JP6426340B2 - Curing agent for epoxy resin, and epoxy resin composition - Google Patents

Description

  The present invention relates to a curing agent for epoxy resin, and an epoxy resin composition.

  Epoxy resins are used in a wide range of applications such as insulating materials, sealing materials, adhesives, and conductive materials of electric and electronic parts. In particular, as electronic devices become more sophisticated, smaller and thinner, smaller integration of semiconductor chips, higher density of circuits, significant improvement of productivity, and portability and reliability in mobile applications of electronic devices Improvement is required.

  As a method of solving them with a curing agent for epoxy resin, there is a method of improving the flowability of the epoxy resin composition to the gap and the adhesion of the cured product together with a method of curing the epoxy resin at lower temperature and shorter time. It will be necessary.

  As a method of curing the epoxy resin composition at a low temperature and in a short time, a so-called two-component epoxy resin composition (hereinafter referred to as "two-component epoxy") in which two components of an epoxy resin and a curing agent are mixed and cured at the time of use. In the resin composition, it may be described that the liquid amine-based curing agent is used. However, although the two-component epoxy resin composition can be cured well at low temperatures when a liquid amine-based curing agent is used, it is necessary to separately store the epoxy resin and the curing agent, or both in use. After weighing, it is necessary to mix them quickly and uniformly. Once the epoxy resin and the curing agent are mixed, the usable time after that is limited, so it is not possible to mix them in large amounts beforehand. In addition, among the liquid amine-based curing agents, when an aliphatic amine having excellent low-temperature curability is used, the two-part epoxy resin composition is cured at a low temperature and then cured at a high temperature without curing. The elastic modulus and adhesive strength at high temperature of the object may be inferior. Moreover, when the aromatic amine which is excellent in heat resistance is used, a two-component epoxy resin composition is slow in curing at low temperature due to weak basicity and steric hindrance of the aromatic ring.

  That is, the conventional two-component epoxy resin composition satisfies the requirements at practical level in all points such as ease of storage, handleability, blending frequency (production efficiency), low-temperature rapid curability, and physical properties of the cured product. It is difficult and there is still room for improvement.

In order to satisfy these requirements, some one-component epoxy resin compositions (hereinafter sometimes referred to as "one-component epoxy resin compositions") have been proposed. As such a one-part epoxy resin composition, for example, a one-part epoxy resin composition in which a latent curing agent such as dicyandiamide, BF ₃ -amine complex, amine salt, modified imidazole compound, etc. is compounded into an epoxy resin is It can be mentioned. However, in these one-component epoxy resin compositions, those having excellent storage stability tend to be inferior in curability (high temperature or long time is required for curing) and those having excellent curability are It tends to have poor storage stability (for example, storage at low temperatures such as -20 ° C is required).

  Under such circumstances, a so-called microcapsule type curing agent in which a core containing an amine curing agent is coated with a specific shell has been proposed (see, for example, Patent Document 1). Furthermore, in order to further enhance the low temperature curing property, a microcapsule type curing agent has been proposed, which is a curing agent for epoxy resin in which the core portion of the microcapsule type curing agent has an amine adduct and a low molecular weight compound as main components. (For example, refer to patent documents 2 and 3).

  In addition, as a method of improving the flowability of the epoxy resin composition into the gaps and the adhesion of the cured product, for example, a method of blending a low viscosity reactive diluent (see, for example, Patent Document 4), or filling A method of increasing fluidity by using a spherical filler having a particle diameter of 5 μm or less as the filler, a method of using a multifunctional epoxy resin, a silicone-modified epoxy resin, etc. (see, for example, Patent Documents 5 and 6) It can be mentioned.

Japanese Patent Application Publication No. 01-070523 WO 2007/037378 pamphlet Patent No. 4877716 JP 2012-158730 A JP 2001-279058 A Unexamined-Japanese-Patent No. 2012-25924

  However, when the conventional epoxy resin composition described above is compounded with a special thermosetting resin having poor curability to improve the properties, the curing temperature becomes a high temperature of 150 ° C. or higher, or a low temperature curing In the case of using a special curing agent of a mold, the glass transition temperature (Tg) of the cured product is lowered, which makes it difficult to ensure the reliability, or the productivity decreases due to the control of the curing temperature. . When a special filler is used, the effect on the Tg and the adhesive strength of the cured product is small and the sufficient effect can not be obtained although the production cost is high.

  Furthermore, in recent years, particularly, due to the miniaturization and weight reduction of mobile devices, connections between fine circuits, and connections between fine terminals and fine circuits are increasing. The resulting cured product has high modulus of elasticity, high glass transition temperature (hereinafter also referred to as “Tg”), high adhesive strength while curing at low temperature and in a short time to improve impact resistance and reliability of these connections. It is required for the one-component epoxy resin composition to be excellent in gap permeability and liquid flow while exhibiting. However, the prior art has not been able to sufficiently meet such requirements, and there is still room for improvement.

  The present invention has been made in view of such circumstances, and it is possible to improve the interstitial permeability and liquid flow of an epoxy resin composition and to obtain a cured product having high Tg, elastic modulus and adhesive strength. An object of the present invention is to provide a curing agent for epoxy resin which can be cured. Another object of the present invention is to provide a microcapsule type latent curing agent for epoxy resin which can obtain excellent storage stability in an epoxy resin composition by encapsulating the curing agent for epoxy resin. . Furthermore, it aims at providing an epoxy resin composition containing the curing agent and a material containing the epoxy resin composition.

  As a result of intensive studies, the present inventors have found that the curing agent for epoxy resin containing an amine adduct, a low molecular weight amine compound and fine particles of inorganic compound of nano size can solve the above-mentioned problems. The present invention has been completed.

That is, the present invention is as follows.
[1]
A curing agent (D) for an epoxy resin containing an amine adduct (A), a low molecular weight amine compound (B), and nano-sized inorganic compound fine particles (C).
[2]
The curing agent (D) for an epoxy resin according to [1], wherein the content of the inorganic compound fine particles (C) is 0.1% by mass or more and 20% by mass or less.
[3]
The curing agent (D) for an epoxy resin according to [1] or [2], wherein the content of the amine adduct (A) is 24% by mass to 99% by mass.
[4]
The curing agent (D) for an epoxy resin according to any one of [1] to [3], wherein the content of the low molecular weight amine compound (B) is 0.5% by mass to 75% by mass.
[5]
The hardening | curing agent (D) for epoxy resins in any one of [1]-[4] which is solid state at 25 degreeC.
[6]
The amine adduct (A) is obtained by the reaction of 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) with an amine compound (a1) Containing amine adducts,
The curing agent (D) for an epoxy resin according to any one of [1] to [5], wherein the molecular weight distribution (weight average molecular weight / number average molecular weight) of the amine adduct (A) is 1 or more and 7 or less.
[7]
The molecular weight of the low molecular weight amine compound (B) is 31 or more and 600 or less,
The low molecular weight amine compound (B) according to any one of [1] to [6], having at least one amino group selected from the group consisting of a primary amino group, a secondary amino group and a tertiary amino group. Curing agent for epoxy resin (D).
[8]
The curing agent (D) for an epoxy resin according to any one of [1] to [7], wherein an average particle diameter of primary particles of the nanosized inorganic compound fine particles (C) is 1 nm or more and 100 nm or less.
[9]
The curing agent (D) for an epoxy resin according to any one of [1] to [8], wherein the specific surface area of the nanosized inorganic compound fine particles (C) is 10 m ² / g or more and 1000 m ² / g or less.
[10]
The curing agent (D) for an epoxy resin according to any one of [1] to [9], wherein the inorganic compound forming the nanosized inorganic compound fine particles (C) contains an inorganic oxide and / or an inorganic complex oxide ).
[11]
The inorganic compound forming the nano-sized inorganic compound fine particles (C) includes at least one inorganic compound selected from the group consisting of silica, alumina, magnesia, titania, zirconia, calcium carbonate, zeolite and talc, [1 ] The hardening | curing agent (D) for epoxy resins in any one of -10.
[12]
The curing agent (D) for an epoxy resin according to any one of [1] to [11], wherein the surface of the nanosized inorganic compound fine particles (C) is hydrophobized by a functional group.
[13]
The surface of the nanosized inorganic compound fine particles (C) is at least one selected from the group consisting of alkylsilanes, polyalkylsiloxanes, phenylsilanes, phenylalkylsilanes, silanols, chlorosilanes, alkoxysilanes, silazanes, siloxanes and halogenated silanes. The hardening | curing agent (D) for epoxy resins in any one of [1]-[12] hydrophobized from the functional group originating in the compound of seed | species.
[14]
Including core and shell,
The microcapsule type latent curing agent (F) for epoxy resins in which this core contains the curing agent (D) for epoxy resins in any one of [1]-[13].
[15]
The average particle size of the curing agent for epoxy resin (D) contained in the core is more than 0.3 μm and 12 μm or less,
A reaction product obtained by reacting two or more selected from the group consisting of an isocyanate compound, an active hydrogen compound, a curing agent for an epoxy resin (h1), an epoxy resin (e2) and a low molecular weight amine compound (G) [14] The microcapsule type latent curing agent (F) for epoxy resin according to [14].
[16]
100 parts by mass of the microcapsule type latent curing agent (F) for epoxy resin according to [14] or [15], and at least one epoxy resin selected from the group consisting of monoepoxy resin and polyvalent epoxy resin ( E) The epoxy resin composition which contains 10-50000 mass parts.
[17]
[14] or [15], containing the microcapsule type latent curing agent (F) for epoxy resin, epoxy resin (E) and nitrogen-containing heterocyclic compound (P),
The epoxy resin composition whose content of the said nitrogen-containing heterocyclic compound (P) is 0.01 mass part or more and 15 mass parts or less with respect to 100 mass parts of said epoxy resin (E).
[18]
The nitrogen-containing heterocyclic compound (P) is described in [17], including at least one derivative selected from the group consisting of pyridine derivatives, pyrimidine derivatives, pyrazine derivatives, triazine derivatives, quinoline derivatives, isoquinoline derivatives and purine derivatives. Epoxy resin composition.
[19]
The epoxy resin composition according to [17] or [18], wherein the nitrogen-containing heterocyclic compound (P) contains a pyridine derivative.
[20]
The epoxy resin composition according to any one of [16] to [19], further comprising at least one thermosetting resin selected from the group consisting of oxetane resin, monoepoxy resin and polyvalent epoxy resin.
[21]
A curing agent (h2) for at least one epoxy resin selected from the group consisting of an acid anhydride based curing agent, a phenol based curing agent, a hydrazide based curing agent, a guanidine based curing agent and a thiol based curing agent, [16 ] The epoxy resin composition in any one of-20.
[22]
The material containing the epoxy resin composition as described in any one of the microcapsule type latent curing agent (F) for epoxy resins as described in [14] or [15], or [16]-[21].
[23]
Adhesive, bonding paste, conductive material, anisotropic conductive material, insulating material, sealing material, coating material, coating composition, prepreg, heat conductive material, separator for fuel cell, and flexible wiring board The material according to [22], which is one selected from the group of overcoat materials.

  According to the present invention, it is possible to provide a curing agent capable of curing at low temperature which can improve the void permeability and liquid flow of the epoxy resin composition and obtain a cured product having high Tg, elastic modulus and adhesive strength. can do. Further, by using a microcapsule type latent curing agent for epoxy resin encapsulating the curing agent for epoxy resin, an epoxy resin composition having excellent storage stability and a material containing the epoxy resin composition are provided. can do.

  Hereinafter, modes for carrying out the present invention (hereinafter, abbreviated as “the present embodiment”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can variously deform and implement within the range of the summary.

«Hardener for epoxy resin»
The curing agent (D) for an epoxy resin of the present embodiment contains an amine adduct (A), a low molecular weight amine compound (B), and nano-sized inorganic compound fine particles (C). Each component will be described below.

<Amine adduct (A)>
In the curing agent (D) for an epoxy resin of the present embodiment, the content of the amine adduct (A) is preferably 24% by mass to 99% by mass, more preferably 35% by mass to 96% by mass, and further preferably The content is preferably 45% by mass to 92% by mass, more preferably 50% by mass to 90% by mass, and even more preferably 55% by mass to 85% by mass.

  By controlling the content of the amine adduct (A) to 24% by mass or more, fusion and aggregation of particles can be suppressed when controlling the average particle diameter of the curing agent (D) for an epoxy resin. Moreover, it also becomes easy to form the below-mentioned microcapsule type latent curing agent (F) for epoxy resin. By setting the content of the amine adduct (A) to 99% by mass or less, the curing agent can exhibit excellent curability.

  The amine adduct (A) is not particularly limited, and for example, at least one compound selected from the group consisting of carboxylic acid compounds, sulfonic acid compounds, urea compounds, isocyanate compounds, and epoxy resin (e1), and amine compounds The compound obtained by reaction with (a1) is mentioned.

  The carboxylic acid compound is not particularly limited, and examples thereof include succinic acid, adipic acid, sebacic acid, phthalic acid, dimer and the like.

  The sulfonic acid compound is not particularly limited, and examples thereof include ethanesulfonic acid, p-toluenesulfonic acid and the like.

  The urea compound is not particularly limited, and examples thereof include urea, methyl urea, 1,3-dimethyl urea, ethyl urea, tert-butyl urea and the like.

  The isocyanate compound is not particularly limited. For example, aliphatic monoisocyanate, aliphatic diisocyanate, alicyclic monoisocyanate, alicyclic diisocyanate, aromatic monoisocyanate, aromatic diisocyanate, aliphatic triisocyanate, polyisocyanate etc. It can be mentioned.

  Specific examples of the aliphatic monoisocyanate include, but not limited to, ethyl isocyanate, propyl isocyanate, isopropyl isocyanate, butyl isocyanate, hexyl isocyanate, heptyl isocyanate, dodecyl isocyanate, octadecyl isocyanate and the like. Although it does not specifically limit as a specific example of aliphatic diisocyanate, For example, ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate etc. are mentioned. Although it does not specifically limit as a specific example of an alicyclic monoisocyanate, For example, a cyclopentyl isocyanate, a cyclohexyl isocyanate, etc. are mentioned. Specific examples of the alicyclic diisocyanate are not particularly limited. For example, isophorone diisocyanate, 4-4′-dicyclohexylmethane diisocyanate, norbornane diisocyanate, 1,4-isocyanatocyclohexane, 1,3-bis (isocyanatomethyl) -Cyclohexane, 1,3-bis (2-isocyanatopropyl-2-yl) -cyclohexane and the like can be mentioned. Specific examples of the aromatic monoisocyanate are not particularly limited. For example, phenyl isocyanate, benzyl isocyanate, o-toluyl isocyanate, m-toluyl isocyanate, p-toluyl isocyanate, 3,5-dimethylphenyl isocyanate, 4-ethylphenyl An isocyanate, 2, 6- dimethylphenyl isocyanate etc. are mentioned. Although it does not specifically limit as a specific example of aromatic diisocyanate, For example, tolylene diisocyanate, 4,4'- diphenylmethane diisocyanate, xylene diisocyanate, 1, 5- naphthalene diisocyanate etc. are mentioned. Although it does not specifically limit as a specific example of aliphatic triisocyanate, For example, 1, 3, 6 triisocyanate methyl hexane, 2, 6- diisocyanato hexanoic acid 2-isocyanato ethyl etc. are mentioned. Although it does not specifically limit as a specific example of polyisocyanate, For example, polymethylene polyphenyl polyisocyanate and polyisocyanate derived from the above-mentioned diisocyanate compound are mentioned. The polyisocyanate derived from the above diisocyanate is not particularly limited, and examples thereof include isocyanurate type polyisocyanate, burette type polyisocyanate, urethane type polyisocyanate, allophanate type polyisocyanate, carbodiimide type polyisocyanate and the like.

  Although it does not specifically limit as an epoxy resin (e1), For example, a mono-epoxy compound and a polyvalent epoxy compound are mentioned.

  The monoepoxy compound is not particularly limited. Examples thereof include butyl glycidyl ether, hexyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, p-tert-butylphenyl glycidyl ether, ethylene oxide, propylene oxide, p Xylyl glycidyl ether, glycidyl acetate, glycidyl butyrate, glycidyl hexoate, glycidyl benzoate and the like.

  The polyvalent epoxy compound is not particularly limited, but, for example, an epoxy resin obtained by glycidylating polyhydric phenols, an aliphatic ether type epoxy resin obtained by glycidylating polyhydric alcohol, an ether ester type epoxy obtained by glycidylating hydroxycarboxylic acid Examples thereof include resins, ester-type epoxy resins obtained by glycidylating polycarboxylic acid, glycidyl-type epoxy resins such as amine-type epoxy resins, and alicyclic epoxides.

  The epoxy resin obtained by glycidylating polyhydric phenols is not particularly limited. For example, bisphenol type epoxy resin obtained by glycidylating bisphenol, epoxy resin obtained by glycidylating dihydric phenol, epoxy obtained by glycidylating trisphenol The resin, the epoxy resin which glycidylated tetrakis phenols, the novolak-type epoxy resin which glycidylated novolaks etc. are mentioned.

  The bisphenols in the bisphenol type epoxy resin obtained by glycidylating bisphenols are not particularly limited, and examples thereof include bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol AD, Examples thereof include tetramethylbisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A, tetrafluorobisphenol A and the like.

  Although it does not specifically limit as an epoxy resin which glycidylated dihydric phenols, For example, chain | strand-shaped alkyl group (For example, a methyl group, an ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, sec-butyl, tert-butyl, isobutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, isohexyl, n-heptyl, n-octyl etc.) or cyclic Epoxy resin obtained by glycidyl dihydric phenol having alkyl group (for example, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group etc.) or allyl group or aryl group (phenyl group, benzyl group etc.) , Biphenol, 3,3 ′, 5,5′-tetraalkyl-4,4′-biphenyl Enol, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 9,9- The epoxy resin etc. which glycidylated bis (4-hydroxyphenyl) fluorene etc. are mentioned.

  The trisphenols in the epoxy resin obtained by glycidylating trisphenols are not particularly limited, and examples thereof include 1,1,1-tris (4-hydroxyphenyl) methane, 4,4- (1- (4- (1) -(4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) bisphenol etc. are mentioned.

  The tetrakisphenols in the epoxy resin obtained by glycidylating tetrakisphenols are not particularly limited, and examples thereof include 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane and the like.

  The novolacs in the novolac epoxy resin obtained by glycidylating novolacs are not particularly limited, and examples thereof include phenol novolac, cresol novolac, bisphenol A novolac, brominated phenol novolac, brominated bisphenol A novolac and the like.

  The polyhydric alcohol in the aliphatic ether type epoxy resin obtained by glycidylating the polyhydric alcohol is not particularly limited, and examples thereof include glycerin and polyethylene glycol.

  Although it does not specifically limit as a hydroxycarboxylic acid in the ether-ester type epoxy resin which glycidylated hydroxycarboxylic acid, For example, p-hydroxybenzoic acid, (beta)-oxy naphthoic acid etc. are mentioned.

  Although it does not specifically limit as a polycarboxylic acid in ester-type epoxy resin which glycidylated polycarboxylic acid, For example, phthalic acid, a terephthalic acid, etc. are mentioned.

  The amine-type epoxy resin in glycidyl-type epoxy resins such as amine-type epoxy resins is not particularly limited. For example, glycidyl compounds of amine compounds such as 4, 4-diaminodiphenylmethane and m-aminophenol, triglycidyl isocyanurate, etc. It can be mentioned.

  The alicyclic epoxide is not particularly limited, and examples thereof include 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexane carboxylate and the like.

  The epoxy resin (e1) is preferably a polyvalent epoxy compound from the viewpoint of storage stability. Among polyvalent epoxy compounds, glycidyl type epoxy resins are more preferable from the viewpoint of high productivity of amine adduct (A), and epoxy resins obtained by glycidylating polyhydric phenols from the viewpoint of being excellent in elastic modulus and Tg of a cured product Are more preferred, and bisphenol epoxy resins are even more preferred. And as a specific example of bisphenol type epoxy resin, the epoxy resin which glycidylated bisphenol A and the epoxy resin which glycidylated bisphenol F are preferable, and the epoxy resin which glycidylated bisphenol A is more preferable.

  As an epoxy resin (e1), you may use individually by 1 type mentioned above, and 2 or more types may be used together.

  The epoxy equivalent of the epoxy resin (e1) is preferably 85 g / eq or more and 1000 g / eq or less, more preferably 100 g / eq or more and 800 g / eq or less, still more preferably 105 g / eq or more and 700 g / eq or less Still more preferably, it is 110 g / eq or more and 650 g / eq or less. Molecular weight distribution (Mw / Mn) represented by a ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) of amine adduct (A) by setting the epoxy equivalent of the epoxy resin (e1) to 1000 g / eq or less Is easy to control, and the low temperature short time curability of the epoxy resin composition is further improved. In addition, by setting the epoxy equivalent of the epoxy resin (e1) to 1000 g / eq or less, the diffusivity of the curing agent component to the epoxy resin and the homogeneity of the cured product can be improved, and the elastic modulus and Tg of the cured product And it is advantageous to make adhesive strength high, and also the productivity of amine adduct (A) is further improved. Further, by setting the epoxy equivalent of the epoxy resin (e1) to 85 g / eq or more, it becomes easier to control the average particle diameter of the curing agent (D) for an epoxy resin within a desired range. The epoxy equivalent can be measured in accordance with JIS K7236.

