JP6619628B2 - Epoxy resin composition for adhesive film. - Google Patents

Description

  The present invention relates to an epoxy resin composition suitable for an adhesive film, and particularly to an epoxy resin composition suitable for circuit connection.

  As an adhesive for a semiconductor element or a liquid crystal display element, a thermosetting resin composition including an epoxy resin having excellent adhesiveness and high reliability is used. As a component of the adhesive, a curing agent such as an epoxy resin, a phenol resin having reactivity with the epoxy resin, and a thermal latent catalyst that promotes a reaction between the epoxy resin and the curing agent are generally used. . The thermal latent catalyst is an important factor for determining the curing temperature and curing rate of the adhesive, and various compounds are used from the viewpoints of storage stability at room temperature and curing rate during heating ( For example, see Patent Document 1). Taking advantage of these characteristics, the epoxy resin composition is used for an anisotropic conductive film excellent in storage stability (see, for example, Patent Document 2).

International Publication No. 2007/037378 Pamphlet Japanese Patent Laid-Open No. 9-25467

  In recent years, especially in the field of electronic equipment, in order to cope with higher circuit density and higher connection reliability, or to use materials with low heat resistance to reduce the weight of mobile devices, the productivity has been greatly improved. For this purpose, there is a strong demand for an epoxy resin composition used as one of connection materials to further improve the curability of the composition without impairing the storage stability of the curing agent. However, an adhesive using an epoxy resin as described in Patent Document 2 is insufficient for recent demands for pressure bonding and connection reliability at a low temperature and in a short time.

  Therefore, the present invention provides, for example, an epoxy resin composition for an adhesive film that has a high connection reliability and includes a curing agent for an epoxy resin that has good storage stability and excellent curability when formed into a film using a solvent. The purpose is to provide.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have suppressed the aggregation of particles by using specific curing agent particles for epoxy resin, and by adjusting the particle size distribution well, The inventors have found that this can be solved, and have completed the present invention.

That is, the present invention relates to the following.
[1]
Containing an epoxy resin (e1), curing agent particles for epoxy resin (H), and a film-forming material,
The epoxy resin curing agent particles (H) are solid at 25 ° C.,
The specific surface area value (m ² / g) of the epoxy resin curing agent particles (H) and the particle size D ₅₀ (μm) of 50% cumulative fraction under sieve are expressed by the following formula (1). An epoxy resin composition for an adhesive film that fills.
^{4.0X -1 ≦ Y ≦ 8.3X -1 (} 1)
(In the formula (1), X represents a particle size D ₅₀ having an under-sieving fraction of 50%, and Y represents a specific surface area value.)
[2]
In the epoxy resin curing agent particles (H), the particle size D ₅₀ having a 50% integrated fraction under sieve is more than 0.3 μm and 12 μm or less, and the particle size D ₉₉ having a 99% integrated sieve fraction is The particle size distribution represented by the ratio (D ₉₉ / D ₅₀ ) with the particle size D ₅₀ having a 50% cumulative fraction under sieve is 6 or less,
The epoxy resin composition for adhesive films according to [1], wherein the moisture content in the epoxy resin curing agent particles (H) is 1.5% by mass or less.
[3]
The epoxy resin composition for an adhesive film according to [1] or [2], wherein the epoxy resin curing agent particles (H) include a modified imidazole compound.
[4]
A core (C) formed using the epoxy resin curing agent particles (H) as a starting material, and a shell (S) covering the core (C);
Wherein the shell (S), at least, a binding group to absorb wave number 1630 cm ^-1 or 1680 cm ^-1 The following infrared (x), the wave number 1680 cm ^-1 or 1725 cm ^-1 or less of the binding group that absorbs infrared ray (y) The epoxy resin composition for adhesive films according to any one of [1] to [3], which has, on its surface, a bonding group (z) that absorbs infrared rays having a wave number of from 1730 cm ^{−1 to} 1755 cm ⁻¹ .
[5]
The epoxy resin composition for an adhesive film according to [4], wherein the shell (S) has a urea bond and substantially does not have an ester bond in its structure.
[6]
The ratio of the thickness of the shell (S) for the particle size D ₅₀ of the epoxy resin curing agent particles (H) is 1.5 / 100 or 18/100 or less, according to [4] or [5] Epoxy resin composition for adhesive film.
[7]
The shell (S) is at least two selected from the group consisting of isocyanate compounds, active hydrogen compounds, epoxy resin curing agents (h2), other epoxy resins (e3), and low molecular amine compounds (B). The epoxy resin composition for adhesive films according to any one of [4] to [6], comprising a reaction product obtained as a raw material.
[8]
The total total chlorine amount of the total chlorine content contained in the epoxy resin curing agent particles (H) and the total chlorine content contained in the epoxy resin (e1) or the epoxy resin (e3) is 2500 mass ppm or less. The epoxy resin composition for adhesive films according to any one of [1] to [7].
[9]
The epoxy resin composition for adhesive films according to any one of [1] to [8], wherein the epoxy resin (e1) contains a naphthalene skeleton-containing epoxy resin and / or a resorcin-type epoxy resin.
[10]
The epoxy resin composition for adhesive films according to any one of [1] to [9], wherein the film forming material is a resin, and the weight average molecular weight of the resin is 10,000 or more.
[11]
The epoxy resin composition for adhesive films according to [10], wherein the skeleton of the film forming material contains one or more epoxy groups.
[12]
Furthermore, the epoxy resin composition for adhesive films in any one of [1]-[11] containing an additive.
[13]
The epoxy resin composition for a film according to [12], wherein the additive includes one or more selected from the group consisting of an inorganic filler, conductive particles, and a thermoplastic polymer.
[14]
The film using the epoxy resin composition for adhesive films in any one of [1]-[13].

  According to the present invention, for example, an epoxy resin composition for an adhesive film having a high long-term reliability containing a curing agent for an epoxy resin that has good storage stability and excellent curability when formed into a film using a solvent. Can be provided.

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

[Epoxy resin composition for adhesive film]
The epoxy resin composition for adhesive films of this embodiment is
Containing an epoxy resin (e1), curing agent particles for epoxy resin (H), and a film forming material,
The epoxy resin curing agent particles (H) are solid at 25 ° C.,
The specific surface area value (m ² / g) in the epoxy resin curing agent particles (H) and the particle size D ₅₀ (μm) of 50% integrated fraction under sieve are expressed by the following formula (1). Fulfill.
^{4.0X -1 ≦ Y ≦ 8.3X -1 (} 1)
(In the formula (1), X represents a particle size D _{50 of} 50% of the cumulative fraction under sieving, and Y represents a specific surface area value.)

(1) Epoxy resin (e1)
Although it does not specifically limit as epoxy resin (e1) (henceforth "component (e1)" and "(e1)") used for this embodiment, For example, either of a mono epoxy compound and a polyhydric epoxy compound Or a mixture thereof.

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

  Although it does not specifically limit as a polyhydric epoxy compound, For example, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol AD, tetramethyl bisphenol S, tetrabromo bisphenol A Bisphenol type epoxy resin obtained by glycidylation of bisphenols such as tetrachlorobisphenol A and tetrafluorobisphenol A; glycidyl other dihydric phenols such as biphenol, dihydroxynaphthalene and 9,9-bis (4-hydroxyphenyl) fluorene 1,1,1-tris (4-hydroxyphenyl) methane, 4,4- (1- (4- (1- (4-hydroxyphenyl) -1- Epoxy resin obtained by glycidylation of trisphenols such as tilethyl) phenyl) ethylidene) bisphenol; epoxy resin obtained by glycidylation of tetrakisphenols such as 1,1,2,2, -tetrakis (4-hydroxyphenyl) ethane; phenol novolac , Cresol novolak, bisphenol A novolak, brominated phenol novolak, novolak type epoxy resin obtained by glycidylation of novolak such as brominated bisphenol A novolak, etc .; epoxy resin obtained by glycidylation of polyhydric phenols, glycerin, polyethylene glycol, etc. Aliphatic ether type epoxy resin obtained by glycidylation of monohydric alcohol; ether ester type epoxide obtained by glycidylation of hydroxycarboxylic acid such as p-oxybenzoic acid and β-oxynaphthoic acid Xy resin; ester type epoxy resin obtained by glycidylation of polycarboxylic acid such as phthalic acid or terephthalic acid; amine type such as glycidated product of amine compounds such as 4,4-diaminodiphenylmethane and m-aminophenol, and triglycidyl isocyanurate Examples thereof include glycidyl type epoxy resins such as epoxy resins and alicyclic epoxides such as 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate.

Among these, it is preferable to contain a naphthalene skeleton-containing epoxy resin and a resorcin-type epoxy resin from the viewpoint of reducing the viscosity and improving the curing rate.
An epoxy resin (e1) may be used individually by 1 type, and may be used together 2 or more types.

(2) Curing agent particles for epoxy resin (H)
The epoxy resin curing agent particles (H) used in the present embodiment are solid at 25 ° C. and have a particle shape. Further, in the curing agent particles for epoxy resin used in the present embodiment, the specific surface area value (m ² / g) of the particles and the particle size D ₅₀ (μm) of 50% cumulative fraction under sieve are expressed by the following formula (1 ) Is satisfied.
^{4.0X -1 ≦ Y ≦ 8.3X -1 (} 1)
(In the formula (1), X represents a particle size D _{50 of} 50% of the cumulative fraction under sieving, and Y represents a specific surface area value.)
As a method of obtaining an epoxy resin curing agent particles (H) which satisfies the relation represented by the above formula (1) is not particularly limited, for example, a method of appropriately adjusting the specific surface area and particle size D ₅₀ of the later Can be mentioned.

As will be described later, in the epoxy resin curing agent particles (H), the particle size D ₅₀ having a 50% integrated fraction under sieve is preferably more than 0.3 μm and 12 μm or less. Preferably, the epoxy resin has a particle size distribution represented by a ratio (D ₉₉ / D ₅₀ ) of a particle size D ₉₉ having a fraction of 99% and a particle size D ₅₀ having a cumulative fraction under the sieve of 50% (D ₉₉ / D ₅₀ ). The moisture content in the curing agent particles (H) for use is preferably 1.5% by mass or less.

  Since the epoxy resin curing agent particles (H) used in the present embodiment are configured as described above, the aggregation ratio of the epoxy resin curing agent particles is reduced, and the curability is stored in a solvent dispersion. It can be set as the hardening | curing agent for epoxy resins which is excellent in all of stability. That is, according to the present embodiment, it is possible to provide a curing agent for an epoxy resin that is suitable when formed into a film without impairing the storage stability during solvent dispersion while maintaining the curing performance. More specifically, the epoxy resin curing agent particles (H) used in the present embodiment reduce the specific surface area of the particles by correcting the shape of the particles, and suppress aggregation of the curing agents (particles). , Curing performance, storage stability, and dispersibility of the curing agent are improved.

