelerator is used in combination to lower the curing temperature, for example, curing at 130 ° C. is possible, but on the other hand, storage stability at room temperature becomes insufficient, and storage at low temperature is unavoidable. Therefore, there is a strong demand for compositions that can achieve both high curability and excellent storage stability.

  In recent years, especially in the field of electronic equipment, in order to respond to higher circuit density and improved connection reliability, or to use materials with low heat resistance as lighter mobile devices, the productivity has been greatly increased. For the purpose of improvement, there is a strong demand for a one-part epoxy resin composition used as one of connection materials to further improve the curability without impairing the storage stability of the curing agent.

  In addition, recent demands for electronic device equipment are diverse, such as downsizing, high functionality, light weight, high functionality, and multi-functionality. In semiconductor chip mounting technology, electrode pads and pad pitches are made finer. Therefore, further miniaturization, downsizing, and higher density are demanded. There is an underfill as an adhesive that protects the bump connection portion and the circuit surface of the chip in the gap between the chip and the substrate. However, with the fine pitch, the ability to penetrate between narrower gaps is required. In order to improve the permeability to a narrow gap, it is strongly desired to reduce the particle size of the curing agent particles and improve the fluidity of the underfill material.

  Numerous studies have been conducted to meet these requirements. For example, a method of obtaining a spherical amine compound / epoxy compound adduct particle by using a solvent in which an amine compound and an epoxy compound are dissolved in a solvent but not an adduct, and a dispersion stabilizer coexisting is proposed. (For example, refer to Patent Document 1). Further, even when a bifunctional or higher functional epoxy resin is used, a spherical amine-based latent curing agent is proposed that is not limited to an amine compound having only one active hydrogen (for example, a patent) Reference 2). Furthermore, there has been proposed a microcapsule type epoxy resin curing agent that corrects the shape of the particles and does not decrease the fluidity even if it does not contain a dispersant (see, for example, Patent Document 3).

JP-A-4-31427 JP 2010-265392 A JP 2011-26539 A

  However, all of the above-mentioned methods produce a sphere by using a curing agent for epoxy resin using heat or a solvent, and the production method is also limited. In the method of preparing an adduct of an amine compound and an epoxy compound described in Patent Document 1 in an insoluble solvent, the fluidity of a masterbatch type epoxy resin curing agent having a reduced viscosity due to the influence of a dispersion medium added to the system is lowered. There is a problem of end up. Moreover, there is a problem that a sufficient drying process is necessary, and when manufacturing in large quantities, it takes time to dry due to its high bulk density. On the other hand, according to the shape correction method by heat treatment described in Patent Document 2, the specific surface area is decreased and the curing reactivity is improved. However, since the particle size distribution of the epoxy resin curing agent is not adjusted, the storage stability is improved. It is difficult to balance. If the particle size distribution is too narrow, the crevice permeability test, curing performance, and storage stability will be adversely affected. This is because a small particle size increases curing performance and crevice penetration, while curing performance increases and storage stability tends to decrease. A large particle size increases storage stability while curing performance and crevice penetration. This is because the balance of particle size is important in order to reduce the properties. In addition, since a preheating step is included once, the particles are likely to melt and cause fusion, and the particles whose shape should be corrected aggregate. Aggregated particles become coarse particles, so that the permeability to narrow gaps is deteriorated, and the particle size is increased, resulting in a decrease in curing performance. Storage stability also decreases due to the influence of water. Furthermore, since the particle size distribution after shape correction becomes unstable due to aggregation, it also affects the stability of quality during particle production. Furthermore, in the method by heat treatment described in Patent Document 3, since the temperature / humidity control of the cooling air after the heat treatment of the epoxy resin curing agent particles is not performed together with the adjustment of the particle size distribution, the heat-cured epoxy resin curing agents depend on moisture. There is a problem that aggregation tends to occur and coarse particles are formed in which particles are aggregated in the same manner as described above.

  The present invention has been made in view of the problems of the above-described conventional technology, and not only has sufficient curability, but also reduces the aggregation ratio between particles of the curing agent for epoxy resin, and provides storage stability and clearance. It aims at providing the hardening | curing agent for epoxy resins which is excellent in all of osmosis | permeability.

  As a result of intensive studies to solve the above problems, the present inventors have reduced the specific surface area of the epoxy resin curing agent powder, that is, the particles by adjusting the moisture content and specific surface area of the powder particles. It has been found that the above-mentioned problems can be solved by suppressing the aggregation of the particles and adjusting the particle size distribution well, and the present invention has been completed.

That is, the present invention provides the following.
[1]
A curing agent for epoxy resin that is solid at 25 ° C. and contains particles,
The particle size D ₅₀ of the cumulative fraction under sieving 50% of the particles is more than 0.3 μm and 12 μm or less,
The particle size distribution defined by the ratio (D ₉₉ / D ₅₀ ) of the particle size D _{99 of} 99% cumulative fraction of the particles to the particle size D _{50 of} 50% cumulative fraction of the sieve is 6 or less,
The specific surface area value (Y) and particle size D ₅₀ (X) of the particles satisfy the relationship represented by the following formula (1),
The epoxy resin curing agent, wherein the epoxy resin curing agent has a water content of 1.5% or less.
^{4.0X -1 ≦ Y ≦ 8.3X -1 (} 1)
[2]
A core (C) formed using the epoxy resin curing agent (H) according to [1] as a starting material;
A shell (S) covering the core (C);
Have
It said shell (S) is a bonding group that absorbs infrared wave number 1630~1680cm ^-1 (x), binding group that absorbs infrared wave number 1680～1725Cm ^-1 and (y), of the wavenumber 1730～1755Cm ^-1 A microcapsule-type epoxy resin curing agent having a bonding group (z) that absorbs infrared rays at least on its surface.
[3]
The microcapsule type epoxy resin curing agent according to [2], wherein the shell (S) has a urea bond in its structure and no ester bond.
[4]
A core (C) formed using the epoxy resin curing agent (H) according to [1] as a starting material;
A shell (S) covering the core (C);
Have
The shell (S) has a urea bond in its structure and no ester bond,
The ratio of the thickness of the shell (S) to D ₅₀ of the epoxy resin curing agent (H) is 100: 1.5 to 100: 18, and the microcapsule type epoxy resin curing agent.
[5]
The shell (S) is made from two or more selected from the group consisting of an isocyanate compound, an active hydrogen compound, a curing agent for epoxy resin (h2), an epoxy resin (e2), and a low molecular amine compound (B). The hardening | curing agent for microcapsule-type epoxy resins in any one of [2]-[4] containing the reaction product obtained.
[6]
The total chlorine content contained in the epoxy resin curing agent (H) and the epoxy resin (e1) or the epoxy resin (e2) is 2500 ppm or less, according to any one of [2] to [5]. Hardener for microcapsule type epoxy resin.
[7]
[2] to [6] The microcapsule-type epoxy resin curing agent according to any one of the above and an epoxy resin (e3): (epoxy resin curing agent): (epoxy resin (e3)) (mass ratio) As a masterbatch type epoxy resin curing agent composition, which is contained at a blending ratio of 100: 0.1 to 100: 1000.
[8]
The hardening | curing agent composition for masterbatch type epoxy resins as described in [7] whose total chlorine amount which the said epoxy resin (e3) contains is 2500 ppm or less.
[9]
The masterbatch type epoxy according to [7] or [8], wherein the proportion of the diol terminal component in the epoxy resin (e3) is 0.001 to 30% by mass of the basic structural component of the epoxy resin (e3). Hardener composition for resin.
[10]
[7] to [9] further comprising at least one epoxy resin curing agent (h3) selected from the group consisting of acid anhydrides, phenols, hydrazides, and guanidines, or a cyclic borate ester compound. ] The hardening | curing agent composition for master batch type epoxy resins in any one of.
[11]
The curing agent composition for a masterbatch type epoxy resin according to [10], wherein the cyclic borate ester compound is 2,2′-oxybis (5,5′-dimethyl-1,3,2-dioxaborinane).
[12]
The hardening | curing agent composition for masterbatch type epoxy resins as described in [10] or [11] whose content rate of the said cyclic borate ester compound is 0.001-10 mass%.
[13]
The masterbatch type epoxy resin curing agent composition according to any one of [7] to [12] and an epoxy resin (e4): (masterbatch type epoxy resin curing agent composition): (epoxy resin ( e4)) A one-component epoxy resin composition containing a mass ratio of 100: 0.001 to 100: 1000.
[14]
[7] A processed product obtained from the masterbatch type epoxy resin curing agent composition according to any one of [12] or the one-component epoxy resin composition according to [13].
[15]
Paste composition, film composition, adhesive, bonding paste, bonding film, conductive material, anisotropic conductive material, anisotropic conductive film, insulating material, sealing material, coating material, paint The processed product according to [14], which is a composition, a prepreg, a thermally conductive material, a fuel cell separator material, or a flexible wiring board overcoat material.

  According to the present invention, there is provided an epoxy resin curing agent that not only has sufficient curability but also has a reduced aggregation ratio between particles of the curing agent for epoxy resin, and is excellent in both storage stability and gap permeability. can do.

  Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be appropriately modified within the scope of the gist.

(I-1) Curing Agent for Epoxy Resin The curing agent for epoxy resin of the present embodiment is solid at room temperature of 25 ° C. and contains particles. Further, in the curing agent for epoxy resin of the present embodiment, the particle size D ₅₀ of the particle under-sieving cumulative fraction 50% is more than 0.3 μm and not more than 12 μm, and the particle under-sieving integrated fraction 99 % Particle size distribution as defined by the ratio (D ₉₉ / D ₅₀ ) of the particle size D ₉₉ % of the particle size and the particle size D _{50 of} 50% of the sieving cumulative fraction, and the specific surface area value (Y) of the particles And the particle size D ₅₀ (X) satisfies the relationship represented by the following formula (1), and the water content of the epoxy resin curing agent is 1.5% or less.
^{4.0X -1 ≦ Y ≦ 8.3X -1 (} 1)

  Since the curing agent for epoxy resin of the present embodiment is configured as described above, the agglomeration ratio between particles of the curing agent for epoxy resin is reduced, and any of curability, storage stability, and gap permeability is achieved. An excellent curing agent for epoxy resin can be obtained. That is, according to the present embodiment, it is possible to provide an epoxy resin curing agent that improves the dispersibility of the curing agent and the permeability to the narrow gap without impairing the storage stability while maintaining the curing performance. More specifically, the curing agent for epoxy resin of this embodiment reduces the specific surface area of the powder by correcting the shape of the powder, suppresses aggregation of the curing agents (particles), and is a one-pack type epoxy. Curing performance, storage stability, dispersibility of the curing agent, and penetration into narrow gaps when used as a curing agent for resin are improved.

  First, the configuration of the epoxy resin curing agent of the present embodiment will be described in detail. The epoxy resin curing agent of the present embodiment is not limited to the following, and examples thereof include an amine-based curing agent as a main component. Examples of amine curing agents include, but are not limited to, for example, amine adducts, modified polyamines, aliphatic polyamines, heterocyclic polyamines, alicyclic polyamines, aromatic amines, polyamidoamines, ketimines. Examples thereof include commonly used amine curing agents such as urethane and urethane amine. Among these, from the viewpoint of having an appropriate reactivity, an amine-based curing agent comprising a low molecular amine compound (a1) and an amine adduct is preferable. Here, “having the amine-based curing agent as a main component” means that it accounts for 50% by mass or more, preferably 70% by mass or more, and more preferably 90% by mass or more.

  Here, the low molecular amine compound (a1) is not limited to the following, for example, a compound having at least one primary amino group and / or secondary amino group but not having a tertiary amino group; Examples thereof include compounds having at least one tertiary amino group and at least one active hydrogen group.

Examples of the compound having at least one primary amino group and / or secondary amino group but having no tertiary amino group include 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; dimethylamine, diethylamine, di Propylamine, dibutylamine, dipentylamine, dihexylamine, dimethanolamine, diethanolamine, dipropanolamine, dicyclohexylamine, piperidine, piperidine Pyrrolidone, diphenylamine, phenylmethylamine, and phenyl ethyl amine, such as secondary amines having no tertiary amino groups.