  The total chlorine content in the epoxy resin (e1) is preferably 2500 ppm or less, more preferably 2000 ppm or less, from the viewpoint of further improving the balance between the curability and storage stability of the epoxy resin composition. Preferably it is 1500 ppm or less, still more preferably 1000 ppm or less.

  The term "total chlorine content" as used herein refers to the total amount of organic chlorine and inorganic chlorine contained in a sample (compound, epoxy resin, epoxy resin composition or the like), and is a mass-based value. The total chlorine content contained in an epoxy resin (e1) can be measured as follows based on JIS K7243-3. That is, 1 to 10 g of a sample is precisely weighed so as to have a titer of 3 to 7 mL, and dissolved in 25 mL of ethylene glycol monobutyl ether. To the resulting solution is added 25 mL of a propylene glycol solution of 1N KOH, the mixture is boiled for 20 minutes, and the solution after boiling is titrated with an aqueous silver nitrate solution. The total chlorine amount is obtained by calculation from the titration amount.

  Of the total chlorine, chlorine contained in the 1,2-chlorohydrin group is generally called hydrolyzable chlorine. The amount of hydrolyzable chlorine in the epoxy resin (e1) is preferably 50 ppm from the viewpoint of further improving the balance between the curability and storage stability of the epoxy resin composition and securing the long-term reliability of the cured product. Or less, more preferably 20 ppm or less, and still more preferably 10 ppm or less. The lower limit of the amount of hydrolyzable chlorine in the epoxy resin (e1) is preferably 0.01 ppm or more, and more preferably 0.05 ppm or more.

  The "hydrolyzable chlorine content" referred to herein can be measured as follows according to JIS K7243-2. That is, 3 g of a sample is dissolved in 50 mL of toluene, 20 mL of a 0.1 N KOH solution in methanol is added to the obtained solution, the mixture is boiled for 15 minutes, and the boiled solution is titrated with an aqueous silver nitrate solution. The amount of hydrolyzable chlorine is determined by calculation from the titer.

  The number average molecular weight of the epoxy resin (e1) is not particularly limited, but is preferably 100 to 700. The number average molecular weight is calculated from the molecular weight determined in terms of polystyrene using the gel permeation chromatography (GPC) method described later.

  The amine compound (a1) is not particularly limited as long as it contains an amino group. Examples of the amine compound (a1) include primary amino group-containing amine compounds, secondary amino group-containing amine compounds, tertiary amino group-containing amine compounds, and compounds having a tertiary amino group and an active hydrogen group in combination. Be Here, the active hydrogen group is not particularly limited, and examples thereof include a primary amino group, a secondary amino group, a hydroxyl group, a thiol group, a carboxyl group and a hydrazide group.

  The amine adduct (A) is an amine adduct (AD1) having an active hydrogen derived from a primary amino group and / or a secondary amino group having curing ability by addition type reaction to an epoxy group, or an epoxy group Although any one or two or more of the amine adducts (AD2) having a tertiary amino group having curing ability by catalytic reaction may be contained in combination, the curing ability by catalytic reaction It is preferable to contain an amine adduct (AD2) having a tertiary amino group having

  The ratio of the epoxy resin (e1) to the amine compound (a1) when the epoxy resin (e1) and the amine compound (a1) are reacted to obtain the amine adduct (A) is 1 in the amine compound (a1). When an active hydrogen derived from a secondary amino group and / or a secondary amino group is present, the active hydrogen group in the amine compound (a1) is preferably 0. 1 to 1 equivalent of the epoxy group of the epoxy resin (e1). The range is 8 equivalents to 20 equivalents, more preferably 0.9 equivalents to 12 equivalents, and still more preferably 0.95 equivalents to 10 equivalents. By reacting the epoxy resin (e1) with the amine compound (a1) in the above ratio, the molecular weight distribution (Mw) represented by the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) of the amine adduct (A) / Mn) can be efficiently created to 1 or more and 7 or less. Furthermore, the unreacted amine compound (a1) is efficiently recovered by setting the ratio of the active hydrogen group in the amine compound (a1) to one equivalent of the epoxy group of the above-mentioned epoxy resin (e1) to 20 equivalents or less. Can be done and it is economical.

  The active hydrogen equivalent (hv) derived from the primary amino group and / or the secondary amino group possessed by the amine adduct (AD1) is not particularly limited, but is preferably 4.0 mmol / g or more and 15 mmol / g or less. By setting the active hydrogen equivalent (hv) of the amine adduct (AD1) to 4.0 mmol / g or more, a thin and dense shell (S) can be formed in the microcapsule type latent curing agent described later, and an epoxy resin composition Storage stability is further improved. Containing amine adduct (AD1), low molecular weight amine compound (B), and nanosized inorganic compound fine particles (C) at a specific ratio by setting the active hydrogen equivalent of amine adduct (AD1) to 15.0 mmol / g or less It becomes much easier to control the curing agent (D) for epoxy resin to a desired average particle diameter.

  The active hydrogen equivalent of the amine adduct (AD1) can be determined according to the following method.

  First, the preparation weight (w1) of the epoxy resin (e1) charged to produce the amine adduct (AD1), the weight (w2) of the amine compound (a1), and after removing the unreacted amine compound (a1) after the reaction From the weight (w3) of the amine adduct (AD1) recovered, based on the following formula (i), the weight (w4) of the amine compound (a1) consumed to form the amine adduct (AD1) by the reaction Calculate

    w4 = (w1 + w2) -w3 (i)

  Next, an amine adduct (AD1) is formed based on the following formula (ii) from the molecular weight (mw1) of the amine compound (a1) and the number (n) of active hydrogens held by one molecule of the amine compound (a1) The total amount (h1) of the number of moles of active hydrogen which the amine compound (a1) consumed to be consumed holds before the reaction is determined.

    h1 = (w4 / mw1) × n (ii)

  In addition, when using together 2 or more types of compounds as an amine compound (a1), the reaction ratio of these amine compounds (a1) shall be allocated and calculated based on the weight ratio of these at the time of preparation.

  And from the preparation weight (w1) of the preparation epoxy resin (e1) and the epoxy equivalent (ev1) (the weight of the epoxy resin (e1) per equivalent), based on the following formula (iii), Calculate the total amount (ep1) mol.

    ep1 = w1 / ev1 (iii)

  When using multiple types together as an epoxy resin (e1), ep1 is calculated from the sum of the preparation weight of each epoxy resin (e1), and the quantity of the epoxy group calculated | required from an epoxy equivalent.

  Epoxy resin (e1) charged to form amine adduct (AD1) out of the total number (h1) of the number of active hydrogens held by amine compound (a1) consumed to form amine adduct (AD1) The total amount of active hydrogen is reduced by the reaction of the amine compound (a1) in an amount equivalent to the total amount of epoxy groups of Therefore, the total amount (h2) mol of active hydrogens held by the recovered amine adduct (AD1) is calculated by the following formula (iv).

    h2 = h1-ep1 (iv)

  From the total amount (h2) mol of active hydrogen held by the recovered amine adduct (AD1) and the weight (w4) of the recovered amine adduct (AD1), based on the following formula (v), the amine adduct (AD1) The active hydrogen equivalent (hv) is calculated.

    hv = h2 / w4 (v)

  The amine adduct (AD2) is preferably an amine adduct obtained by the reaction of an epoxy resin (e1) or an isocyanate compound (N1) with an amine compound (a2) having 1 to 15 carbon atoms.

  The amine compound (a2) reacts with the epoxy resin (e1) or the isocyanate compound (N1) to obtain an amine adduct (AD2) having a tertiary amino group having a curing ability by a catalytic reaction with respect to the epoxy group. It is a C1-C15 amine compound which can be. The amine compound (a2) is not particularly limited, but the amine compound (a2) may be obtained from the viewpoint that the obtained cured product exhibits high elastic modulus, high Tg and high adhesive strength in the low temperature short time curing of the epoxy resin composition. Amine compounds containing a tertiary amino group and an active hydrogen group in an aliphatic structure, an alicyclic structure, or an aromatic cyclic structure containing a nitrogen atom or an oxygen atom, an epoxy resin (e1) or an isocyanate compound (N1) Preferred are amine compounds having a structure that produces a tertiary amino group upon reaction with

  Specific examples of the amine compound (a2) include, but are not limited to, 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, for example. Amino alcohols such as 1-butoxymethyl-2-dimethylaminoethanol, methyldiethanolamine, triethanolamine, N-β-hydroxyethyl morpholine, 1-azabicyclo [2.2.2] octan-3-ol; 2- ( Aminophenols such as dimethylaminomethyl) phenol and 2,4,6-tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole , 2- Henylimidazole, 1-aminoethyl-2-methylimidazole, 1- (2-hydroxyethyl) -imidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-methylimidazole, 1- (2-hydroxy-3) -Phenoxypropyl) -2-ethyl-4-methylimidazole, 1- (2-hydroxy-3-butoxypropyl) -2-methylimidazole, 1- (2-hydroxy-3-butoxypropyl) -2-ethyl-4 Imidazoles such as -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-methylimidazoline, 1,2-phenylene-bis-imidazoline, 1,3-phenylene-bis-imidazoline, 1,4-phenylene-bis-imidazoline, 1,4-phenylene- Imidazolines such as bis-4-methylimidazoline; dimethylaminopropylamine, diethyla Nopropylamine, dipropylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, dipropylaminoethylamine, dibutylaminoethylamine, N-methylpiperazine, N-aminoethylpiperazine, 1-amino-4-methylpiperazine And tertiary aminoamines such as diethylaminoethyl piperazine; 2-dimethylaminoethanethiol, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptopyridine, aminomercapto mercaptans such as 4-mercaptopyridine; N, N- Aminocarboxylic acids such as dimethylaminobenzoic acid, N, N-dimethylglycine, nicotinic acid, isonicotinic acid, picolinic acid, etc .; N, N-dimethylglycine hydrazide, nicolic acid Aminohydrazides such as acid hydrazide and isonicotinic acid hydrazide; 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, Aminopyridines such as 3,5-diaminopyridine, pyridine-2,3,6-triamine, 2- (methylamino) pyridine, 4- (methylamino) pyridine, 2-methoxy-6-methylaminopyridine and the like; 2.2.1] Heptane-2,5-diylbis (methylamine), bicyclo [2.2.1] heptane-2,6-diylbis (methylamine), 1-azabicyclo [2.2.2] octane Aliphatic heterocyclic amine compounds such as 3-amine can be mentioned.

  The method for producing the amine adduct (AD2) having a tertiary amino group obtained by the reaction of the epoxy resin (e1) or the isocyanate compound (N1) with the amine compound (a2) having 1 to 15 carbon atoms is not particularly limited. In consideration of the desired structure of the amine adduct (AD2) and the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the amine adduct (AD2) Appropriate suitable conditions can be selected.

  When making an epoxy resin (e1) and an amine compound (a2) react, about the ratio of an epoxy resin (e1) and an amine compound (a2), an amine compound is carried out with respect to 1 equivalent of epoxy groups of an epoxy resin (e1). The active hydrogen group in (a2) is preferably in the range of 0.5 to 10 equivalents, more preferably 0.8 to 5 equivalents, still more preferably 0.95 to 4 equivalents. Moreover, when making an isocyanate compound (N1) and an amine compound (a2) react, about the ratio of an isocyanate compound (N1) and an amine compound (a2), the isocyanate compound (N1) calculated | required from the molecular weight of an isocyanate compound (N1) The active hydrogen group in the amine compound (a2) is preferably in the range of 0.9 equivalent or more and 1.2 equivalents or less with respect to the isocyanate equivalent (nv1) of). By reacting the epoxy resin (e1) with the amine compound (a2) at the above ratio, an amine adduct (AD2) having a tertiary amino group with a molecular weight distribution of 1 or more and 7 or less can be efficiently obtained.

  As reaction conditions which synthesize | combine amine adduct (A), conditions which are made to react at the temperature of 0-250 degreeC for 0.1 to 10 hours in presence of a solvent as needed are preferable. The solvent is not particularly limited, but, for example, hydrocarbons such as benzene, toluene, xylene, cyclohexane, hexane, heptane, octane, mineral spirit, naphtha; linear ethers such as dimethyl ether, diethyl ether, ethyl methyl ether; Cyclic ethers such as tetrahydrofuran, tetrahydropyran; nitriles such as acetonitrile, propionitrile, butyronitrile; amides such as acetamide, formamide, N, N-dimethylacetamide, N, N-dimethylformamide; dimethyl sulfoxide, diethyl sulfoxide, etc. Sulfoxides; acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), ketones such as isophorone; ethyl acetate, n-butyl acetate, propylene glycol Esters such as monomethyl ether acetate; methanol, ethanol, isopropanol, n- butanol, butyl cellosolve, alcohols such as butyl carbitol; water and the like. These solvents may be used alone or in combination of two or more. The solvent used is a method of removing the reaction solution in which the amine adduct (A) dissolves from the reaction system by distillation after completion of the reaction, a method of filtering and separating the amine adduct (A) precipitated by the reaction and the solvent, amine adduct A solution in which an amine adduct (A) is dissolved using a liquid-liquid separation tank after adding a poor solvent having poor solubility of amine adduct (A) to a reaction solution in which (A) dissolves and separating into two phases After the extraction and concentration separation, the solvent is preferably removed by distillation or the like to separate the amine adduct (A).

  The amine adduct (AD2) can carry out a catalytic curing reaction on the epoxy resin. Therefore, the content of the amine adduct (AD2) is preferably 5 parts by mass or more, more preferably 15 parts by mass or more, still more preferably 30 parts by mass or more, based on 100 parts by mass of the entire amine adduct (A). More preferably, it is 50 parts by mass or more, particularly preferably 75 parts by mass or more. The entire amount of the amine adduct (A) may be the amine adduct (AD2). By setting the content of the amine adduct (AD2) in 100 parts by mass of the amine adduct (A) to 5 parts by mass or more, the crosslink density in the cured product of the epoxy resin composition is adjusted to express a desired elastic modulus It is considered that the glass transition temperature (Tg) of the cured product can be set to a suitable temperature, and excellent long-term reliability can be ensured (however, the function of the present embodiment is not limited thereto).

  The amine adduct (AD1) and the amine adduct (AD2) in the amine adduct (A) may be used alone or in combination of two or more. A plurality of amine compounds (a1) and an amine compound (a2) may be simultaneously used for synthesis, or a plurality of independently synthesized amine adducts may be mixed so as to be uniform after synthesis . Among the carboxylic acid compound, sulfonic acid compound, isocyanate compound, urea compound and epoxy resin (e1) which can be used as a raw material of the amine adduct (A), a viewpoint which is excellent in curability and storage stability of the epoxy resin composition It is preferable to use an epoxy resin (e1) and an isocyanate compound (N1).

  The amine adduct (A) has a molecular weight distribution (Mw / Mn) represented by a ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) of preferably 1 or more and 7 or less, more preferably 1 or more and 5 or more. Or less, more preferably 1 or more and 4 or less. By setting the molecular weight distribution of the amine adduct (A) in the above-mentioned range, the low-temperature short-time curability and storage stability of the epoxy resin composition are further improved. When two or more types of amine adducts are used in combination, the molecular weight distribution of the at least one type of amine adduct may be 1 to 7.

  In addition, in this embodiment, molecular weight distribution can be measured by the method as described in the below-mentioned Example.

<Low molecular weight amine compound (B)>
In the curing agent (D) for an epoxy resin of the present embodiment, the content of the low molecular weight amine compound (B) is preferably 0.5% by mass to 75% by mass, and more preferably 2% by mass to 60%. %, More preferably 4% by mass to 50% by mass, still more preferably 6% by mass to 40% by mass, and even more preferably 8% by mass to 35% by mass.

  By setting the content of the low molecular weight amine compound (B) to 0.5% by mass or more, a curing agent for epoxy resin which can be cured at low temperature can be obtained. By making content of a low molecular weight amine compound (B) into 75 mass% or less, the epoxy resin composition excellent in crevice permeability and liquid flow nature can be obtained.

  The molecular weight of the low molecular weight amine compound (B) is preferably 31 or more and 600 or less, more preferably 65 or more and 350 or less, and still more preferably 80 or more and 270 or less. When the molecular weight of the low molecular weight amine compound (B) is within the above range, the compatibility between the amine adduct (A) and the low molecular weight amine compound (B) becomes good, and when curing the epoxy resin, Tg of the cured product, adhesion It becomes easy to obtain a good strength.

  The low molecular weight amine compound (B) is not particularly limited, and examples thereof include amine compounds having at least one amino group selected from the group consisting of primary amino group, secondary amino group and tertiary amino group. These low molecular weight amine compounds (B) may be used alone or in combination of two or more.

  In the low molecular weight amine compound (B), the compound having a primary amino group and / or a secondary amino group is not particularly limited, and, for example, methylamine, ethylamine, propylamine, butylamine, ethylenediamine, propylenediamine, hexamethylene Primary amines having no tertiary amino group such as diamine, diethylenetriamine, triethylenetetramine, ethanolamine, propanolamine, cyclohexylamine, isophoronediamine, aniline, toluidine, diaminodiphenylmethane, diaminodiphenyl sulfone, etc .; dimethylamine, diethylamine, Dipropylamine, dibutylamine, dipentylamine, dihexylamine, dimethanolamine, diethanolamine, dipropanolamine, dicyclohexylamine Secondary amines having no tertiary amino group such as piperidine, piperazine, diphenylamine, phenylmethylamine and phenylethylamine; primary amino groups such as tris (2-aminoethyl) amine and tris (3-aminopropyl) amine And amino groups having a tertiary amino group; 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 3,5 Primary amino group such as -diaminopyridine, pyridine-2,3,6-triamine, 2- (methylamino) pyridine, 4- (methylamino) pyridine, 2-methoxy-6-methylaminopyridine or secondary amino Aminopyridines having a group; 2-amino-3-picoline, 2-amino-4-picoline, 3-amino-4 Aminopicolines such as picolin, 5-amino-2-picoline, 6-amino-2-picoline, 6-amino-3-picoline; guanidines such as guanidine, biguanide, dicyandiamide, 1-o-tolylbiguanide; succinic acid Hydrazides, such as dihydrazide and adipic acid dihydrazide, etc. are mentioned.

  The compound having at least one tertiary amino group is not particularly limited, and, for example, a low molecular weight compound having a tertiary amino group but having no active hydrogen in addition to the amine compound mentioned as an example of the amine compound (a2) An amine compound is mentioned. The low molecular weight amine compound having a tertiary amino group but not having active hydrogen is not particularly limited, and examples thereof include trimethylamine, triethylamine, benzyldimethylamine, N, N-dimethyl-ethylamine, N, N-dimethyl-butylamine N, N-dimethyldecylamine, N, N-dimethyl-m-toluidine, N, N-dimethyl-p-toluidine, 2,6,10-trimethyl-2,6,10-triazaundecane, N, N '-Dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane, 1-azabicyclo [2.2.2] octan-3-one, 1,8-diazabicyclo (5,4,0) -undecene- 7, 1, 5-Diazabicyclo (4, 3, 0) -nonene-5, tertiary amines such as hexamethylenetetramine; 1-methylimidazo Imidazoles such as 1,2-dimethylimidazole, 1-vinylimidazole, 1-allylimidazole, 2-methyl-1-vinylimidazole, N-acetylimidazole; dimethylamino benzhydrol, bis [4- (dimethylamino) Aromatic tertiary amines such as phenyl) methane, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 2-diethylamino-N- (2,6-dimethylphenyl) acetamide and the like And aminopyridines having a tertiary amino group such as 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2- (N-methyl-2-pyridylamino) ethanol and the like.

  The melting point of the low molecular weight amine compound (B) is preferably 30 ° C. or more and 240 ° C. or less, more preferably 40 ° C. or more and 220 ° C. or less, and still more preferably 60 ° C. or more and 200 ° C. or less. When the melting point of the low molecular weight amine compound (B) is 30 ° C. or more, fusion and aggregation of particles can be suppressed when controlling the average particle diameter of the curing agent (D) for an epoxy resin. In addition, it becomes easy to form a microcapsule type latent curing agent (F) for epoxy resin. By setting the melting point of the low molecular weight amine compound (B) to 240 ° C. or less, the curing agent can exhibit excellent curability.

  The low molecular weight amine compound (B) preferably has at least one tertiary amino group. The low molecular weight amine compound (B) having a tertiary amino group can promote the curing reaction catalytically in a small amount to the epoxy resin, which is advantageous in increasing the elastic modulus and Tg of the cured product.

  In the production of the curing agent (D) for an epoxy resin of the present embodiment, the low molecular weight amine compound (B) may be mixed with the amine adduct (A) after the production of the amine adduct (A), or the amine adduct (A) And / or may be mixed during manufacture. In addition, an amine adduct (AD1) and an amine compound (a1) which is a raw material of the amine adduct (AD2) or an unreacted product of the amine compound (a2) may be used as the low molecular weight amine compound (B).

<Nano-sized inorganic compound fine particles (C)>
In the curing agent (D) for an epoxy resin of the present embodiment, the content of the nanosized inorganic compound fine particles (C) is preferably 0.1% by mass or more and 20% by mass or less, and more preferably 0.2% by mass. % Or more and 15% by mass or less, more preferably 0.5% by mass or more and 12% by mass or less, and still more preferably 1% by mass or more and 10% by mass or less.