  First, each structure of the hardening | curing agent particle | grains (H) for epoxy resins used for this embodiment is demonstrated in detail. Although it does not specifically limit as a hardening | curing agent particle | grains (H) for epoxy resins used for this embodiment, For example, the particle | grains which have an amine-type hardening | curing agent as a main component are mentioned. The amine curing agent is not particularly limited. For example, an amine adduct, a modified polyamine, an aliphatic polyamine, a heterocyclic polyamine, an alicyclic polyamine, an aromatic amine, a polyamidoamine, and a ketimine And urethane amine type curing agents. Among these, from the viewpoint of having an appropriate reactivity, an amine curing agent composed of a low molecular amine compound (a1) and an amine adduct is preferable. Here, “having an amine-based curing agent as a main component” means 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more, based on the total amount (100% by mass) of the curing agent particles. Means to contain.

  The low molecular amine compound used for the amine curing agent (hereinafter also referred to as “low molecular amine compound (a1)”, “component (a1)”, “(a1)”)) is not particularly limited. Compounds having at least one primary amino group and / or secondary amino group but not having a tertiary amino group; compounds having at least one tertiary amino group and at least one active hydrogen group It is done.

  The compound having at least one primary amino group and / or secondary amino group but not having a tertiary amino group is not particularly limited. For example, methylamine, ethylamine, propylamine, butylamine, ethylenediamine, propylene Primary amines having no tertiary amino group such as diamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, ethanolamine, propanolamine, cyclohexylamine, isophoronediamine, aniline, toluidine, diaminodiphenylmethane, diaminodiphenylsulfone; dimethyl Amine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, dimethanolamine, diethanolamine, dipropanolamine, dicyclohexyl Amine, piperidine, piperidone, diphenylamine, phenylmethylamine, secondary amines having no tertiary amino group such as a phenyl ethyl amine.

  The compound having at least one tertiary amino group and at least one active hydrogen group is not particularly limited, and examples thereof include 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl. Amino alcohols such as 2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, methyldiethanolamine, triethanolamine, N-β-hydroxyethylmorpholine; 2- (dimethylaminomethyl) Aminophenols such as phenol and 2,4,6-tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl Midazole, 1-aminoethyl-2-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-ethyl-4-methyl Imidazoles such as imidazole, 1- (2-hydroxy-3-butoxypropyl) -2-methylimidazole, 1- (2-hydroxy-3-butoxypropyl) -2-ethyl-4-methylimidazole; 1- (2 -Hydroxy-3-phenoxypropyl) -2-phenylimidazoline, 1- (2-hydroxy-3-butoxypropyl) -2-methylimidazoline, 2-methylimidazoline, 2,4-dimethylimidazoline, 2-ethylimidazoline, 2 -Ethyl-4-methylimidazoline, 2-benzylimidazoline, 2 -Phenylimidazoline, 2- (o-tolyl) -imidazoline, tetramethylene-bis-imidazoline, 1,1,3-trimethyl-1,4-tetramethylene-bis-imidazoline, 1,3,3-trimethyl-1, 4-tetramethylene-bis-imidazoline, 1,1,3-trimethyl-1,4-tetramethylene-bis-4-methylimidazoline, 1,3,3-trimethyl-1,4-tetramethylene-bis-4- Imidazolines such as methylimidazoline, 1,2-phenylene-bis-imidazoline, 1,3-phenylene-bis-imidazoline, 1,4-phenylene-bis-imidazoline, 1,4-phenylene-bis-4-methylimidazoline; Dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, Tertiary aminoamines such as butylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, dipropylaminoethylamine, dibutylaminoethylamine, N-methylpiperazine, N-aminoethylpiperazine, diethylaminoethylpiperazine; 2-dimethylaminoethanethiol; Amino mercaptans such as 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptopyridine, 4-mercaptopyridine; N, N-dimethylaminobenzoic acid, N, N-dimethylglycine, nicotinic acid, isonicotinic acid, Aminocarboxylic acids such as picolinic acid; aminohydrazides such as N, N-dimethylglycine hydrazide, nicotinic acid hydrazide, and isonicotinic acid hydrazide.

  Among these low molecular amine compounds (a1), an imidazole compound is preferable from the viewpoint of having an appropriate reactivity. That is, it is preferable that the hardening | curing agent particle | grain particle | grains (H) for epoxy resins contain what modified | denatured the imidazole compound.

  Although it does not specifically limit as an amine adduct, For example, 1 type, or 2 or more types of compounds selected from the group which consists of a carboxylic acid compound, a sulfonic acid compound, a urea compound, an isocyanate compound, and an epoxy resin (e2), and an amine The compound which has an amino group obtained by reaction with a compound (a2) is mentioned.

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

  Although it does not specifically limit as a sulfonic acid compound, For example, ethanesulfonic acid and p-toluenesulfonic acid are mentioned.

  Although it does not specifically limit as a urea compound, For example, urea, methyl urea, dimethyl urea, ethyl urea, and t-butyl urea are mentioned.

  Although it does not specifically limit as an isocyanate compound, For example, aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, aliphatic triisocyanate, and polyisocyanate are mentioned. Although it does not specifically limit as aliphatic diisocyanate, For example, ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate are mentioned. The alicyclic diisocyanate is not particularly limited. For example, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, norbornane diisocyanate, 1,4-isocyanatocyclohexane, 1,3-bis (isocyanatomethyl) -cyclohexane, And 1,3-bis (2-isocyanatopropyl-2-yl) -cyclohexane. The aromatic diisocyanate is not particularly limited, and examples thereof include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylene diisocyanate, and 1,5-naphthalene diisocyanate. The aliphatic triisocyanate is not particularly limited, and examples thereof include 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, and 1,3,6-triisocyanate methylhexane. . Although it does not specifically limit as polyisocyanate, For example, polymethylene polyphenyl polyisocyanate and the polyisocyanate induced | guided | derived from the said diisocyanate compound are mentioned. The polyisocyanate derived from the diisocyanate is not particularly limited, and examples thereof include isocyanurate type polyisocyanate, burette type polyisocyanate, urethane type polyisocyanate, allophanate type polyisocyanate, and carbodiimide type polyisocyanate.

  As the epoxy resin used for the amine adduct (hereinafter also referred to as “epoxy resin (e2)”, “component (e2)”, “(e2)”), the same epoxy resin (e1) described above is used. it can. Here, the total chlorine amount indicates the total amount of organic chlorine and inorganic chlorine contained in the epoxy resin, and is a value based on mass with respect to the epoxy resin. The total chlorine content of the epoxy resin is measured by the following method.

  Washing and filtering with xylene is repeated until all of the epoxy resin contained in the epoxy resin (e2) is extracted. Next, the filtrate containing the extracted epoxy resin is distilled off under reduced pressure at 100 ° C. or lower to obtain an epoxy resin. 1-10 g of the obtained epoxy resin sample is precisely weighed so that the titration amount is 3 to 7 mL, dissolved in 25 mL of ethylene glycol monobutyl ether, added with 25 mL of a 1N KOH propylene glycol solution, and added for 20 minutes. After boiling, it is calculated from the titration titrated with an aqueous silver nitrate solution.

  The total chlorine content of the epoxy resin (e2) is preferably 0.01 mass ppm or more, more preferably 0.02 mass ppm or more, from the viewpoint of facilitating the control of the shell formation reaction. Preferably it is 0.05 mass ppm or more, More preferably, it is 0.1 mass ppm or more, More preferably, it is 0.2 mass ppm or more, More preferably, it is 0.5 mass ppm or more. Furthermore, when the total chlorine amount is 0.1 mass ppm or more, the shell formation reaction is efficiently performed on the core surface containing the curing agent, and a curing agent having further excellent storage stability tends to be obtained.

  The preferable range of the total chlorine content of the epoxy resin (e2) is 0.01 to 200 ppm by mass, the more preferable range is 0.2 to 80 ppm by mass, and the more preferable range is 0.00. It is 5 mass ppm or more and 50 mass ppm or less.

  Here, chlorine contained in the 1,2-chlorohydrin group in the total chlorine of the epoxy resin (e2) is referred to as hydrolyzable chlorine. The amount of hydrolyzable chlorine in the epoxy resin (e2) is preferably 50 mass ppm or less, more preferably 0.01 mass ppm or more and 20 mass ppm or less, and further preferably 0.05 mass ppm or more and 10 mass ppm or less. . When the hydrolyzable chlorine content is 50 mass ppm or less, it is preferable from the viewpoint of achieving both high curability and storage stability, and the cured product tends to exhibit excellent electrical characteristics.

  Here, hydrolyzable chlorine is measured by the following method. That is, 3 g of epoxy resin (e2) is dissolved in 50 mL of toluene, 20 mL of 0.1 N KOH in methanol is added thereto, boiled for 15 minutes, and then calculated from titration titrated with an aqueous silver nitrate solution.

  Examples of the amine compound used in the amine adduct (hereinafter, also referred to as “amine compound (a2)”, “component (a2)”, “(a2)”)) are the examples of the low-molecular amine compound (a1) described above. And the same amine compounds as mentioned above.

  Among the amine adducts described above, a compound having an amino group obtained by a reaction between the epoxy resin (e2) and the amine compound (a2) is preferable. The amine adduct obtained by the reaction between the epoxy resin (e2) and the amine compound (a2) is also preferable from the viewpoint that the unreacted amine compound (a2) can be used as the low molecular amine compound (a1).

  The amine adduct obtained by the reaction of the epoxy resin (e2) and the amine compound (a2) is, for example, the epoxy resin (e2) and the amine compound (a2) with respect to 1 equivalent of the epoxy group of the epoxy resin (e2). The active hydrogen group of the amine compound (a2) is preferably in the range of 0.5 to 10 equivalents, more preferably 0.8 to 5 equivalents, and even more preferably 0.95 to 4 equivalents. In the presence of a solvent as required, for example, it is obtained by reacting at a temperature of 50 to 250 ° C. for 0.1 to 10 hours. When the equivalent ratio of active hydrogen groups to epoxy groups is 0.5 or more, it is advantageous to obtain an amine adduct having a molecular weight distribution measured by gel permeation chromatography (GPC) of 7 or less. Adduct fluidity tends to increase. Furthermore, it is preferable to use the amine adduct as described above from the viewpoints of storage stability and low temperature curability. An equivalent ratio of 10 or less is advantageous because the unreacted amine compound (a2) can be used as it is as the low-molecular amine compound (a1) without being recovered.

  In the reaction for obtaining an amine adduct by the epoxy resin (e2) and the amine compound (a2), the solvent used as necessary is not particularly limited, and examples thereof include benzene, toluene, xylene, cyclohexane, mineral spirit, naphtha and the like. Hydrocarbons such as acetone, methyl ethyl ketone, methyl isobutyl ketone (MIBK), etc .; esters such as ethyl acetate, n-butyl acetate, propylene glycol monomethyl ether acetate; methanol, isopropanol, n-butanol, butyl cellosolve, butyl Alcohols such as carbitol; water. These solvents may be used alone or in combination of two or more.