  Examples of the compound having at least one tertiary amino group and at least one active hydrogen group include, but are not limited to, for example, 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxy Amino alcohols such as methyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, methyldiethanolamine, triethanolamine, N-β-hydroxyethylmorpholine; 2- (dimethylaminomethyl) ) Aminophenols such as phenol and 2,4,6-tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2- Feni Imidazole, 1-aminoethyl-2-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-ethyl-4-methyl Imidazoles such as imidazole, 1- (2-hydroxy-3-butoxypropyl) -2-methylimidazole, 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-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-methylimidazoline, 1,3,3-trimethyl-1,4-tetramethylene-bis-4 -Imidazolines such as -methylimidazoline, 1,2-phenylene-bis-imidazoline, 1,3-phenylene-bis-imidazoline, 1,4-phenylene-bis-imidazoline, 1,4-phenylene-bis-4-methylimidazoline Dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine Tertiary aminoamines such as dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, dipropylaminoethylamine, dibutylaminoethylamine, N-methylpiperazine, N-aminoethylpiperazine, diethylaminoethylpiperazine; 2-dimethylaminoethanethiol; Amino mercaptans such as 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptopyridine, 4-mercaptopyridine; N, N-dimethylaminobenzoic acid, N, N-dimethylglycine, nicotinic acid, isonicotinic acid, Examples include aminocarboxylic acids such as picolinic acid; aminohydrazides such as N, N-dimethylglycine hydrazide, nicotinic acid hydrazide, and isonicotinic acid hydrazide. Among these low-molecular amine compounds (a1), imidazoles are preferable from the viewpoint of appropriate reactivity.

  Next, the amine adduct is not limited to the following, but for example, at least one compound selected from the group consisting of a carboxylic acid compound, a sulfonic acid compound, a urea compound, an isocyanate compound, and an epoxy resin (e1) and an amine compound. Examples thereof include compounds having an amino group obtained by reaction with (a2).

  Examples of the carboxylic acid compound include, but are not limited to, succinic acid, adipic acid, sebacic acid, phthalic acid, and dimer acid. Examples of the sulfonic acid compound include, but are not limited to, for example, ethanesulfonic acid, p-toluenesulfonic acid, and the like. Examples of the urea compound include, but are not limited to, urea, methylurea, dimethylurea, ethylurea, Examples thereof include t-butylurea.

  Examples of the isocyanate compound include, but are not limited to, aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, aliphatic triisocyanate, and polyisocyanate.

  Examples of the aliphatic diisocyanate include, but are not limited to, ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate.

  Examples of the alicyclic diisocyanate include, but are not limited to, 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.

  Examples of the aromatic diisocyanate include, but are not limited to, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylene diisocyanate, 1,5-naphthalene diisocyanate, and the like.

  Examples of the aliphatic triisocyanate include, but are not limited to, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-triisocyanate methylhexane, and the like. It is done.

  Examples of the polyisocyanate include, but are not limited to, polymethylene polyphenyl polyisocyanate and polyisocyanate derived from the diisocyanate compound. Examples of the polyisocyanate derived from the diisocyanate include, but are not limited to, isocyanurate type polyisocyanate, burette type polyisocyanate, urethane type polyisocyanate, allophanate type polyisocyanate, and carbodiimide type polyisocyanate.

  Examples of the epoxy resin (e1) include, but are not limited to, any one of a monoepoxy compound and a polyvalent epoxy compound, or a mixture thereof.

  Examples of the monoepoxy compound include, but are not limited to, for example, butyl glycidyl ether, hexyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, para-tert-butylphenyl glycidyl ether, ethylene oxide, propylene oxide, paraxylyl glycidyl ether, Examples thereof include glycidyl acetate, glycidyl butyrate, glycidyl hexoate, and glycidyl benzoate.

  Examples of the polyvalent epoxy compound include, but are not limited to, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol AD, tetramethyl bisphenol S, tetrabromobisphenol. A, bisphenol type epoxy resin obtained by glycidylation of bisphenols such as tetrachlorobisphenol A and tetrafluorobisphenol A; other dihydric phenols such as biphenol, dihydroxynaphthalene and 9,9-bis (4-hydroxyphenyl) fluorene Glycidylated epoxy resin; 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 Novolak type epoxy resins obtained by glycidylation of novolaks such as novolak, cresol novolak, bisphenol A novolak, brominated phenol novolak, brominated bisphenol A novolak, etc .; epoxy resins obtained by glycidylation of polyhydric phenols, glycerin, polyethylene glycol, etc. Aliphatic ether type epoxy resins obtained by glycidylation of polyhydric alcohols; ether ester type resins obtained by glycidylation of hydroxycarboxylic acids such as p-oxybenzoic acid and β-oxynaphthoic acid Poxy resin; ester-type epoxy resin obtained by glycidylation of polycarboxylic acid such as phthalic acid and terephthalic acid; amine type such as glycidylated amine compounds such as 4,4-diaminodiphenylmethane and m-aminophenol, and triglycidyl isocyanurate Examples thereof include glycidyl type epoxy resins such as epoxy resins and alicyclic epoxides such as 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate.

  The total chlorine content of the epoxy resin (e1) is preferably 2500 ppm or less, more preferably 2000 ppm or less, and still more preferably, from the viewpoint of obtaining a curing agent for epoxy resins having an excellent balance between curability and storage stability. Is 1500 ppm or less, more preferably 800 ppm or less, more preferably 400 ppm or less, even more preferably 180 ppm or less, particularly preferably 100 ppm or less, and most preferably 80 ppm or less, and most preferably Is 50 ppm or less.

  Here, the total chlorine amount indicates the total amount of organic chlorine and inorganic chlorine contained in the epoxy resin, and is a value based on mass with respect to the epoxy resin. The total chlorine content of the epoxy resin is measured 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. 1-10 g of the obtained epoxy resin sample is precisely weighed so that the titration amount is 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 calculated from the titration titrated with an aqueous silver nitrate solution.

  In addition, the total chlorine content of the epoxy resin (e1) is preferably 0.01 ppm or more, more preferably 0.02 ppm or more, and still more preferably 0.8 ppm, from the viewpoint of facilitating control of the shell formation reaction. It is 05 ppm or more, more preferably 0.1 ppm or more, particularly preferably 0.2 ppm or more, and very preferably 0.5 ppm or more. Furthermore, when the total chlorine amount is 0.1 ppm or more, the shell forming reaction is efficiently performed on the core surface containing the curing agent, and a shell having further excellent storage stability tends to be obtained.

  From the above, the preferable range of the total chlorine content of the epoxy resin (e1) is 0.01 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. .

  Here, the chlorine contained in the 1,2-chlorohydrin group out of the total chlorine is generally called hydrolyzable chlorine. The amount of hydrolyzable chlorine in the epoxy resin (e1) is preferably 50 ppm or less, more preferably 0.01 to 20 ppm, and still more preferably 0.05 to 10 ppm. When the amount of hydrolyzable chlorine is 50 ppm or less, it is advantageous from the viewpoint of achieving both high curability and storage stability, and the cured product tends to exhibit excellent electrical characteristics.

  Here, hydrolyzable chlorine is measured by the following method. That is, 3 g of a sample is dissolved in 50 mL of toluene, 20 mL of 0.1 N KOH in methanol is added thereto, boiled for 15 minutes, and then calculated from titration titrated with an aqueous silver nitrate solution.

  As amine compound (a2), the amine compound mentioned as an example of the low molecular amine compound (a1) mentioned above can be used.

  Among these amine adducts, those obtained by reaction of the epoxy resin (e1) and the amine compound (a2) are particularly preferable. The amine adduct obtained by the reaction between the epoxy resin (e1) and the amine compound (a2) is also preferable from the viewpoint that the unreacted amine compound (a2) can be used as the low molecular amine compound (a1).

  The amine adduct obtained by the reaction of the epoxy resin (e1) and the amine compound (a2) is, for example, the epoxy resin (e1) and the amine compound (a2) with respect to 1 equivalent of the epoxy group of the epoxy resin (e1). Necessary as long as the active hydrogen group of the amine compound (a2) is preferably 0.5 equivalent to 10 equivalent, more preferably 0.8 equivalent to 5 equivalent, and still more preferably 0.95 equivalent to 4 equivalent) In the presence of a solvent, for example, it is obtained by reacting at a temperature of 50 to 250 ° C for 0.1 to 10 hours. When the equivalent ratio of active hydrogen groups to epoxy groups is 0.5 or more, it is advantageous to obtain an amine adduct having a molecular weight distribution measured by gel permeation chromatography (GPC) of 7 or less. Adduct fluidity tends to increase. Furthermore, it is preferable to use the amine adduct as described above from the viewpoints of storage stability and low temperature curability. An equivalent ratio of 10 or less is advantageous because the unreacted amine compound (a2) can be used as it is as the low-molecular amine compound (a1) without being recovered.

  In the reaction for obtaining an amine adduct by the epoxy resin (e1) and the amine compound (a2), the solvent used as necessary is not limited to the following, but for example, benzene, toluene, xylene, cyclohexane, mineral spirit, naphtha Hydrocarbons such as acetone; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone (MIBK); esters such as ethyl acetate, n-butyl acetate, and propylene glycol monomethyl ether acetate; methanol, isopropanol, n-butanol, butyl cellosolve, Examples include alcohols such as butyl carbitol; water and the like. These solvents may be used in combination.

  Next, adjustment of the specific surface area will be described. By using a method of precipitating the amine compound / epoxy compound adduct particles in an insoluble solvent as a method for preparing the curing agent particles for epoxy resin, a product having a specific surface area lower than that of the particle preparation method by pulverization or the like can be obtained. It is also possible to adjust and lower the specific surface area by correcting the shape after obtaining particles by pulverizing the curing agent for epoxy resin. Examples of the shape correction method include, but are not limited to, a shape correction method in a physical particle collision with a jet mill or the like, a shape correction method using heat, and the like. Regardless of which method is used, the moisture content is adjusted by sufficient temperature and humidity control before and after adjusting the specific surface area. That is, from the viewpoint of ensuring good product quality, the specific surface area and the moisture content are adjusted simultaneously.

  As a method for preparing the curing agent for epoxy resin by adjusting the specific surface area, in the shape correction method by the heat treatment described above, it is possible to perform both moisture removal and shape correction. There are many epoxy resin curing agents that easily absorb moisture, especially after adjusting the specific surface area using heat, etc., the moisture tends to evaporate due to heat and easily absorb moisture. It can be said that it is difficult to adjust the amount of water because it contains water immediately. Therefore, it can be said that it is preferable to prepare a curing agent for an epoxy resin in which both the specific surface area and the moisture content are adjusted, particularly in an environment in which the temperature and humidity are sufficiently controlled, from the viewpoint of obtaining the desired effect of the present embodiment. .

  The method for correcting the shape by heat is not limited to the following. For example, the hot air injection nozzle that injects hot air downward and the outlet of the hot air injection nozzle are disposed and injected from the hot air injection nozzle. A raw material injection nozzle that injects solid epoxy resin curing agent particles toward the center of hot air, and heat insulation that is provided outside the raw material injection nozzle to prevent the temperature of the solid epoxy resin curing agent from rising above the melting point. Curing agent for epoxy resin which has a mechanism and corrects the shape by using a collision member that diffuses and supplies solid curing agent particles for solid epoxy resin sprayed from a raw material injection nozzle into hot air by collision. Can be mentioned. Advantages of this apparatus include that it has a heat insulating mechanism and is cooled by a cooling jacket, thereby preventing particles from sticking into the raw material injection nozzle. In addition, the epoxy resin curing agent (particles) is corrected in shape by heat, but the particles collide with the collision member to disperse outwards, and hot air is jetted downward to rapidly cool the particles. Can be prevented from adhering to the collision member.