  In the epoxy resin composition excellent in interstitial permeability and liquid flowability by setting the content of the nano-sized inorganic compound fine particles (C) to 0.1 mass% or more, Tg after curing, elastic modulus, adhesive strength A cured product for epoxy resin can be obtained. By setting the content of the nanosized inorganic compound fine particles (C) to 20% by mass or less, it is possible to obtain a thermosetting resin composition excellent in clearance permeability and liquid flowability.

  In the present embodiment, nano-sized inorganic compound fine particles mean particles of inorganic compounds in which the average particle diameter of primary particles is nano-sized (1 nm or more and 999 nm or less).

  The average particle diameter of primary particles of the nano-sized inorganic compound fine particles (C) is preferably 1 nm to 100 nm, more preferably 3 nm to 75 nm, still more preferably 5 nm to 50 nm, still more preferably 7 nm or more 30 nm or less. The average particle size of the nanosized inorganic compound particles can be measured by a laser diffraction / scattering method, a dynamic light scattering method, a centrifugal sedimentation method or the like in addition to observation by an electron microscope.

  The shape of the primary particles of the nanosized inorganic compound fine particles (C) is not particularly limited, and may be, for example, spherical, square, polyhedron, indeterminate or the like. Among these, from the viewpoint of handling at the time of processing into an epoxy resin composition, it is preferably spherical. The term "spherical" includes not only true spheres but also irregular shapes with rounded corners.

  By making the average particle diameter of the primary particles of the nano-sized inorganic compound fine particles (C) 100 nm or less, when the epoxy resin composition is allowed to penetrate gaps, uniform dispersion of the curing agent for epoxy resin and the epoxy resin The state becomes good, and the cured product finally obtained can suppress unevenness, and can express high Tg, adhesive strength and the like.

  The amine adduct (A) and the low molecular weight amine compound (B) contain nanosized inorganic compound microparticles (C) by setting the average particle size of primary particles of nanosized inorganic compound microparticles (C) to 1 nm or more In the operation, the operation of dispersing agglomerates formed by the aggregation of primary particles of nanosized inorganic compound fine particles (C) is facilitated, and the curing agent (D) for epoxy resin can be industrially produced.

The specific surface area of nano-sized inorganic compound fine particles (C) is preferably not more than 10 m ² / g or more 1000 m ² / g, more preferably, 25 m ² / g or more 700 meters ² / g or less, more preferably 50 m ² / It is g or more and 500 m ² / g or less.

When the epoxy resin composition is allowed to penetrate into gaps or the like by setting the specific surface area of the nanosized inorganic compound fine particles (C) to 10 m ² / g or more, the uniformly dispersed state of the curing agent for epoxy resin and the epoxy resin The cured product finally obtained can suppress unevenness, and can exhibit high Tg, adhesive strength, and the like.

Operation to make the amine adduct (A) and the low molecular weight amine compound (B) contain the nanosized inorganic compound fine particles (C) by setting the specific surface area of the nanosized inorganic compound fine particles (C) to 1000 m ² / g or less Can be easily produced, and the curing agent for epoxy resin (D) can be industrially produced.

  Here, in the present embodiment, the "specific surface area" refers to the specific surface area measured by the BET equation using nitrogen / helium gas.

  The inorganic compound fine particles (C) of nanosize are preferably those having an average particle diameter and a specific surface area of primary particles in the above-mentioned range, and two or more kinds of them can be mixed and used.

  The nano-sized inorganic compound fine particles (C) are preferably fine particles formed of an inorganic oxide or an inorganic complex oxide. Although it does not specifically limit as an inorganic oxide or inorganic complex oxide, For example, a silica, an alumina, magnesia, a titania, a zirconia, a calcium carbonate, a zeolite, a talc is mentioned. As these inorganic oxides or inorganic complex oxides, any one kind or a mixture of two or more kinds can be used. Among them, silica and alumina are preferable, and silica is particularly preferable.

There are several methods of preparing these inorganic oxides or inorganic complex oxides into primary particles of desired average particle size and nano-sized particles having a specific surface area. The method of producing nano-sized particles is roughly classified into three methods, a solid phase method, a liquid phase method, and a gas phase method. In the solid phase method, large particles are crushed by applying mechanical energy to form particles of about several hundreds nm in size, which are classified. However, it is difficult to produce particles of 100 nm or less by this method, and generally, nano-sized particles are produced by a liquid phase method or a gas phase method. The liquid phase method is not particularly limited, and examples thereof include coprecipitation method, sol gel method, liquid phase reduction method, hydrothermal synthesis method and the like. The gas phase method is not particularly limited, and examples thereof include an electric furnace method, a chemical flame method, a flame hydrolysis method, an arc method, a laser method, a thermal plasma method and the like. Among these, in a wet method such as a coprecipitation method which is a liquid phase method, the obtained nanosized inorganic compound fine particles have a structure having pores. Therefore, it becomes difficult to reduce the specific surface area of the nanosized inorganic compound fine particles (C) to 1000 m ² / g or less, or the amine adduct (A) and the low molecular weight amine compound (B) make nanosized inorganic compound fine particles ( In the operation in which C) is contained, air bubbles in the pores may remain, which may impair the physical properties and appearance of the cured product in the epoxy resin composition. As a preparation method of the nanosized inorganic compound fine particles (C), a gas phase method, particularly a flame hydrolysis method is preferable in terms of productivity and uniformity of the nanosized particles. The nanosized inorganic compound fine particles (C) prepared by the flame hydrolysis method are not particularly limited, and examples thereof include so-called fumed silica.

  The fumed silica is not particularly limited, but, for example, “Leoro seal QS-09”, “Leoro seal QS-10”, “Leoro seal QS-102”, “Leoro seal CP-102”, “Leoro seal QS-” of Tokuyama Corp. 20 "," Leolo seal QS-20L "," Leoro seal QS-30 "," Leoro seal QS-30C "," Leoro seal QS-40 "," Leoro seal MT-10 "," Leoro seal MT-10 C "," Leoro seal DM-10 "Leoroseal DM-10C", "Leoroseal DM-20S", "Leoroseal DM-30", "Leoroseal DM-30S", "Leoroseal KS-20SC", "Leoroseal HM-20L", "Leoroseal HM-30S" , "Leorosil PM-20", "Leorothy PM-20L, "Excerica UF-103", "Excerica UF-103A", "Excerica UF-305", "Excerica UF-310", "Exerica UF-320", "AEROSIL OX50" of Nippon Aerosil Co., Ltd. , "AEROSIL 50", "AEROSIL 90G", "AEROSIL 130", "AEROSIL 150", "AEROSIL 200", "AEROSIL 300", "AEROSIL 380", "AEROSIL R972", "AEROSIL R974", "AEROSIL R976" "AEROSIL R976S", "AEROSIL RX50", "AEROSIL NAX50", "AEROSIL NX90", "AEROSIL RX200", "AEROSIL RX30" , "AEROSIL R812", "AEROSIL R812S", "AEROSIL RY50", "AEROSIL NY50", "AEROSIL RY200S", "AEROSIL R202", "AEROSIL RY200", "AEROSIL RY300", "AEROSIL R104", "AEROSIL R106" , "AEROSIL NA50H", "AEROSIL NA50Y", "AEROSIL RA200H", "AEROSIL RA200HS", "AEROSIL R805", "AEROSIL R816", "AEROSIL RM50", "AEROSIL R711", "AEROSIL R7200", "AEROSIL R7200" And “AEROSIL R9200” etc.

  It is preferable that the surface of the nanosized inorganic compound fine particles (C) is hydrophobized by a functional group. The functional group for hydrophobizing the surface of the nano-sized inorganic compound fine particles (C) is made of alkylsilane, polyalkylsiloxane, phenylsilane, phenylalkylsilane, silanol, chlorosilane, alkoxysilane, silazane, siloxane and halogenated silane. It is preferably a functional group derived from at least one compound selected from the group. In addition, two or more types of nano-sized inorganic compound fine particles (C) having one type of functional group for surface treatment may be mixed and used.

  Several methods are mentioned as a method of hydrophobizing the surface of a nanosized inorganic compound fine particle (C) by a functional group. Specifically, although not particularly limited, for example, when the inorganic compound fine particles (C) are silica fine particles, the silica fine particles of nanosize are brought into contact with hexamethyldisilazane in the presence of water vapor and a basic gas, Method to introduce trimethylsilyl group by chemical bond to OH group on the surface of fine particle, Method to introduce alkyl halogenosilyl group by contacting nanosize silica fine particle with alkyl halogenosilane such as methyltrichlorosilane and dimethyldichlorosilane, silicone oil After performing primary surface treatment with a system treatment agent, a method of highly hydrophobization by performing a secondary surface treatment with an alkyl silazane series treatment agent in a dry or wet manner after being crushed and the like can be mentioned.

  When the surface of the nano-sized inorganic compound fine particles (C) is hydrophobized by a functional group, fusion and aggregation of particles are caused when controlling the average particle diameter of the curing agent (D) for an epoxy resin of the present embodiment. It is advantageous in suppressing In addition, an epoxy resin or a thermosetting resin is obtained using the epoxy resin curing agent (D) of this embodiment or the microcapsule type latent curing agent (F) for epoxy resin having the curing agent (D) for epoxy resin as a core. When the curing resin is heated and cured, the surface of the nano-sized inorganic compound fine particles (C) is hydrophobized with a functional group to make an amine adduct (A) which is a curing agent component contained in the curing agent (D) for epoxy resin And, the diffusion of the low molecular weight amine compound (B) is in a good state, and a cured product with less curing unevenness can be obtained, which is advantageous for the cured product to exhibit high Tg, high adhesive strength and high reliability.

<Method of producing curing agent (D) for epoxy resin>
In the curing agent (D) for an epoxy resin of the present embodiment, the content of the amine adduct (A) is 24% by mass to 99.5% by mass, and the content of the low molecular weight amine compound (B) is 0.5 It is preferable that it is mass% or more and 75 mass% or less, and content of the nanosized inorganic compound fine particle (C) is 0.1 mass% or more and 20 mass% or less.

  As the method for producing the curing agent (D) for epoxy resin by containing the amine adduct (A), the low molecular weight amine compound (B) and the nano-sized inorganic compound fine particles (C) in the specific ratio as described above, Can be mentioned. Specifically, although not particularly limited, for example, after preparing a solution using a solvent that dissolves an amine adduct (A) and a low molecular weight amine compound (B), nanosized inorganic compound fine particles ( C) in powder form or in the form of a suspension uniformly dispersed in a solvent, and mixing and thereafter removing the solvent by distillation or the like to obtain a bulk epoxy resin curing agent (D), or an amine adduct After preparing a solution using a solvent that dissolves (A) and the low molecular weight amine compound (B), nano-sized inorganic compound fine particles (C) are dispersed uniformly in the solution with a powder or a solvent. Method for obtaining powdery curing agent (D) for epoxy resin by directly drying and granulating the solution added and mixed in the form of suspension with a spray dryer, amine adduct (A) and low molecular weight amine compound ( B) Added to solid component nanosized inorganic compound fine particles (C) a powder consisting of, and a method for producing an epoxy resin curing agent (D) by kneading to homogeneity by melt-kneader and the like. Moreover, it is not specifically limited as a solvent which can be used when making an amine adduct (A), a low molecular weight amine compound (B), and an inorganic compound fine particle (C) of nano size into a uniform state using a solvent. For example, the solvent used in the synthesis of the amine adduct (A) can be used. Moreover, you may use a solvent in mixture of 1 type, or 2 or more types.

  From the viewpoint of handling when an epoxy resin composition is formed using the above-mentioned curing agent for epoxy resin (D), it is desired that the uncured time until heat curing be performed, that is, the so-called pot life has a sufficient time. Therefore, the curing agent (D) for epoxy resin is preferably solid at 25 ° C. That is, the softening point of the curing agent (D) for an epoxy resin is preferably more than 25 ° C. and 150 ° C. or less, more preferably 40 ° C. or more, and still more preferably 60 ° C. or more. The softening point of the curing agent (D) for an epoxy resin is measured by the method according to the "Testing method of softening point of epoxy resin" described in JIS K7234.

<< Microcapsule type latent curing agent for epoxy resin (F) >>
The microcapsule type latent curing agent (F) for epoxy resin of the present embodiment includes a core and a shell, and the core includes the above-mentioned curing agent for epoxy resin (D).

  The microcapsule-type latent curing agent for epoxy resin of the present embodiment has a core containing the above-mentioned curing agent for epoxy resin (D) and a shell (S), whereby the void permeability of the epoxy resin composition and Disclosed is an epoxy resin composition capable of improving liquid flow, obtaining a cured product having high Tg, elastic modulus and adhesive strength, and having excellent storage stability, and a material containing the epoxy resin composition. be able to.

  In the microcapsule type latent curing agent for epoxy resin of the present embodiment, the average particle diameter of the curing agent (D) for epoxy resin contained in the core is preferably more than 0.3 μm and 12 μm or less.

  When the average particle diameter of the curing agent for epoxy resin (D) contained in the core exceeds 0.3 μm, the curing agents for epoxy resin are less likely to aggregate with each other, and the microcapsule type latent curing agent for epoxy resin (F) Formation of the epoxy resin composition tends to be easy, and the storage stability of the epoxy resin composition tends to be sufficient. When the average particle diameter of the curing agent (D) for an epoxy resin contained in the core is 12 μm or less, a homogeneous cured product tends to be obtained. In addition, when the average particle size of the curing agent for epoxy resin (D) contained in the core is within the above range, the epoxy resin composition is characterized by including a diluent, a filler, a pigment, a dye, a flow control agent, and a thickener Hard to form aggregates when blended with toughening agents, mold release agents, wetting agents, stabilizers, flame retardants, surfactants, organic solvents, conductive fine particles, crystalline alcohols, other resins, etc. The elastic modulus and Tg of the material tend to be high, and the adhesive strength also tends to be high.

  From the above viewpoint, the average particle diameter of the epoxy resin curing agent (D) contained in the core is preferably 0.7 μm or more and 10 μm or less, more preferably 1 μm or more and 5 μm or less. The average particle diameter as referred to herein means an average particle diameter defined by a median diameter. More specifically, it refers to a Stokes diameter measured by a laser diffraction / light scattering method using a particle size distribution analyzer ("HORIBA LA-920" manufactured by Horiba, Ltd.).

  Here, the method for controlling the average particle diameter of the curing agent (D) for epoxy resin is not particularly limited, and several methods may be mentioned. For example, a method of performing precise control in the grinding process of a bulk curing agent for epoxy resin, a coarse grinding process and a milling process as a grinding process of a bulk curing agent for epoxy resin, and using a more accurate classification device A method of classifying the desired average particle diameter, a method of spray-drying a curing agent solution for epoxy resin having a bulk curing agent for epoxy resin dissolved in a solvent, a high solubility of the curing agent for epoxy resin By adding a poor solvent with poor solubility of the curing agent for epoxy resin to the curing agent solution for epoxy resin dissolved by adding a solvent and adding it under strong stirring, a curing agent particle for epoxy resin having a desired particle diameter is precipitated And the like.

  The apparatus used for the pulverization is not particularly limited, but for example, a ball mill, an attritor, a bead mill, a jet mill or the like can be adopted as necessary, and it is preferable to use an impact type pulverizer. The impact type pulverizing apparatus is not particularly limited, and examples thereof include jet mills such as a swirling powder impact type jet mill and a powder impact type counter jet mill. The jet mill is an apparatus for colliding solid materials with one another by means of a high-speed jet flow using air or the like as a medium, to form fine particles. The method of precisely controlling the pulverization is not particularly limited, and examples thereof include a method of controlling the temperature at the time of pulverization, humidity, the amount of pulverization per unit time, and the like.

  The method for precisely classifying the pulverized product is not particularly limited. For example, a sieve (for example, a standard sieve such as 325 mesh or 250 mesh) is used to obtain powder particles having a predetermined average particle diameter by classification after pulverization. A method of classification using a classifier, a method of classification using wind power according to the specific gravity of particles, and the like can be mentioned. Although it does not specifically limit as a classifier to be used, For example, a wet classifier and a dry classifier are mentioned, Generally, a dry classifier is preferable. Such classifiers are not particularly limited. For example, “Elbow Jet” manufactured by Nittetsu Mining Co., Ltd., “Fine Sharp Separator” manufactured by Hosokawa Micron Corporation, “Variable impactor” manufactured by Sankyo Denki Co., Ltd., manufactured by Seishin Enterprise Co., Ltd. 'Specic Classifier', 'Donaselec' from Nippon Donaldson, 'Yem Microcassette' from Yaskawa Shoji, 'Turbo Classifier' from Nisshin Engineering, and various other air separators, micron separators, micro breakfasts, Dry classification devices such as Accucut are listed.

  The method for directly granulating the particles instead of grinding is not particularly limited, but for example, there is a method of spray-drying a curing agent solution for epoxy resin in which a bulk curing agent for epoxy resin is dissolved in a solvent. Specifically, there is a method of uniformly dissolving the curing agent (D) for an epoxy resin in a suitable organic solvent, and then spraying it as a microdroplet in a solution state and then drying it with hot air or the like. Although it does not specifically limit as a drying apparatus in this case, For example, a normal spray-drying apparatus is mentioned. In addition, after the curing agent for epoxy resin (D) is uniformly dissolved in a suitable organic solvent, the poor solution of the curing agent for epoxy resin (D) is added while vigorously stirring the uniform solution, thereby curing the epoxy resin. Agent (D) is precipitated in the form of fine particles, and the precipitated particles are separated by filtration, and then the solvent is removed by drying at a temperature lower than the melting point of the curing agent for epoxy resin (D). There is also a method of obtaining a curing agent for resin (D).

  The method for adjusting the average particle diameter of the epoxy resin curing agent (D) in the particle state by a method other than classification is not particularly limited. For example, by mixing a plurality of particles having different average particle diameters, The method etc. which adjust an average particle diameter are mentioned. For example, in the case of a large particle size epoxy resin curing agent which is difficult to grind or classify, the average particle size becomes the above range by adding and mixing another small particle size epoxy resin curing agent. It can also be used as a curing agent for epoxy resin. The epoxy resin curing agent (D) thus obtained may be further classified, if necessary.

  The mixer used for the purpose of mixing such powder is not particularly limited. For example, a container rotation type mixer for rotating a container main body containing powder to be mixed, a container main body containing powder The container fixed type mixer which mixes by mechanical stirring and airflow stirring without rotating, the compound type mixer which rotates a container containing powder, and mixes using other external force etc. is mentioned.

  The shape of the curing agent (D) for an epoxy resin contained in the core is not particularly limited, and may be, for example, spherical, granular, powdery, indeterminate or the like. Among these, from the viewpoint of handling in processing of the epoxy resin composition, the spherical shape is preferable. The term "spherical" includes not only true spheres but also irregular shapes with rounded corners.

  The epoxy resin curing agent (D) contained in the core may be used singly or in combination of two or more.

<Shell (S)>
The microcapsule type latent curing agent (F) for an epoxy resin of the present embodiment has a core containing a curing agent (D) for an epoxy resin having an average particle diameter of more than 0.3 μm and 12 μm or less, and the surface of the core It is preferable to have a structure covered by a shell (S) containing a synthetic resin. The synthetic resin contained in the shell (S) is not particularly limited, but among synthetic resins, for example, epoxy resins, from the viewpoint of film stability, ease of breakage at the time of heating, and uniformity of a cured product. And phenolic resins, polyester resins, polyethylene resins, nylon resins, polystyrene resins, urethane resins and the like. Among these, epoxy resins, phenol resins and urethane resins are preferable.

  The epoxy resin is not particularly limited. For example, an epoxy resin having two or more epoxy groups, a resin produced by a reaction of a compound having two or more epoxy groups and a compound having two or more active hydrogens, The reaction product etc. of the compound which has the above epoxy group, the compound which has one active hydrogen and a carbon-carbon double bond, etc. are mentioned. Among these, from the viewpoint of the stability of the epoxy resin composition and the low-temperature short-time curability, a resin formed by the reaction of a compound having two or more epoxy groups and a compound having two or more active hydrogens, particularly an amine type The reaction product of a curing agent with a compound having two or more epoxy groups is preferred. Among these, the reaction product of an amine curing agent and an epoxy resin is preferable from the viewpoint of the film stability and the low-temperature short-time curability of the epoxy resin composition.

  The phenolic resin is not particularly limited. For example, polycondensate of phenol and formaldehyde, polycondensate of cresol and formaldehyde, polycondensate of resorcinol and formaldehyde, polycondensate of bisphenol A and formaldehyde, Examples thereof include polyethylenepolyamine modified products of polycondensates of phenol and formaldehyde.

  The polyester resin is not particularly limited. For example, a polycondensate of ethylene glycol, terephthalic acid and polypropylene glycol, a polycondensate of ethylene glycol, butylene glycol and terephthalic acid, terephthalic acid, ethylene glycol and polyethylene glycol And the like.

  The polyethylene-based resin is not particularly limited, and examples thereof include a copolymer of ethylene, propylene and vinyl alcohol, a copolymer of ethylene and vinyl acetate, a copolymer of ethylene, vinyl acetate and acrylic acid, and the like. Be

  The nylon-based resin is not particularly limited. For example, a polycondensate of adipic acid and hexamethylene diamine, a polycondensate of sebacic acid and hexamethylene diamine, a polycondensate of p-phenylenediamine and terephthalic acid, etc. Can be mentioned.