The specific surface area value of the epoxy resin curing agent particles (H) is not particularly limited as long as the relationship represented by the above formula (1) is satisfied, but is preferably 0.3 m ² / g or more and 30 m ² / g or less. 0.5 m ² / g or more and 25 m ² / g or less is more preferable, and 0.7 m ² / g or more and 20 m ² / g or less is further preferable. When the specific surface area value is 0.3 or more, the curing rate tends to be improved, and when the specific surface area value is 30 m ² / g or less, aggregation of the curing agent particles is suppressed and stability tends to be improved. is there. In order to obtain the epoxy resin curing agent particles (H) having a specific surface area value in the above range, it is obtained by a pulverization method without pulverizing to a predetermined size or producing a porous body. The method is mentioned. Here, a specific surface area value can be measured according to the method described in the Example mentioned later.

  Next, adjustment of the specific surface area of the curing agent particles (H) for epoxy resin will be described. As a method of preparing the curing agent particles (H) for epoxy resin, for example, by using a method of precipitating amine compound / epoxy compound adduct particles in an insoluble solvent, the specific surface area is larger than the particle preparation method by pulverization or the like. A low product is obtained. It is also possible to adjust and lower the specific surface area by correcting the shape after obtaining particles by pulverizing the curing agent for epoxy resin. The shape correction method is not particularly limited, and examples thereof include a shape correction method when physical particles collide with a jet mill or the like, and a shape correction method using heat. Regardless of which method is used, it is preferable to adjust the amount of water by sufficient temperature and humidity control before and after adjusting the specific surface area. That is, from the viewpoint of ensuring good product quality, it is preferable to adjust the specific surface area and the water content at the same time.

  As a method for preparing the curing agent particles (H) for epoxy resin by adjusting the specific surface area, in the shape correction method by the above-described heat treatment, it is possible to perform both moisture removal and shape correction. There are many epoxy resin curing agents that easily absorb moisture, especially after adjusting the specific surface area using heat, etc., the moisture tends to evaporate due to heat and easily absorb moisture. It can be said that it is difficult to adjust the amount of water because it contains water immediately. Therefore, from the viewpoint of obtaining the desired effect of the present embodiment without any inadequacy, the epoxy resin curing agent particles (H) in which both the specific surface area and the moisture content are adjusted, particularly in an environment in which the temperature and humidity are sufficiently controlled, are produced. It can be said that it is preferable.

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

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

The above formula (1) shows the relationship between the particle size D ₅₀ (X) and the specific surface area (Y) of a certain sieving cumulative fraction of 50%. The relationship between X and Y of the epoxy resin curing agent (particles) having an indefinite shape that has not undergone shape correction is represented by “Y = 10.4X ⁻¹ ”. The upper limit “Y = 8.3X ⁻¹ ” in the formula (1) is a physical shape correction for the irregularly shaped epoxy resin curing agent particles, specifically, a shape correction method to such an extent that the particles do not cause pulverization. By controlling the shape, the shape of the epoxy resin curing agent is corrected by collision with the particles and the device, and the upper limit value of Y in the epoxy resin curing agent particles (H) used in this embodiment is reduced in specific surface area. It is shown. On the other hand, when it is calculated on the assumption that all the particles exist as perfect spheres, the lower limit value of Y is represented by “Y = 2.5X ⁻¹ ”. Therefore, the lower limit value of Y is never less than “2.5X ⁻¹ ”. Further, when adjustment is performed by a method using heat, the lower limit value of Y can be expressed by “Y = 4.0X ⁻¹ ”. This lower limit value considers the surface tension of the curing agent particles for epoxy resin, and takes into consideration that the shape having a smaller specific surface area is obtained by applying heat. Thus epoxy resin curing agent particles used in the present embodiment (H) is theoretically "2.5X ^-1 ≦ Y ≦ 8.3X ^-1" and, more essentially the formula (1) "4. It is configured to have a specific surface area (Y) that satisfies “0X ⁻¹ ≦ Y ≦ 8.3X ⁻¹ ” ”. By adjusting the specific surface area represented by the formula (1), the aggregation of the curing agent particles is suppressed, and the curing performance, storage stability, and curing agent when used as a curing agent for one-pack type epoxy resin. Dispersibility and penetration into narrow gaps can be improved. This is considered to be due to the fact that the particle packing density can be increased by correcting the shape of the particles and the viscosity of the resin particles is reduced.

Next, the median diameter of the epoxy resin curing agent particles (H) used in the present embodiment (that is, the particle diameter D ₅₀ having a 50% cumulative fraction under sieving) will be described. The epoxy resin curing agent particles (H) used in the present embodiment are defined by the median diameter from the viewpoint of obtaining a homogeneous cured product and from ensuring the good physical properties of the cured product by preventing aggregation of the particles. The average particle diameter (particle diameter D ₅₀ ) is preferably more than 0.3 μm and 12 μm or less, more preferably 1 μm or more and 10 μm or less, and further preferably 1.5 μm or more and 5 μm or less. Moreover, the microcapsule-type epoxy resin curing agent is formed using the above particles as a starting material. Here, the average particle diameter (particle diameter D ₅₀ ) defined by the median diameter refers to the Stokes diameter measured by a laser diffraction / light scattering method. Moreover, the shape is not specifically limited, For example, any of spherical shape, granule shape, powder shape, and an indefinite shape may be sufficient. When the particle diameter D _{50 of the} curing agent particles for epoxy resin (H) is 12 μm or less, a homogeneous cured product can be obtained. Moreover, when mix | blending a composition, the production | generation of the aggregate of a large particle diameter can be suppressed and the physical property of hardened | cured material can be maintained. When the particle diameter D _{50 of the} epoxy resin curing agent particles (H) exceeds 0.3 μm, aggregation between the starting material particles can be suppressed, and formation of a thin shell is facilitated. As a result, capsule film formation is improved, and storage stability and solvent resistance can be maintained.
The adjustment of the particle diameter D ₅₀ of the epoxy resin curing agent particles (H) is not particularly limited, but can be performed, for example, according to the method described in Examples described later.
In the present embodiment, the particle size D ₅₀ of the epoxy resin curing agent particles (H) can be measured by the method described in Examples set forth below.

The particle size distribution of the curing agent particles for epoxy resin (H) used in the present embodiment is the ratio of the particle size D ₉₉ of 99% integrated sieve fraction to the particle size D ₅₀ of 50% integrated sieve fraction (hereinafter, It is also simply expressed as “D ₉₉ / D ₅₀ ”). In the particle size distribution of the epoxy resin curing agent particles (H), D ₉₉ / D ₅₀ is preferably 6 or less from the viewpoint of preventing aggregation of the particles, and more preferably 5.5 from the same viewpoint. Or less, more preferably 5 or less. When D ₉₉ / D ₅₀ is 6 or less, there are few coarse particles in the powder particles, and the formation of aggregates is suppressed, and the physical properties of the cured product tend to be impaired. D ₉₉ / D ₅₀ means that the smaller the particle size distribution is, the easier it is to obtain a homogeneous cured product and better curing performance. In addition, since the value of D ₉₉ / D ₅₀ is 6 or less, the particle size distribution is narrow and particles having a relatively large particle size are less likely to be present, so that the permeability to the gap when a compound is prepared is excellent. There is a tendency. Further, D ₉₉ / D ₅₀ is preferably 1.2 or more. When D ₉₉ / D ₅₀ is 1.2 or more, there is a tendency to suppress the formation of many gaps between the curing agent particles, and preferably, from the same viewpoint, more preferably 1.5 or more, Preferably it is 1.7 or more, More preferably, it is 2.0 or more.
The method for obtaining the epoxy resin curing agent particles (H) having D ₉₉ / D ₅₀ in the above range is not particularly limited, and examples thereof include a method of removing small particle size particles.
In the present embodiment, the particle diameter D ₉₉ of the epoxy resin curing agent particles (H) can be measured by the method described in the examples described later.

  Next, the water content of the epoxy resin curing agent particles (H) used in the present embodiment will be described. It is preferable that the moisture content of the epoxy resin curing agent particles (H) used in this embodiment with the specific surface area adjusted is 1.5% by mass or less with respect to the mass (100% by mass) of the curing agent particles. More preferably, it is 0.8 mass% or less, More preferably, it is 0.6 mass% or less. When the moisture content of the epoxy resin curing agent particles (H) is 1.5% by mass or less, the occurrence of defects tends to be suppressed. In other words, a decrease in curing performance and storage stability of the curing agent particles for epoxy resin, a decrease in productivity due to a decrease in fluidity as particles, a decrease in dispersibility of the curing agent for epoxy resin due to the occurrence of aggregates, There is a tendency to suppress the occurrence of defects such as a decrease in yield. When the moisture content of the epoxy resin curing agent particles (H) is 0.8% by mass or less, blocking after the corrected shape can be more preferably suppressed and the physical properties tend to be stable. More preferably, it is 6 mass% or less. When producing a microcapsule type epoxy resin curing agent, the epoxy resin curing agent particles obtained by adjusting the specific surface area and the amount of water should be further incorporated with water during capsule film production. In addition, the surface shell formation efficiency is improved, and the formed shell tends to be a film having better storage stability and solvent resistance. The water content can be measured by the Karl Fischer method using specific surface area and coulometric titration.

The epoxy resin composition for an adhesive film of the present embodiment is a core (hereinafter also referred to as “core (C)” or “(C)”) formed using the epoxy resin curing agent particles (H) as a starting material. And a shell covering the core (C) (hereinafter also referred to as “shell (S)” or “(S)”), and the shell (S) has a wave number of 1630 cm ⁻¹ or more and 1680 cm ^−1. binding group that absorbs less infrared (hereinafter "bonding group (x)", also referred to as "(x)".) and the linking group to absorb wave number 1680 cm ^-1 or 1725 cm ^-1 the following infrared (hereinafter " Bonding group (y) ”and“ (y) ”) and a bonding group that absorbs infrared rays having a wave number of 1730 cm ⁻¹ or more and 1755 cm ⁻¹ or less (hereinafter,“ bonding group (z) ”,“ (z) ”). It is more preferable to have at least the surface thereof. Since it is comprised in this way, it exists in the tendency for the aggregation ratio of the particle | grains derived from the hardening | curing agent for epoxy resins to be reduced, and to be excellent in all of sclerosis | hardenability, storage stability, and crevice permeability. Furthermore, from the same viewpoint, the epoxy resin curing agent particles (H) are more preferably mainly composed of an amine adduct obtained by a reaction between the epoxy resin (e2) and the amine compound (a2). Here, “having an amine adduct as a main component” means containing 50% by mass or more, preferably 70% by mass or more, and more preferably 90% by mass or more with respect to the mass of the curing agent particles (H). Say.

  Next, the core (C) will be described. Examples of the starting material particles for forming the core (C) include the above-described curing agent particles for epoxy resin before forming the shell. As for the particle diameter of the epoxy resin curing agent particles, the average particle diameter defined by the median diameter is preferably more than 0.3 μm and 12 μm or less, preferably 1.0 μm or more and 10 μm or less, and 1.5 μm. More preferably, it is 5.0 μm or less. Here, the particle diameter of the starting material particles refers to the Stokes diameter measured by a laser diffraction / light scattering method. When the particle diameter of the starting material particles is 12 μm or less, there is a tendency that a homogeneous cured product can be obtained. When the particle diameter is 0.3 μm or more, aggregation between the starting material particles can be suppressed, and a thin shell is obtained. Tends to be easier to form.