  Since the specific surface area value in the specific average particle diameter of the curing agent (particle) for epoxy resin of the present embodiment is adjusted, when preparing a latent 1-pack type curing agent for epoxy resin using the same. Low viscosity can be achieved. This is because the average particle size is the same and the amount of the curing agent particles contained in the epoxy resin is the same, but the particles with a smaller specific surface area have a smaller specific surface area where the particles are in contact with the epoxy resin. It is inferred that the shape will be excellent. When the value of the average particle size changes, the value of the specific surface area also changes. For this reason, in this embodiment, not only the specific surface area value but also the specific surface area value at a certain average particle diameter is adjusted.

The above-described formula (1) is obtained by calculating a particle size D ₅₀ (X) and a specific surface area (Y) of a certain sieving cumulative fraction of 50%.
Shows the relationship. The relationship between X and Y of the epoxy resin curing agent (particles) having an indefinite shape that has not undergone shape correction is represented by “Y = 10.4X ⁻¹ ”. The upper limit “Y = 8.3X ⁻¹ ” in the formula (1) is a physical shape correction for the irregularly shaped epoxy resin curing agent particles, specifically, a shape correction method to such an extent that the particles do not cause pulverization. The upper limit value of Y in the curing agent for epoxy resin of the present embodiment in which the shape of the curing agent for epoxy resin is corrected by collision with particles or by controlling the particles to lower the specific surface area is shown. On the other hand, when it is calculated on the assumption that all the particles exist as perfect spheres, the lower limit value of Y is represented by “Y = 2.5X ⁻¹ ”. Therefore, the lower limit value of Y is never less than “2.5X ⁻¹ ”. Further, when adjustment is performed by a method using heat, the lower limit value of Y can be expressed by “Y = 4.0X ⁻¹ ”. This lower limit value considers the surface tension of the curing agent for epoxy resin, and takes into consideration that the shape having a smaller specific surface area is obtained by applying heat. The curing agent of this embodiment therefore, theoretically "2.5X ^-1 ≦ Y ≦ 8.3X ^-1" and, more essentially the formula (1) "4.0X ^-1 ≦ Y ≦ 8.3X ⁻¹ ”and having a specific surface area (Y). By adjusting to the range of the specific surface area represented by the formula (1), the aggregation of the curing agents is suppressed, and the curing performance, storage stability, and curing agent of the one-pack type epoxy resin are set. Dispersibility and penetration into narrow gaps can be improved. This is considered to be due to the fact that the particle packing density can be increased by correcting the shape of the particles and the viscosity of the resin particles is reduced.

Next, the median diameter of the epoxy resin curing agent of the present embodiment (that is, the particle diameter D ₅₀ having a 50% cumulative fraction under sieving) will be described. The epoxy resin curing agent (particles) of the present embodiment is an average particle defined by the median diameter from the viewpoint of obtaining a homogeneous cured product and preventing aggregation of the particles to ensure good physical properties of the cured product. The diameter exceeds 0.3 μm and is 12 μm or less, preferably 1 μm or more and 10 μm or less, more preferably 1.5 μm or more and 5 μm or less. Using the particles as a starting material, the microcapsule-type epoxy resin curing agent of this embodiment is formed. Here, the average particle diameter defined by the median diameter refers to the Stokes diameter measured by a laser diffraction / light scattering method. Moreover, the shape is not specifically limited, For example, any of spherical shape, granule shape, powder shape, and an indefinite shape may be sufficient. If the particle size is larger than 12 μm, a homogeneous cured product cannot be obtained. In addition, when the composition is blended, aggregates having a large particle diameter are likely to be generated, and the physical properties of the cured product are impaired. When the particle size is 0.3 μm or less, aggregation occurs between the starting material particles, and it is difficult to form a thin shell. As a result, there is an incomplete portion of the capsule film formation, which impairs storage stability and solvent resistance.

Next, the particle size distribution of the epoxy resin curing agent of the present embodiment will be described. Aggregation of particles is prevented in the particle size distribution defined by the ratio (D ₉₉ / D ₅₀ ) of the particle size D _{99 of} 99% cumulative fraction under the sieve and the particle size D _{50 of} 50% cumulative fraction under the sieve. From the viewpoint, D ₉₉ / D ₅₀ is 6 or less. From the same viewpoint, it is preferably 5.5 or less, more preferably 5 or less. When D ₉₉ / D ₅₀ is larger than 6, since there are many coarse particles in the powder particles, aggregates are likely to be generated, and the physical properties of the cured product may be impaired. A smaller D ₉₉ / D ₅₀ means that the particle size distribution is not broader, and it becomes easier to obtain a homogeneous cured product and better curing performance. In addition, when the value of D ₉₉ / D ₅₀ is larger than 6, since there are particles having a wide particle size distribution and a relatively large particle size, the compound has a D ₉₉ / D ₅₀ value of 6 or less. Therefore, the permeability to the gap at the time of producing is inferior.

  Next, the moisture content of the epoxy resin curing agent of this embodiment will be described. The moisture content of the curing agent for epoxy resin of the present embodiment with the specific surface area adjusted is 1.5% or less, preferably 0.8% or less, more preferably 0.6% or less. If the water content is more than 1.5%, problems occur. In other words, the curing performance of epoxy resin curing agents and storage stability deteriorated, the productivity decreased due to the decrease in fluidity as a powder, the dispersibility of epoxy resin curing agents decreased due to the occurrence of aggregates, There is a problem such as a decrease in rate. If the moisture content of the curing agent for epoxy resin is 0.8% or less, blocking after the corrected shape can be more preferably prevented, and the physical properties tend to be stable. preferable. In preparing the microcapsule type epoxy resin curing agent of this embodiment, the capsule film was prepared with respect to 100 parts of the epoxy resin curing agent of this embodiment obtained by adjusting the specific surface area and water content. Occasionally, water is further added to improve the surface shell formation efficiency, and the formed shell tends to be a film with better storage stability and solvent resistance. The water content can be measured by the Karl Fischer method using specific surface area and coulometric titration.

The epoxy resin curing agent of this embodiment can be used to obtain the microcapsule type epoxy resin curing agent of this embodiment. That is, the microcapsule type epoxy resin curing agent of this embodiment includes a core (C) formed using the epoxy resin curing agent (H) of this embodiment as a starting material, and a shell covering the core (C). and (S), has, the shell (S) is a bonding group that absorbs infrared wave number 1630~1680cm ^-1 (x), binding group that absorbs infrared wave number 1680~1725cm ^-1 (y) And a bonding group (z) that absorbs infrared rays having a wave number of 1730 to 1755 cm ⁻¹ at least on the surface. Since it is configured in this manner, the microcapsule type epoxy resin curing agent of the present embodiment has a reduced aggregation ratio between particles derived from the epoxy resin curing agent, and has curability, storage stability, and gap permeability. Both are excellent. Further, from the same viewpoint, the epoxy resin curing agent (H) preferably contains an amine adduct (A) obtained by a reaction between the epoxy resin (e1) and an amine compound as a main component. Here, “having the amine adduct (A) as a main component” means occupying 50% by mass or more, preferably 70% by mass or more, and more preferably 90% by mass or more.

  Next, the core (C) will be described. The particle diameter of the starting material particles (epoxy resin curing agent of the present embodiment) for forming the core (C) is such that the average particle diameter defined by the median diameter is more than 0.3 μm and not more than 12 μm. The thickness is preferably 1 μm to 10 μm, and more preferably 1.5 μm to 5 μm. Here, the particle diameter of the starting material particles refers to the Stokes diameter measured by a laser diffraction / light scattering method. The particle diameter of the starting material particles can be measured according to the method described in the examples described later. When the particle diameter of the starting material particles is 12 μm or less, a homogeneous cured product can be obtained, and when it is 0.3 μm or more, aggregation between the starting material particles can be suppressed and formation of a thin shell is facilitated. .

  The starting particles are solid at 25 ° C. The temperature of the hot air when the particles are treated with hot air is preferably 100 ° C. or higher and 400 ° C. or lower. When the temperature of the hot air is 100 ° C. or higher, the core surface is sufficiently heated and tends to be easily controlled to a desired circularity, and when it is 400 ° C. or lower, the core (C) is thermally decomposed. It tends to be better controlled. From the above viewpoint, the hot air temperature is more preferably 150 ° C. or higher and 300 ° C. or lower, and further preferably 180 ° C. or higher and 250 ° C. or lower.

  The weight average molecular weight of the starting material particles is preferably 50 or more and 50000 or less. When the molecular weight of the starting material particles is 50 or more, the fusion between the particles can be more favorably suppressed at the stage of the hot air treatment, and the particle size tends to be prevented from becoming too large. The softening temperature does not become too high, and the desired circularity tends to be obtained more easily in the hot air treatment. From the above viewpoint, the range of the weight average molecular weight of the starting material particles is more preferably 70 or more and 10,000 or less, further preferably 100 or more and 5000 or less, still more preferably 500 or more and 4000 or less, and particularly preferably 1000. It is 3000 or more. Here, the weight average molecular weight can be measured by gel permeation chromatography (GPC).

  In addition to amine-based curing agents, particles used as starting materials for forming the core (C) include acid anhydride-based curing such as phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, and methylnadic acid. Agents: phenolic hardeners such as phenol novolak, cresol novolak, bisphenol A novolak; mercaptan hardeners such as propylene glycol-modified polymercaptan, trimethylolpropane thiogluconate, polysulfide resin, etc .; halogens such as ethylamine salt of trifluoroborane Boron halide salt curing agent; 1,8-diazabicyclo (5,4,0) -undec-7-ene quaternary ammonium salt curing agent; 3-phenyl-1,1-dimethylurea, etc. Urea curing agent; triphenylphosphine, tetraphenylphosphine Phosphonium tetraphenylborate and the like of a phosphine-based curing agents other curing agents for epoxy resin such as a (h1) may be used in combination. However, it is not limited only to the above.

(I-2) First shell (S1)
The shell (S) in the present embodiment covers the core (C) and includes at least the first shell (S1). First shell (S1) is to coat the surface of the core (C) directly bonded group that absorbs infrared wave number 1630~1680cm ^-1 (x), binding group that absorbs infrared wave number 1680～1725Cm ^-1 (Y), and a bond group (z) that absorbs infrared rays having a wave number of 1730 to 1755 cm ⁻¹ , and the bond to the total concentration (Cx + Cy + Cz) of the bond groups (x), (y), and (z) The ratio (Cx / (Cx + Cy + Cz)) of the concentration Cx of the group (x) is preferably 0.50 or more and less than 0.75. Here, Cx represents the concentration of the bonding group (x) in the shell (S1), Cy represents the concentration of the bonding group (y) in the shell (S1), and Cz represents the concentration in the shell (S1). Represents the concentration of the linking group (z).

  Here, although infrared absorption can be measured using an infrared spectrophotometer, it is particularly preferable to use a Fourier transform infrared spectrophotometer (FT-IR).

  The linking group (x) is preferably a urea linking group. The linking group (y) is preferably a burette group. The linking group (z) is preferably a urethane linking group. In addition, when the concentration ratio Cx / (Cx + Cy + Cz) is 0.50 or more, the solvent resistance tends to be further improved. In addition, when the concentration ratio Cx / (Cx + Cy + Cz) is less than 0.75, fusion / aggregation of the particles of the microcapsule type epoxy resin curing agent can be suppressed more favorably, and a better viscosity can be secured. is there. As a result, the epoxy resin curing agent composition can be managed with stable quality, and the storage stability tends to be further improved.

  The first shell (S1) of the present embodiment preferably has a urea group and does not have an ester group, has a urea group, a burette group and a urethane group, and has an ester group. More preferably not. Since the ester bond site is susceptible to hydrolysis, the shell (S1) is sufficiently maintained even under high humidity conditions, and the storage stability and moisture resistance of the curing agent for epoxy resin and the epoxy resin composition containing the same are cured. From the viewpoint of sufficiently securing the physical properties of the cured product obtained in this manner, it is preferable to do as described above.

  As the first shell (S1), an amine-based curing agent that can be included in the particles used as a starting material for forming the above-described core (C), and an epoxy resin curing agent (h1) and isocyanate that can be used in combination therewith. A reaction product of a compound is preferable, and a reaction product of an amine curing agent and an isocyanate compound is particularly preferable.

  Here, the isocyanate compound mentioned as an example of the raw material of the amine adduct contained in the above-mentioned core (C) can be used as the isocyanate compound.