  The polystyrene resin is not particularly limited. For example, a copolymer of styrene and butadiene, a copolymer of styrene, butadiene and acrylonitrile, a copolymer of acrylonitrile, styrene and divinylbenzene, styrene and propenyl alcohol And copolymers of the above.

  The urethane-based resin is not particularly limited, but examples thereof include butyl isocyanate, cyclohexyl isocyanate, octadecyl isocyanate, phenyl isocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tolidine diisocyanate, naphthalene diisocyanate, and triethyl isocyanate. An isocyanate monomer such as phenylmethane triisocyanate or a condensate thereof, a polymer thereof, and a polycondensate of a monoalcohol and a polyhydric alcohol, and the like can be mentioned. Among these, a urethane resin which is an addition product of monoalcohol or polyhydric alcohol and monoisocyanate or polyhydric isocyanate is preferable.

  In addition, as the shell (S), at least two selected from the group consisting of an isocyanate compound, an active hydrogen compound, a curing agent for an epoxy resin (h1), an epoxy resin (e2), and a low molecular weight amine compound (G) are reacted It is preferable to include the reaction product obtained by

  Although it does not specifically limit as an isocyanate compound of the raw material of the said reaction product, For example, the isocyanate compound demonstrated as a raw material of amine adduct (A) can be used.

  The active hydrogen compound is not particularly limited, and examples thereof include water, a compound having at least one primary amino group and / or a secondary amino group, and a compound having at least one hydroxyl group. Moreover, an active hydrogen compound may be used individually by 1 type, and may use 2 or more types together.

  The compound having at least one primary amino group and / or secondary amino group is not particularly limited, and examples thereof include aliphatic amines, alicyclic amines, aromatic amines and the like.

  The aliphatic amine is not particularly limited, and examples thereof include alkylamines such as methylamine, ethylamine, propylamine, butylamine and dibutylamine, alkylene diamines such as ethylene diamine, propylene diamine, butylene diamine and hexamethylene diamine; diethylene triamine and triethylene Polyalkylene polyamines such as tetramine and tetraethylene pentamine; and polyoxyalkylene polyamines such as polyoxypropylene diamine and polyoxyethylene diamine.

  The alicyclic amine is not particularly limited, and examples thereof include cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, isophorone diamine and the like.

  The aromatic amine is not particularly limited, and examples thereof include aniline, toluidine, benzylamine, naphthylamine, diaminodiphenylmethane, diaminodiphenyl sulfone and the like.

  The compound having at least one hydroxyl group is not particularly limited, and examples thereof include alcohol compounds and phenol compounds.

  The alcohol compound is not particularly limited, and, for example, methyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, dotesil alcohol, Mono compounds such as stearyl alcohol, eicosyl alcohol, allyl alcohol, crotyl alcohol, propargyl alcohol, cyclopentanol, cyclohexanol, benzyl alcohol, cinnamyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monobutyl and the like Alcohols; ethylene glycol, polyethylene glycol, propylene glycol Polyhydric alcohols such as polypropylene glycol, 1,3-butanediol, 1,4-butanediol, hydrogenated bisphenol A, neopentyl glycol, glycerin, trimethylolpropane and pentaerythritol; compounds having at least one epoxy group And one or more compounds having two or more secondary hydroxyl groups in one molecule, which are obtained by the reaction of a compound having at least one hydroxyl group, carboxyl group, primary amino group, secondary amino group, or thiol group. Alcohol and the like. Among these alcohol compounds, any of primary alcohol, secondary alcohol and tertiary alcohol may be used.

  The phenol compound is not particularly limited, and examples thereof include monophenols such as carlic acid, cresol, xylenol, carvacrol, motile, naphthol, catechol, resorcinol, hydroquinone, bisphenol A, bisphenol F, pyrogallol, phloroglucin, 2- (dimethyl) Polyphenols such as aminomethyl) phenol and 2,4,6-tris (dimethylaminomethyl) phenol are listed.

  The compound having at least one hydroxyl group is preferably a polyhydric alcohol or polyhydric phenol, and more preferably a polyhydric alcohol, from the viewpoint of latent ability or solvent resistance.

  The curing agent (h1) for an epoxy resin may be the same as or different from the curing agent (D) for an epoxy resin described above, but is preferably the same.

  Although it does not specifically limit as an epoxy resin (e2), For example, the epoxy resin mentioned by the epoxy resin (e1) mentioned above can be used. Among these, preferred is a polyvalent epoxy compound. The epoxy resin (e2) may be the same as or different from the epoxy resin (e1), a polyvalent epoxy resin described later, and the like. As an epoxy resin (e2), you may use individually by 1 type, and may use 2 or more types together.

  The low molecular weight amine compound (G) is not particularly limited, but, for example, the low molecular weight amine compounds mentioned for the low molecular weight amine compound (B) described above can be used.

  The conditions for reacting any two or more of the above-mentioned isocyanate compound, active hydrogen compound, curing agent for epoxy resin (h1), epoxy resin (e2), and low molecular weight amine compound (G) are as follows: Although it does not specifically limit, For example, it is the reaction time of 10 minutes-12 hours in the temperature range of -10 degreeC-150 degreeC.

  The compounding ratio in the case of using an isocyanate compound and an active hydrogen compound is preferably (isocyanate group in the isocyanate compound) :( active hydrogen in the active hydrogen compound) (equivalent ratio), preferably 1: 0.1 to 1: 1000. Range.

  The compounding ratio in the case of using the curing agent (h1) for an epoxy resin and the epoxy resin (e2) is preferably 1 as (curing agent for an epoxy resin (h1)) :( epoxy resin (e2)) (mass ratio) : 0.001 to 1: 1000, and more preferably 1: 0.01 to 1: 100.

  The above reaction can be carried out in a dispersion medium, if necessary. The dispersion medium is not particularly limited, and examples thereof include a solvent, a plasticizer, and resins. The solvent is not particularly limited, but, for example, hydrocarbons such as benzene, toluene, xylene, cyclohexane, hexane, heptane, octane, mineral spirits, naphtha; linear ethers such as dimethyl ether, diethyl ether, ethyl methyl ether; Cyclic ethers such as tetrahydrofuran, tetrahydropyran; nitriles such as acetonitrile, propionitrile, butyronitrile; amides such as acetamide, formamide, N, N-dimethylacetamide, N, N-dimethylformamide; dimethyl sulfoxide, diethyl sulfoxide, etc. Sulfoxides; acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), ketones such as isophorone; ethyl acetate, n-butyl acetate, propylene glycol Esters such as monomethyl ether acetate; methanol, ethanol, isopropanol, n- butanol, butyl cellosolve, alcohols such as butyl carbitol; water and the like. The plasticizer is not particularly limited. For example, phthalic acid diester plasticizers such as dibutyl phthalate and di (2-ethylhexyl) phthalate; Aliphatic dibasic acid ester such as di (2-ethylhexyl) adipate Plasticizers; phosphate triester plasticizers such as tricresyl phosphate; and glycol ester plasticizers such as polyethylene glycol esters. The resins are not particularly limited, and examples thereof include silicone resins, epoxy resins, and phenol resins.

  Among the above, in the reaction of the epoxy resin (e2) and the epoxy resin curing agent (h1), the reaction temperature is preferably -10 ° C to 150 ° C, more preferably 0 ° C to 100 ° C, and the reaction time is Preferably, it is 1 hour to 168 hours, more preferably 2 hours to 72 hours. The dispersion medium is preferably a solvent or a plasticizer.

  The proportion of the reaction product obtained by the above reaction in the shell (S) is usually 1% by mass or more, preferably 50% by mass or more, and may be 100% by mass. .

In the microcapsule type latent curing agent (F) for epoxy resin of the present embodiment, the method for forming the shell (S) for covering the surface of the core is not particularly limited, but for example, the following methods may be mentioned Be
(1) After dissolving and dispersing the components of the shell (S) and the curing agent for epoxy resin (D) having an average particle diameter of more than 0.3 μm and 12 μm or less in a solvent which is a dispersion medium, The method of making the solubility of the component of the shell (S) in a dispersion medium lower, and depositing a shell (S) on the surface of the particle | grains of the hardening agent for epoxy resins (D).
(2) The particles of the curing agent for epoxy resin (D) having an average particle diameter of more than 0.3 μm and 12 μm or less are dispersed in a dispersion medium, and the material forming the above shell (S) is added to the dispersion medium Method of depositing the shell (S) on the particles of the curing agent (D) for epoxy resin.
(3) The raw material component which forms said shell (S) to a dispersion medium is added, and the surface of the particle | grains of the hardening agent for epoxy resins (D) which is 12 micrometers or less exceeding average particle diameter 0.3 micrometer is shell (S 2.) A method of precipitating a shell (S) as a place of reaction of the formed material.

  Here, the methods (2) and (3) are preferable because the reaction and the coating can be performed simultaneously. The dispersion medium is not particularly limited, and examples thereof include solvents, plasticizers, and resins. The solvent, the plasticizer and the resin are not particularly limited. For example, the above-mentioned isocyanate compound, active hydrogen compound, curing agent for epoxy resin (h1), epoxy resin (e2), and the low molecular weight amine compound (G The solvents, plasticizers and resins listed as examples of the resin which can be used to obtain a reaction product by reacting any two or more of the above can be used.

  The method for separating the microcapsule type latent curing agent (F) for epoxy resin from the dispersion medium after forming the shell (S) by the methods (2) and (3) is not particularly limited, but the shell (S) It is preferable to separate and remove the unreacted raw material with the dispersion medium after the formation of. As such a method, although not particularly limited, for example, a method of removing the dispersion medium and unreacted shell-forming material by filtration may be mentioned.

  After removing the dispersion medium, it is preferable to wash the microcapsule type latent curing agent (F) for epoxy resin. By washing the microcapsule type latent curing agent (F) for epoxy resin, an unreacted shell (S) adhering to the surface of the microcapsule type latent curing agent (F) for epoxy resin is formed. The material can be removed.

  The washing method is not particularly limited, but the residue by the above-mentioned filtration may be washed using a dispersion medium or a solvent which does not dissolve the microcapsule type latent curing agent (F) for epoxy resin. The microcapsule type latent curing agent (F) for epoxy resin can be obtained in a powdery form by drying the microcapsule type latent curing agent (F) for epoxy resin after filtration and washing. Although the method of drying is not particularly limited, a method of drying at a temperature equal to or lower than the melting point or softening point of the curing agent (D) for an epoxy resin is preferable, and, for example, vacuum drying can be mentioned. Compounding with the epoxy resin (E) can be easily applied by making the microcapsule type latent curing agent (F) for epoxy resin into a powder form. Moreover, when an epoxy resin (E) is used as a dispersion medium, an epoxy resin composition containing an epoxy resin (E) and a microcapsule type latent curing agent (F) for an epoxy resin can be obtained simultaneously with shell formation. Because it is suitable.

  In the formation reaction of the shell (S), the reaction temperature is preferably −10 ° C. to 150 ° C., more preferably 0 ° C. to 100 ° C., and the reaction time is preferably 10 minutes to 72 hours, more preferably 30 minutes to 24 hours.

Also, the shell (S), from the viewpoint of the balance of the storage stability of the epoxy resin composition and the reactivity, and urea bond group that absorbs infrared wave number 1630～1680Cm ^-1, infrared wave number 1680～1725Cm ^-1 It is preferable to have the burette bonding group which absorbs and the urethane bonding group which absorbs the infrared rays of wavenumber 1730-1755 cm < ^-1 >.

  Such a shell (S) having a urea bonding group, a burette bonding group and a urethane bonding group is, for example, an isocyanate compound, an active hydrogen compound, a curing agent for an epoxy resin (h1), an epoxy resin (e2), and a low molecular weight amine It can form by making 2 or more types selected from the group which consists of a compound (G) react.

  The urea bond group, the buret bond group and the urethane bond group can be measured using a Fourier transform infrared spectrophotometer (hereinafter sometimes referred to as "FT-IR"). Moreover, it can be confirmed by microscopic FT-IR that the shell (S) has a urea bonding group, a buret bonding group and a urethane bonding group. Specifically, it can be confirmed by the method described in the examples described later.

  The thickness of the shell (S) is preferably 5 nm to 1000 nm, and more preferably 10 nm to 100 nm. The storage stability of the epoxy resin composition can be further improved by setting the thickness of the shell (S) to 5 nm or more. Further, by setting the thickness of the shell (S) to 1000 nm or less, the curability of the epoxy resin composition can be further improved. Here, the thickness is an average layer thickness and can be measured by a transmission electron microscope.

«Epoxy resin composition»
The epoxy resin composition of the present embodiment is
100 parts by mass of the above-mentioned microcapsule type latent curing agent (F) for epoxy resin, and 10 parts by mass or more of at least one epoxy resin (E) selected from the group consisting of monoepoxy resin and polyvalent epoxy resin It is preferable to contain 50000 mass parts or less.

  In the epoxy resin composition of the present embodiment, the content of the epoxy resin (E) is more preferably 50 parts by mass or more and 10000 parts by mass with respect to 100 parts by mass of the microcapsule type latent curing agent (F) for epoxy resin Or less, more preferably 100 parts by mass or more and 5000 parts by mass or less. By making content of the epoxy resin (E) with respect to 100 mass parts of microcapsule type latent curing agents (F) for epoxy resin into the said range, the storage stability of an epoxy resin composition and the low temperature short-time curability are further improved. At the same time, the modulus of elasticity, Tg and adhesive strength of the cured product are further improved.

  As said epoxy resin (E), the same epoxy resin as said epoxy resin (e1) can be used, Especially, a polyvalent epoxy compound can be used suitably. It is also possible to use multiple types in combination. Among them, epoxy resins obtained by glycidylating polyhydric phenols are preferable from the viewpoints of adhesion and heat resistance of the cured product to be obtained, and bisphenol type epoxy resins are particularly preferable. In particular, glycidyl compounds of bisphenol A and glycidyl compounds of bisphenol F are preferred. As described above, since the impurity end to which chlorine in the molecule of the epoxy resin is bonded adversely affects the electrical properties of the cured product, the total amount of chlorine contained in the epoxy resin (E) is preferably 2500 ppm or less. More preferably, it is 1500 ppm or less, still more preferably 500 ppm or less. Moreover, chlorine contained in the 1,2-chlorohydrin group among the total chlorine is generally called hydrolyzable chlorine. The hydrolyzable chlorine content of the epoxy resin (E) is preferably 50 ppm or less from the viewpoint of further improving the balance between the curability and storage stability of the epoxy resin composition and securing the long-term reliability of the cured product. More preferably, it is 20 ppm or less, and more preferably 10 ppm or less. The lower limit of the hydrolyzable chlorine content of the epoxy resin (E) is preferably 0.01 ppm or more, and preferably 0.05 ppm or more.

  The epoxy resin composition of the present embodiment contains the aforementioned microcapsule type latent curing agent for epoxy resin (F), an epoxy resin (E) and a nitrogen-containing heterocyclic compound (P), and the nitrogen-containing heterocyclic compound described above It is preferable that content of (P) is 0.01 mass part or more and 15 mass parts or less with respect to 100 mass parts of said epoxy resins (E).

（式（１）中、ｎは０又は１を表し、
ｘは２以上１５以下の整数、ｙは３以上３０以下の整数、ｚは０以上５以下の整数を表し、
Ｒ₁は、炭素数１〜１５のアルキル基、炭素数１〜６のアルコキシ基、アミノ基、カルボキシル基、カルボン酸エステル基、カルバミン酸エステル基、スルホ基、スルホニル基、ヒドロキシ基、及びニトロ基からなる群より選ばれる少なくとも１価の基を表し、
ａは１以上５以下の整数を表す。ａが２以上のときは、複数のＲ₁は同一でも異なっていてもよい。） <Nitrogen-containing heterocyclic compound (P)>
The nitrogen-containing heterocyclic compound (P) used in the present embodiment is not limited as long as it contains a nitrogen atom in the ring structure, but preferably has a structure represented by the following formula (1).

(In the formula (1), n represents 0 or 1;
x is an integer of 2 to 15, y is an integer of 3 to 30, and z is an integer of 0 to 5,
R ₁ is an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an amino group, a carboxyl group, a carboxylic acid ester group, a carbamic acid ester group, a sulfo group, a sulfonyl group, a hydroxy group, and a nitro group And at least one monovalent group selected from the group consisting of
a represents an integer of 1 or more and 5 or less. When a is 2 or more, plural R _{1 s} may be the same or different. )

  The nitrogen-containing heterocyclic compound (P) is a monocyclic, bicyclic or tricyclic hetero ring having 3 to 16 atoms forming a ring and containing one or more and six or less nitrogen atoms. The aryl group may be an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an amino group, a carboxyl group, a carboxylic acid ester group, a carbamic acid ester group, a sulfo group, a sulfonyl group, a hydroxy group, and a nitro group Compounds having at least a monovalent group selected from the group consisting of

  Here, each of the alkyl group, alkoxy group, amino group, carboxyl group, carboxylic acid ester group, carbamic acid ester group, sulfo group and sulfonyl group may have a substituent, and the substituent is not particularly limited. Examples thereof include an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an alkylene group, an alkoxy group, a hydroxy group, an aryl group and an aralkyl group. The alkyl group of the substituent may have a hydroxy group or a carboxyl group.

  In the above formula (1), the alkyl group is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s-butyl group and an i-butyl group, C1-C15 alkyl groups, such as t-butyl group, n-pentyl group, n-hexyl group, etc. are mentioned. The cycloalkyl group means a monovalent cyclic group composed of 3 to 15 carbon atoms, and may be saturated, partially saturated or unsaturated. Such a cycloalkyl group is not particularly limited, and examples thereof include cycloalkyl groups having 3 to 15 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and adamantane structures. Can be mentioned. The cycloalkenyl group is not particularly limited, and examples thereof include cyclopropenyl, cyclobutenyl, 1,3-cyclobutadienyl, cyclopentenyl, 1,3-cyclopentadienyl, cyclohexenyl, 1,3-cyclohexadienyl, and the like. 1, 4- cyclohexadienyl etc. are mentioned. The alkenyl group is not particularly limited, and examples thereof include a vinyl group, an allyl group, 1-propenyl group, isopropenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-butenyl group, The alkenyl group having 2 to 15 carbon atoms such as 2-butenyl group, 3-butenyl group, 1-pentenyl group, 1-hexenyl group, 1,3-hexadienyl group, 1,5-hexadienyl group and the like can be mentioned. The alkynyl group is not particularly limited, and examples thereof include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-ethynyl-2-propynyl group, 1 The alkynyl group having 2 to 15 carbon atoms, such as -methyl-2-propynyl group, 1-pentynyl group, 1-hexynyl group, 1,3-hexadiinyl group, 1,5-hexadiinyl group and the like can be mentioned. The aryl group means a monocyclic or polycyclic aryl group. Here, in the case of a polycyclic aryl group, in addition to full unsaturation, a partially saturated group is also included. Such an aryl group is not particularly limited, and examples thereof include phenyl group, indenyl group, naphthyl group, azulenyl group, heptalenyl group, biphenyl group, indasenyl group, acenaphthylenyl group, fluorenyl group, phenalenyl group, phenanthrenyl group, anthracenyl group. And aryl groups having 6 to 15 carbon atoms such as cyclopentacyclooctenyl group or benzocyclooctenyl group. The alkoxy group is not particularly limited. For example, carbon such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, s-butoxy group, i-butoxy group, t-butoxy group and the like A number 1-15 alkoxy group is mentioned.

  The aralkyl group is a group in which the above-mentioned aryl group and alkyl group are bonded, and is not particularly limited. For example, benzyl group, phenethyl group, 3-phenyl-n-propyl group, 1-phenyl-n-hexyl group, Aryl group having 6 to 10 carbon atoms such as naphthalene-1-ylmethyl group, naphthalene-2-ylethyl group, 1-naphthalen-2-yl-n-propyl group, inden-1-ylmethyl group and the like, and 1 to 6 carbon atoms The group which the alkyl group couple | bonded is mentioned.

  CxHyNz and CHn in the above formula (1) may be directly linked or may be linked by another linking group. The linking group is not particularly limited, and examples thereof include an alkylene group and an alkylene oxide group. The alkylene group is not particularly limited. For example, methylene group, ethylene group, methyl ethylene group, ethyl ethylene group, 1,1-dimethyl ethylene group, 1,2-dimethyl ethylene group, trimethylene group, 1-methyl trimethylene Groups, and C1-C15 alkylene groups, such as a 2-methyl trimethylene group and a tetramethylene group, are mentioned.

  The epoxy resin composition of the present embodiment contains a nitrogen-containing heterocyclic compound (P) and is a cured product having excellent storage stability and short-term short-term curability, high elastic modulus, high Tg and high adhesive strength. Is obtained. Although this mechanism is not clear, the present inventors think as follows. That is, the epoxy resin composition of the present embodiment contains the nitrogen-containing heterocyclic compound (P), thereby uniformly diffusing the curing agent component of the microcapsule type latent curing agent (F) for epoxy resin at the time of low temperature curing. In a situation where the hardening and curing growth reactions proceed in parallel, it is presumed that it suppresses the formation of oligomers due to the partial curing growth reaction, and has the function of contributing to the improvement of the elastic modulus of the cured product, Tg improvement and adhesive strength expression. ing. In addition, even when elution of the curing agent component or the like occurs in the step of processing the epoxy resin composition of the present embodiment, the curing and growth reaction is temporarily suppressed, without impairing the homogeneity of the cured product, It is presumed that it effectively acts on the physical properties of the cured product at a desired curing temperature.