  The starting material particles are solid at 25 ° C. The temperature of the hot air when the starting material particles are treated with hot air is preferably 100 ° C. or higher and 400 ° C. or lower. When the temperature of the hot air is 100 ° C. or higher, the core surface is sufficiently heated and tends to be easily controlled to a desired circularity. When the temperature of the hot air is 400 ° C. or lower, the core (C) There is a tendency that the thermal decomposition of can be suppressed better. From the same viewpoint as the above viewpoint, the hot air temperature is more preferably 150 ° C. or higher and 300 ° C. or lower, and further preferably 180 ° C. or higher and 250 ° C. or lower.

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

  The starting material particles for forming the core (C) include acid anhydrides such as phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, and methylnadic acid, in addition to the amine-based curing agent described above. Phenolic curing agents such as phenol novolak, cresol novolak, bisphenol A novolak; propylene glycol-modified polymercaptan, thiogluconic acid ester of trimethylolpropane, mercaptan curing agent such as polysulfide resin; ethylamine salt of trifluoroborane, etc. Boron halide salt curing agent: quaternary ammonium salt curing agent such as phenol salt of 1,8-diazabicyclo (5,4,0) -undec-7-ene; 3-phenyl-1,1-dimethylurea Urea curing agents such as triphenylphosphine, tetra Combined use with other curing agents for epoxy resins such as phenylphosphonium tetraphenylborate (hereinafter referred to as “curing agent for epoxy resin (h1)”, “curing agent (h1)”, “(h1)”) You can also However, (h1) is not limited to the above.

(2-2) First shell (S1)
The shell (S) covers the core (C) and includes at least a first shell (hereinafter also referred to as “shell (S1)” or “(S1)”). Shell (S1), the core surface is coated directly in (C), binding group to absorb wave number 1630 cm ^-1 or 1680 cm ^-1 The following infrared (x), the wave number 1680 cm ^-1 or 1725 cm ^-1 The following infrared And a bonding group (z) that absorbs infrared rays having a wave number of 1730 cm ⁻¹ or more and 1755 cm ⁻¹ or less. Further, the ratio (Cx / (Cx + Cy + Cz)) of the concentration Cx of the bonding group (x) to the total concentration (Cx + Cy + Cz) of the bonding groups (x), (y) and (z) is 0.50 or more and less than 0.75. It is preferable that Here, Cx represents the concentration of the bonding group (x) in the shell (S1), Cy represents the concentration of the bonding group (y) in the shell (S1), and Cz represents the bonding group in the shell (S1) ( z) represents the concentration. Here, the infrared absorption can be measured using an infrared spectrophotometer, and it is particularly preferable to use a Fourier transform infrared spectrophotometer (FT-IR).

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

  The shell (S) and / or (S1) of the present embodiment preferably has a urea group and substantially does not have an ester group, has a urea group, a burette group, and a urethane group, and More preferably, it does not have an ester group. Since the ester bond site is susceptible to hydrolysis, the shell (S1) is sufficiently maintained even under high humidity conditions, and the storage stability and moisture resistance of the curing agent for epoxy resin and the epoxy resin composition containing the same are cured. From the viewpoint of sufficiently securing the physical properties of the cured product obtained in this manner, the shell (S) or (S1) having the above configuration is preferable. Here, “substantially has no ester group” means that a compound having an ester group in the shell (S) or (S1) is not used as a constituent material of the shell. Therefore, the shell (S) and (S1) may contain a compound having an ester group contained as an impurity.

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

  When the shell (S1) is a reaction product of an amine curing agent or another epoxy resin curing agent (h1) and an isocyanate compound, the shell (S1) is a starting material for forming the core (C). Compared to the case of the amine-based curing agent that can be contained in the material particles, or the reaction product of the epoxy resin curing agent (h1) and the epoxy resin that can be used in combination therewith, the bonding group (x) and the bonding group (Y) and the content of the bonding group (z) tend to increase more, and the microcapsule type epoxy resin curing agent having such a shell (S1) has better storage stability and solvent resistance. There is a tendency to be able to demonstrate.

  The first shell containing the linking group (x), the linking group (y), and the linking group (z) is not particularly limited, and may be an amine-based curing agent that can be included in the starting material particles, or an epoxy that can be used in combination therewith. Amine-based curing agent that can be contained in the starting material particles at a temperature lower than the temperature at which the curing agent for resin (h1) reacts with the epoxy resin, and the curing agent for epoxy resin (h1) and isocyanate compound that can be used in combination with this It can obtain by making it react.

The ratio of the thickness of the shell (S) to the particle size D ₅₀ of the epoxy resin curing agent particles (H) is preferably 1.5 / 100 or more and 18/100 or less, and 3.0 / 100 or more. More preferably, it is -15/100 or less, More preferably, it is 5.0 / 100 or more and 10/100 or less.
The method for obtaining the curing agent particles for epoxy resin (H) in which the ratio of the thickness of the shell (S) to the particle size D ₅₀ is within the above range is not particularly limited. Examples thereof include a method of adjusting the amount of the curing agent particles to form a shell, and a method of adjusting the amount of the capsule film agent and the curing agent particles in a solvent to form the shell.
In the present embodiment, the thickness of the shell (S) can be measured by the method described in Examples described later.
Since the core-shell type curing agent for epoxy resin is configured in this manner, it tends to have an excellent balance between storage stability and curability. Furthermore, from the same viewpoint, it is preferable that the curing agent particle for epoxy resin (H) is mainly composed of an amine adduct (A) obtained by a reaction between the epoxy resin (e1) and an amine compound. Here, the “main component” of the amine adduct (A) is 50% by mass or more, preferably 70% by mass or more, and more preferably 90% by mass with respect to the mass (100% by mass) of the curing agent particles. It occupies the above. The “core shell type” is also referred to as a “capsule type”.

(2-3) Shell (S)
From the viewpoint of the balance between storage stability and curability, the shell (S) is an isocyanate compound, an active hydrogen compound, a curing agent for epoxy resin (hereinafter, other curing agent for epoxy resin used for the shell is referred to as “for epoxy resin”). Curing agent (h2) "," component (h2) ", also referred to as" (h2) "), epoxy resin (hereinafter, epoxy resin used for the shell is" epoxy resin (e3) "," component (e3) " , “(E3)”), and low molecular weight amine compounds (hereinafter, low molecular weight amine compounds used for the shell are referred to as “low molecular weight amine compound (B)”, “component (B)”, “(B)”). It is also preferable to include a reaction product obtained using as a raw material two or more selected from the group consisting of: Further, a second shell (hereinafter referred to as “shell (S2)” or “(S2)”) made of a reaction product of the shell (S1) and the epoxy resin (e3) is formed on the surface of the shell (S1). More preferably). Here, (h2) can be the same as (h1), (e3) can be the same as (e2), and (B) has an amine-based curing. The same as (a1) used for the agent can be used.

  The shell (S2) is preferably a reaction product of the shell (S1) and the epoxy resin (e3). As the epoxy resin (e3), the polyvalent epoxy compounds mentioned as examples of the epoxy resin (e2) used as the raw material for the amine adduct contained in the core (C) can be used. These epoxy resins (e3) may be used individually by 1 type, and may use 2 or more types together.

  The epoxy resin (e3) is the same as the epoxy resin (e4) contained in the masterbatch type epoxy resin curing agent composition to be described later, or a part of the epoxy resin (e4) is a mixture, and storage stability. And a microcapsule type epoxy resin curing agent excellent in solvent resistance is preferable.

  The epoxy resin has an impure end in which chlorine is bonded in the molecule, but it is preferable to reduce such an impure end from the viewpoint of sufficiently securing the electric characteristics of the cured product. Therefore, the total chlorine content of the epoxy resin (e3) is preferably 2500 mass ppm or less, more preferably 1500 mass ppm or less, and still more preferably 500 mass ppm or less.

  From the same viewpoint as the viewpoint regarding the above (e3), in this embodiment, the total chlorine amount contained in the curing agent particles for epoxy resin (H) and the epoxy resin (e2) or the epoxy resin (e3) are contained. The total amount of chlorine with the total amount of chlorine is more preferably 2500 mass ppm or less, more preferably 1500 mass ppm or less, and still more preferably in the range of 50 to 1000 mass ppm.

  The reaction between the epoxy resin (e3) and the shell (S1) can be performed in a dispersion medium. Although it does not specifically limit as a dispersion medium, For example, a solvent, an epoxy resin, and a plasticizer are mentioned. As a solvent and a plasticizer, what is mentioned as an example of the solvent and plasticizer which can be used by reaction of the isocyanate compound and active hydrogen compound mentioned later can be used.

  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, a compound having at least one hydroxyl group, and the like. What does not contain is mentioned. These compounds may be used alone or in combination of two or more.

  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, and aromatic amines. Examples of the aliphatic amine include, but are not limited to, alkylamines such as methylamine, ethylamine, propylamine, butylamine, and dibutylamine; alkylenediamines such as ethylenediamine, propylenediamine, butylenediamine, and hexamethylenediamine; diethylenetriamine, triethylene Examples include polyalkylene polyamines such as tetramine and tetraethylenepentamine; polyoxyalkylene polyamines such as polyoxypropylene diamine and polyoxyethylene diamine. The alicyclic amine is not particularly limited, and examples thereof include cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, and isophoronediamine. The aromatic amine is not particularly limited, and examples thereof include aniline, toluidine, benzylamine, naphthylamine, diaminodiphenylmethane, and diaminodiphenylsulfone.

  Although it does not specifically limit as a compound which has at least 1 hydroxyl group, For example, an alcohol compound and a phenol compound are mentioned. Examples of the alcohol compound include, but are not limited to, for example, methyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, dodecyl alcohol, Stearyl alcohol, eicosyl alcohol, allyl alcohol, crotyl alcohol, propargyl alcohol, cyclopentanol, cyclohexanol, benzyl alcohol, cinnamyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol mono Monoalcohols such as butyl; ethylene glycol, polyester Glycol, propylene glycol, polypropylene glycol, 1,3-butanediol, 1,4-butanediol, hydrogenated bisphenol A, neopentyl glycol, glycerol, trimethylolpropane, polyhydric alcohols such as pentaerythritol. Further, two secondary hydroxyl groups obtained by reaction of a compound having at least one epoxy group with a compound having at least one hydroxyl group, carboxyl group, primary or secondary amino group, or mercapto group in one molecule. The compounds having the above are also exemplified as polyhydric alcohols. These alcohol compounds may be any of primary, secondary, or tertiary alcohols. Although it does not specifically limit as a phenol compound, For example, polyhydric phenols, such as monophenols, such as carboxylic acid, cresol, xylenol, carvacrol, motile, naphthol, catechol, resorcin, hydroquinone, bisphenol A, bisphenol F, pyrogallol, phloroglucin Kind. The compound having at least one hydroxyl group is preferably a polyhydric alcohol or a polyhydric phenol, more preferably a polyhydric alcohol.