When the first shell is a reaction product of an amine curing agent or another epoxy resin curing agent (h1) and an isocyanate compound, the first shell is a starting point for forming the core (C). Infrared rays having a wave number of 1630 to 1680 cm ⁻¹ as compared to the case of an amine-based curing agent that can be contained in the material particles or a reaction product of an epoxy resin curing agent (h1) that can be used in combination with this. tendency for the content of binding groups to absorb binding group absorbing (x) and the infrared wave number 1680~1725cm ^-1 (y) and the bonding group that absorbs infrared wave number 1730~1755cm ^-1 (z) increases more the Therefore, the microcapsule-type epoxy resin curing agent having such a first shell tends to exhibit better storage stability and solvent resistance.

Binding group that absorbs infrared bonding group (y) and the wave number 1730～1755Cm ^-1 to absorb binding group that absorbs infrared of the wave number 1630～1680Cm ^-1 (x) and the infrared wave number 1680~1725cm ^-1 ( The first shell containing z) is at a temperature lower than the temperature at which the epoxy resin reacts with the amine-based curing agent that can be contained in the starting particles or the epoxy resin curing agent (h1) that can be used in combination therewith. Further, it can be obtained by reacting an amine-based curing agent that can be contained in particles as a starting material, or an epoxy compound curing agent (h1) that can be used in combination with this, and the like.

In addition, another microcapsule type epoxy resin curing agent of the present embodiment covers the core (C) formed using the epoxy resin curing agent (H) of the present embodiment as a starting material, and the core (C). The shell (S) has a urea bond in its structure and does not have an ester bond, and the above-mentioned curing agent for epoxy resin (H) with respect to D ₅₀ The ratio of the thickness of the shell (S) is 100: 1.5 to 100: 18. Since the other microcapsule-type epoxy resin curing agent of the present embodiment is configured as described above, it has an excellent balance between storage stability and curability. Further, from the same viewpoint, the epoxy resin curing agent (H) preferably contains an amine adduct (A) obtained by a reaction between the epoxy resin (e1) and an amine compound as a main component. Here, “having the amine adduct (A) as a main component” means occupying 50% by mass or more, preferably 70% by mass or more, and more preferably 90% by mass or more.

(I-3) Shell (S2)
The shell (S) in the present embodiment includes an isocyanate compound, an active hydrogen compound, a curing agent for epoxy resin (h2), an epoxy resin (e2), and a low molecular amine compound (from the viewpoint of the balance between storage stability and curability. It is preferable to include a reaction product obtained by using two or more selected from the group consisting of B) as raw materials. Furthermore, it is more preferable that the surface of the first shell (S1) described above includes a second shell (S2) made of a reaction product of the first shell (S1) and the epoxy resin (e2).

  The second shell (S2) is preferably a reaction product of the first shell (S1) and the epoxy resin (e2). As the epoxy resin (e2), the polyvalent epoxy compounds mentioned as examples of the epoxy resin (e1) used as a raw material for the amine adduct contained in the core (C) can be used. These epoxy resins may be used alone or in combination.

  Further, the epoxy resin (e2) is the same as the epoxy resin (e3) contained in the hardener composition for a masterbatch type epoxy resin described later, or when the epoxy resin (e3) is a mixture, A microcapsule type epoxy resin curing agent excellent in stability and solvent resistance tends to be obtained, which is preferable.

  Epoxy resins usually have impure ends with chlorine bonded in the molecule, but it is preferable to reduce such impure ends from the viewpoint of ensuring sufficient electrical properties of the cured product. Therefore, the total chlorine content of the epoxy resin (e2) is preferably 2500 ppm or less, more preferably 1500 ppm or less, and further preferably 500 ppm or less. From the same viewpoint as described above, in the present embodiment, the total chlorine content contained in the epoxy resin curing agent (H) and the epoxy resin (e1) or the epoxy resin (e2) may be 2500 ppm or less. Particularly preferred.

  The reaction between the epoxy resin (e2) and the first shell (S1) can be performed in a dispersion medium. Examples of the dispersion medium include, but are not limited to, a solvent, an epoxy resin, and a plasticizer. As a solvent and a plasticizer, what was mentioned as an example of the solvent and plasticizer which can be used by reaction of the isocyanate compound and active hydrogen compound mentioned later can be used.

  Examples of the active hydrogen compound include, but are not limited to, water, a compound having at least one primary amino group and / or a secondary amino group, a compound having at least one hydroxyl group, and the like. In which no ester group is contained. These compounds can also be used in combination.

  Examples of the compound having at least one primary amino group and / or secondary amino group include, but are not limited to, aliphatic amines, alicyclic amines, and aromatic amines.

  Examples of the aliphatic amine include, but are not limited to, for example, alkylamines such as methylamine, ethylamine, propylamine, butylamine, and dibutylamine, alkylenediamines such as ethylenediamine, propylenediamine, butylenediamine, and hexamethylenediamine; Examples include polyalkylene polyamines such as ethylene tetramine and tetraethylene pentamine; polyoxyalkylene polyamines such as polyoxypropylene diamine and polyoxyethylene diamine.

  Examples of the alicyclic amine include, but are not limited to, cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, and isophoronediamine.

  Examples of the aromatic amine include, but are not limited to, aniline, toluidine, benzylamine, naphthylamine, diaminodiphenylmethane, diaminodiphenylsulfone, and the like.

  Examples of the compound having at least one hydroxyl group include, but are not limited to, alcohol compounds and phenol compounds.

  Examples of alcohol compounds include, but are not limited to, methyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, and dodecyl alcohol. , Stearyl alcohol, eicosyl alcohol, 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 Monoalcohols such as monobutyl; ethylene glycol, poly Ji glycol, propylene glycol, polypropylene glycol, 1,3-butanediol, 1,4-butanediol, hydrogenated bisphenol A, neopentyl glycol, glycerol, trimethylolpropane, polyhydric alcohols such as pentaerythritol. Further, two secondary hydroxyl groups obtained by reaction of a compound having at least one epoxy group with a compound having at least one hydroxyl group, carboxyl group, primary or secondary amino group, or mercapto group in one molecule. The compounds having the above are also exemplified as polyhydric alcohols. These alcohol compounds may be any of primary, secondary, or tertiary alcohols.

  Examples of the phenol compound include, but are not limited to, monophenols such as carboxylic acid, cresol, xylenol, carvacrol, motile, naphthol, and the like, polyvalents such as catechol, resorcin, hydroquinone, bisphenol A, bisphenol F, pyrogallol, and phloroglucin. Phenols are mentioned.

  As the compound having at least one hydroxyl group, polyhydric alcohols and polyhydric phenols are preferable, and polyhydric alcohols are particularly preferable.

  Although reaction of an isocyanate compound and an active hydrogen compound is not limited to the following, Usually, it is performed by the reaction time for 10 minutes-12 hours in the temperature range of -10 degreeC-150 degreeC.

  Moreover, reaction of an isocyanate compound and an active hydrogen compound can be performed in a dispersion medium as needed. Examples of the dispersion medium include, but are not limited to, a solvent, a plasticizer, and resins. Examples of the solvent include, but are not limited to, hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirit, and naphtha; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone (MIBK); ethyl acetate, acetic acid- Examples include esters such as n-butyl and propylene glycol monomethyl ethyl ether acetate; alcohols such as methanol, isopropanol, n-butanol, butyl cellosolve and butyl carbitol; water and the like. Examples of the plasticizer include, but are not limited to, phthalic acid diesters such as dibutyl phthalate and di (2-ethylhexyl) phthalate; aliphatic dibasic acid esters such as di (2-ethylhexyl) adipate; Examples thereof include phosphate triesters such as tricresyl phosphate; glycol esters such as polyethylene glycol ester. Examples of the resins include, but are not limited to, silicone resins, epoxy resins, phenol resins, and the like.

  Such a reaction product of an isocyanate compound and an active hydrogen compound has a urea bond, but preferably does not have an ester bond at the same time, and preferably has a burette bond and a urethane bond. When the reaction product has a burette bond and a urethane bond, the solvent resistance of the resulting microcapsule type curing agent tends to increase.

  The method for forming the shell (S) so as to cover the core (C) is not particularly limited. For example, the particles used as the starting material for forming the core (C) are dispersed in a dispersion medium, and this dispersion is performed. Add a material that forms a shell to the medium and deposit it on the starting material particles, or add a raw material of the material that forms the shell to the dispersion medium and use the surface of the starting material particles as a reaction field, where the shell forming material The method etc. which produce | generate are mentioned. The latter method is preferable because the reaction and the coating can be performed simultaneously. Examples of the dispersion medium include a solvent, a plasticizer, and a resin. As the solvent, plasticizer, and resin, those mentioned as examples of the solvent, plasticizer, and resin that can be used in the reaction of the above-mentioned isocyanate compound and active hydrogen compound can be used. Here, it is preferable to use an epoxy resin as a dispersion medium because a masterbatch type epoxy resin curing agent composition can be obtained simultaneously with shell formation.

  The formation reaction of the first shell (S1) is not limited to the following, but is usually −10 ° C. to 100 ° C., preferably 0 ° C. to 50 ° C., more preferably 20 ° C. to 40 ° C. for 10 minutes to The reaction is performed for 24 hours, preferably 2 hours to 10 hours. When the reaction temperature is −10 ° C. or higher, the reaction is fast and industrially preferable. When the reaction temperature is 100 ° C. or lower, the core material can be prevented from being eluted into the reaction system, and storage stability, solvent resistance, etc. Can be further improved.

  In addition, if the material for forming the shell is present at the initial stage of the shell formation reaction, the first shell (S1) is more effectively formed, and the effects such as storage stability and solvent resistance are more remarkably exhibited. Tend to be.

  The second shell (S2) can be formed by reacting the core (C) covered with the first shell (S1) with an epoxy resin. The reaction temperature at that time is usually in the temperature range of −10 ° C. to 150 ° C., preferably 0 ° C. to 100 ° C., more preferably 10 ° C. to 70 ° C., and the reaction time is usually 10 minutes to 24 hours, preferably 2 hours to 10 hours.

  Moreover, when the formation reaction temperature of the second shell (S2) is higher than the first shell (S1) formation reaction temperature, the effects of the present embodiment such as storage stability and solvent resistance tend to be more prominently exhibited. is there.

  In the microcapsule-type epoxy resin curing agent in the present embodiment, the content of the dispersion stabilizer with respect to the core (C) is preferably 8% by mass or less. The smaller the amount of the dispersion stabilizer contained in the microcapsule type epoxy resin curing agent, the more the viscosity can be reduced when the microcapsule type epoxy resin curing agent is mixed with the epoxy resin. It is in the tendency which can fully secure property and can ensure sufficient adhesiveness with a to-be-adhered body. That is, not only can the cured product have good moisture resistance and penetrability, but it also tends to have better solvent resistance and filler resistance. As a result, there is a tendency that the reliability of the electrical component when used for the electrical component or the like can be sufficiently secured. From such a viewpoint, the content of the dispersion stabilizer with respect to the core (C) in the microcapsule type epoxy resin curing agent is preferably 8% by mass or less, more preferably 5% by mass or less, and further preferably 1% by mass. % Or less, more preferably 0.5% by mass or less, and particularly preferably 0.1% by mass or less. In addition, about content of the said dispersion stabilizer, it can quantify from observation of the peak characteristic to a dispersion stabilizer by FT-IR.

  The dispersion stabilizer has a function of dispersing each component contained in the microcapsule type epoxy resin curing agent, and is not particularly limited. For example, the following graft copolymer, block copolymer, random copolymer is used. Examples thereof include polymers and other polymers. In the microcapsule type epoxy resin curing agent of the present embodiment, the total amount of the graft copolymer, block copolymer, random copolymer and other polymer used as a dispersion stabilizer is 8% by mass or less. Is preferred.