  In addition, unlike organic metal compounds such as organic chelating agents, nitrogen-containing heterocyclic compounds (P) are compounds that are less harmful to the environment, and do not require complicated separation processing even at the time of disposal and recycling. It is useful.

  In the epoxy resin composition of the present embodiment, the content of the nitrogen-containing heterocyclic compound (P) is preferably 0.01 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the epoxy resin (E). More preferably, it is 0.05 parts by weight or more and 12 parts by weight or less, more preferably 0.1 parts by weight or more and 10 parts by weight or less, still more preferably 0.2 parts by weight or more and 8 parts by weight or less. The epoxy resin composition of the present embodiment contains the nitrogen-containing heterocyclic compound (P) in an amount of 0.01 parts by mass or more based on 100 parts by mass of the epoxy resin (E), whereby the elastic modulus, Tg and Demonstrates the effect of improving adhesion strength. The epoxy resin composition in which the content of the nitrogen-containing heterocyclic compound (P) is 15 parts by mass or less does not inhibit the low temperature curing property of the microcapsule type latent curing agent (F) for epoxy resin, and the elasticity of the cured product It is possible to suppress the decrease in the rate, Tg and adhesive strength.

  Here, the nitrogen-containing heterocyclic compound (P) preferably contains at least one derivative selected from the group consisting of pyridine derivatives, pyrimidine derivatives, pyrazine derivatives, triazine derivatives, quinoline derivatives, isoquinoline derivatives, and purine derivatives. . Among these derivatives, derivatives having a carboxyl group are more preferable.

  The pyridine derivative is not particularly limited. For example, 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine, 2,3-dihydroxypyridine, 2,4-dihydroxypyridine, 2-hydroxy-3-nitropyridine 2-hydroxy-5-nitropyridine, 3-hydroxy-2-nitropyridine, 4-hydroxy-3-nitropyridine, 2-amino-3-hydroxypyridine, 2-hydroxy-4-methylpyridine, 2-hydroxy-5 -Methylpyridine, 2-hydroxy-6-methylpyridine, 3-hydroxy-2-methylpyridine, nicotinic acid, isonicotinic acid, 2-hydroxynicotinic acid, 3-hydroxy-2-pyridinecarboxylic acid, 6-hydroxynicotinic acid 6-hydroxy-2-pyridinecarboxylic acid 2,6-Dihydroxyisonicotinic acid, 2,6-dimethyl-3-hydroxypyridine, 3-hydroxy-6-methyl-2-pyridinemethanol, 2-hydroxy-6-methylnicotinic acid, 2-methoxynicotinic acid, 3 -Pyridinesulfonic acid, 4-hydroxy-3-pyridinesulfonic acid, 2-hydrazinopyridine, 2-acetamidopyridine, 2- (2-pyridylamino) ethanol, N- (2-pyridyl) -β-alanine, 2-amino Nicotinic acid, 4-aminonicotinic acid, 6-aminonicotinic acid, 6-methylnicotinic acid, 2-pyridinemethanol, 3-pyridinemethanol, 4-pyridinemethanol, 2-pyridinecarboxylic acid, 2,3-pyridinedicarboxylic acid, 2,5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,4-pyridine Gindicarboxylic acid, 3,5-pyridinedicarboxylic acid, 5-ethylpyridine-2,3-dicarboxylic acid, 2,2'-bipyridine-3,3'-dicarboxylic acid, 2,2'-bipyridine-4,4 ' -Dicarboxylic acid, nicotinamide, 2-pyridine ethanol etc. are mentioned.

  The pyrimidine derivative is not particularly limited. For example, 2-pyrimidine carboxylic acid, 3-pyrimidine carboxylic acid, 4-pyrimidine carboxylic acid, 5-pyrimidine carboxylic acid, 6-hydroxy-4-pyrimidine carboxylic acid, 4-pyrimidine carboxylic acid Acid methyl, 4,6-dihydroxy-5-nitropyrimidine, 4,6-dimethoxy-2- (methylsulfonyl) pyrimidine and the like.

  The pyrazine derivative is not particularly limited. For example, pyrazine carboxylic acid, 5-methylpyrazine-2-carboxylic acid, 3-aminopyrazine-2-carboxylic acid, 2,3-pyrazinedicarboxylic acid, pyrazine-2,3- Dicarboxylic acid monoamide etc. are mentioned.

  The triazine derivative is not particularly limited. For example, 1,2,4-triazine-3-carboxylic acid, 1,4,5,6-tetrahydro-4,6-dioxo-1,3,5-triazine-2 -Carboxylic acid etc. are mentioned.

  The quinoline derivative is not particularly limited. For example, 2-quinolinecarboxylic acid, 3-quinolinecarboxylic acid, 4-quinolinecarboxylic acid, 6-quinolinecarboxylic acid, 8-quinolinecarboxylic acid, 2-phenylquinoline-4-carboxylic acid Acid, methyl 6-quinolinecarboxylate, 2-hydroxyquinoline-4-carboxylic acid, 4-hydroxyquinoline-2-carboxylic acid, 8-hydroxyquinoline-7-carboxylic acid, 4,8-dihydroxyquinoline-2-carboxylic acid , Quinoline-2,3-dicarboxylic acid, 8-hydroxyquinoline-5-sulfonic acid, 2,2'-bicinchoninic acid, 5-nitroquinoline, 6-nitroquinoline, 8-nitroquinoline and the like.

  The isoquinoline derivative is not particularly limited, and examples thereof include isoquinoline-1-carboxylic acid, isoquinoline-3-carboxylic acid, isoquinoline-5-sulfonic acid, 5-nitroisoquinoline and the like.

  The purine derivative is not particularly limited, and examples thereof include 1H-purine-6-carboxylic acid, 9-methyl-9H-purine-8-carboxylic acid and the like.

  Particularly preferably, 2,3-pyridinedicarboxylic acid, 2,5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid, 2,2'-bipyridine-3,3'-dicarboxylic acid And 2,2'-bipyridine-4,4'-dicarboxylic acid, quinoline-2,3-dicarboxylic acid and 2,2'-bicinchoninic acid.

  Among the above compounds, the nitrogen-containing heterocyclic compound (P) is preferably a pyridine derivative, and more preferably 2,3-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, and quinoline-2,3-dicarboxylic acid.

«Method for producing epoxy resin composition»
In the method for producing the epoxy resin composition of the present embodiment, general stirring and mixing equipment and processing conditions similar to the method for producing an ordinary epoxy resin composition are applied. When the microcapsule type latent curing agent for epoxy resin (F) and the nitrogen-containing heterocyclic compound (P) are mixed with the epoxy resin (E), the mixing order is not particularly limited. For example, a microcapsule type latent curing agent for epoxy resin (F) and a nitrogen-containing heterocyclic compound (P) are added to an epoxy resin (E), and mixing rolls such as three rolls, dissolvers, planetary mixers, kneaders A method of mixing with an extruder etc., a method of adding a nitrogen-containing heterocyclic compound (P) after mixing the microcapsule type latent curing agent (F) for epoxy resin with the epoxy resin (E) by the above method, There is a method of uniformly mixing the nitrogen-containing heterocyclic compound (P) with the epoxy resin (E) and then mixing the microcapsule type latent curing agent (F) for the epoxy resin. The processing conditions may be heating to dissolve and / or reduce the viscosity of the epoxy resin (E) and improve the stirring and mixing efficiency, or after adding the solvent and making it uniform, the solvent is heated and removed. A method may be used. Also, cooling may be performed to remove frictional heat, reaction heat, and the like. The time of stirring and mixing may be determined as necessary, and is not particularly limited.

<Thermosetting resin>
In addition, the epoxy resin composition of the present embodiment can further contain at least one thermosetting resin selected from the group consisting of an oxetane resin, a monoepoxy resin, and a polyvalent epoxy resin.

  The oxetane resin is not particularly limited, and examples thereof include 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 1,3-bis (3-ethyloxetan-3-ylmethoxy) benzene, and 1,4-bis ( 3-ethyloxetan-3-ylmethoxy) benzene, 3-ethyl 3 {[(3-ethyloxetan-3-yl) methoxy] methyl} oxetane, 3-ethyl-3- (vinyloxymethyl) oxetane, 3-ethyl- 3- (methoxymethyl) oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (cyclohexyloxymethyl) oxetane, 3-ethyl-3-[(benzyloxy) methyl] oxetane etc. Be

  As the monoepoxy resin and the polyvalent epoxy resin, the above-mentioned epoxy resin (e1) can be mentioned as an example.

  The oxetane resin, monoepoxy resin and polyvalent epoxy resin may be used alone or in combination of two or more.

  In the epoxy resin composition of the present embodiment, the content of at least one thermosetting resin selected from the group consisting of oxetane resin, monoepoxy resin, and polyvalent epoxy resin is preferably 0.1% by mass or more and 99%. It is mass% or less, More preferably, it is 1 to 80 mass%, More preferably, it is 5 to 50 mass%.

<Hardener for epoxy resin (h2)>
In addition, the epoxy resin composition of the present embodiment is at least one epoxy selected from the group consisting of an acid anhydride curing agent, a phenol curing agent, a hydrazide curing agent, a guanidine curing agent, and a thiol curing agent. The resin curing agent (h2) can be further contained.

  The acid anhydride curing agent is not particularly limited, and examples thereof include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3-chlorophthalic anhydride, and anhydride- 4-chlorophthalic acid, benzophenone tetracarboxylic acid anhydride, succinic acid anhydride, methyl succinic acid anhydride, dimethyl succinic acid anhydride, dichloro succinic acid anhydride, methyl nadic acid, dogesic acid succinic acid, chlorendic acid anhydride, maleic acid anhydride and the like.

  The phenolic curing agent is not particularly limited, and examples thereof include phenol novolak, cresol novolac, bisphenol A novolac, liquid phenol novolac and the like.

  The hydrazide curing agent is not particularly limited. For example, succinic acid dihydrazide, adipic acid dihydrazide, phthalic acid dihydrazide, isophthalic acid dihydrazide terephthalic acid dihydrazide, p-hydroxybenzoic acid hydrazide, salicylic acid hydrazide, phenylaminopropionic acid hydrazide, maleic acid Acid dihydrazide etc. are mentioned.

  The guanidine curing agent is not particularly limited, and examples thereof include dicyandiamide, methyl guanidine, ethyl guanidine, propyl guanidine, butyl guanidine, butyl guanidine, dimethyl guanidine, trimethyl guanidine, phenyl guanidine, diphenyl guanidine, toluyl guanidine and the like.

  The thiol-based curing agent is not particularly limited. For example, trimethylolpropane tris (thioglycollate), pentaerythritol tetrakis (thioglycolate), ethylene glycol dithioglycollate, trimethylolpropane tris (β-thiopropionate) ), A thiol compound obtained by the esterification reaction of a thiol organic acid with a polyol such as pentaerythritol tetrakis (β-thiopropionate), dipentaerythritol poly (β-thiopropionate), and 1,4-butanedithiol Obtained by the reaction of an alkyl polythiol compound such as 1,6-hexanedithiol, 1,10-decanedithiol, etc., a terminal thiol group-containing polyether, a terminal thiol group-containing polythioether, an epoxy compound and hydrogen sulfide Thiol compounds, thiol compounds and the like having a terminal thiol group obtained by the reaction of a polythiol with the epoxy compound.

  In the epoxy resin composition of the present embodiment, the content of the curing agent (h2) for an epoxy resin is preferably 0.1% by mass to 99% by mass, and more preferably 1% by mass to 80% by mass. More preferably, they are 5 mass% or more and 50 mass% or less.

<Other ingredients>
In the epoxy resin composition of the present embodiment, as necessary, as a component other than the above-described components, a diluent, a filler, a pigment, a dye, a flow control agent, a thickener, a reinforcing agent, a mold release agent, and a wetting agent The composition may further contain an agent, a flame retardant, a surfactant, an organic solvent, conductive fine particles, crystalline alcohol, resins and the like.

  The diluent is not particularly limited, and for example, reactive diluents and non-reactive diluents can be used.

  The reactive diluent is not particularly limited, and examples thereof include cresol, ethylphenol, propylphenol, p-butylphenol, p-amylphenol, hexylphenol, octylphenol, nonylphenol, dodecylphenol, octadecylphenol and terpene phenol. . The nonreactive diluent is not particularly limited, and examples thereof include dioctyl phthalate, dibutyl phthalate, benzyl alcohol and the like.

  The filler is not particularly limited. For example, coal tar, glass fiber, asbestos fiber, boron fiber, carbon fiber, cellulose, polyethylene powder, polypropylene powder, quartz powder, mineral silicate, mica, asbestos powder, Slate powder etc. are mentioned.

  The pigment is not particularly limited. For example, kaolin, aluminum oxide trihydrate, aluminum hydroxide, chalk powder, gypsum, calcium carbonate, antimony trioxide, penton, silica, aerosol, lithopone, barite, titanium dioxide and the like It can be mentioned.

  The dyes are not particularly limited, but include, for example, natural dyes such as plant-derived dyes such as mulberry and mulberry, mineral-derived dyes such as loess and red earth, synthetic dyes such as alizarin and indigo, fluorescent dyes and the like Be

  The flow control agent is not particularly limited. For example, silane coupling agents; organic titanium compounds such as titanium tetraisopropoxide and titanium diisopropoxy bis (acetylacetonate); zirconium tetra normal butoxide and zirconium tetra acetyl aceton And organic zirconium compounds such as nitrate.

  The thickener is not particularly limited. For example, animal thickeners such as gelatin; vegetable thickeners such as polysaccharides and celluloses; polyacrylics, modified polyacrylics, polyethers, urethanes Modified polyethers, chemically synthesized thickeners such as carboxymethyl cellulose, and the like can be mentioned.

  Examples of the toughening agent include, but are not limited to, polyethylene sulfone powder such as "Sumica Excel PES" manufactured by Sumitomo Chemical Co., Ltd .; nanosized functional group-modified core-shell rubber particles such as "Kaneace MX" manufactured by Kaneka Co., Ltd .; Examples thereof include silicone-based toughening agents such as siloxane.

  Although it does not specifically limit as a mold release agent, For example, a fluorine-type mold release agent, a silicone type mold release agent, glycidyl (meth) acrylate, and a C16-C22 linear alkyl (meth) acrylic acid ester are co-produced. The acrylic mold release agent etc. which consist of polymers are mentioned.

  The wetting agent is not particularly limited, and examples thereof include unsaturated polyester copolymer-based wetting agents having an acidic group, such as acrylic polyphosphate esters.

  The flame retardant is not particularly limited. Examples thereof include metal hydroxides such as aluminum hydroxide and magnesium hydroxide, halogen-based flame retardants such as chlorine compounds and bromine compounds, phosphorus-based flame retardants such as condensed phosphate, and the like. Antimony flame retardants such as antimony oxide and antimony pentoxide; inorganic oxides such as silica filler; and the like.

  The surfactant is not particularly limited, but, for example, anionic surfactants such as alkyl benzene sulfonate and alkyl polyoxyethylene sulfate, cationic surfactants such as alkyl dimethyl ammonium salt, alkyl dimethyl amine oxide and alkyl Examples include amphoteric surfactants such as carboxybetaine, and nonionic surfactants such as linear alcohols having 25 or more carbon atoms and fatty acid esters.

  The organic solvent is not particularly limited, and examples thereof include toluene, xylene, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), ethyl acetate, butyl acetate and the like.

  The conductive fine particles are not particularly limited. For example, carbon black, graphite, carbon nanotube, fullerene, iron oxide, gold, silver, aluminum powder, iron powder, nickel, copper, zinc, chromium, solder, metal of nano size Crystals, intermetallic compounds and the like can be mentioned.

  The crystalline alcohol is not particularly limited, and examples thereof include 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, pentaerythritol, sorbitol, sucrose, trimethylolpropane and the like.

  The resins are not particularly limited. Examples thereof include polyester resins, polyurethane resins, acrylic resins, polyether resins, melamine resins, and urethane-modified epoxy resins, rubber-modified epoxy resins, and modified epoxy resins such as alkyd-modified epoxy resins. Be

  These added components can be added in functionally equivalent amounts, for example pigments and / or dyes can be added in amounts that will give the composition the desired color. In the epoxy resin composition of the present embodiment, the total amount of the additives is preferably 0 to 20% by mass, more preferably 0.5 to 5% by mass, and still more preferably 0.5 to 3%. %.

«Applications»
The material of this embodiment contains the above-mentioned microcapsule type latent curing agent for epoxy resin (F), or the above-mentioned epoxy resin composition.

  The material of the present embodiment can be formed, for example, by using the above-mentioned epoxy resin composition as a paste-like or film-like composition, and can be used for all uses (processed goods etc.) by processing as necessary. it can. In particular, the material of the present embodiment includes an adhesive, a bonding paste, a conductive material, an anisotropic conductive material, an insulating material, a sealing material, a coating material, a paint composition, a prepreg, a thermally conductive material, a fuel It can be suitably used as a battery separator material, an overcoat material for a flexible wiring board, and the like. Details will be described below.

  The adhesive and the bonding paste are not particularly limited, but are useful, for example, as a liquid adhesive, a film adhesive, a die bonding material, and the like. It does not specifically limit as a manufacturing method of a liquid adhesive agent, A well-known method can also be employ | adopted, for example, the method etc. which were described in Unexamined-Japanese-Patent No. 2000-319620 are mentioned. As an example, the following method may be mentioned. First, 100 parts by mass of bisphenol A epoxy resin as epoxy resin, 10 parts by mass of polymethacrylate (average particle diameter 1 μm) as particulate thermoplastic resin, and 10 parts by mass of isophthalic acid dihydrazide with average particle diameter 2 μm as particulate curing agent Blend and knead with a mixer. A liquid adhesive can be obtained by adding and dispersing an epoxy resin composition to this so that it may become a density | concentration of 30 mass%.

  The conductive material is not particularly limited, and examples thereof include conductive films and conductive pastes. Although it does not specifically limit as an anisotropically conductive material other than an anisotropically conductive film, For example, an anisotropically conductive paste etc. are mentioned. It does not specifically limit as a manufacturing method of a conductive material, A well-known method can also be employ | adopted, for example, the method etc. which were described in Unexamined-Japanese-Patent No. 2000-021236 are mentioned. More specifically, although not particularly limited, for example, solder particles which are conductive materials used in an anisotropic conductive film, nickel particles, nano-sized metal crystals, particles obtained by coating the surface of a metal with another metal, Resin particles such as graded particles of copper and silver, styrene resin, urethane resin, melamine resin, epoxy resin, acrylic resin, phenol resin, styrene-butadiene resin, etc. covered with conductive thin film such as gold, nickel, silver, copper, solder The particles and the like given above are made into spherical particles of about 1 to 20 μm, to which an epoxy resin composition is added, and if necessary, other solid epoxy resin, epoxy resin, etc. are added and mixed and dispersed with a triple roll etc. And a method of obtaining an anisotropic conductive paste.

  The insulating material is not particularly limited, and examples thereof include an insulating adhesive film and an insulating adhesive paste. By using the above-described bonding film, an insulating adhesive film which is an insulating material can be obtained. Moreover, an insulating adhesive paste can be obtained by mix | blending an insulating filler with an epoxy resin composition.

  Although it does not specifically limit as a sealing material, For example, a solid sealing material, a liquid sealing material, a film-form sealing material etc. are mentioned. In particular, the liquid sealing material is useful as an underfill material, potting material, dam material and the like. It does not specifically limit as a manufacturing method of sealing material, A well-known method is also employable, For example, the method etc. which were described in Unexamined-Japanese-Patent No. 05-043661 and Unexamined-Japanese-Patent No. 2002-226675 are mentioned. . More specifically, a sealing material can be obtained by adding bisphenol A type epoxy resin and further spherical fused silica powder and uniformly mixing, and adding the epoxy resin composition thereto and uniformly mixing.

  The coating material is not particularly limited, and examples thereof include a coating material of an electronic material, an overcoat material for a cover of a printed wiring board, a resin composition for interlayer insulation of a printed circuit board, and the like. The method for producing the coating material is not particularly limited, and a known method can be adopted, and for example, JP-B-04-006116, JP-A 07-304931, JP-A 08-064960, Methods described in JP-A-2003-246838 and the like can be mentioned. More specifically, a filler of silica, a bisphenol A type epoxy resin, a phenoxy resin, a rubber modified epoxy resin, etc. are blended, an epoxy resin composition is further blended with this, and a 50% solution with methyl ethyl ketone (MEK) Prepare and use as coating material. After the obtained coating material is applied on a surface of a polyimide film or the like to a thickness of about 50 μm, a coating material can be obtained by drying MEK. By laminating the film coated in this manner and a copper foil, laminating at 60 to 150 ° C., and then heat curing at 180 to 200 ° C., it is possible to obtain a laminate coated with a layer of a coating material it can.