  Although reaction of an isocyanate compound and an active hydrogen compound is not specifically limited, It is preferable to carry out by the reaction time of 10 minutes-12 hours in the temperature range of -10 degreeC-150 degreeC.

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

  Such a reaction product of an isocyanate compound and an active hydrogen compound has a urea bond, but preferably has substantially no ester bond, and more preferably has a burette bond and a urethane bond. preferable. If the reaction product has a burette bond and a urethane bond, the solvent resistance of the resulting core-shell type curing agent particles tends to increase.

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

  The formation reaction of the shell (S1) is not particularly limited, but is preferably −10 ° C. to 100 ° C., more preferably 0 ° C. to 50 ° C., further preferably 20 ° C. to 40 ° C., preferably 10 minutes to The reaction time is 24 hours, more preferably 2.0 hours to 10 hours. When the reaction temperature is −10 ° C. or higher, the reaction is fast and industrially preferable. When the reaction temperature is 100 ° C. or lower, the core material can be prevented from being eluted into the reaction system, and storage stability, solvent resistance, etc. Tends to be improved.

  Further, if the material for forming the shell is present at the initial stage of the shell formation reaction, the shell (S1) is formed more effectively, and the effects such as storage stability and solvent resistance are more remarkably exhibited. There is a tendency.

  The shell (S2) can be formed by reacting the core (C) covered with the shell (S1) with an epoxy resin. The reaction temperature at that time is preferably -10 ° C to 150 ° C, more preferably 0 ° C to 100 ° C, and further preferably 10 ° C to 70 ° C, and the reaction time is preferably 10 minutes to 24 hours. More preferably, it is 2.0 hours to 10 hours.

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

  In the core-shell type epoxy resin curing agent particles used in this embodiment, the content of the dispersion stabilizer with respect to the core (C) is preferably 8.0% by mass or less. The smaller the amount of the dispersion stabilizer contained in the core-shell type epoxy resin curing agent particles, the lower the viscosity when the core-shell type epoxy resin curing agent particles are mixed with the epoxy resin. It is possible to sufficiently secure the fluidity of the film and to ensure sufficient adhesion with the adherend. That is, not only can the cured product have good moisture resistance and penetrability, but it also tends to have better solvent resistance and filler resistance. As a result, the reliability of the electrical component when the cured product is used for the electrical component or the like tends to be sufficiently secured. From such a viewpoint, the content of the dispersion stabilizer with respect to the core (C) in the core-shell type curing agent particle for epoxy resin is preferably 8.0% by mass or less, more preferably 5.0% by mass or less. More preferably, it is 1.0 mass% or less, More preferably, it is 0.5 mass% or less, More preferably, it is not containing. In addition, about content of the said dispersion stabilizer, it can quantify from observing the peak characteristic of a dispersion stabilizer by FT-IR.

  The dispersion stabilizer has a function of dispersing each component contained in the core-shell type epoxy resin curing agent particle, and is not particularly limited. For example, the following graft copolymer, block copolymer, random Examples include copolymers and other polymers.

  The graft copolymer is not particularly limited. For example, methyl methacrylate / methacrylic acid copolymer obtained by graft copolymerization with styrene, methyl methacrylate / 2-hydroxyethyl methacrylate copolymer, poly 2-hydroxy methacrylate, poly 2, Graft copolymerized 3-dihydroxypropyl methacrylate, polyacrylamide-2-methylpropanesulfonic acid, polyvinyl alcohol, polyvinyl acetate, polymethacrylic acid, polyacrylamide, polyethylene oxide, poly-4-vinyl-ethylpyridium bromide, methyl methacrylate Methyl methacrylate / methacrylic acid copolymer, glycidyl methacrylate / styrene copolymer, methyl methacrylate / fluoroalkyl acrylate copolymer, methacrylic acid Raft copolymerized polybutadiene, methyl methacrylate / glycidyl methacrylate copolymer, polymethyl methacrylate grafted with N-methylol acrylamide, 2-hydroxyethyl methacrylate copolymer, poly grafted with 1,2-hydroxystearic acid Methyl methacrylate, ethyl acrylate / methacrylic acid copolymer, methyl acrylate / methacrylic acid copolymer, styrene / methacrylic acid copolymer, polymethyl methacrylate obtained by graft copolymerization with 2-hydroxyethyl methacrylate, poly (ethylene copolymerized with ethylene oxide) Examples thereof include styrene / glycidyl methacrylate obtained by graft copolymerization of vinyl chloride and methyl methacrylate.

  The block copolymer is not particularly limited. For example, polylauryl methacrylate / polymethacrylic acid block copolymer, polystyrene / polymethacrylic acid block copolymer, polyethylene oxide / polystyrene / polyethylene oxide block copolymer, and poly 12-hydroxystearic acid / polyethylene glycol / poly-12-hydroxystearic acid.

  Although it does not specifically limit as a random copolymer, For example, a vinyl acetate / vinyl alcohol copolymer, a vinyl acetate / N-vinyl pyrrolidone copolymer, and N-vinyl pyrrolidone / methyl methacrylate are mentioned.

  The other polymer is not particularly limited, and examples thereof include cationized amine-modified polyester.

  Although it does not specifically limit as a weight average molecular weight of a dispersion stabilizer, Preferably it is 1000-2,000,000.

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

(3) Film-forming material Film-forming material is a mechanical property that makes it easy to handle the film when the liquid is solidified and the constituent composition is made into a film shape, and does not easily tear, crack, or stick. Etc., and can be handled as a film in a normal state (normal temperature and normal pressure).

  Although it does not specifically limit as a film formation material, For example, a phenoxy resin, polyvinyl formal resin, a polystyrene resin, polyvinyl butyral resin, a polyester resin, a polyamide resin, a xylene resin, and a polyurethane resin are mentioned, for example. Among these, it is preferable to contain one or more epoxy groups from the viewpoint of compatibility, and a phenoxy resin is preferable because of excellent adhesiveness, heat resistance, and mechanical strength.

  The phenoxy resin is a resin obtained by reacting a bifunctional phenol and epihalohydrin until they are polymerized or by polyaddition of a bifunctional epoxy resin and a bifunctional phenol. For example, the phenoxy resin contains 1 mol of a bifunctional phenol and 0.985 to 1.015 mol of epihalohydrin in the presence of a catalyst such as an alkali metal hydroxide at a temperature of 40 to 120 ° C. in a non-reactive solvent. It can be obtained by reacting.

  Further, as the phenoxy resin, from the viewpoint of the mechanical properties and thermal properties of the resin, the blending equivalent ratio of the bifunctional epoxy resin and the bifunctional phenols is particularly preferably epoxy group / phenol hydroxyl group = 1 / 0.9. To 1 / 1.1, in the presence of a catalyst such as an alkali metal compound, an organophosphorus compound, or a cyclic amine compound, such as an amide, ether, ketone, lactone, alcohol or the like having a boiling point of 120 ° C. or higher. What was obtained by heating to 50-200 degreeC on the conditions whose reaction solid content is 50 mass% or less in the organic solvent was obtained.

  As the bifunctional epoxy resin used, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, and bisphenol S type epoxy resin can be used. Bifunctional phenols have two phenolic hydroxyl groups, and examples thereof include bisphenol compounds such as hydroquinones, bisphenol A, bisphenol F, bisphenol AD, and bisphenol S.

  The phenoxy resin may be modified with a radical polymerizable functional group. A phenoxy resin can be used individually by 1 type or in mixture of 2 or more types.

When the film forming material is a resin, the weight average molecular weight of the resin is preferably 10,000 or more from the viewpoint of film forming properties. Further, when the film forming material is a thermoplastic resin, and the weight average molecular weight of the thermoplastic resin is less than 1000000, mixing with other components tends to be facilitated.
In the present embodiment, the weight average molecular weight can be measured by gel permeation chromatography (GPC).

  In the epoxy resin composition for an adhesive film of this embodiment, the content of the film forming material is 50 to 140 parts by mass with respect to 100 parts by mass in total of the epoxy resin (e1) and the epoxy resin curing agent particles (H). It is preferable that it is 60 to 120 parts by mass.

  Moreover, in the epoxy resin composition for adhesive films of this embodiment, the mass ratio of the epoxy resin (e1) and the curing agent particles for epoxy resin (H) is an epoxy resin with respect to 100 parts by mass of the epoxy resin (e1). The curing agent particles (H) for use are preferably 100 to 20 parts by mass, more preferably 90 to 30 parts by mass, and still more preferably 80 to 35 parts by mass.

(4) Additive It is preferable that the epoxy resin composition for adhesive films of this embodiment further contains an additive.
Although it does not specifically limit as an additive, For example, the hardening | curing agent for other epoxy resins, an inorganic filler, an organic filler, an electrically-conductive particle, a thermoplastic polymer is mentioned, These are used individually, or 2 or more types are used together. Can be used. Among these, the additive preferably contains one or more selected from the group consisting of inorganic fillers, conductive particles, and thermoplastic polymers.

  Other epoxy resin curing agents include those mentioned as examples of amine-based curing agents and other epoxy resin curing agents (h1) contained in the particles used as starting materials for forming the core (C). Any of those generally used as a curing agent for epoxy resins can be used, and in particular, at least one selected from the group consisting of an acid anhydride curing agent, a phenol curing agent, a hydrazide curing agent, and a guanidine curing agent. A kind of curing agent for epoxy resin is preferred.

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

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

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

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

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

  Examples of inorganic fillers include, but are not limited to, for example, silicates such as talc, calcined clay, unfired clay, my strength, glass; titanium oxide, alumina, fused silica (fused spherical silica, fused crushed silica), Oxides such as silica powder such as synthetic silica and crystalline silica; carbonates such as calcium carbonate, magnesium carbonate and hydrotalcite; hydroxides such as aluminum hydroxide, magnesium hydroxide and calcium hydroxide; barium sulfate and calcium sulfate Sulfates such as calcium sulfite; sulfites such as calcium sulfite; borates such as zinc borate, barium metaborate, aluminum borate, calcium borate, sodium borate; nitrides such as aluminum nitride, boron nitride, silicon nitride, etc. Can be mentioned. Among these, fused silica, crystalline silica, and synthetic silica powder are preferable from the viewpoint of improving heat resistance, moisture resistance, strength, and the like. By using these, the thermal linear expansion coefficient can be suppressed, so that improvement of the cooling cycle test and the like are expected. These fillers may be used alone or in combination of two or more.

  Although content of an inorganic filler is not specifically limited, Preferably it is 10-90 mass%, More preferably, it is 20-85 mass%. By setting the content of the inorganic filler to the above lower limit value or more, excellent low linear expansion can be realized. By making content of an inorganic filler below the said upper limit, the raise of an elasticity modulus can be suppressed more.