  Examples of the graft copolymer include, but are not limited to, methyl methacrylate / methacrylic acid copolymer grafted with styrene, methyl methacrylate / 2-hydroxyethyl methacrylate copolymer, poly-2-hydroxy methacrylate, poly 2 , 3-dihydroxypropyl methacrylate, polyacrylamide-2-methylpropanesulfonic acid, polyvinyl alcohol, polyvinyl acetate, polymethacrylic acid, polyacrylamide, polyethylene oxide, poly-4-vinyl-ethylpyridinium bromide, methyl methacrylate Methyl methacrylate / methacrylic acid copolymer, glycidyl methacrylate / styrene copolymer, methyl methacrylate / fluoroalkyl acrylate copolymer, methacrylic acid Graft copolymerized polybutadiene, methyl methacrylate / glycidyl methacrylate copolymer, polymethyl methacrylate grafted with N-methylolacrylamide, 2-hydroxyethyl methacrylate copolymer, poly grafted with 1,2-hydroxystearic acid Methyl methacrylate, ethyl acrylate / methacrylic acid copolymer, methyl acrylate / methacrylic acid copolymer, styrene / methacrylic acid copolymer, polymethyl methacrylate obtained by graft copolymerization with 2-hydroxyethyl methacrylate, poly (ethylene copolymerized with ethylene oxide) Examples thereof include styrene / glycidyl methacrylate obtained by graft copolymerization of vinyl chloride and methyl methacrylate.

  Examples of the block copolymer include, but are not limited to, for example, polylauryl methacrylate / polymethacrylic acid block copolymer, polystyrene / polymethacrylic acid block copolymer, polyethylene oxide / polystyrene / polyethylene oxide block copolymer, and poly Examples thereof include 12-hydroxystearic acid / polyethylene glycol / poly-12-hydroxystearic acid.

  Examples of the random copolymer include, but are not limited to, vinyl acetate / vinyl alcohol copolymer, vinyl acetate / N-vinyl pyrrolidone copolymer, N-vinyl pyrrolidone / methyl methacrylate, and the like.

  Examples of other polymers include, but are not limited to, cationized amine-modified polyesters and the like.

  Although it does not specifically limit as a weight average molecular weight of a dispersion stabilizer, Usually, it is 1000-2 million.

  Examples of commercially available dispersion stabilizers include, but are not limited to, for example, styrene / glycidyl methacrylate (Reeta GP300, manufactured by Toagosei Co., Ltd.) grafted with methyl methacrylate, and methyl methacrylate grafted with methyl methacrylate. /32.3% MIBK solution of methacrylic acid copolymer (Toa Gosei Co., Ltd., Reseda GP101S), styrene / acrylic graft copolymer system (Toa Gosei Co., Ltd., Reseda GP-310S), acrylic / PMMA graft copolymer system ( Toagosei Co., Ltd., Reseda GP-301, Reseda GP-102S) and the like.

II. Masterbatch type epoxy resin curing agent composition From the viewpoint of handleability, the masterbatch type epoxy resin curing agent composition in this embodiment is the epoxy resin (e3) and the microcapsule type epoxy resin curing agent in this embodiment. The mass ratio (epoxy resin: microcapsule type epoxy resin curing agent) is preferably 100: 0.1 to 100: 1000, more preferably 100: 1 to 100: 500, More preferably, it is 100: 10-100: 100.

  The curing agent composition for a masterbatch type epoxy resin in the present embodiment is preferably liquid at room temperature or a paste having a viscosity at 25 ° C. of 50 mPa · s to 10 million mPa · s. It is preferable to use a liquid or paste in the above viscosity range because workability is high, the amount of adhesion to an adherend such as a container can be reduced, and the amount of waste generated tends to be reduced.

  Below, the manufacturing method of an epoxy resin (e3) and a masterbatch type epoxy resin hardening | curing agent composition is demonstrated in detail.

(II-1) Epoxy resin (e3)
As the epoxy resin (e3), the polyvalent epoxy compounds mentioned as examples of the epoxy resin (e1) used as the raw material for the amine adduct contained in the core (C) can be used. These epoxy resins may be used alone or in combination. Among these, from the viewpoint of adhesiveness and heat resistance of the obtained cured product, an epoxy resin obtained by glycidylation of polyhydric phenols is preferable, a bisphenol type epoxy resin is more preferable, a glycidylated product of bisphenol A and a glycidylated product of bisphenol F. Is more preferable.

  As described above, from the viewpoint of sufficiently securing the electrical characteristics of the cured product, it is preferable to reduce the number of impure terminals to which chlorine in the molecule of the epoxy resin is bonded. Therefore, the total chlorine content of the epoxy resin (e3) contained in the masterbatch type epoxy resin curing agent composition in this embodiment is preferably 2500 ppm or less, more preferably 1500 ppm or less, and even more preferably 500 ppm or less. is there.

  Furthermore, it is preferable that not only the epoxy resin (e3) but the total chlorine content of the entire masterbatch type epoxy resin curing agent composition is 2500 ppm or less.

  Moreover, it is preferable that the diol terminal impure component of an epoxy resin (e3) is 0.001-30 mass% of the basic structural component of an epoxy resin (e3). Here, the diol-terminated impurity component is an epoxy group at one or both ends as described in “Review Epoxy Resin Vol. 1 Basic Edition I” (published by Epoxy Resin Technology Association, 2003). Refers to an epoxy resin having a structure in which 1,2-glycol is formed by ring opening.

  The basic structural component and the diol terminal impure component of the epoxy resin (e3) are the methods described in the literature cited in the above-mentioned “Review Epoxy Resin Vol. 1 Basic Edition I” (published by the Epoxy Resin Technology Association, 2003). Can be measured according to.

  When the ratio of the diol terminal impurity component of the epoxy resin (e3) to the basic structural component of the epoxy resin (e3) is 30% by mass or less, the water resistance of the cured product tends to be sufficiently secured, and 0.001% by mass In the above case, the curability of the epoxy resin composition tends to be sufficiently secured. From the above viewpoint, the ratio of the diol terminal impurity component of the epoxy resin (e3) to the basic structural component of the epoxy resin (e3) is preferably 0.001 to 30% by mass, more preferably 0.1 to 20% by mass. More preferably, it is 0.5-18 mass%, Most preferably, it is 1.2-15 mass%.

(II-2) Manufacturing method Although it does not specifically limit as a method of manufacturing the masterbatch type epoxy resin hardening | curing agent composition in this embodiment, For example, a three-roll etc. are used for the hardening agent for microcapsule type | mold epoxy resins. The method of dispersing in the epoxy resin (e3) and the generation reaction of the microcapsule type epoxy resin curing agent in the epoxy resin (e3) to obtain the microcapsule type epoxy resin curing agent, and at the same time, the master batch And a method of obtaining a mold epoxy resin curing agent composition. Among these, the latter method is preferable because productivity tends to be high.

III. One-part epoxy resin composition The masterbatch type epoxy resin curing agent composition in the present embodiment can be further diluted with an epoxy resin to form a one-part epoxy resin composition. What is preferable as such a one-component epoxy resin composition includes the epoxy resin (e4) and the curing agent composition for masterbatch type epoxy resin of the present embodiment, and the mass ratio thereof (epoxy resin (e4): master). Batch type epoxy resin curing agent composition) is in the range of 100: 0.001 to 100: 1000.

  Here, as the epoxy resin (e4), the polyvalent epoxy compounds mentioned as examples of the epoxy resin (e1) used as a raw material for the amine adduct contained in the core (C) can be used. Moreover, as a manufacturing method of a one-component epoxy resin composition, the method mentioned as an example of the manufacturing method of the above-mentioned masterbatch type epoxy resin hardening | curing agent composition can be utilized.

IV. Additives The masterbatch type epoxy resin curing agent composition and one-part epoxy resin composition of the present embodiment have a filler, reinforcing material, filler, pigment, organic solvent, etc., as long as the function is not reduced. Other additives can be contained. The content of other additives is preferably less than 30% by mass. The masterbatch type epoxy resin curing agent composition of this embodiment is at least one selected from the group consisting of acid anhydrides, phenols, hydrazides, and guanidines from the viewpoint of promoting the curing action. It is preferable that the epoxy resin curing agent (h3) or a cyclic borate compound is further included.

  Examples of other additives include, but are not limited to, an epoxy resin curing agent (h3). Examples of the epoxy resin curing agent (h3) include amine-based curing agents and other epoxy resin curing agents (h1) contained in the particles used as the starting material for forming the core (C). Any of those generally used as curing agents for epoxy resins can be used, but in particular, selected from the group consisting of acid anhydride curing agents, phenol curing agents, hydrazide curing agents, and guanidine curing agents. At least one epoxy resin curing agent is preferred.

  Examples of the acid anhydride curing agent include, but are not limited to, for example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, -3-chlorophthalic anhydride, anhydrous Examples include -4-chlorophthalic acid, benzophenone tetracarboxylic anhydride, succinic anhydride, methyl succinic anhydride, dimethyl succinic anhydride, dichlor succinic anhydride, methyl nadic acid, dodecyl succinic acid, maleic anhydride and the like.

  Examples of the phenolic curing agent include, but are not limited to, phenol novolak, cresol novolak, bisphenol A novolak, and the like.

  Examples of the hydrazide-based curing agent include, but are not limited to, succinic acid dihydrazide, adipic acid dihydrazide, phthalic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, p-oxybenzoic acid hydrazide, salicylic acid hydrazide, and phenylaminopropionic acid hydrazide. And maleic acid dihydrazide.

  Examples of the guanidine-based curing agent include, but are not limited to, dicyandiamide, methylguanidine, ethylguanidine, propylguanidine, butylguanidine, dimethylguanidine, trimethylguanidine, phenylguanidine, diphenylguanidine, toluylguanidine, and the like.

  Here, the epoxy resin curing agent (h3) is the same as the amine-based curing agent and other epoxy resin curing agents (h1) contained in the particles used as the starting material for forming the core (C). However, it is preferable that they are different.

  Moreover, a cyclic boric acid ester compound can be added to the masterbatch type epoxy resin curing agent composition and the one-component epoxy resin composition in order to improve the storage stability of the composition. The cyclic borate ester compound is a compound in which boron is contained in a cyclic structure, and 2,2′-oxybis (5,5′-dimethyl-1,3,2-oxaborinane) is particularly preferable. It is preferable that content of a cyclic borate ester compound is 0.001-10 mass% with respect to the masterbatch type epoxy resin property hardening | curing agent composition or a one-component epoxy resin composition.

  The masterbatch type epoxy resin curing agent composition and one-part epoxy resin composition of the present embodiment have storage stability, curability, moisture resistance, workability, fluidity, reliability, adhesion, water resistance, water resistance, and the like. It is excellent in solvent property and can be used in various applications in the form of paste or film. That is, the processed product of the present embodiment is obtained from the masterbatch type epoxy resin curing agent composition or the one-component epoxy resin composition of the present embodiment. In particular, in addition to adhesives, bonding pastes, and bonding films, paste-like compositions and films that can provide high connection reliability, sealing properties, and adhesive properties even under low temperature or short-time curing conditions. Composition, conductive material, anisotropic conductive material, anisotropic conductive film, insulating material, sealing material, coating material, coating composition, prepreg, thermal conductive material, fuel cell separator material, flexible It is useful as an overcoat material for wiring boards. That is, the processed product of this embodiment includes a paste-like composition, a film-like composition, an adhesive, a joining paste, a joining film, a conductive material, an anisotropic conductive material, an anisotropic conductive film, and an insulating material. It is preferably a sealing material, a coating material, a coating composition, a prepreg, a heat conductive material, a fuel cell separator material or a flexible wiring board overcoat material.

  The adhesive, bonding paste, and bonding film are not limited to the following, but are useful as, for example, a liquid adhesive, a film adhesive, a die bonding material, and the like. The production method of the film adhesive is not limited to the following, and examples thereof include methods described in JP-A-62-141083 and JP-A-5-295329. 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 mass. A varnish is prepared by adding and dispersing 30% by mass of the curing agent composition for a masterbatch type epoxy resin of the present embodiment to the solution. This varnish is applied to, for example, a peeling polyethylene terephthalate substrate having a thickness of 50 μm so that the thickness becomes 30 μm after toluene is dried. By drying toluene, it is possible to obtain a bonding film that is inactive at room temperature and exhibits adhesiveness by the action of the latent curing agent by heating.