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

  It does not specifically limit as a manufacturing method of a prepreg, A well-known method can be employ | adopted, For example, the method described in Unexamined-Japanese-Patent No. 09-071633, the international publication 98/044017 etc. is mentioned. More specifically, there is a method of impregnating a reinforcing substrate with an epoxy resin composition and heating it. Examples of the solvent for the varnish to be impregnated include methyl ethyl ketone (MEK), acetone, ethyl cellosolve, methanol, ethanol, isopropyl alcohol and the like. It is preferable that these solvents do not remain in the prepreg. The type of the reinforcing substrate is not particularly limited, and examples thereof include paper, glass cloth, glass nonwoven fabric, aramid cloth, liquid crystal polymer and the like. The ratio of the epoxy resin composition component to the reinforcing substrate is also not particularly limited, but in general, it is preferable that the epoxy resin composition component in the prepreg is prepared to be 20 to 80% by mass.

  It does not specifically limit as a manufacturing method of a heat conductive material, A well-known method is employable, For example, Unexamined-Japanese-Patent No. 06-136244, 10-237410, 2000-003987 is mentioned. And the like. More specifically, an epoxy resin as a thermosetting resin, a phenol novolac curing agent as a curing agent, and a graphite powder as a heat conductive filler are mixed and uniformly kneaded.

The method for producing the fuel cell separator material is not particularly limited, and any known method can be employed. For example, the methods described in JP-A-2002-332328 and JP-A-2004-075954 can be used. It can be mentioned. More specifically, materials are mixed with a mixer using an artificial graphite material as a conductive material, an epoxy resin as a thermosetting resin, a biphenyl type epoxy resin, a resol type phenol resin, and a novolac type phenol resin. The epoxy resin composition is added to the obtained mixture and uniformly dispersed to obtain a sealant molding material for a fuel cell. By compression molding this fuel cell sealing material molding material composition at a mold temperature of 170 to 190 ° C. and a molding pressure of 150 to 300 kg / cm ² , the conductivity is excellent and the gas impermeability is also good. A fuel cell separator material excellent in processability can be obtained.

  The method for producing the overcoat material for the flexible wiring substrate is not particularly limited, and any known method can be adopted, and it is described, for example, in WO00 / 064960 pamphlet, JP-A-2006-137838, etc. Methods are listed. More specifically, an epoxy resin, a carboxyl-modified polybutadiene reactive with the epoxy resin, rubber particles and the like are appropriately added to prepare an overcoat material for a flexible wiring board. The epoxy resin composition is added to this as a hardening accelerator, and it disperse | distributes uniformly. This is dissolved and dispersed in MEK to prepare an overcoat material solution for a flexible wiring board having a solid content concentration of 30% by mass. Furthermore, as a dicarboxylic acid, succinic acid is dissolved in pure water and added as a 5% by mass aqueous solution to the overcoat material solution for a flexible wiring board. An overcoat material solution for a flexible wiring substrate is applied to a polyimide film having a thickness of 65 μm so that the film thickness after drying becomes 25 μm, and further dried at 150 ° C. for 20 minutes to obtain an over flexible wiring substrate. Coating material can be obtained.

  Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the present invention is not limited to these examples. In addition, unless there is particular notice in the following, "part" represents a "mass part." In addition, the values obtained in the following physical property measurements are evaluated as “◎”, “○”, “Δ”, “×” or “××”, but “、” unless otherwise noted. If it is "(circle)" and "(triangle | delta)", it was judged as a practically sufficient value.

  In addition, unless otherwise indicated, the "triethylene tetramine" used the reagent by Wako Pure Chemical Industries, Ltd. without purifying in particular. These were each an ethylene amine mixture. In calculation of the preparation amount at the time of reaction, the equivalent was calculated assuming that the total amount is triethylenetetramine which is a linear (linear) structure.

〔viscosity〕
The viscosity was measured using a BM viscometer at 25 ° C.

[Epoxy equivalent (g / eq)]
An epoxy equivalent (g / eq) is mass (g) of the epoxy resin containing an epoxy group of 1 equivalent, and it calculated | required based on JISK7236.

[Total chlorine content (ppm)]
The total chlorine amount (ppm) was determined in accordance with JIS K7243-3. Specifically, an epoxy resin (E), an epoxy resin (e1), or an epoxy resin (e2) is heated under high temperature conditions in the presence of excess KOH to decompose all bound chlorine in each epoxy resin to generate The total amount of chlorine in each epoxy resin was determined by performing titration with silver nitrate (AgNO ₃ ) in a non-aqueous system using the obtained Cl ⁻ ion.

  As an automatic potentiometric titrator, "AT-400" manufactured by Kyoto Denshi Kogyo Co., Ltd. was used. As an electrode, a glass electrode "H-112" and a silver electrode "M-214" were used. For heating, a hot plate with a stirring stirrer function (manufactured by As One, "DP-1S") was used. A heat resistant glass container was used as a container for weighing and measuring a sample.

More specifically, the total chlorine amount was measured as follows.
1 to 10 g of the measurement sample was precisely weighed in a heat resistant glass container such that the titration amount was 3 to 7 mL. To the glass container, 25 mL of ethylene glycol monobutyl ether was added, and 25 mL of a propylene glycol solution of 1N KOH was added while stirring using a fluorocarbon stirrer, and the mixture was boiled at 240 ° C. or more for 20 minutes. The propylene glycol vapor generated at the time of boiling was refluxed to the heat resistant glass container by cooling and condensing. After boiling, the resulting solution was allowed to cool to room temperature. Thereafter, 200 mL of acetic acid is added to the solution, and the obtained solution is subjected to potentiometric titration in an automatic analysis mode using a 0.01 mol / L silver nitrate aqueous solution for analysis (manufactured by Wako Pure Chemical Industries, Ltd.) in an automatic analysis mode. I asked for. At that time, when the titration amount was 3 mL or less, or 7 mL or more, the weight of the sample precisely weighed in the heat resistant glass container was adjusted and measured again. And the titration amount of the blank which is a state without a sample was similarly calculated | required, and the total chlorine content in a sample was computed based on the following formula.

Total chlorine content (ppm) = {(v-v ₀ ) x f x 10 x 35.5} / W
(W: sample weight (g), v: titration amount (mL), v ₀ : blank titration amount (mL), f: factor of silver nitrate aqueous solution)

[Hydrolyzable chlorine content (ppm)]
The amount of hydrolyzable chlorine (ppm) was determined in accordance with JIS K7243-2. Specifically, hydrolyzable chlorine in the epoxy resin (E), the epoxy resin (e1), or the epoxy resin (e2) was determined in accordance with the following procedure.

  As an automatic potentiometric titrator, "AT-400" manufactured by Kyoto Denshi Kogyo Co., Ltd. was used. As an electrode, glass electrode "H-112" and silver electrode "M-214" were used. For heating (boiling), a hot plate with a stirring stirrer function (manufactured by As One, "DP-1S") was used. A heat-resistant glass container was used as a container for weighing and measuring the sample.

  3 g of the sample for measurement was precisely weighed in a heat resistant glass container. 50 mL of toluene was added to the glass container, 20 mL of a 0.1 N KOH solution in methanol was added while stirring with a fluorocarbon resin-made stirrer, and the mixture was boiled at 120 ° C. or more for 15 minutes. The vapor of toluene and methanol generated at the time of boiling was refluxed to the heat resistant glass container by cooling and condensing. After boiling, the resulting solution was allowed to cool to room temperature. Thereafter, 1 mL of acetic acid is added to the solution, and the obtained solution is subjected to potentiometric titration in an automatic analysis mode using a 0.002 mol / L silver nitrate aqueous solution for analysis (manufactured by Wako Pure Chemical Industries, Ltd.). I asked for. At that time, when the titration amount was 3 mL or less, or 7 mL or more, the weight of the sample precisely weighed in the heat resistant glass container was adjusted and measured again. And the titration amount of the blank which is a state without a sample was calculated | required similarly, and the amount of hydrolysable chlorine in a sample was computed based on the following formula.

Amount of hydrolyzable chlorine (ppm) = {(v−v ₀ ) × f × 2 × 35.5} / W
(W: sample weight (g), v: titration amount (mL), v ₀ : blank titration amount (mL), f: factor of silver nitrate aqueous solution)

[Active hydrogen equivalent]
The active hydrogen equivalent was calculated as follows.
Charged weight (w1) of epoxy resin (e1) charged to produce amine adduct (A), weight (w2) of amine compound (a1), and recovered after removal of unreacted amine compound (a1) after reaction From the weight (w3) of the amine adduct (A), the weight (w4) of the amine compound (a2) consumed to form the amine adduct (d1) by reaction was calculated based on the following formula (i) .

  w4 = (w1 + w2) -w3 (i)

  Next, an amine adduct (A) is formed based on the following formula (ii) from the molecular weight (mw1) of the amine compound (a1) and the number (n) of active hydrogens held by one molecule of the amine compound (a1) The total amount (h1) of the number of moles of active hydrogen which the amine compound (a1) consumed to produce was held before the reaction was determined.

  h1 = (w4 / mw1) × n (ii)

  In addition, when using 2 or more types of compounds together as an amine compound (a1), the reaction ratio of these amine compounds (a1) was allocated and calculated based on the weight ratio of these at the time of preparation.

  And from the preparation weight (w1) of the preparation epoxy resin (e1) and the epoxy equivalent (ev1) (the weight of the epoxy resin (e1) per equivalent), based on the following formula (iii), The total amount (ep1) mol was calculated.

  ep1 = w1 / ev1 (iii)

  When two or more compounds were used in combination as the epoxy resin (e1), ep1 was calculated from the sum of the preparation weight of each epoxy resin (e1) and the amount of epoxy groups determined from the epoxy equivalent.

  Epoxy resin (e1) charged to form amine adduct (A) out of the total number (h1) of the number of active hydrogens held by amine compound (a1) consumed to form amine adduct (A) The total amount of active hydrogen is reduced by the reaction of the amine compound (a1) in an amount equivalent to the total amount of epoxy groups of Therefore, the total amount (h2) mol of active hydrogens held by the recovered amine adduct (A) was calculated by the following formula (iv).

  h2 = h1-ep1 (iv)

  From the total amount (h2) of active hydrogen held by the recovered amine adduct (A) and the weight (w4) of the recovered amine adduct (A), based on the following formula (v), amine adduct (d1) The active hydrogen equivalent (hv) of was calculated.

  hv = h2 / w4 (v)

[Gel Permeation Chromatograph (GPC) Measurement of Amine Adduct (AD1) and Amine Adduct (AD2)]
Weight average molecular weight (Mw) and number average molecular weight (Am 1) of an amine adduct (AD1) and an amine adduct (AD 2) using a gel permeation chromatography analyzer (Tosoh Corp. “HLC-8220”, detector: RI) Mn) was measured. Depending on the polarity of the amine adduct (AD1) and the amine adduct (AD2), suitable conditions were selected among the following two conditions.

(Measurement condition-1)
A calibration curve was prepared using polyoxyethylene as a standard substance and quantified.

Standard substance: TSK standard polyethylene oxide Toso Co., Ltd. “TypeSE-2”, “TypeSE-5”, “TypeSE-8”, and Wako Pure Chemical Industries, “polyethylene glycol 200” “polyethylene glycol 400” Polyethylene glycol 1000 "," polyethylene glycol 1500 "," polyethylene glycol 2000 "," polyethylene glycol 4000 "," polyethylene glycol 8000 ", and" polyethylene glycol 20000 "were used.
Analysis software: Toso Corp. "GPC-8020 model II data collection Ver. 6" was used. As the analysis conditions, the calibration curve was approximated by a first order, and the calculation method used standard conditions.
Column: Tosoh company make, "TSK-GEL G4000HXL" and "TSK-GEL G3000HXL" were used in series.
Eluent: A dimethylformamide solution containing 0.1 mol / L of ethylenediamine was used.
Flow rate: 0.8 mL / min

The sample preparation conditions of the calibration sample, and the amine adduct (AD1) and the amine adduct (AD2) were as follows.
The sample was dissolved at a ratio of 1 L of eluate to 0.5 g of sample to prepare a solution.
Detector: Measured at 280 nm using “UV 8020” manufactured by Tosoh Corporation.

(Measurement condition-2)
A calibration curve was prepared using polystyrene as a standard substance and quantified.

Standard substance: Polystyrene having a molecular weight of 580, 1060, 1940, 5000, 10050, 21000, 50400 manufactured by Tosoh Corporation was used as a standard substance.
Analysis software: Toso Corp. "GPC-8020 model II data collection Ver. 6" was used. As the analysis conditions, the calibration curve was approximated by a first order, and the calculation method used standard conditions.
Column: Two “PLgel 3 μ MIXED-E” manufactured by Polymer Laboratory, Inc. were used in series.
Eluent: A dimethylformamide solution containing 1% of lithium bromide was used.
Flow rate: 0.8 mL / min

The sample preparation conditions of the calibration sample, and the amine adduct (AD1) and the amine adduct (AD2) were as follows.
The sample was dissolved at a ratio of 1 L of eluate to 0.5 g of sample to prepare a solution.
Detector: Toso, “differential refractometer RI-8020” was used.

  Thereafter, the calibration curve data and the analysis data are analyzed in the same manner as in the measurement condition-1, and the molecular weight distribution (Mw / Mn) determined from the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is calculated. did.

[Average particle size (μm)]
4 mg of a sample is added to 32 g (concentration of surfactant: 1% by mass) of a cyclohexane solution of surfactant ("Aeros OT-75" manufactured by Mitsui Cytec Co., Ltd.), and an ultrasonic cleaner (manufactured by Honda Electronics, "MODEL" The dispersion was obtained by ultrasonic irradiation for 5 minutes at W-211 ′ ′). The water temperature in the ultrasonic cleaner at this time was adjusted to 19 ± 2 ° C. About the obtained dispersion liquid, the measurement (measurement of the small particle size content rate) of average particle diameter and particle size distribution was performed using the particle size distribution analyzer (The Horiba, Ltd. make, "HORIBA LA-920").

[Infrared absorption characteristics in shell (S)]
The epoxy resin (E) and the nitrogen-containing heterocyclic compound (P) were removed from the epoxy resin composition by washing the epoxy resin composition to be measured with xylene. Specifically, the sample was washed with xylene until the epoxy resin (E) contained in the sample and the nitrogen-containing heterocyclic compound (P) disappeared, and the work of filtering the solution was repeated. Thereafter, the obtained residue was vacuum-dried at 40 ° C. to obtain a microcapsule type latent curing agent (F) for an epoxy resin, and the mass was determined. Furthermore, in order to take out the shell (S) from the obtained microcapsule type latent curing agent (F) for epoxy resin, methanol washing and filtration of the microcapsule type latent curing agent (F) for epoxy resin are repeated And the insoluble component shell (S) was separated and recovered (separation of the shell (S) from the microcapsule type latent curing agent (F) for epoxy resin). The separated and recovered shell (S) was vacuum dried at 40 ° C. to obtain a shell sample. 3 g of the obtained shell sample was ground in an agate mortar to obtain a ground product (1). 2 mg of the obtained ground product (1) was ground with 50 mg of potassium bromide (KBr) powder to obtain a ground product (2). From the resulting crushed product (2), a tablet for FT-IR measurement was produced using a tablet molding machine. The infrared spectrum of this tablet was obtained by "FT / IR-410" manufactured by JASCO Corporation.

[Presence or absence of a urea bonding group, a burette bonding group, and a urethane bonding group]
First, as a method of obtaining a standard infrared absorption (IR) spectrum calibration curve, the following method was adopted. As a standard substance, tetramethylsuccinic acid nitrile was prepared. Furthermore, a model compound (1) having a urea bonding group having an absorption band of 1630 to 1680 cm ^-1 but not having a burette bonding group and a urethane bonding group; a bonding group having a absorption band of 1680 to 1725 cm ^-1 (burette bonding Model compound (2) having a group (a group) but not having a urea bonding group and a urethane bonding group; a model having a urethane bonding group having an absorption band of 1730 to 1755 cm ^-1 but having no urea bonding group and a burette bonding group Compound (3) was prepared respectively.

(Standard substance for obtaining a standard IR spectrum calibration curve)

Model compound (1) having a urea bonding group having an absorption band of 1630 to 1680 cm ^-1 but having no buret bonding group and no urethane bonding group:

Model compound (2) having a burette bonding group having an absorption band of 1680 to 1725 cm ^-1 but not having a urea bonding group and a urethane bonding group:

Model compound (3) having a urethane bonding group having an absorption band of 1730 to 1755 cm ^-1 but having no urea bonding group and no buret bonding group:

The ratio of the area of the absorption band of 1630 to 1680 cm ^-1 of the model compound (1) to the area of the absorption band of 2240 to 2260 cm ^-1 of tetramethyl succinic acid nitrile of the standard substance was determined. That is, the ordinate represents the mass ratio of the calibration sample which is a mixture of the model compound (1) and the standard substance, and the abscissa represents the area of the absorption band at 1630 to 1680 cm ^-1 in the model compound (1) and tetramethyl of the standard substance. A calibration curve was prepared by linear regression of the relationship between the area ratio of the infrared absorption band and the mass ratio of the inclusion as a ratio of the area of the 2240-2260 cm ^-1 absorption band of the succinic acid nitrile to the area of the absorption band. Similarly, for each of the model compounds (2) and (3), a calibration curve was prepared by linear regression of the relationship between the area ratio of the infrared absorption band and the mass ratio of the inclusion from the respective measured values.

The measurement of the infrared absorption spectrum was performed according to the following procedures.
As model compounds (1), (2), (3) and tetramethyl succinic acid nitrile which is a standard substance, reagent grades manufactured by Tokyo Chemical Industry Co., Ltd. were used. As a measuring instrument, JASCO Corporation Fourier Transform Infrared Spectrophotometer "FT / IR-410" was used. Subsequently, the shell (S) separated by the above-mentioned method was vacuum dried at 40 ° C. to obtain a shell sample. 3 g of the obtained shell sample was ground in an agate mortar, and 2 mg of tetramethyl succinic acid nitrile as a standard substance and 50 mg of potassium bromide (KBr) powder were further charged, and these were ground to obtain a ground product. And the tablet for FT / IR measurement was produced from this ground material using the tablet molding machine. An infrared spectrum was obtained by FT / IR measurement of this tablet. The presence or absence of the urea bonding group, the buret bonding group, and the urethane bonding group in the shell was confirmed by comparing the obtained infrared spectrum chart with a standard IR spectrum calibration curve.

[Storage stability]
The viscosity before and after the epoxy resin composition (M) was stored at 30 ° C. for one week was measured using a BM type viscometer (25 ° C.). The ratio (viscosity increase rate) of the viscosity of the epoxy resin composition after storage to the viscosity of the epoxy resin composition before storage was calculated, and the storage stability was evaluated based on the following criteria.
◎: When the viscosity increase rate is less than 2 times.
:: When the viscosity increase rate is at least 2 times and less than 5 times.
Δ: When the viscosity increase rate is 5 times or more and less than 10 times.
X: When the viscosity increase rate is 10 times or more.
××: When the epoxy resin composition is solidified after storage and viscosity measurement is impossible.

[Low temperature short time curing property]
Based on 50 parts by mass of the epoxy resin composition (M), bisphenol A type epoxy resin (manufactured by Asahi Kasei E-Materials, "AER2603", epoxy equivalent: 189 g / eq, total chlorine content: 1,800 ppm, hydrolyzable chlorine content: A thermosetting resin composition was obtained by uniformly mixing 150 parts by mass of 50 ppm, viscosity: 12000 mPa · s). The obtained thermosetting resin composition was measured for the dynamic viscoelastic behavior at the time of thermosetting using a viscosity / viscoelasticity measuring apparatus “REOSTRESS RS600” manufactured by Harke GmbH of Germany to obtain an epoxy resin composition. Low temperature short time curability was evaluated. Specifically, it was evaluated as follows. The sensor used was PP20Disp type of a parallel plate sensor, and the control mode used a stress control (CS) mode. The viscosity change by hardening of the thermosetting resin composition in temperature 70 degreeC, stress 30 Pa, frequency 2 Hz, and gap 0.2 mm was measured, and the viscosity-time curve was created. The time to reach a viscosity of 10000 Pa · s or more was calculated using this viscosity-time curve, and the low-temperature short-time curability of the epoxy resin composition was evaluated based on the following criteria.
◎: When the time to reach the viscosity of 10 ⁴ Pa · s or more is less than 1800 seconds.
○: When the time to reach a viscosity of 10 ⁴ Pa · s or more is from 1800 seconds to less than 2400 seconds.
Fair: The time to reach a viscosity of 10 ⁴ Pa · s or more was 2400 seconds or more and less than 4800 seconds.
X: When the time to reach a viscosity of 10 ⁴ Pa · s or more is 4800 seconds or more and less than 5400 seconds.
Xx: When the time to reach the viscosity of 10 ⁴ Pa · s or more is 5400 seconds or more.

[Nair penetration]
Two sheets of a glass preparation (width 20 mm × length 75 mm, thickness 2 mm) were sandwiched by shifting the polyimide film by 10 mm in the length direction as a spacer so as to have a clearance of 15 μm, and heated at 50 ° C. The epoxy resin composition (M) was dropped to one end of the clearance, and the gap permeability was evaluated based on the following criteria based on the time when the epoxy resin composition (M) penetrates to 20 mm ahead.
◎: When it penetrates within 1 minute.
○: When it penetrates within 2 minutes over more than 1 minute Δ: When it penetrates within 3 minutes over more than 2 minutes.
X: When it did not penetrate within 3 minutes.