  The inorganic filler is preferably surface-treated with a silane coupling agent. Even if the silane coupling agent is added to the epoxy resin composition for a liquid adhesive film, the performance is exhibited. However, by performing a surface treatment of the inorganic filler with the silane coupling agent, one layer of the epoxy resin composition can be obtained. Can be achieved.

  Examples of the silane coupling agent include, but are not limited to, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3-aminopropyltri Ethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-chloro Propylmethyldi Tokishishiran, silane coupling agents such as 3-chloropropyl trimethoxysilane. Among these, from the viewpoint of adhesive strength, a silane coupling agent having a polymerizable functional group is preferable.

  Examples of the organic filler include, but are not limited to, acrylic resin, silicone resin, butadiene rubber, polyester, polyurethane, polyvinyl butyral, polyarylate, polymethyl methacrylate, acrylic rubber, polystyrene, NBR, SBR, silicone modified resin, and the like. The copolymer which contains as a component is mentioned. From the viewpoint of improving adhesiveness, as organic fine particles, (meth) acrylic acid alkyl-butadiene-styrene copolymer, (meth) acrylic acid alkyl-silicone copolymer, silicone- (meth) acrylic copolymer, silicone and ( It is preferable to use a complex of (meth) acrylic acid, a complex of (meth) acrylic acid alkyl-butadiene-styrene and silicone, and a complex of (meth) acrylic acid alkyl and silicone. In addition, organic fillers that have a core-shell structure and have different compositions in the core layer and the shell layer can also be used. Specific examples of the core-shell type organic filler include, but not limited to, particles obtained by grafting an acrylic resin with a silicone-acrylic rubber core and particles obtained by grafting an acrylic resin on an acrylic copolymer. . The organic filler has a function as an impact relaxation agent having stress relaxation properties. By including an organic filler in the film, it is possible to further improve the adhesion to various connecting members.

  Examples of the conductive particles include, but are not limited to, metal particles including metals such as Au, Ag, Ni, Cu, and solder, and carbon particles. The conductive particles 5 preferably have a surface layer made of Au, Ag, platinum group noble metals, more preferably Au. When the surface layer of the conductive particles is made of these metals, a sufficient pot life can be obtained. The conductive particles may be those in which the surface of a transition metal such as Ni is coated with a noble metal such as Au. Alternatively, the conductive layer described above may be formed by coating or the like on non-conductive glass, ceramic, plastic, or the like, and the outermost layer may be a noble metal. In the case of coated particles in which the outermost layer is a noble metal and the core is plastic or a hot-melt metal, it is preferable because it has deformability by heating and pressurization, so that the contact area with the electrode is increased at the time of connection and the reliability is improved.

  Although the compounding quantity of electroconductive particle is suitably set with a use, it is the range of 0.1-30 volume parts normally with respect to 100 volume parts of components except a conductive particle among circuit connection materials. In order to prevent a short circuit of an adjacent circuit due to excessive conductive particles, the content is more preferably 0.1 to 10 parts by volume.

  The thermoplastic polymer is not particularly limited, and examples thereof include polyamide resins, polyimides, polyester resins, polyurethane resins, acrylic resins, and polyether resins. Among them, vinyl esters are preferable, and carboxylic acid vinyl esters are more preferable. Furthermore, a monomer copolymerizable with a carboxylic acid vinyl ester may be included as a monomer unit. Examples of such monomers include carboxylic acid allyl esters and (meth) acrylic acid alkyl esters, and specific examples thereof include, but are not particularly limited to, for example, allyl acetate, methyl (meth) acrylate, and (meth). An example is ethyl acrylate.

  It is preferable that it contains an olefin-carboxylic acid vinyl ester copolymer because it is excellent in adhesion to an adherend during temporary pressure bonding and excellent in releasability of the support film, and other resin components constituting the circuit connection material From the viewpoint of compatibility, it is more preferable to include an ethylene-vinyl acetate copolymer.

  These thermoplastic polymer components preferably have a weight average molecular weight (hereinafter referred to as “Mw”) of 40000 to 150,000, more preferably 60000 to 130,000, and still more preferably 70000 to 120,000. If the Mw of the thermoplastic polymer component is 150,000 or less, the solubility in a general-purpose solvent such as toluene, ethyl acetate or methyl ethyl ketone tends to improve, and if it is 40000 or more, the adhesive force tends to improve.

  If necessary, the epoxy resin composition for an adhesive film of the present embodiment further includes additives such as a stabilizer, a liquid low stress agent, a diluent, a flame retardant, and a leveling agent. But you can.

  As the stabilizer, boric acid or a cyclic borate ester compound can be added to improve storage stability. The cyclic borate ester compound is a compound in which boron is contained in a cyclic structure, and 2,2′-oxybis (5,5′-dimethyl-1,3,2-oxaborinane) is particularly preferable.

  Although it does not specifically limit as a liquid low stress agent, For example, organic rubbers, such as polyalkylene glycol and its amine modified body, polybutadiene, and acrylonitrile, silicone rubbers, such as dimethylsiloxane, silicone oil, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.

  Although content of a liquid low stress agent is not specifically limited, Preferably it is 5-40 mass% with respect to an epoxy resin, More preferably, it is 10-20 mass%.

  Although it does not specifically limit as a diluent, For example, the polyfunctional acrylate compound containing an acryl group and the glycidyl type reactive diluent containing a monofunctional glycidyl group are mentioned. These may be used individually by 1 type and may use 2 or more types together.

  Although content of a diluent is not specifically limited, Preferably it is 1-40 mass% with respect to an epoxy resin, More preferably, it is 5-30 mass%.

  Although it does not specifically limit as a flame retardant, For example, a brominated flame retardant, a phosphorus flame retardant, an inorganic flame retardant, etc. are mentioned. Examples of brominated flame retardants include tetrabromophenol. Phosphorus flame retardants include 9,10-dihydro-9-oxa-10-phosphananthrene-10-oxide and its epoxy derivatives, triphenylphosphine and its derivatives, phosphate esters, condensed phosphate esters and phosphazene compounds. Can be mentioned. Examples of the nitrogen-based flame retardant include guanidine-based flame retardant, triazine structure-containing phenol, melamine polyphosphate, isocyanuric acid and the like. Although it does not specifically limit as an inorganic type flame retardant compound, For example, magnesium hydroxide and aluminum hydroxide are mentioned, Magnesium hydroxide is preferable from a heat resistant viewpoint.

  Although content of a flame retardant is not specifically limited, Preferably it is 5-200 mass% with respect to an epoxy resin, More preferably, it is 10-100 mass%.

  Although it does not specifically limit as a leveling agent, For example, a silicon type leveling agent, an acrylic leveling agent, etc. are mentioned.

<the film>
The film of this embodiment uses the above-described epoxy resin composition for adhesive films. The film of this embodiment has good storage stability and excellent connection reliability by using the above-described epoxy resin composition for adhesive films.

  In the following, the present embodiment will be described in more detail based on examples, but the present embodiment is not limited to the following examples. In the following, “part” and “%” are based on mass unless otherwise specified.

(amount of water)
The moisture content of each epoxy resin curing agent was measured by using a Carl Instruments moisture meter CA-100 manufactured by Dia Instruments.

(Specific surface area value)
The specific surface area value of each epoxy resin curing agent is determined by using a fully automatic BET specific surface area measuring device HM model-1201 manufactured by Mountec Co., Ltd. as a mixed gas of N ₂ / He = 30/70 (volume ratio). The specific surface area was measured.

(Under sieve average particle diameter D ₅₀ , Under sieve average particle diameter D ₉₉ )
Each epoxy resin curing agent was measured using a dry particle size distribution meter, a 50% cumulative under fraction sieve and undersize average particle diameter D _50, undersize average particle diameter D ₉₉ of 99% cumulative under fraction sieve It was.

(Shell thickness)
The thickness of the shell of each epoxy resin curing agent was measured by image observation with a scanning electron microscope (SEM).

(Chlorine content)
The amount of chlorine in each epoxy resin curing agent was measured according to JIS K7246.

(Production Example 1)
1 equivalent of a liquid epoxy resin (trade name “AER260” manufactured by Asahi Kasei E-Materials) and 1 equivalent of 2-methylimidazole (in terms of active hydrogen) in a 1: 1 mixed solvent of n-butanol and toluene, 80 The reaction was carried out at ° C. Thereafter, excess amine was distilled off together with the solvent under reduced pressure to obtain a solid block epoxy resin curing agent at 25 ° C.

Next, the block-like epoxy resin curing agent was jet milled and solid at 25 ° C., the water content was 1.1 mass%, the specific surface area value was 3.63 m ² / g, and the average particle size D ₅₀ under the sieve was Particles (pulverized product, epoxy resin curing agent particle I) having 2.4 μm and D ₉₉ / D ₅₀ of 8.6 were obtained.

  200 parts by mass of liquid epoxy resin (trade name “AER260” manufactured by Asahi Kasei E-Materials Co., Ltd.) 400 ") 30 parts by mass was added, and the reaction was continued for 3 hours while stirring at 50 ° C to obtain a curing agent II for epoxy resin.

(Production Example 2)
Epoxy resin curing agent particles I were used, and a kryptron orb manufactured by Earth Technica Co., Ltd. was used. Under an environment of a temperature of 10 ° C. and a humidity of 30%, a rotation speed of 13500 rpm, a supply speed of 10 kg / hr, an air volume of 3 m ³ / min Then, shape correction treatment was performed, a specific surface area value was adjusted by attaching a cyclone-type collector and a bag filter, and a specific surface area value of 2.67 m ² / g, a moisture content of 0.6% by mass, D _{50 by} classification operation. The hardener particles III for epoxy resin having a particle size distribution with a particle size of 3.1 μm and D ₉₉ / D ₅₀ of 4.5 were prepared by classification using a classifier. After adjusting the specific surface area value, 200 parts by mass of liquid epoxy resin (trade name “AER260” manufactured by Asahi Kasei E-Materials Co., Ltd.), 100 parts by mass of the curing agent particles for epoxy resin, and encapsulating agent (product of Nippon Polyurethane Co., Ltd.) 20 parts by mass of “MR-400”) was added, and the reaction was continued for 3 hours while stirring at 50 ° C. to obtain a curing agent IV for epoxy resin.

(Production Example 3)
Using a curing agent I for epoxy resin, Meteolevo-MR-10 manufactured by Nippon Pneumatic Co., Ltd., heat treatment was performed under conditions of a feed rate of the curing agent particles of 7.0 kg / hr and a processing temperature of 275 ° C. A collector and a bag filter are attached, and air cooled at a temperature of 25 ° C and a humidity of 10% is controlled by circulating circulating cooling water at 0 ° C through the wall of the powder recovery unit so that the internal temperature of the vessel is 40 ° C or lower. Was introduced as cooling air after hot air treatment at 275 ° C., and classification operation was performed by a classifier, whereby a specific surface area value of 1.3 m ² / g, a moisture content of 0.6% by mass, D ₅₀ of 3.1 μm and D ₉₉ / Particles having a particle size distribution with D ₅₀ of 4.7 (curing agent particles V for epoxy resin) were produced.
Thereafter, 200 parts by mass of a liquid epoxy resin (trade name “AER260” manufactured by Asahi Kasei E-Materials Co., Ltd.), 100 parts by mass of the particles (curing agent particles V for epoxy resin) and an encapsulating agent (trade name of Nippon Polyurethane Co., Ltd.) “MR-400”) 9.75 parts by mass was added, and the reaction was continued for 3 hours while stirring at 50 ° C. to obtain a curing agent VI for epoxy resin.