  Examples of the conductive material include, but are not limited to, a conductive film and a conductive paste. Examples of the anisotropic conductive material include, but are not limited to, anisotropic conductive films and anisotropic conductive pastes. Although the manufacturing method is not limited to the following, for example, the method described in JP-A No. 1-113480 can be mentioned. More specifically, for example, in the production of the bonding film described above, by mixing and dispersing conductive materials and anisotropic conductive materials at the time of preparing the varnish, by applying to the substrate for peeling and drying Can be manufactured. Examples of the 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, styrene resin, urethane resin, melamine, and the like. Particles obtained by coating resin particles such as resin, 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. Although it does not limit to the following as a base material in the case of making a film, For example, the method of drying a solvent after apply | coating to base materials, such as polyester, polyethylene, a polyimide, a polytetrafluoroethylene, etc. are mentioned.

  Examples of the insulating material include, but are not limited to, 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 fillers described above.

  Although it does not limit to the following as a sealing material, For example, it is useful as a solid sealing material, a liquid sealing material, a film-form sealing material, etc. Although it does not limit to the following as a liquid sealing material, For example, it is useful as an underfill material, a potting material, a dam material, etc. The method for producing the sealing material is not limited to the following. For example, in Japanese Patent Application Laid-Open No. 5-43661, Japanese Patent Application Laid-Open No. 2002-226675, etc., a method for producing a molding material for sealing / impregnating electric / electronic parts The method described as is mentioned. More specifically, a bisphenol A type epoxy resin and a curing agent such as methylhexahydrophthalic anhydride, which is an acid anhydride curing agent, and spherical fused silica powder are added and mixed uniformly, and then the master of this embodiment. A sealing material can be obtained by adding the curing agent composition for batch type epoxy resins and mixing them uniformly.

  Examples of the coating material include, but are not limited to, a coating material for an electronic material, an overcoat material for a cover of a printed wiring board, and a resin composition for interlayer insulation of a printed board. The method for producing the coating material is not limited to the following, but is described in, for example, JP-B-4-6116, JP-A-7-304931, JP-A-8-64960, JP-A-2003-246838, and the like. Various methods are mentioned. More specifically, silica or the like is selected from the filler, and in addition to the bisphenol A type epoxy resin, a phenoxy resin, a rubber-modified epoxy resin, etc. are blended as the filler, and further, curing for the masterbatch type epoxy resin of this embodiment. The agent composition is formulated and a 50% solution is prepared with methyl ethyl ketone (MEK). This is coated on a polyimide film with a thickness of 50 μm, and a copper foil is stacked and laminated at 60 to 150 ° C., and the laminate is heated and cured at 180 to 200 ° C., so that the interlayer is coated with the epoxy resin composition. A laminated board can be obtained.

  Although it does not limit to the following as a manufacturing method of a coating composition, For example, the method described in Unexamined-Japanese-Patent No. 11-323247, Unexamined-Japanese-Patent No. 2005-113103, etc. are mentioned. More specifically, titanium dioxide, talc, and the like are blended into bisphenol A type epoxy resin, and a 1: 1 mixed solvent of methyl isobutyl ketone (MIBK) / xylene is added as a mixed solvent, stirred and mixed to form the main agent. . The coating composition (epoxy coating composition) can be obtained by adding the masterbatch type epoxy resin curing agent composition of this embodiment to this and dispersing it uniformly.

  The method for producing the prepreg is not limited to the following, but, for example, the masterbatch type epoxy resin of the present embodiment as described in JP-A-9-71633, WO98 / 44017, etc. It can be obtained by impregnating a reinforcing base material into a reinforcing base material and heating. Examples of the varnish solvent to be impregnated include methyl ethyl ketone, acetone, ethyl cellosolve, methanol, ethanol, isopropyl alcohol and the like, and it is preferable that these solvents do not remain in the prepreg. In addition, although it does not specifically limit as a kind of reinforcement base material, For example, paper, a glass cloth, a glass nonwoven fabric, an aramid cloth, a liquid crystal polymer etc. are mentioned. The ratio of the curing agent composition for the masterbatch type epoxy resin and the reinforcing base material is not particularly limited, but it is usually preferable that the resin content in the prepreg is adjusted to 20 to 80% by mass.

  The manufacturing method of the heat conductive material is not limited to the following, but is described in, for example, the methods described in JP-A-6-136244, JP-A-10-237410, and JP-A-2000-3987. Method. 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. A heat conductive resin paste can be obtained by blending the masterbatch type epoxy resin curing agent composition of the present embodiment into this.

  Hereinafter, the present embodiment will be specifically described by way of examples. However, the present embodiment is not limited to these examples.

(Penetration of one-part epoxy resin composition)
Disperse by uniformly dispersing 40 parts by mass of HN-2200 (manufactured by Hitachi Chemical Co., Ltd.) mainly composed of methyl phthalic anhydride as a curing agent in 50 parts by mass of bisphenol A type epoxy resin (AER2603, manufactured by Asahi Kasei Chemicals) did. A syringe was filled with a one-part epoxy resin composition obtained by adding 5 parts by mass of a curing agent composition for a masterbatch type epoxy resin. Two 50 mm square glass plates were aligned at the top and shifted by 10 mm, and a 10 micron spacer was sandwiched between the top and fixed horizontally. The one-component epoxy resin composition was dropped into the gap between the glass plates, and the state of penetration of the epoxy resin composition at room temperature was observed. The case where the epoxy resin composition is dropped at a temperature of 40 ° C. and the time required to penetrate a distance of 40 mm from the end face is less than 15 minutes is “◎”, the case where it is 15 minutes or more and less than 30 minutes is “◯”, 30 A case where it was at least 45 minutes but less than 45 minutes was judged as “Δ”, and a case where it was 45 minutes or longer was judged as “x”.

(Curability of one-part epoxy resin composition)
The gel plate is kept at 130 ° C., and 0.4 mL of the one-component epoxy resin composition sample is placed on the plate, and after the placement, the sample is stirred with a stir bar and the time until the yarn is not pulled, that is, until gelation is reached. The time (seconds) was measured. “◎” when the gelation time is 90 seconds or less, “◯” when 90 to 120 seconds, “Δ” when 120 to 180 seconds, and “×” when 180 seconds or more. Judged.

(Storage stability)
As a storage stability evaluation method, evaluation was performed based on a viscosity increase ratio when the prepared masterbatch type epoxy resin curing agent was stored in a constant temperature bath at 40 ° C. for one week. “◎” when the storage magnification is 1.2 times or less, “◯” when the storage magnification is 1.2 times or more and less than 1.5 times, “△” when the storage magnification is 1.5 times or more and 1.8 times or less, The case of 1.8 times or more was determined as “x”.

(Moisture content)
The measurement was performed using a Karl Fischer moisture meter CA-100 manufactured by Dia Instruments.

(Specific surface area measurement)
The specific surface area is measured by using a fully automatic BET specific surface area measuring device HM model-1201 manufactured by Mountec Co., Ltd. and using a mixed gas of N ₂ / He = 30/70 (volume ratio) as an adsorbed gas. did.

(Particle size measurement)
As a method for measuring the particle size, 4 mg of the particle powder was put into 32 g of a cyclohexane solution of 0.1% by mass surfactant (manufactured by Mitsui Cytec Co., Ltd., Aerosol OT-75), and an ultrasonic cleaner (manufactured by Honda Electronics Co., Ltd., MODEL). W-211) was dispersed by ultrasonic irradiation for 5 minutes. The water temperature in the ultrasonic cleaner at this time was adjusted to 19 ± 2 ° C. A part of the resulting dispersion was taken, particle size distribution measurement was performed with HORIBA LA-920 (manufactured by Horiba, Ltd., particle size distribution analyzer HORIBA LA-920), and the average particle size was determined based on this.

(Agglomerated powder particle ratio)
The epoxy resin curing agent is observed with a scanning electron microscope (SEM), and the total number of particles aggregated or fused is 5 or more in the image of the number of powder particles of 300 or more. When it is divided by the number of items, it is “◎” if it is less than 5%, “◯” if it is 5% or more and less than 10%, “△” if it is 10% or more, and “△” if it is 15% or more. It was determined as “x”.

(Dispersibility)
In order to see the dispersibility of the curing agent in the epoxy resin, 1 g of the epoxy batch curing agent for epoxy resin was dispersed in 9 g of bisphenol A type epoxy resin (AER2603, manufactured by Asahi Kasei Chemicals) and mixed with a non-bubbling kneader. Thereafter, microscope image observation was performed at a magnification of 1000 times, and when the number of aggregated particles of 5 or more in an image of the number of powder particles of 100 or more was divided by the total number, less than 5% Then, “” was determined as “◯” when 5% or more and less than 10%, “Δ” when 10% or more and 15% or more, and “X” when 15% or more.

Example 1
1 equivalent of bisphenol A epoxy resin and 1 equivalent of 2-methylimidazole (in terms of active hydrogen) were reacted at 80 ° C. in a 1: 1 mixed solvent of n-butanol and toluene. Thereafter, excess amine was distilled off together with the solvent under reduced pressure to obtain a solid block epoxy resin curing agent 1 at 25 ° C. Subsequently, the block-shaped epoxy resin curing agent 1 was jet mill pulverized to obtain particles (ground product) having a solid under-sieving average particle diameter D ₅₀ of 2.4 μm at 25 ° C. Using Meteorenbo-MR-10 manufactured by Nippon Pneumatic Co., Ltd., heat treatment was performed under the conditions of a curing agent particle feed rate of 3.7 kg / hr and a treatment temperature of 275 ° C., and a cyclone collector and bag filter were attached. Cooling air after hot air treatment at 275 ° C was performed by passing circulating cooling water at 0 ° C through the powder recovery unit wall so that the internal temperature of the container was 40 ° C or lower and controlling the temperature to 25 ° C and humidity of 10%. Introducing a curing agent for epoxy resin having a specific surface area value of 1.3 m ² / g, a moisture content of 0.4%, a D _{50 of} 3.1 μm and a particle size distribution of D ₉₉ / D ₅₀ of 4.7 It was prepared by classification operation using a machine. After adjusting the specific surface area value, a masterbatch type epoxy resin curing agent was prepared. As the preparation method, 100 parts by mass of the particles and 3 parts by mass of the encapsulating agent are added to 200 parts by mass of the liquid epoxy resin, and the reaction is continued for 3 hours while stirring at 50 ° C. Got.

(Example 2)
Using the pulverized product of Example 1, using Meteolevo-MR-10 manufactured by Nippon Pneumatic Co., Ltd., heat treatment was performed under the conditions of a feed rate of the curing agent particles of 3.7 kg / hr and a treatment temperature of 275 ° C. A type collector and a bag filter were attached, and circulating cooling water of 0 ° C was passed through the wall of the powder recovery part to cool the container so that the internal temperature of the container was 40 ° C or lower, and the temperature was controlled to 20 ° C and humidity 30%. By introducing air as cooling air after treatment with hot air at 275 ° C., a specific surface area value of 1.3 m ² / g, moisture of 0.8%, D _{50 of} 3.1 μm and D ₉₉ / D ₅₀ of 4.9 can be obtained. A curing agent for epoxy resin having a distribution was prepared by classification using a classifier. A masterbatch type epoxy resin curing agent was obtained in the same manner as in Example 1.

(Example 3)
Using the pulverized product of Example 1, using Meteolevo-MR-10 manufactured by Nippon Pneumatic Co., Ltd., heat treatment was performed under the conditions of a feed rate of the curing agent particles of 3.7 kg / hr and a treatment temperature of 275 ° C. A type collector and a bag filter are attached, and circulating cooling water at 0 ° C. is passed through the wall of the powder recovery unit to cool the inside temperature of the vessel to 40 ° C. or lower, and the temperature is controlled to 30 ° C. and humidity 35%. By introducing air as cooling air after treatment with hot air at 275 ° C., the specific surface area is 1.3 m ² / g, moisture is 1.5%, D _{50 is} 3.1 μm and D ₉₉ / D ₅₀ is 4.5. A curing agent for epoxy resin having a distribution was prepared by classification using a classifier. A masterbatch type epoxy resin curing agent was obtained in the same manner as in Example 1.