Liquid flowability
Based on 50 parts by mass of the epoxy resin composition (M), bisphenol A type epoxy resin (manufactured by Asahi Kasei E-Materials, "AER2603", epoxy equivalent: 189 g / eq, total chlorine content: 1,800 ppm, hydrolyzable chlorine content: A thermosetting resin composition was produced by uniformly mixing 100 parts by mass of 50 ppm and a viscosity of 12000 mPa · s. This thermosetting resin composition was poured into a mold (80 mmφ semicircle) for spiral flow measurement according to EMMI-1-66 at an injection pressure of 7 MPa, and then the flow length at a curing temperature of 120 ° C. was measured. Based on this measurement value, the flowability was evaluated according to the following criteria.
◎: When the flow length is 200 cm or more.
○: When the flow length is 150 cm or more and less than 200 cm.
Δ: When the flow length is 100 cm or more and less than 150 cm.
×: When the flow length is more than 50 cm and less than 100 cm.
Xx: When the flow length is 50 cm or less.

[Elastic modulus of cured product-1]
Based on 50 parts by mass of the epoxy resin composition (M), bisphenol A type epoxy resin (manufactured by Asahi Kasei E-Materials, "AER2603", epoxy equivalent: 189 g / eq, total chlorine content: 1,800 ppm, hydrolyzable chlorine content: A thermosetting resin composition was obtained by uniformly mixing 100 parts by mass of 50 ppm and a viscosity of 12000 mPa · s. The obtained thermosetting resin composition was measured for the dynamic viscoelastic behavior at the time of thermosetting using a viscosity / viscoelasticity measuring apparatus “REOSTRESS RS600” manufactured by Harke GmbH of Germany to obtain an epoxy resin composition. The elastic modulus at low temperature and short time curing was evaluated. Specifically, it was evaluated as follows. The sensor used was PP20Disp type of a parallel plate sensor, and the control mode used a stress control (CS) mode. The storage elastic modulus (G ') by hardening of the thermosetting resin composition in temperature 70 degreeC, stress 30 Pa, frequency 2 Hz, and gap 0.2 mm was measured. The storage modulus (G ′) after 30 minutes at 70 ° C. was evaluated for the modulus of the epoxy resin composition at the time of low temperature and short time curing.
:: storage elastic modulus (G ′) is 10 ⁶ Pa or more ○: storage elastic modulus (G ′) is 5 × 10 ⁵ Pa or more and less than 10 ⁶ Pa Δ: storage elastic modulus (G ′) is 3 × 10 ⁵ Pa Above, less than 5 × 10 ⁵ Pa x: Storage elastic modulus (G ′) is 1 × 10 ⁵ Pa or more, less than 3 × 10 ⁵ Pa ××: Storage elastic modulus (G ′) is less than 1 × 10 ⁵ Pa

[Measurement of elastic modulus of cured product-2 and glass transition temperature (Tg) of cured product]
Based on 50 parts by mass of the epoxy resin composition (M), bisphenol A type epoxy resin (manufactured by Asahi Kasei E-Materials, "AER2603", epoxy equivalent: 189 g / eq, total chlorine content: 1,800 ppm, hydrolyzable chlorine content: A thermosetting resin composition was obtained by uniformly mixing 100 parts by mass of 50 ppm and a viscosity of 12000 mPa · s. The resulting thermosetting resin composition is uniformly coated on a 20 cm square and 0.2 mm thick aluminum plate to a thickness of 300 μm or more and less than 500 μm, and then 30 minutes in a hot air oven at 80 ° C. It was cured by heating.

  The obtained cured product was carefully peeled off, and a flaky cured product sample having a width of 5 mm and a length of 25 mm was cut out. Using this cured product sample, the storage elastic modulus is measured with a tensile mode, a frequency of 1 Hz, and a temperature rising rate of 2 ° C./min with a dynamic viscoelasticity measuring apparatus “RHEOVIBRON DDV-25 FP” manufactured by Orientec Co., Ltd. The loss elastic modulus and the peak of tan δ were determined as Tg, and the storage elastic modulus at 45 ° C. of the cured product and Tg were respectively evaluated.

[Shear bond strength]
The shear bond strength of the epoxy resin composition was measured according to the following procedure.
50 parts by mass of epoxy resin composition (M), bisphenol A type epoxy resin (Asahi Kasei E-Materials, “AER 2603”, epoxy equivalent weight: 189 g / eq, total chlorine content: 1,800 ppm, hydrolyzable chlorine content: 50 ppm, viscosity : 12000 mPa · s) 50 parts by mass were mixed to obtain a thermosetting resin composition. Test pieces were produced from the obtained thermosetting resin composition in accordance with JIS K6850. Moreover, the adherend (cold-rolled steel plate) of width 25 mm x length 100 mm x thickness 1.6 mm based on JISC3141 was used as a to-be-adhered body. Then, on the adherend, the test piece was thermally cured at 70 ° C. for 1 hour. Thereafter, the bonding surface between the test piece and the adherend was broken, and the maximum load when the test piece was separated from the adherend was measured. This measured value was taken as the shear adhesive strength of the epoxy resin composition.

Production Example 1-1
(Production of amine adduct (AD1-1))
In a mixed solution of 100 g of xylene and 100 g of isopropyl alcohol, 103 g of diethylenetriamine (molecular weight: 103) was dissolved as an amine compound (a1). Thereafter, bisphenol A type epoxy resin (manufactured by Asahi Kasei E-Materials, "AER2603", epoxy equivalent weight: 189 g / eq, total chlorine content: 1,800 ppm) was added to the obtained solution as an epoxy resin (e1) at 60 to 100 ° C. A degradable chlorine: 50 ppm (hereinafter also referred to as “e1-1”) 189 g was added, and the reaction was carried out to obtain a reaction liquid. Then, the reaction solution was heated under reduced pressure to distill off xylene as a solvent and isopropyl alcohol from the reaction solution, and unreacted diethylenetriamine was also distilled off from the reaction solution. By distilling off until the content of unreacted diethylenetriamine in the reaction liquid is less than 0.01% by mass, 265 g of an amine adduct (AD1-1) was obtained. It was confirmed as follows by gas chromatography (GC) that the content of unreacted diethylenetriamine in the amine adduct (AD1-1) is less than 0.01% by mass.

  As an analysis device, Shimadzu Corp. make, "GC-17A" was used, and the flame ion detector (Flame Ionization Detector ;; FID) was used as a detector. As a column, "Capillary column InterCap for Amines" (length: 15 m, internal diameter: 0.32 mm) manufactured by GL Science, Inc. was used. Helium was used as a carrier gas. The calibration curve for quantifying the diethylenetriamine (amine compound (a1)) used for the synthesis was created using the solvent used in the synthesis of the amine adduct. Based on the calibration curve, the content of unreacted diethylenetriamine in the amine adduct (AD1-1) was determined.

  The ratio of the number average molecular weight (Mn) to the weight average molecular weight (Mw) of the obtained amine adduct (AD1-1) (molecular weight distribution; Mw / Mn) was 3.5. The weight of diethylenetriamine (amine compound (a1)) consumed and added to form an amine adduct (AD1-1) is 76 g, and the active hydrogen equivalent carried by the amine adduct (AD1-1) is 10.3 mmol / g Met.

[Production Example 1-2 to 1-5]
Amine adducts (AD1-2) to (AD1-5) were produced in the same manner as in Production Example 1-1 except that the raw materials and solvents were changed as shown in Table 1, and the obtained amine adducts (AD1-2) to Physical properties of (AD1-5) were measured. The measurement results are shown in Table 1. In Production Example 1-4, a bisphenol A-type epoxy resin ("AER 6061" manufactured by Asahi Kasei E-Materials Co., Ltd., "AER 6061", epoxy equivalent weight: 530 g / eq, total chlorine content: 1100 ppm, hydrolyzable chlorine) as epoxy resin (e1): 30 ppm, hereinafter referred to as "e1-2") was used.

Production Example 2-1
(Production of amine adduct (AD2-1))
First, 220 g of 2-ethyl-4-methylimidazole as an amine compound (a2) is added to 408 g of a solution in which 1-butanol and toluene are mixed at a ratio of 1/1 (mass ratio), and 80 with an oil bath while stirring. By heating to 0 C, 2-ethyl-4-methylimidazole was dissolved to prepare a 2-ethyl-4-methylimidazole solution.

  Then, to 250 g of a solution in which 1-butanol and toluene were mixed at a ratio of 1/1 (mass ratio), bisphenol A epoxy resin (Asahi Kasei E-Materials, "AER2603", epoxy equivalent) as an epoxy resin (e1) A bisphenol A epoxy resin solution was prepared by dissolving 378 g of 189 g / eq, total chlorine content: 1,800 ppm, hydrolyzable chlorine content: 50 ppm, hereinafter also referred to as "e1-1").

  In a reaction vessel, a bisphenol A epoxy resin solution was added dropwise over a period of 180 minutes to a 2-ethyl-4-methylimidazole solution using an equal pressure dropping funnel. After completion of the dropwise addition, the reaction solution obtained was reacted by heating at 80 ° C. for 5 hours. Thereafter, the reaction solution was further heated to 180 ° C. to distill off the solvent from the reaction solution. Thereafter, while maintaining the temperature of the reaction solution at 180 ° C., the pressure in the reaction vessel is reduced to 10 mmHg or less to distill unreacted 2-ethyl-4-methylimidazole from the reaction solution together with the residual solvent. I left it. The reaction was distilled off until the content of unreacted 2-ethyl-4-methylimidazole in the reaction solution was less than 0.01% by mass, to obtain an amine adduct (AD2-1). It was confirmed by gas chromatography (GC) as follows that the content of unreacted 2-ethyl-4-methylimidazole in the amine adduct (AD2-1) is less than 0.01% by mass.

  As an analyzer, "GC-17A" manufactured by Shimadzu Corporation was used, and as a detector, a hydrogen ion detector (Flame Ionization Detector: FID) was used. As a column, capillary column InterCap for Amines (length: 15 m, internal diameter: 0.32 mm) manufactured by GL Science, Inc. was used. The carrier gas used helium. A calibration curve for quantifying 2-ethyl-4-methylimidazole was prepared using the solvent used in synthesizing the amine adduct. Using this calibration curve, the content of unreacted 2-ethyl-4-methylimidazole remaining in the amine adduct (AD2-1) was determined.

  The molecular weight distribution (Mw / Mn) of the obtained amine adduct (AD2-1) was 3.2.

[Production Examples 2-2 to 2-6]
Amine adducts (AD2-2) to (AD2-6) were produced in the same manner as in Production Example 2-1 except that the raw materials, the solvent and the reaction temperature were changed as shown in Table 2, and the obtained amine adducts (AD2-) were obtained. 2) Physical properties of (AD 2-6) were measured. The measurement results are shown in Table 2.

[Production Example 1a]
(Production of a curing agent for epoxy resin (D-1))
50 g of amine adduct (AD1-1), 100 g of amine adduct (AD2-1), and 10 g of 1,2-dimethylimidazole (molecular weight: 96, melting point: 38 ° C.) as the low molecular weight amine compound (B) and 4-dimethylaminopyridine 10 g was charged into a flask and mixed while stirring at 150 ° C. until uniform. Thereafter, "AEROSIL R972" manufactured by Nippon Aerosil Co., Ltd. was added as a nanosized inorganic compound particle (C) to a 10 g flask, and stirring and mixing were continued until uniform, to obtain a mixture. The obtained mixture was recovered and cooled to obtain a curing agent (D-1) for epoxy resin which is solid at room temperature (25 ° C.). It was 92 degreeC when the softening point of the hardening | curing agent (D-1) for epoxy resins was measured.

  In this example, the softening point of the curing agent (D) for an epoxy resin was measured by a method according to "Testing method of softening point of epoxy resin" described in JIS K7234.

  The resulting solid curing agent for epoxy resin (D-1) is crushed by a grinder "ROT PLEX" (manufactured by Hosokawa Micron Corporation) to an average particle size of about 0.1 to 2 mm, and the coarse powder is obtained. Obtained. The obtained crude product is supplied to a pneumatic jet mill ("CJ 25 type" manufactured by Nisshin Engineering Co., Ltd.) at a feed rate of 5.0 kg / hour, and grinding twice at a grinding pressure of 0.6 MPa · s. Repeatedly, a crushed material was obtained. Thereafter, the obtained pulverized material is classified by an air classifier ("Turbo classifier" manufactured by Nisshin Engineering Co., Ltd.) to remove coarse particles, and finely pulverized product of a curing agent for epoxy resin (D-1). I got The average particle diameter of the finely pulverized material of the obtained curing agent for epoxy resin (D-1) was 3.5 μm.

[Production Example 2a]
(Production of Hardener for Epoxy Resin (D-2))
50 g of amine adduct (AD1-2), 100 g of amine adduct (AD2-2), and as a low molecular weight amine compound (B), 1,4-diazabicyclo [2.2.2] octane (molecular weight: 102, melting point: 155 ° C. 25 g), 100 g of toluene as a solvent and 100 g of 1-butanol were charged in a flask, and stirred and dissolved until uniform while heating at 100 ° C. to obtain a solution. The resulting solution was then warmed to 150 ° C. to remove toluene and 1-butanol from the flask by distillation. After making the balance of toluene and 1-butanol in the flask less than 0.1% by mass, add “AEROSIL RX300” from Nippon Aerosil Co., Ltd. to a 15 g flask as nano-sized inorganic compound fine particles (C). Stir mixing was continued until uniform, to obtain a mixture. The obtained mixture was recovered and cooled to obtain a curing agent (D-2) for epoxy resin which is solid at room temperature (25 ° C.). It was 88 degreeC when the softening point of the hardening agent for epoxy resins (D-2) was measured.

  The resulting solid curing agent for epoxy resin (D-2) is coarsely pulverized, pulverized, and classified under the same conditions as in Production Example 1a, and finely pulverized of the curing agent for epoxy resin (D-2) I got The average particle diameter of the finely pulverized product of the obtained curing agent for epoxy resin (D-2) was 2.7 μm.

[Production example 3a]
(Production of Hardener for Epoxy Resin (D-3))
30 g of amine adduct (AD1-3), 70 g of amine adduct (AD2-3), and 20 g of "Leorosil QS-10" of Tokuyama Corp. as a nanosized inorganic compound fine particle (C), 100 g of toluene as a solvent -100 g of butanol was charged into a flask, stirred and dissolved until uniform while heating at 100 ° C to obtain a solution. The resulting solution was then warmed to 150 ° C. to remove toluene and 1-butanol from the flask by distillation. After the balance of toluene and 1-butanol in the flask is less than 0.1 wt%, 1-azabicyclo [2.2.2] octan-3-ol (molecular weight: 127) is used as the low molecular weight amine compound (B-1). Melting point: 222 ° C.) 10 g, 10 g of 1,4-diazabicyclo [2.2.2] octane (molecular weight: 102, melting point: 155 ° C.) as the low molecular weight amine compound (B-2) is added to the flask, 180 Stir mixing continued until uniform while warming at ° C to obtain a mixture. The obtained mixture was recovered and cooled to obtain a solid epoxy resin curing agent (D-3) at room temperature (25 ° C.). It was 90 degreeC when the softening point of the hardening agent for epoxy resins (D-3) was measured.

  The resulting solid curing agent for epoxy resin (D-3) is coarsely pulverized, finely pulverized and classified under the same conditions as in Production Example 1a to obtain finely pulverized product of curing agent for epoxy resin (D-3) I got The average particle diameter of the finely pulverized product of the obtained curing agent for epoxy resin (D-3) was 2.2 μm.

[Production Examples 4a to 10a]
Hardeners for epoxy resin (D-4) to (D-10) and finely pulverized products thereof are produced and obtained in the same manner as in Production Example 2a except that the types and amounts of raw materials are changed as shown in Table 3. The softening point of each of the curing agents (D-4) to (D-10) for epoxy resin and the average particle diameter of the finely pulverized product thereof were measured. The measurement results are shown in Table 3. The curing agents (D-4) to (D-10) for epoxy resin were solid at room temperature (25 ° C.).

Production Example 1b
(Production of microcapsule type latent curing agent (F-1) for epoxy resin)
As a dispersion medium, 140 g of methylcyclohexane was used. In the dispersion medium, 70 g of a finely pulverized product of a curing agent for epoxy resin (D-1) is added and dispersed, and then 4.0 g of water, 25.2 g of isophorone diisocyanate, and bisphenol A as an epoxy resin (e2) Type epoxy resin (Asahi Kasei E-Materials, “AER 2603”, epoxy equivalent: 189 g / eq, total chlorine content: 1,800 ppm, hydrolyzable chlorine content: 50 ppm, hereinafter also referred to as “e2-1”) 6.0 g is added The reaction was carried out at 50.degree. C. for 4 hours. After completion of the reaction, the obtained reaction liquid was filtered, washed and dried to obtain a microcapsule type latent curing agent (F-1) for an epoxy resin.

  The obtained microcapsule type latent curing agent for epoxy resin (F-1) has a structure in which the surface of the core is covered with a shell (S) with the curing agent for epoxy resin (D-1) as a core. I had it.

Also, the shell (S) was separated from the obtained microcapsule type latent curing agent for epoxy resin (F-1). Was subjected to FT-IR measured on the shell (S), the shell (S) is a urea linking group that absorbs infrared wave number 1630～1680Cm ^-1, biuret bond that absorbs infrared wave number 1680～1725Cm ^-1 It was confirmed that it has a urethane bond group which absorbs an infrared ray having a wave number of 1730 to 1755 cm ⁻¹ .

[Production Example 2b]
150 g of n-hexane was used as a dispersion medium. In the dispersion medium, 70 g of a finely pulverized product of a curing agent for epoxy resin (D-2) is added and dispersed, and then 1.0 g of water, 5.5 g of hexamethylene diisocyanate, and bisphenol as an epoxy resin (e2) Add A-type epoxy resin (Asahi Kasei E-Materials, "AER2603", epoxy equivalent: 189 g / eq, total chlorine content: 1,800 ppm, hydrolyzable chlorine content: 50 ppm) 3.0 g and add at 40 ° C for 2 hours It was made to react. After completion of the reaction, the obtained reaction liquid was filtered, washed and dried to obtain a microcapsule type curing agent (F-2) for an epoxy resin.

  The obtained microcapsule type latent curing agent for epoxy resin (F-2) has a structure in which the surface of the core is covered with a shell (S) with the curing agent for epoxy resin (D-2) as a core I had it.

Moreover, shell (S) was isolate | separated from the obtained microcapsule-type hardening | curing agent for epoxy resins (F-2). Was subjected to FT-IR measured on the shell (S), the shell (S) is a urea linking group that absorbs infrared wave number 1630～1680Cm ^-1, biuret bond that absorbs infrared wave number 1680～1725Cm ^-1 It was confirmed that it has a urethane bond group which absorbs an infrared ray having a wave number of 1730 to 1755 cm ⁻¹ .

Production Example 3b
As a dispersion medium and epoxy resin (e2), 150 g of bisphenol A type epoxy resin (manufactured by Asahi Kasei E-Materials, “AER 2603”, epoxy equivalent weight: 189 g / eq, total chlorine content: 1800 ppm, hydrolyzable chlorine content: 50 ppm) Using.
100 g of a finely pulverized product of a curing agent for epoxy resin (D-3) is added to the dispersion medium and epoxy resin (e2) and dispersed, and then 1.0 g of water and 5.5 g of tolylene diisocyanate are added. And allowed to react at 25 to 50 ° C. for 3 hours. After completion of the reaction, the reaction solution obtained was filtered and separated while washing with xylene, and then dried to obtain a microcapsule type curing agent for epoxy resin (F-3).

  The obtained microcapsule type latent curing agent for epoxy resin (F-3) has a structure in which the surface of the core is covered with a shell (S) with the curing agent for epoxy resin (D-3) as a core I had it.

Moreover, shell (S) was isolate | separated from the obtained microcapsule-type hardening | curing agent for epoxy resins (F-3). Was subjected to FT-IR measured on the shell (S), the shell (S) is a urea linking group that absorbs infrared wave number 1630～1680Cm ^-1, biuret bond that absorbs infrared wave number 1680～1725Cm ^-1 It was confirmed that it has a urethane bond group which absorbs an infrared ray having a wave number of 1730 to 1755 cm ⁻¹ .

[Production example 4b]
As a dispersion medium and epoxy resin (e2), bisphenol F-type epoxy resin (manufactured by DIC, “EXA-830 CRP”, epoxy equivalent: 171 g / eq, total chlorine content: 800 ppm, hydrolyzable chlorine content: 10 ppm, below “e2- 2 g)) was used. 100 g of a finely pulverized product of a curing agent for epoxy resin (D-4) is added to the dispersion medium and epoxy resin (e2) and dispersed, then 0.1 g of water and polymethylene phenylene polyisocyanate (Nippon polyurethane Epoxy resin composition containing microcapsule type latent curing agent (F-4) for epoxy resin by adding 2.5 g of MR-200 (manufactured by Kogyo Co., Ltd.) and reacting at 25 to 50 ° C. for 3 hours I got

  The epoxy resin composition containing the microcapsule type latent curing agent (F-4) for epoxy resin is filtered and separated while being washed with xylene, and then dried to obtain the microcapsule type latent curing for epoxy resin An agent (F-4) was obtained.

  The obtained microcapsule type latent curing agent for epoxy resin (F-4) has a structure in which the surface of the core is covered with a shell (S) with the curing agent for epoxy resin (D-4) as a core I had it.