(Production Example 4)
The epoxy resin curing agent particles V obtained in Production Example 3 were spread evenly on a metal petri dish and allowed to stand for 4 hours in an environment of a temperature of 23 ° C. and a humidity of 50%. After the standing, this epoxy resin curing agent particle VII was obtained. As a result of measuring the moisture content of the epoxy resin curing agent particles VII, the moisture content in the epoxy resin curing agent particles VII was 1.5% by mass, and other physical properties were not changed.
Thereafter, liquid epoxy resin (trade name “AER260” manufactured by Asahi Kasei E-Materials Co., Ltd.) 200 parts by mass, 100 parts by mass of epoxy resin curing agent particles VI after standing, encapsulating agent (product of Nippon Polyurethane Co., Ltd.) 9.75 parts by mass of the name “MR-400” was added, and the reaction was continued for 3 hours while stirring at 50 ° C. to obtain a curing agent VIII for epoxy resin.

(Production Example 5)
The epoxy resin curing agent particles VII obtained in Production Example 4 were further allowed to stand for 2 hours in an environment of a temperature of 23 ° C. and a humidity of 50%. After the standing, this epoxy resin curing agent particle IX was obtained. As a result of measuring the moisture content of the epoxy resin curing agent particles IX, the moisture content in the epoxy resin curing agent particles IX was 1.6 mass%, and other physical properties were not changed. Thereafter, liquid epoxy resin (trade name “AER260” manufactured by Asahi Kasei E-Materials Co., Ltd.) 200 parts by mass, epoxy resin curing agent particles IX 100 parts by mass after standing, encapsulating agent (trade name, manufactured by Nippon Polyurethane Co., Ltd.) “MR-400”) 9.75 parts by mass was added, and the reaction was continued for 3 hours while stirring at 50 ° C. to obtain a curing agent X for epoxy resin.

(Production Example 6)
Graft copolymer of 2-methylimidazole (2MZ, 0.34 equivalent) and poly ((styrene-co-glycidyl methacrylate) -g-methyl methacrylate) as a dispersion stabilizer (Toagosei Co., Ltd.) The product, Reseda GP-300, number average molecular weight 30000), was added, and methyl isobutyl ketone (MIBK) was added thereto, and then the temperature was raised to 80 ° C. to completely dissolve. Then, a 50% methyl isobutyl ketone (MIBK) solution (0.34 equivalent) of Epicoat 828 was added, and the contents were reacted at 80 ° C. for 9 hours while stirring at a speed of 300 rpm. Thereafter, the reaction solution was cooled to room temperature and spray-dried with an organic solvent-based spray dryer (manufactured by Yamato Kagaku Co., Ltd., model GS-31) to recover the epoxy resin curing agent particles XI. The epoxy resin curing agent particles XI thus obtained had a specific surface area of 1.6 m ² / g, a moisture content of 2.0 mass%, a D ₅₀ of 2.8 μm, and a D ₉₉ / D ₅₀ of 2.0. 200 parts by mass of a liquid epoxy resin (trade name “AER260” manufactured by Asahi Kasei E-Materials), 100 parts by mass of the epoxy resin curing agent particles XI, and an encapsulating agent (trade name “MR-400” manufactured by Nippon Polyurethane Co., Ltd.) 12 parts by mass was added, and the reaction was continued for 3 hours with stirring at 50 ° C. to obtain an epoxy resin curing agent XII.

(Production Example 7)
A specific surface area value of 1. is obtained by using Meteolevo-MR-10 manufactured by Nippon Pneumatic Co., Ltd. using a curing agent I for epoxy resin and a feed rate of curing agent particles of 7.0 kg / hr and hot air treatment at 275 ° C. Particles (curing agent for epoxy resin XIII) having a particle size distribution of 6 m ² / g, water content 1.5% by mass, D ₅₀ of 3.1 μm and D ₉₉ / D ₅₀ of 8.5 were prepared. Thereafter, 200 parts by mass of liquid epoxy resin (trade name “AER260” manufactured by Asahi Kasei E-Materials Co., Ltd.), 100 parts by mass of the particles (curing agent particle XIII for epoxy resin), and encapsulating agent (trade name of Nippon Polyurethane Co., Ltd.) “MR-400”) 12.0 parts by mass was added, and the reaction was continued for 3 hours while stirring at 50 ° C. to obtain a curing agent XIV for epoxy resin.

(Production Example 8)
1 equivalent of liquid epoxy resin (trade name “AER260” manufactured by Asahi Kasei E-Materials) and 0.7 equivalent of isophoronediamine (in terms of active hydrogen) in a 1: 1 mixed solvent of n-butanol and toluene, 80 The reaction was carried out at ° C. Thereafter, 0.3 equivalent of a phenol resin was added to the resulting modified polyamine and mixed uniformly, and then the excess amine was distilled off together with the solvent under reduced pressure at 180 ° C. to obtain a solid block epoxy resin curing agent at 25 ° C. It was. Next, the obtained block-shaped epoxy resin curing agent was jet mill pulverized and classified by a classifier to be solid at 25 ° C., having a moisture content of 1.6 mass% and a specific surface area of 2.23 m ² / g, Particles (ground product, epoxy resin curing agent XV) having an average particle diameter D ₅₀ under sieve of 4.7 μm and D ₉₉ / D ₅₀ of 1.9 were obtained.
After that, heat treatment was performed using Meteolevo-MR-10 manufactured by Nippon Pneumatic Co., Ltd. using curing agent particles XV for epoxy resin, with a feed rate of curing agent particles of 7.0 kg / hr and a processing temperature of 275 ° C. A cyclone type collector and a bag filter are attached, and circulating cooling water of 0 ° C is passed through the powder recovery unit wall surface to cool the inside of the container to 40 ° C or less, and the temperature is 25 ° C and humidity is 10%. Controlled air was introduced as cooling air after hot air treatment at 275 ° C., and classification operation was performed by a classifier, whereby a specific surface area value of 1.6 m ² / g, a water content of 1.2% by mass, D ₅₀ of 4.6 μm and Particles having a particle size distribution with D ₉₉ / D ₅₀ of 1.6 (curing agent particles XVI for epoxy resin) were produced.
Thereafter, 200 parts by mass of liquid epoxy resin (trade name “AER260” manufactured by Asahi Kasei E-Materials Co., Ltd.), 100 parts by mass of the particles (curing agent XVI for epoxy resin), and encapsulating agent (trade name “manufactured by Nippon Polyurethane Co., Ltd.” MR-400 ") 12.0 parts by mass was added, and the reaction was continued for 3 hours while stirring at 50 ° C to obtain a curing agent XVII for epoxy resin.

<Preparation of varnish 1>
100 parts by mass of phenoxy resin (trade name: PKHC, weight average molecular weight 43,000, manufactured by InChem) and bisphenol A type liquid epoxy resin (trade name “AER2601” manufactured by Asahi Kasei E-Materials, epoxy equivalent 188 g / eq) 90 Part by mass is dissolved in 200 parts by mass of a 1: 1 (mass ratio) toluene / ethyl acetate solution, and after dissolution, 60 parts by mass of epoxy resin curing agent, silane coupling agent (trade name KBM, manufactured by Shin-Etsu Chemical Co., Ltd.) -403) 2.5 parts by mass and 17 parts by mass of gold-plated plastic particles (trade name “Micropearl AU” manufactured by Sekisui Chemical Co., Ltd.) were mixed to prepare an adhesive varnish 1 (an epoxy resin composition for an adhesive film).

<Preparation of varnish 2>
Adhesive varnish 2 (epoxy resin composition for adhesive film) was prepared in the same manner as varnish preparation 1 except that only ethyl acetate was used instead of a 1: 1 (mass ratio) solution of toluene / ethyl acetate. .

<Preparation of varnish 3>
Adhesive varnish 3 (epoxy resin composition for adhesive film) was prepared in the same manner as varnish preparation 1 except that only 2-butanone was used instead of a 1: 1 (mass ratio) solution of toluene / ethyl acetate. did.

<Evaluation>
◇ Varnish viscosity ratio Viscosity immediately after varnish preparation (n1) and viscosity after leaving the varnish at room temperature 23 ° C. and humidity 40% RH for 4 hours (n4) were measured in a 23 ° C. environment using a BH viscometer. . The viscosities of the two were compared to determine the viscosity magnification (n4 / n1). When the viscosity ratio is 1.0 or more and less than 2.0, ◎, when it is 2.0 or more and less than 3.0, ◯, when it is 3.0 or more and less than 4.0, Δ, and when it is more, ×.

◇ Residual amount of epoxy Immediately after the varnish was prepared, the varnish was applied to a thickness of about 20 μm using a coating machine, and then dried in an oven at 60 ° C. to obtain a film adhesive. Further, the varnish was allowed to stand at room temperature of 23 ° C. and humidity of 40% RH for 4 hours, and then coated using the same coating machine to obtain a film adhesive. Each of the obtained film adhesives was subjected to FT-IR measurement, and the peak ratio was measured using the 926 cm @ -1 peak derived from the epoxy group as a reference to the peak derived from the phenyl group. The peak ratio (F4) after standing for 4 hours is compared with the peak ratio (F1) of the epoxy group at the time of varnish production 0 hour, and the residual peak ratio of the epoxy group (F4 / F1 × 100) is 90. % If it is not less than 99% and not less than 99%, ○ if it is 70% or more and less than 90%, Δ if it is 50% or more and less than 70%, and x if it is less than 50%.

◇ Reaction rate measurement Immediately after the varnish was prepared, it was applied to a thickness of about 20 μm using a coating machine, and then dried in an oven at 60 ° C. to obtain a film adhesive. The obtained film adhesive was heated at 170 ° C. for 5 seconds, and the consumption rate of the epoxy group was measured. When the epoxy group consumption rate is 85% or more, ◎, 80% or more and less than 85% are indicated by ○, 70% or more and less than 80% by Δ, and less than 70% by ×.