Example 4
Using the kryptron orb manufactured by Earth Technica Co., Ltd. using the pulverized product of Example 1, under an environment of a temperature of 10 ° C. and a humidity of 30%, a rotation speed of 13500 rpm, a supply speed of 10 kg / hr, and an air volume of 3 m ³ / min. , Correct the shape, attach a cyclone-type collector and bag filter, adjust the specific surface area value, and by classification operation, the specific surface area value is 2.67 m ² / g, moisture 0.4%, D ₅₀ 3.1 μm In addition, an epoxy resin curing agent having a particle size distribution with D ₉₉ / D ₅₀ of 4.5 was prepared by classification using a classifier. A masterbatch type epoxy resin curing agent was obtained in the same manner as in Example 1.

(Example 5)
The block-shaped epoxy resin curing agent 1 was attached to a bag filter and jet mill pulverized to obtain particles (ground product) having an average particle diameter D ₅₀ under sieve of 0.8 μm that were solid at 25 ° C. from the bag filter. Using Meteorenbo-MR-10 manufactured by Nippon Pneumatic Co., Ltd., heat treatment was performed under the conditions of a curing agent particle feed rate of 3.7 kg / hr and a treatment temperature of 275 ° C., and a cyclone collector and bag filter were attached. Cooling air after hot air treatment at 275 ° C was performed by passing circulating cooling water at 0 ° C through the powder recovery unit wall so that the internal temperature of the container was 40 ° C or lower and controlling the temperature to 25 ° C and humidity of 10%. A curing agent for epoxy resin having a specific surface area value of 5.0 m ² / g, moisture content of 0.4%, D ₅₀ of 0.8 μm and D ₉₉ / D ₅₀ of 4.7 particle size distribution. It was prepared by a classification operation using a classifier. A masterbatch type epoxy resin curing agent was obtained in the same manner as in Example 1.

(Example 6)
Using a kryptron orb manufactured by Earth Technica Co., Ltd. using the pulverized product of Example 5, under an environment of a temperature of 10 ° C. and a humidity of 30%, a rotation speed of 13500 rpm, a supply speed of 10 kg / hr, and an air volume of 3 m ³ / min, 3Pass shape correction treatment was performed, and a specific surface area value was adjusted by attaching a cyclone collector and a bag filter, and a specific surface area value 10.30 m ² / g, moisture 0.4%, D ₅₀ 0.8 μm by classification operation. In addition, an epoxy resin curing agent having a particle size distribution with D ₉₉ / D ₅₀ of 4.5 was prepared by classification using a classifier. A masterbatch type epoxy resin curing agent was obtained in the same manner as in Example 1.

(Example 7)
The block-shaped epoxy resin curing agent 1 was attached to a bag filter and jet mill pulverized to obtain particles (ground product) having an average under-sieving particle diameter D ₅₀ of 1.1 μm at 25 ° C. from the bag filter. Using Meteorenbo-MR-10 manufactured by Nippon Pneumatic Co., Ltd., heat treatment was performed under the conditions of a curing agent particle feed rate of 3.7 kg / hr and a treatment temperature of 275 ° C., and a cyclone collector and bag filter were attached. Cooling air after hot air treatment at 275 ° C was performed by passing circulating cooling water at 0 ° C through the powder recovery unit wall so that the internal temperature of the container was 40 ° C or lower and controlling the temperature to 25 ° C and humidity of 10%. Introducing a curing agent for epoxy resin having a specific surface area value of 2.90 m ² / g, a moisture content of 0.4%, a D _{50 of} 1.4 μm and a particle size distribution of D ₉₉ / D ₅₀ of 3.2 It was prepared by classification operation using a machine. A masterbatch type epoxy resin curing agent was obtained in the same manner as in Example 1.

(Example 8)
Using a kryptron orb manufactured by Earth Technica Co., Ltd. using the pulverized product of Example 7, under an environment of a temperature of 10 ° C. and a humidity of 30%, a rotation speed of 13500 rpm, a supply speed of 10 kg / hr, an air volume of 3 m ³ / min, Perform shape correction treatment, adjust the specific surface area value by attaching a cyclone collector and bag filter, and by classification operation, specific surface area value 5.9 m ² / g, moisture 0.4%, D ₅₀ 1.4 μm and An epoxy resin curing agent having a particle size distribution with D ₉₉ / D ₅₀ of 3.2 was prepared by a classification operation using a classifier. A masterbatch type epoxy resin curing agent was obtained in the same manner as in Example 1.

Example 9
The block-shaped epoxy resin curing agent 1 was pulverized by jet mill, and particles (ground product) having a solid under-sieving average particle diameter D ₅₀ of 1.6 μm at 25 ° C. were obtained by classification using a classifier. Using Meteorenbo-MR-10 manufactured by Nippon Pneumatic Co., Ltd., heat treatment was performed under the conditions of a curing agent particle feed rate of 3.7 kg / hr and a treatment temperature of 275 ° C., and a cyclone collector and bag filter were attached. Cooling air after hot air treatment at 275 ° C was performed by passing circulating cooling water at 0 ° C through the powder recovery unit wall so that the internal temperature of the container was 40 ° C or lower and controlling the temperature to 25 ° C and humidity of 10%. Introducing a curing agent for epoxy resin having a specific surface area value of 1.90 m ² / g, a moisture content of 0.4%, a D _{50 of} 2.1 μm and a particle size distribution of D ₉₉ / D ₅₀ of 4.0 It was prepared by classification operation using a machine. A masterbatch type epoxy resin curing agent was obtained in the same manner as in Example 1.

(Example 10)
Using a kryptron orb manufactured by Earth Technica Co., Ltd. using the pulverized product of Example 9, under an environment of a temperature of 10 ° C. and a humidity of 30%, a rotation speed of 13500 rpm, a supply speed of 10 kg / hr, and an air volume of 3 m ³ / min, Perform shape correction treatment, adjust the specific surface area value by attaching a cyclone type collector and bag filter, and by the classification operation, the specific surface area value 3.90m ² / g, moisture 0.4%, D ₅₀ 2.1μm and A curing agent for epoxy resin having a particle size distribution with D ₉₉ / D ₅₀ of 4.0 was prepared by classification using a classifier. A masterbatch type epoxy resin curing agent was obtained in the same manner as in Example 1.

(Example 11)
The block-shaped epoxy resin curing agent 1 was pulverized by jet milling, and particles (pulverized product) having a solid under-sieving average particle diameter D ₅₀ of 4.5 μm at 25 ° C. were obtained by classification using a classifier. Using Meteorenbo-MR-10 manufactured by Nippon Pneumatic Co., Ltd., heat treatment was performed under the conditions of a curing agent particle feed rate of 3.7 kg / hr and a treatment temperature of 275 ° C., and a cyclone collector and bag filter were attached. Cooling air after hot air treatment at 275 ° C was performed by passing circulating cooling water at 0 ° C through the powder recovery unit wall so that the internal temperature of the container was 40 ° C or lower and controlling the temperature to 25 ° C and humidity of 10%. Introducing a curing agent for epoxy resin having a specific surface area value of 0.9 m ² / g, a moisture content of 0.4%, a D _{50 of} 4.5 μm, and a particle size distribution of D ₉₉ / D ₅₀ of 3.9 It was prepared by classification operation using a machine.
After adjusting the specific surface area value, a one-component epoxy resin curing agent was prepared. As a method, 100 parts by mass of the particles were mixed with 200 parts by mass of a liquid epoxy resin and stirred for 3 hours.

(Example 12)
Using a kryptron orb manufactured by Earth Technica Co., Ltd. using the pulverized product of Example 11, under an environment of a temperature of 10 ° C. and a humidity of 30%, a rotation speed of 13500 rpm, a supply speed of 10 kg / hr, and an air volume of 3 m ³ / min, Perform shape correction treatment, adjust the specific surface area value by attaching a cyclone collector and bag filter, and by classification operation, the specific surface area value 1.84 m ² / g, moisture 0.4%, D ₅₀ 4.5 μm and An epoxy resin curing agent having a particle size distribution with D ₉₉ / D ₅₀ of 3.9 was prepared by a classification operation using a classifier. A masterbatch type epoxy resin curing agent was obtained in the same manner as in Example 1.

(Example 13)
The block-shaped epoxy resin curing agent 1 was pulverized by jet milling, and particles (pulverized product) having a solid under-sieving average particle diameter D ₅₀ of 5.5 μm at 25 ° C. were obtained by classification using a classifier. Using Meteorenbo-MR-10 manufactured by Nippon Pneumatic Co., Ltd., heat treatment was performed under the conditions of a curing agent particle feed rate of 3.7 kg / hr and a treatment temperature of 275 ° C., and a cyclone collector and bag filter were attached. Cooling air after hot air treatment at 275 ° C was performed by passing circulating cooling water at 0 ° C through the powder recovery unit wall so that the internal temperature of the container was 40 ° C or lower and controlling the temperature to 25 ° C and humidity of 10%. Introducing a curing agent for epoxy resin having a specific surface area value of 0.75 m ² / g, moisture content of 0.4%, D ₅₀ 5.5 μm and a particle size distribution of D ₉₉ / D ₅₀ of 4.5 It was prepared by classification operation using a machine. A masterbatch type epoxy resin curing agent was obtained in the same manner as in Example 1.

(Example 14)
Using a kryptron orb manufactured by Earth Technica Co., Ltd. using the pulverized product of Example 13, under an environment of a temperature of 10 ° C. and a humidity of 30%, a rotational speed of 13500 rpm, a supply speed of 10 kg / hr, and an air volume of 3 m ³ / min, Perform shape correction treatment, adjust the specific surface area value by attaching a cyclone collector and bag filter, and by the classification operation, the specific surface area value 1.50 m ² / g, moisture 0.4%, D ₅₀ 5.5 μm and A curing agent for epoxy resin having a particle size distribution with D ₉₉ / D ₅₀ of 4.5 was prepared by classification using a classifier. A masterbatch type epoxy resin curing agent was obtained in the same manner as in Example 1.

(Example 15)
Block-shaped epoxy resin curing agent 1 was pulverized by jet mill, and particles (ground product) having a solid under-sieving average particle diameter D ₅₀ of 11.0 μm at 25 ° C. were obtained by classification using a classifier. Using Meteorenbo-MR-10 manufactured by Nippon Pneumatic Co., Ltd., heat treatment was performed under the conditions of a curing agent particle feed rate of 3.7 kg / hr and a treatment temperature of 275 ° C., and a cyclone collector and bag filter were attached. Cooling air after hot air treatment at 275 ° C was performed by passing circulating cooling water at 0 ° C through the powder recovery unit wall so that the internal temperature of the container was 40 ° C or lower and controlling the temperature to 25 ° C and humidity of 10%. By introducing a curing agent for epoxy resin having a specific surface area value of 0.40 m ² / g, a moisture content of 0.4%, a D _{50 of} 11 μm and a particle size distribution of D ₉₉ / D ₅₀ of 4.4 by a classifier. It was prepared by classification operation. A masterbatch type epoxy resin curing agent was obtained in the same manner as in Example 1.

(Example 16)
Using a kryptron orb manufactured by Earth Technica Co., Ltd. using the pulverized product of Example 15, under an environment of a temperature of 10 ° C. and a humidity of 30%, a rotation speed of 13500 rpm, a supply speed of 10 kg / hr, and an air volume of 3 m ³ / min, 3Pass shape correction treatment is performed, and a specific surface area value is adjusted by attaching a cyclone collector and a bag filter, and a specific surface area value is 0.75 m ² / g, moisture is 0.4%, D _{50 is} 11 μm and D is classified. _A curing agent for epoxy resin having a particle size distribution with ₉₉ / D ₅₀ of 4.4 was prepared by classification using a classifier. After adjusting the specific surface area value, a one-component epoxy resin curing agent was prepared. As a method, 100 parts by mass of the particles were mixed with 200 parts by mass of a liquid epoxy resin and stirred for 3 hours. A masterbatch type epoxy resin curing agent was obtained in the same manner as in Example 1.