Also, the shell (S) was separated from the obtained microcapsule type latent curing agent for epoxy resin (F-4). Was subjected to FT-IR measured on the shell (S), the shell (S) is a urea linking group that absorbs infrared wave number 1630～1680Cm ^-1, biuret bond that absorbs infrared wave number 1680～1725Cm ^-1 It was confirmed that it has a urethane bond group that absorbs an infrared ray having a wave number of 1730 to 1755 cm ^-1 .

[Production Examples 5b to 10b]
Microcapsule type latent curing agents (F-5) to (F-10) for epoxy resin were produced in the same manner as in Production Example 1b except that production conditions were changed as shown in Table 4.

  The obtained microcapsule type latent curing agents for epoxy resin (F-5) to (F-10) cover the surface of the core by the shell (S) with each curing agent for epoxy resin (D) as a core Had the structure being

Moreover, shell (S) was isolate | separated from the obtained microcapsule type latent curing agent for epoxy resins (F-5)-(F-10), respectively. Was subjected to FT-IR measured on the shell (S), the shell (S) is a urea linking group that absorbs infrared wave number 1630～1680Cm ^-1, biuret bond that absorbs infrared wave number 1680～1725Cm ^-1 It was confirmed that it has a urethane bond group which absorbs an infrared ray having a wave number of 1730 to 1755 cm ⁻¹ .

Example 1
50 g of the microcapsule type latent curing agent (F-1) for epoxy resin obtained above and a bisphenol A type epoxy resin (manufactured by Asahi Kasei E-Materials, “AER2603”, epoxy equivalent weight: 189 g as epoxy resin (E) An epoxy resin composition (M-1) is obtained by mixing / eq, total chlorine content: 1800 ppm, hydrolyzable chlorine content: 50 ppm, viscosity: 12000 mPa · s, hereinafter also referred to as "E-1") 100 g. The The evaluation results of the obtained epoxy resin composition (M-1) are shown in Table 5.

Example 2
50 g of the microcapsule type latent curing agent (F-2) for epoxy resin obtained above and a bisphenol F-type epoxy resin (manufactured by DIC, “EXA-830 CRP” as an epoxy resin (E), epoxy equivalent: 171 g / eq The total amount of chlorine: 800 ppm, the amount of hydrolyzable chlorine: 10 ppm, viscosity: 3500 mPa · s, hereinafter referred to as “E-2”) 100 g were mixed to obtain an epoxy resin composition (M-2). The evaluation results of the obtained epoxy resin composition (M-2) are shown in Table 5.

[Example 3]
50 g of the microcapsule type latent curing agent (F-3) for epoxy resin obtained above and a bisphenol F-type epoxy resin (manufactured by DIC, “EXA-830 CRP” as an epoxy resin (E), epoxy equivalent: 171 g / eq Total chlorine content: 800 ppm, hydrolyzable chlorine content: 10 ppm, viscosity: 3500 mPa · s 80 g and 1,6-dihydroxynaphthalene type liquid epoxy resin (manufactured by DIC, “HP-4032D”, epoxy equivalent: 141 g / eq Total chlorine content: 850 ppm, hydrolyzable chlorine content: 20 ppm, viscosity at 50 ° C .: 600 mPa · s, hereinafter referred to as “E-3”) 20 g, and nitrogen-containing heterocyclic compound (P) An epoxy resin composition (M-3) was obtained by mixing with 2.0 g of pyridine dicarboxylic acid. The evaluation results of the obtained epoxy resin composition (M-3) are shown in Table 5.

[Examples 4 to 11 and Comparative Examples 1 to 3]
Epoxy resin compositions (M-4) to (M-14) were produced in the same manner as in Example 1 except that the raw materials were changed as shown in Tables 5 and 6. The evaluation results of the resulting epoxy resin compositions (M-4) to (M-14) are shown in Tables 5 and 6.

[Example 12]
(Preparation of conductive paste)
50 parts by mass of the epoxy resin composition (M-1) obtained in Example 1 in 50 parts by mass of bisphenol A-type epoxy resin ("AER 2603" manufactured by Asahi Kasei E-Materials Co., Ltd.) Company average particle size: 14 μm, aspect ratio: 11 150 parts by mass, scale-like nickel powder (manufactured by High Purity Chemical Co., Ltd., trade name “NI110104”, average particle size: 10 μm, aspect ratio: 9) 60 parts by mass The mixture was stirred until each component was uniform, and then the components were uniformly dispersed with a triple roll to obtain a conductive paste. The obtained conductive paste was screen-printed on a polyimide film substrate having a thickness of 1.4 mm, and then heat cured at 200 ° C. for 1 hour to obtain a wiring board. As a result of measuring the conductivity of the obtained wiring board, it was found that the obtained conductive paste was useful because the measured value was good.

[Example 13]
(Preparation of anisotropic conductive paste)
40 parts by mass of bisphenol A type epoxy resin (manufactured by Asahi Kasei E-Materials, "AER6071", epoxy equivalent: 480 g / eq), 15 parts by mass of bisphenol A type epoxy resin (manufactured by Asahi Kasei E-materials, "AER2603"), 5 parts by mass of conductive particles (manufactured by Sekisui Chemical Co., Ltd., “Micropearl Au-205, specific gravity: 2.67) were mixed. Thereafter, 70 parts by mass of the epoxy resin composition (M-1) obtained in Example 1 was added to the obtained mixture, and the mixture was further uniformly mixed to obtain an anisotropic conductive paste. The resulting anisotropically conductive paste was applied onto a low alkali glass with indium tin oxide (ITO) electrode. The anisotropic conductive paste coated on low alkali glass was pressure bonded to a test TAB (Tape Automated Bonding) film for 30 seconds at a pressure of 2 MPa with a ceramic tool at 230 ° C. to perform bonding. When the resistance value between adjacent ITO electrodes was measured, it was found that the obtained anisotropic conductive paste was useful because the measured value was good.

Example 14
(Preparation of insulating paste)
70 parts by mass of bisphenol F type epoxy resin (Mitsubishi Chemical Co., Ltd., trade name “YL 983 U”), 4 parts by mass of dicyandiamide, 100 parts by mass of silica powder, 10 parts by mass of phenyl glycidyl ether as a diluent, and organic phosphoric acid ester After mixing 1 mass part of pharmaceutical company make and brand name "PM-2", it further knead | mixed with a three-roll, and obtained the kneaded material. 50 parts by mass of the epoxy resin composition (M-1) obtained in Example 1 is added to the kneaded product, and the mixture is further uniformly mixed, and subjected to vacuum degassing and centrifugal defoaming treatment to obtain an insulating paste. The When the semiconductor chip was heat-hardened at 200 ° C. for 1 hour to be bonded to a resin substrate using the obtained insulating paste, it was found that the obtained insulating paste was useful.

[Example 15]
(Production of sealing material)
50 parts by mass of bisphenol A type epoxy resin (manufactured by Asahi Kasei E-Materials, "AER6071", epoxy equivalent: 480 g / eq), 30 parts by mass of bisphenol A type epoxy resin (manufactured by Asahi Kasei E-materials, "AER2603"), cured 40 parts by weight of "HN-2200" (made by Hitachi Chemical Co., Ltd.) containing phthalic anhydride as a main component and 80 parts by weight of spherical fused silica having an average particle diameter of 16 μm were uniformly dispersed and mixed to obtain a mixture . 20 parts by mass of the epoxy resin composition (M-1) obtained in Example 1 was added to the mixture to obtain an epoxy resin composition. The obtained epoxy resin composition was applied in 1 cm square so as to have a thickness of 60 μm on a printed wiring board, and heated in an oven at 110 ° C. for 10 minutes for semi-curing. After that, a silicon chip of 370 μm thickness and 1 cm square is placed on the semi-cured epoxy resin composition, a load is applied, and complete curing treatment is performed at 220 ° C. for 1 hour while contacting and holding bumps and electrodes of the chip. To obtain a sealing material. The sealing material consisting of the obtained epoxy resin composition was useful without any problem in appearance and chip conduction.

[Example 16]
(Preparation of coating material)
30 parts by mass of bisphenol A type epoxy resin (Asahi Kasei E-Materials, “AER 2603”), 30 parts by mass of phenoxy resin (“NP-50”, manufactured by Nippon Steel Sumikin Chemical Co., Ltd.), methyl ethyl ketone of methoxy group-containing silane-modified epoxy resin A solution (Arakawa Chemical Industries Co., Ltd. make, "compocelan E103") 50 mass parts and 50 mass parts of epoxy resin composition (M-1) obtained in Example 1 are added, and it dilutes to 50 mass% with methyl ethyl ketone, and mixes it. The solution was prepared. The prepared solution is coated on a release PET film ((polyethylene terephthalate) film; Panak Co., Ltd., “SG-1”) using a roll coater, dried and cured at 150 ° C. for 15 minutes, and the film thickness is obtained. A 100 μm peel film-attached semi-cured resin film (dry film) was obtained. The obtained dry film was heat-pressed at 6 ° C. for 10 minutes at 120 ° C. on a copper-clad laminate, returned to room temperature, the release film was removed, and then cured at 200 ° C. for 2 hours. A useful one as a coating material was obtained.

[Example 17]
(Preparation of coating composition)
Thirty parts by mass of titanium dioxide and 70 parts by mass of talc are mixed with 50 parts by mass of bisphenol A type epoxy resin (manufactured by Asahi Kasei E-Materials, "AER6071", epoxy equivalent: 480 g / eq) and methyl isobutyl ketone as a mixed solvent 140 parts by mass of a 1: 1 mixed solvent of (MIBK) / xylene was added, stirred and mixed to obtain a main ingredient. When 50 parts by mass of the epoxy resin composition (M-1) obtained in Example 1 was added to the main agent and uniformly dispersed, a useful one as an epoxy coating composition was obtained.

[Example 18]
[Preparation of Prepreg]
15 parts by mass of novolac epoxy resin (manufactured by DIC, “EPICLON N-740”), 30 parts by mass of bisphenol F-type epoxy resin (manufactured by Mitsubishi Chemical Corp., “epicoat 4005”) in a flask in an oil bath at 130 ° C. 10 parts by mass of bisphenol A epoxy resin (manufactured by Asahi Kasei E-Materials, "AER 2603") was dissolved and mixed, and the mixture was cooled to 80 ° C. to obtain a mixture. Then, 50 parts by mass of the epoxy resin composition (M-1) obtained in Example 1 was added to the mixture, and the mixture was sufficiently stirred and mixed to obtain a resin composition. The obtained resin composition was cooled to room temperature, and was applied onto a release paper at a resin weight of 162 g / m ² using a doctor knife to obtain a resin film. A resin composition is obtained by superposing carbon fiber cloth made by Mitsubishi Rayon (model number: TR3110, 200 g / m ² basis weight) in which carbon fibers with an elastic modulus of 24 tons / mm ² are plain-woven on this resin film. The product was impregnated into a carbon fiber cloth, and then a polypropylene film was further stacked, and then passed through a pair of rolls having a surface temperature of 90 ° C. to produce a cross prepreg. The resin content in the cross prepreg was 45% by mass. The obtained prepreg was further laminated with the fiber direction aligned, and was molded under curing conditions of 150 ° C. for 1 hour to obtain a fiber reinforced resin (FRP) molded body having carbon fibers as reinforcing fibers. . The produced prepreg was useful.

[Example 19]
(Preparation of heat conductive epoxy resin composition)
50 parts by mass of bisphenol A type epoxy resin (Asahi Kasei E-Materials Co., Ltd., "AER2603"), 40 parts by mass of 50% methyl ethyl ketone solution of phenol novolac resin (Arakawa Chemical Industries, "Tamanor 759") as a curing agent for epoxy resin After stirring 15 parts by mass of scale-like graphite powder ("HOPG" manufactured by Union Carbide Co., Ltd.) until uniform, the mixture was uniformly dispersed by a three-roll mill. To the mixture, 50 parts by mass of the epoxy resin composition (M-1) obtained in Example 1 was added, sufficiently stirred and mixed to obtain a conductive paste (heat conductive epoxy resin composition) . Using the obtained conductive paste, a semiconductor chip (1.5 mm square, 0.8 mm thick) mounted on a Cu lead frame is thermally cured at 150 ° C. for 30 minutes for evaluation I got a sample.

The thermal conductivity of the obtained evaluation sample was measured and evaluated by a laser flash method. That is, from the measured thermal diffusivity α, specific heat Cp, and density σ, the thermal conductivity K was determined from the equation: K = α × Cp × σ. As a result, the obtained thermal conductive epoxy resin composition had a thermal conductivity K of 5 × 10 ⁻³ Cal / cm · sec · ° C. or higher, and was useful as a thermal conductive paste.

[Example 20]
(Production of separator material for fuel cell)
Biphenyl epoxy resin 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxybiphenyl glycidyl ether (Mitsubishi Chemical Co., Ltd., "epicoat YX-4000", epoxy equivalent: 195 g / eq) 100 mass Part, 60 parts by mass of phenol novolac resin (manufactured by DIC, "TD-2131"), 10 parts by mass of bisphenol A epoxy resin (manufactured by Asahi Kasei E-Materials, "AER2603"), artificial graphite (manufactured by SEC, "SGP" A mixture obtained by mixing 800 parts by mass of an average particle diameter of 75 μm, 0.5 parts by mass of a mold release agent (calcium stearate), and 0.75 parts by mass of a lubricant (carnauba wax) was obtained by a mixer. To this mixture, 50 parts by mass of the epoxy resin composition (M-1) obtained in Example 1 was added, and uniformly mixed with a three-roll mill to obtain a material. The resulting material was pressure-molded using a mold for a fuel cell separator material under the conditions of a molding pressure of 25 MPa, a molding temperature of 150 ° C., and a molding time of 15 minutes to obtain a fuel cell separator material. The bending strength of the obtained fuel cell separator material was measured according to JIS K 7203 and was 50 MPa. In addition, when the gas permeability of nitrogen gas was measured by the method according to JIS K7126A as the evaluation of gas permeability, the obtained fuel cell separator material had a gas permeability of 0.6 cm ³ / m of nitrogen gas. ^{It was 2} · 24 hours · atm and was useful as a fuel cell separator material.

[Example 21]
(Production of overcoat material for flexible wiring board)
Resin modified with epoxy resin by reaction of polybutadiene dicarboxylic acid resin (manufactured by Nippon Soda Co., Ltd., “NISSO PB C-1000”) and bisphenol type epoxy resin (manufactured by Nippon Soda Co., Ltd., “EPB-13”, epoxy equivalent: 700 g / eq, viscosity: 800 mPa · s) 50 parts by mass, maleated modified polybutadiene resin (Nippon Soda Co., Ltd., “BN-1015”, acid equivalent: 145 g / eq) 70 parts by mass as a resin that reacts with an epoxy group, Example 1 30 parts by mass of the epoxy resin composition (M-1) obtained in the above and 3 parts by mass of rubber fine particles (manufactured by JSR, "EXR-91"), mixed uniformly with a three-roll mill, and mixed Obtained. To the mixture was further added 200 parts by mass of methyl ethyl ketone (MEK), and the mixture was stirred and mixed until uniform by a mixer, and was dissolved and dispersed to obtain an overcoat adhesive solution.

  An adhesive solution for overcoat is applied to a polyimide film of width 35 mm × length 60 mm × thickness 65 μm so that the film thickness after drying becomes 25 μm, and further dried at 150 ° C. for 20 minutes. An overcoat material for a wiring board was obtained. The obtained overcoat material for a flexible wiring substrate was measured for presence or absence of a crack when bent at 180 ° C. and a warp of a polyimide film treated at 150 ° C. for 8 hours at a humidity of 50%, and the measured values It was found that the obtained overcoat material for a flexible wiring board was useful because it was good.

  The epoxy resin composition according to the present invention is used for adhesives, sealing materials, insulating materials, conductive materials, anisotropic conductive materials, coating materials, coating compositions, prepregs, thermally conductive materials, separator materials, and flexible wiring boards It can be suitably used in a wide range of fields including overcoat materials.

Claims (20)

Including core and shell,
Microcapsule type latent curing agent (F) for epoxy resin, wherein the core comprises the following curing agent for epoxy resin (D):
(Hardener for epoxy resin (D))
Containing an amine adduct (A), a low molecular weight amine compound (B), and nano-sized inorganic compound fine particles (C),
Ri average particle diameter der than 100nm or less 1nm of the inorganic compound primary particles of fine particles (C),
Hardener for epoxy resin (D) which is solid at 25 ° C. The microcapsule type latent curing according to claim 1 , wherein the content of the inorganic compound fine particles (C) in the curing agent (D) for an epoxy resin is 0.1% by mass or more and 20% by mass or less. Agent (F) . The microcapsule type latent curing agent for epoxy resin according to claim 1 or 2 , wherein in the curing agent for epoxy resin (D), the content of the amine adduct (A) is 24% by mass to 99% by mass. F) . The epoxy resin according to any one of claims 1 to 3 , wherein the content of the low molecular weight amine compound (B) in the curing agent (D) for an epoxy resin is 0.5% by mass or more and 75% by mass or less. Microcapsule type latent curing agent (F) . The amine adduct (A) is obtained by the reaction of 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) with an amine compound (a1) Containing amine adducts,
The microcapsule type latent curing agent for epoxy resin according to any one of claims 1 to 4 , wherein the molecular weight distribution (weight average molecular weight / number average molecular weight) of the amine adduct (A) is 1 or more and 7 or less. (F) . The molecular weight of the low molecular weight amine compound (B) is 31 or more and 600 or less,
The method according to any one of claims 1 to 5 , wherein the low molecular weight amine compound (B) has at least one amino group selected from the group consisting of a primary amino group, a secondary amino group and a tertiary amino group. Microcapsule type latent curing agent (F) for epoxy resin. The microcapsule type latent curing for epoxy resin according to any one of claims 1 to 6 , wherein the specific surface area of the nanosized inorganic compound fine particles (C) is 10 m ² / g or more and 1000 m ² / g or less. Agent (F) . The microcapsule-type latent resin for epoxy resin according to any one of claims 1 to 7 , wherein the inorganic compound forming the nano-sized inorganic compound fine particles (C) contains an inorganic oxide and / or an inorganic complex oxide. Hardener (F) . The inorganic compound forming the nano-sized inorganic compound fine particles (C) includes at least one inorganic compound selected from the group consisting of silica, alumina, magnesia, titania, zirconia, calcium carbonate, zeolite and talc. Microcapsule-type latent curing agent (F) for epoxy resin according to any one of 1 to 8 . The microcapsule type latent curing agent (F) for epoxy resin according to any one of claims 1 to 9 , wherein the surface of the nanosized inorganic compound fine particles (C) is hydrophobized by a functional group. The surface of the nanosized inorganic compound fine particles (C) is at least one selected from the group consisting of alkylsilanes, polyalkylsiloxanes, phenylsilanes, phenylalkylsilanes, silanols, chlorosilanes, alkoxysilanes, silazanes, siloxanes and halogenated silanes. The microcapsule type latent curing agent (F) for epoxy resin according to any one of claims 1 to 10 , which is hydrophobized from a functional group derived from a compound of a species. The average particle size of the curing agent for epoxy resin (D) contained in the core is more than 0.3 μm and 12 μm or less,
A reaction product obtained by reacting two or more selected from the group consisting of an isocyanate compound, an active hydrogen compound, a curing agent for an epoxy resin (h1), an epoxy resin (e2) and a low molecular weight amine compound (G) The microcapsule type latent curing agent (F) for an epoxy resin according to any one of claims 1 to 11 , comprising: 100 parts by mass of the microcapsule type latent curing agent (F) for epoxy resin according to any one of claims 1 to 12 , and at least one selected from the group consisting of monoepoxy resin and polyvalent epoxy resin The epoxy resin composition which contains 10-50000 mass parts of epoxy resins (E). The microcapsule type latent curing agent (F) for epoxy resin according to any one of claims 1 to 12 , the epoxy resin (E), and the nitrogen-containing heterocyclic compound (P),
The epoxy resin composition whose content of the said nitrogen-containing heterocyclic compound (P) is 0.01 mass part or more and 15 mass parts or less with respect to 100 mass parts of said epoxy resin (E). The nitrogen-containing heterocyclic compound (P) according to claim 14 , wherein the nitrogen-containing heterocyclic compound (P) comprises at least one derivative selected from the group consisting of pyridine derivatives, pyrimidine derivatives, pyrazine derivatives, triazine derivatives, quinoline derivatives, isoquinoline derivatives and purine derivatives. Epoxy resin composition. The epoxy resin composition according to claim 14 or 15 , wherein the nitrogen-containing heterocyclic compound (P) contains a pyridine derivative. The epoxy resin composition according to any one of claims 13 to 16 , further comprising at least one thermosetting resin selected from the group consisting of oxetane resins, monoepoxy resins and polyvalent epoxy resins. The resin composition according to claim 1, further comprising at least one epoxy resin curing agent (h2) selected from the group consisting of an acid anhydride curing agent, a phenol curing agent, a hydrazide curing agent, a guanidine curing agent and a thiol curing agent. The epoxy resin composition according to any one of 13 to 17 . Materials containing epoxy resin composition according to any one of claims epoxy resin microcapsule-type latent curing agent according to any one of claims 1 to 12 (F), or claims 13-18. Adhesive, bonding paste, conductive material, anisotropic conductive material, insulating material, sealing material, coating material, coating composition, prepreg, heat conductive material, separator for fuel cell, and flexible wiring board The material according to claim 19 , which is one selected from the group of overcoat materials.