(Comparative Example 1)
The block-shaped epoxy resin curing agent 1 was attached to a bag filter and pulverized by a jet mill to obtain particles having an average under-sieving particle diameter D ₅₀ of 0.8 μm at 25 ° C. from the bag filter. The raw material particles had a water content of 0.8%, a specific surface area value of 13.0 m ² / g, and a D ₉₉ / D ₅₀ value of 10.3. The specific surface area was not adjusted. A masterbatch type epoxy resin curing agent was obtained in the same manner as in Example 1.

(Comparative Example 2)
Block-shaped epoxy resin curing agent 1 was jet mill pulverized to obtain particles having an average under-sieving particle diameter D ₅₀ of 1.4 μm at 25 ° C. The raw material particles had a water content of 0.8%, a specific surface area value of 7.4 m ² / g, and a D ₉₉ / D ₅₀ value of 10.1. The specific surface area was not adjusted. A masterbatch type epoxy resin curing agent was obtained in the same manner as in Example 1.

(Comparative Example 3)
The block epoxy resin curing agent 1 was jet mill pulverized to obtain particles having an average under-sieving particle diameter D ₅₀ of 2.4 μm at 25 ° C. The raw material particles had a water content of 0.8%, a specific surface area value of 4.30 m ² / g, and a D ₉₉ / D ₅₀ value of 8.5. The specific surface area was not adjusted. A masterbatch type epoxy resin curing agent was obtained in the same manner as in Example 1.

(Comparative Example 4)
100 parts of particles obtained by the same method as in Comparative Example 3 were added to 200 parts by mass of a liquid epoxy resin and stirred at 50 ° C. to obtain a one-part curing agent for epoxy resin.

(Comparative Example 5)
Block-shaped epoxy resin curing agent 1 was jet mill pulverized to obtain particles having an average under-sieving particle diameter D ₅₀ of 3.1 μm at 25 ° C. The raw material particles had a water content of 0.8%, a specific surface area value of 3.1 m ² / g, and a D ₉₉ / D ₅₀ value of 8.6. The specific surface area was not adjusted. A masterbatch type epoxy resin curing agent was obtained in the same manner as in Example 1.

(Comparative Example 6)
The block epoxy resin curing agent 1 was jet mill pulverized to obtain particles having an average under-sieving average particle diameter D ₅₀ of 4.5 μm at 25 ° C. The raw material particles had a water content of 0.8%, a specific surface area value of 2.3 m ² / g, and a D ₉₉ / D ₅₀ value of 8.1. The specific surface area was not adjusted. A masterbatch type epoxy resin curing agent was obtained in the same manner as in Example 1.

(Comparative Example 7)
Block type epoxy resin curing agent 1 was pulverized by jet mill to obtain particles having an average particle diameter D ₅₀ under sieve of 5.5 μm which was solid at 25 ° C. The raw material particles had a water content of 0.8%, a specific surface area value of 1.90 m ² / g, and a D ₉₉ / D ₅₀ value of 8.1. The specific surface area was not adjusted. A masterbatch type epoxy resin curing agent was obtained in the same manner as in Example 1.

(Comparative Example 8)
The block epoxy resin curing agent 1 was jet mill pulverized to obtain particles having an average under-sieving particle diameter D ₅₀ of 11 μm at 25 ° C. The raw material particles had a water content of 0.8%, a specific surface area value of 0.90 m ² / g, and a D ₉₉ / D ₅₀ value of 7.9. The specific surface area was not adjusted. A masterbatch type epoxy resin curing agent was obtained in the same manner as in Example 1.

(Comparative Example 9)
Using the pulverized product of Example 1 using Meteole Invo-MR-10 manufactured by Nippon Pneumatic Co., Ltd., heat treatment was carried out under conditions of a curing agent particle feed rate of 4.0 kg / hr and a treatment temperature of 275 ° C. A specific surface area of 1.6 m ² / g and moisture of 1.0% by introducing cooling air after hot air treatment at 275 ° C with air controlled at 30 ° C and humidity of 40% with a collector and bag filter attached A curing agent for epoxy resin having a particle size distribution of D ₅₀ 3.1 μm and D ₉₉ / D ₅₀ of 8.5 was produced. A masterbatch type epoxy resin curing agent was obtained in the same manner as in Example 1.

(Comparative Example 10)
Using the pulverized product of Example 1, the particle size distribution with a specific surface area value of 3.0 m ² / g, moisture of 1.5%, D _{50 of} 3.3 μm, and D ₉₉ / D ₅₀ of 4.5 by classification operation. A curing agent for epoxy resin having a masterbatch type was prepared by the classification operation using a classifier and was obtained in the same manner as in Example 1.

(Comparative Example 11)
Using the pulverized product of Example 1 using Meteoleumbo-MR-10 manufactured by Nippon Pneumatic Co., Ltd., heat treatment was performed under the conditions of a feed rate of the curing agent particles of 3.7 kg / hr and a processing temperature of 275 ° C. A collector and a bag filter are attached, air circulating at 0 ° C circulating cooling water is passed through the powder recovery unit wall surface to cool the inside temperature of the vessel to 40 ° C or lower, and the temperature is controlled to 35 ° C and humidity 80%. Is introduced as cooling air after treatment with hot air at 275 ° C., so that the specific surface area value is 1.3 m ² / g, moisture is 2.0%, D _{50 is} 3.2 μm, and D ₉₉ / D ₅₀ is 4.4. A curing agent for epoxy resin having a viscosity was prepared by classification using a classifier. A masterbatch type epoxy resin curing agent was obtained in the same manner as in Example 1.

  The specific surface area values were evaluated using epoxy resin curing agents before and after adjustment, and the results are shown in Tables 1 to 4.

  From the above results, the curing performance, stability and permeability are stable with respect to the curing agent in which the amount of water contained in the curing agent for epoxy resin is 1.5% or less and the particle size distribution and specific surface area value are adjusted. The effect was able to be confirmed also about different things. However, as shown in Examples 11 to 14, the permeability and curing performance tend to be impaired as the particle size increases.

  Comparative Examples 1 to 3 and 5 to 8 are the results of setting the curing agent for epoxy resin having a different particle size as the curing agent for masterbatch type epoxy resin without adjusting the specific surface area and adjusting the particle size distribution. is there. The curing agent whose specific surface area was not adjusted is poor in storage stability, dispersibility, and permeability. Moreover, although the comparative example 4 is a result regarding the case where it does not microencapsulate, it resulted in impairing storage stability. As in Examples 13 to 16, while the curing performance is impaired as the particle size is increased, the storage stability is improved.

  The curing agent in which the particle size distribution is not adjusted even when the specific surface area is adjusted as in Comparative Example 9, the storage stability is good for the curing performance, but the particle size is not adjusted, so the amount of aggregated particles is large, For this reason, the permeability is not good. As for the curing agent in which only the particle size distribution was adjusted without adjusting the specific surface area as in Comparative Example 10, the physical properties were hardly improved. As shown in Comparative Example 11, when the moisture content of the curing agent is 1.5% or more, the particles are aggregated, leading to a decrease in physical properties and a decrease in curability and storage stability.

  As described above, the masterbatch type epoxy resin curing agent composition containing the microcapsule type epoxy resin curing agent of the present embodiment has excellent curability and storage stability, and the one-part epoxy resin composition is It was confirmed that it has excellent curability and permeability.

  The curing agent for epoxy resin, the curing agent for microcapsule type epoxy resin, the curing agent composition for masterbatch type epoxy resin, and the one-part epoxy resin composition of the present invention include a conductive film, a conductive paste, and anisotropic conductivity. Film, anisotropic conductive paste, insulating paste, insulating film, sealant, underfill material, coating material, coating composition, prepreg, thermal conductive paste, adhesive material, conductive material, insulating material, sealing material It can be suitably applied to processed products such as coating materials, coating compositions, prepregs, structural adhesives, and heat conductive materials, and has industrial applicability.

Claims (15)

A curing agent for epoxy resin that is solid at 25 ° C. and contains particles,
The particle size D ₅₀ of the cumulative fraction under sieving 50% of the particles is more than 0.3 μm and 12 μm or less,
The particle size distribution defined by the ratio (D ₉₉ / D ₅₀ ) of the particle size D _{99 of} 99% cumulative sieve fraction and the particle size D _{50 of} 50% cumulative sieve fraction is 4.9 or less. Yes,
The specific surface area value (Y) and particle size D ₅₀ (X) of the particles satisfy the relationship represented by the following formula (1),
The epoxy resin curing agent, wherein the epoxy resin curing agent has a water content of 1.5% or less.
^{4.0X -1 ≦ Y ≦ 8.3X -1 (} 1) A core (C) formed using the epoxy resin curing agent (H) according to claim 1 as a starting material;
A shell (S) covering the core (C);
Have
It said shell (S) is a bonding group that absorbs infrared wave number 1630~1680cm ^-1 (x), binding group that absorbs infrared wave number 1680～1725Cm ^-1 and (y), of the wavenumber 1730～1755Cm ^-1 A microcapsule-type epoxy resin curing agent having a bonding group (z) that absorbs infrared rays at least on its surface.   The hardener for a microcapsule type epoxy resin according to claim 2, wherein the shell (S) has a urea bond in its structure and does not have an ester bond. A core (C) formed using the epoxy resin curing agent (H) according to claim 1 as a starting material;
A shell (S) covering the core (C);
Have
The shell (S) has a urea bond in its structure and no ester bond,
The ratio of the thickness of the shell (S) to D ₅₀ of the epoxy resin curing agent (H) is 100: 1.5 to 100: 18, and the microcapsule type epoxy resin curing agent.   The shell (S) is made from two or more selected from the group consisting of an isocyanate compound, an active hydrogen compound, a curing agent for epoxy resin (h2), an epoxy resin (e2), and a low molecular amine compound (B). The microcapsule type epoxy resin curing agent according to any one of claims 2 to 4, comprising the reaction product obtained.   The total amount of chlorine contained in the epoxy resin curing agent (H) and the epoxy resin (e1) or the epoxy resin (e2) is 2500 ppm or less, according to any one of claims 2 to 5. Hardener for microcapsule type epoxy resin.   The microcapsule-type epoxy resin curing agent according to any one of claims 2 to 6 and the epoxy resin (e3), (epoxy resin curing agent): (epoxy resin (e3)) (mass ratio). As a masterbatch type epoxy resin curing agent composition, which is contained at a blending ratio of 100: 0.1 to 100: 1000.   The hardening | curing agent composition for masterbatch type epoxy resins of Claim 7 whose total chlorine amount which the said epoxy resin (e3) contains is 2500 ppm or less.   The master batch type epoxy resin according to claim 7 or 8, wherein a proportion of the diol terminal component in the epoxy resin (e3) is 0.001 to 30% by mass of the basic structural component of the epoxy resin (e3). Hardener composition.   The hardener (h3) for epoxy resins selected from the group consisting of acid anhydrides, phenols, hydrazides, and guanidines (h3) or a cyclic borate ester compound is further included. The hardener composition for master-batch type epoxy resins according to any one of the above.   The curing agent composition for a masterbatch type epoxy resin according to claim 10, wherein the cyclic borate ester compound is 2,2'-oxybis (5,5'-dimethyl-1,3,2-dioxaborinane).   The hardening | curing agent composition for masterbatch type epoxy resins of Claim 10 or 11 whose content rate of the said cyclic borate ester compound is 0.001-10 mass%.   The masterbatch type epoxy resin curing agent composition according to any one of claims 7 to 12 and the epoxy resin (e4): (masterbatch type epoxy resin curing agent composition): (epoxy resin ( e4)) A one-component epoxy resin composition containing a mass ratio of 100: 0.001 to 100: 1000.   A processed product obtained from the masterbatch type epoxy resin curing agent composition according to any one of claims 7 to 12, or the one-component epoxy resin composition according to claim 13.   Paste composition, film composition, adhesive, bonding paste, bonding film, conductive material, anisotropic conductive material, anisotropic conductive film, insulating material, sealing material, coating material, paint The processed product according to claim 14, which is a composition, a prepreg, a thermally conductive material, a fuel cell separator material, or a flexible wiring board overcoat material.