◇ Connection reliability evaluation Tantalum wiring (0) so that gold bumps on an aluminum thin film of a semiconductor chip are connected to a gold bump on an adjacent aluminum thin film on a non-alkali glass with a thickness of 0.5 mm. Then, a connection pad (42 μm wide, 120 μm long) of an indium tin oxide film (1400 mm) was formed. Each time 20 gold bumps are connected, an indium tin oxide thin film lead wiring is formed on the connection pad, and an aluminum titanium thin film (titanium 1%, 3000 mm) is formed on the lead wiring to form a connection evaluation board. . Immediately after the preparation of varnish 1 was applied, the varnish was applied to a thickness of about 20 μm using a coating machine, and then dried in an oven at 60 ° C. to obtain an anisotropic conductive film. After aligning the connection pads of the connection evaluation board and the gold bumps of the semiconductor chip with the anisotropic conductive film, or after temporarily bonding the anisotropic conductive film to the connection evaluation board, the connection pads of the connection evaluation board and The semiconductor device was aligned with the gold bumps of the semiconductor chip and pressure-bonded with a load of 40 MPa at 190 ° C. for 10 seconds to produce a semiconductor device. After crimping, resistance was measured with a four-terminal resistance meter between the lead wires (daisy chain of 20 gold bumps) to obtain an initial connection resistance value. This connection resistance measurement board is stored in an environment of 85 ° C. and 85% RH for 500 hours, taken out, measured at 25 ° C. for 1 hour, and the average value is obtained. When the average resistance increase amount was less than 30Ω, it was evaluated as ◎, when it was 30Ω or more and less than 50Ω, ◯, when it was 50Ω or more and less than 100Ω, Δ, and when it was 100Ω or more or short-circuited, it was evaluated as ×.

◇ Insulation test evaluation A tantalum wiring (0.8μm) is formed on a non-alkali glass with a thickness of 0.5mm so that two gold bumps on an aluminum thin film of a semiconductor chip are connected to each other. Then, a connection pad (42 μm wide, 120 μm long) of an indium tin oxide film (1400 mm) was formed. A connection wiring of an indium tin oxide thin film was formed so that every other five connection pads could be connected. An indium tin oxide thin film (1400 mm) lead wiring was formed on each connection wiring, and an aluminum titanium thin film (titanium 1%, 3000 mm) was formed on the lead wiring to provide an insulating evaluation substrate. Immediately after the preparation of varnish 1 was applied, the varnish was applied to a thickness of about 20 μm using a coating machine, and then dried in an oven at 60 ° C. to obtain an anisotropic conductive film. After aligning the connection pads of the insulation resistance evaluation board and the gold bumps of the semiconductor chip with the anisotropic conductive film, or temporarily bonding the anisotropic conductive film to the connection evaluation board, the connection pads of the connection evaluation board and the semiconductor The gold bumps of the chip were aligned and pressure-bonded with a load of 40 MPa at 190 ° C. for 10 seconds to obtain an insulation resistance test substrate. While maintaining this insulation resistance test substrate at 85 ° C. and 85% RH, a DC voltage of 30 V was applied between the pair of lead wires using a low voltage low current power source. The insulation resistance between the wires was measured every 5 minutes, the time until the insulation resistance became 10 MΩ or less was measured, and the value was taken as the insulation decrease time. The case where the insulation lowering time was less than 500 hours was evaluated as x, the case where it was 500 hours or more and less than 1000 hours was evaluated as Δ, and the case where it was 1000 hours or more was evaluated as ○.

Example 1
Varnishes 1 to 3 were prepared as described above using epoxy resin curing agent IV, and evaluated according to the above evaluation method. The evaluation results are shown in Table 1.

Example 2
Varnishes 1 to 3 were prepared as described above using curing agent V for epoxy resin, and evaluated according to the above evaluation method. The evaluation results are shown in Table 1.

Example 3
Varnishes 1 to 3 were prepared as described above using epoxy resin curing agent VI, and evaluated according to the above evaluation methods. The evaluation results are shown in Table 1.

Example 4
Varnishes 1 to 3 were prepared as described above using epoxy resin curing agent VII, and evaluated according to the above evaluation method. The evaluation results are shown in Table 1.

Example 5
Using the epoxy resin curing agent X, varnishes 1 to 3 were prepared as described above, and evaluated according to the above evaluation methods. The evaluation results are shown in Table 1.

Example 6
Varnishes 1 to 3 were prepared as described above using epoxy resin curing agent XII, and evaluated according to the evaluation method described above. The evaluation results are shown in Table 1.

Example 7
Varnishes 1 to 3 were prepared as described above using epoxy resin curing agent XIV, and evaluated according to the above evaluation method. The evaluation results are shown in Table 1.

Example 8
Varnishes 1 to 3 were prepared as described above using epoxy resin curing agent XVI, and evaluated according to the above evaluation method. The evaluation results are shown in Table 1.

Example 9
Varnishes 1 to 3 were prepared as described above using epoxy resin curing agent XVII, and evaluated according to the above evaluation method. The evaluation results are shown in Table 1.

Comparative Example 1
Varnishes 1 to 3 were prepared as described above using the epoxy resin curing agent II, and evaluated according to the evaluation method described above. The evaluation results are shown in Table 2.

Comparative Example 2
Varnishes 1 to 3 were prepared as described above using epoxy resin curing agent XV, and evaluated according to the above evaluation method. The evaluation results are shown in Table 2.

  From the examples and comparative examples, it was found that the stability and the reliability were improved more than those satisfying the general formula (1) than those not satisfying the general formula (1).

Example 10
Using epoxy resin curing agent VI, 90 parts by mass of bisphenol A type liquid epoxy resin (trade name “AER2601”, epoxy equivalent 188 g / eq, manufactured by Asahi Kasei E-Materials Co., Ltd.) at the time of varnish production, Resin (trade name “AER2601” manufactured by Asahi Kasei E-Materials Co., Ltd., epoxy equivalent 188 g / eq) 45 parts by mass, naphthalene type epoxy resin (trade name “Epiclon HP-4032D” manufactured by DIC) 45 parts by mass As described above, varnishes 1 to 3 were prepared and evaluated according to the above evaluation method. The evaluation results are shown in Table 3.

Example 11
Using epoxy resin curing agent VI, 90 parts by mass of bisphenol A type liquid epoxy resin (trade name “AER2601”, epoxy equivalent 188 g / eq, manufactured by Asahi Kasei E-Materials Co., Ltd.) at the time of varnish production, Resin (trade name “AER2601” manufactured by Asahi Kasei E-Materials, Inc., epoxy equivalent 188 g / eq) 45 parts by mass, resorcin-type epoxy resin (trade name “RDGE-H” manufactured by PTI Japan) 45 parts by mass As described above, varnishes 1 to 3 were prepared and evaluated according to the above evaluation method. The evaluation results are shown in Table 3.

  From the results of Examples 10 and 11, it was found that an increase in the reaction rate can be expected while maintaining the storage stability by adding the naphthalene skeleton-containing epoxy resin or the resorcin-type epoxy resin to the epoxy resin (e1).

Example 12
Using epoxy resin curing agent VI, 100 parts by mass of phenoxy resin (InChem, trade name: PKHC, weight average molecular weight 43,000) and bisphenol A type liquid epoxy resin (trade name “Asahi Kasei E-Materials” AER2601 ", epoxy equivalent of 188 g / eq) 90 parts by mass are dissolved in 200 parts by mass of a 1: 1 (mass ratio) solution of toluene / ethyl acetate, and after dissolution, 60 parts by mass of curing agent for epoxy resin, and silane cup 2.5 parts by mass of a ring agent (trade name KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed to produce a varnish for an insulating film, and tests other than the connection reliability test were evaluated by the above evaluation methods. The evaluation results are shown in Table 3.
From the evaluation results, it was found that this composition was also suitable for an insulating film.

Claims (14)

Containing an epoxy resin (e1), curing agent particles for epoxy resin (H), and a film forming material,
The epoxy resin curing agent particles (H) are particles mainly composed of an amine curing agent,
The epoxy resin curing agent particles (H) are solid at 25 ° C.,
The specific surface area value (m ² / g) in the epoxy resin curing agent particles (H) and the particle size D ₅₀ (μm) of 50% integrated fraction under sieve are expressed by the following formula (1). An epoxy resin composition for an adhesive film that fills.
^{4.0X -1 ≦ Y ≦ 8.3X -1 (} 1)
(In the formula (1), X represents a particle size D _{50 of} 50% of the cumulative fraction under sieving, and Y represents a specific surface area value.) In the epoxy resin curing agent particles (H), the particle size D ₅₀ having a 50% cumulative fraction under sieve is greater than 0.3 μm and 12 μm or less, and the particle size D ₉₉ having a 99% cumulative fraction under sieve is The particle size distribution represented by the ratio (D ₉₉ / D ₅₀ ) with the particle size D ₅₀ having a 50% cumulative fraction under sieve is 6 or less,
The epoxy resin composition for adhesive films according to claim 1, wherein the moisture content in the epoxy resin curing agent particles (H) is 1.5 mass% or less.   The epoxy resin composition for adhesive films according to claim 1 or 2, wherein the epoxy resin curing agent particles (H) contain a modified imidazole compound. A core (C) formed using the epoxy resin curing agent particles (H) as a starting material, and a shell (S) covering the core (C);
Wherein the shell (S), at least, a binding group to absorb wave number 1630 cm ^-1 or 1680 cm ^-1 The following infrared (x), the wave number 1680 cm ^-1 or 1725 cm ^-1 or less of the binding group that absorbs infrared ray (y) has binding group that absorbs less infrared wave number 1730 cm ^-1 or 1755 cm ^-1 and (z), to its surface, the adhesive film for the epoxy resin composition according to any one of claims 1 to 3.   The epoxy resin composition for an adhesive film according to claim 4, wherein the shell (S) has a urea bond and substantially no ester bond in the structure. The ratio of the thickness of the shell with respect to the particle size D ₅₀ of the epoxy resin curing agent particles (H) (S) is 1.5 / 100 or 18/100 or less, the adhesive according to claim 4 or 5 Epoxy resin composition for film.   The shell (S) is at least two selected from the group consisting of isocyanate compounds, active hydrogen compounds, epoxy resin curing agents (h2), other epoxy resins (e3), and low molecular amine compounds (B). The epoxy resin composition for adhesive films according to any one of claims 4 to 6, comprising a reaction product obtained as a raw material.   The total total chlorine content of the total amount of chlorine contained in the epoxy resin curing agent particles (H) and the total amount of chlorine contained in the epoxy resin (e1) or the epoxy resin (e3) is 2500 mass ppm or less. The epoxy resin composition for adhesive films according to any one of claims 1 to 7, wherein   The epoxy resin composition for adhesive films according to any one of claims 1 to 8, wherein the epoxy resin (e1) contains a naphthalene skeleton-containing epoxy resin and / or a resorcin type epoxy resin.   The epoxy resin composition for adhesive films according to any one of claims 1 to 9, wherein the film forming material is a resin, and the resin has a weight average molecular weight of 10,000 or more.   The epoxy resin composition for adhesive films according to claim 10, wherein the skeleton of the film forming material contains one or more epoxy groups.   Furthermore, the epoxy resin composition for adhesive films as described in any one of Claims 1-11 containing an additive.   The epoxy resin composition for an adhesive film according to claim 12, wherein the additive includes one or more selected from the group consisting of an inorganic filler, conductive particles, and a thermoplastic polymer. The film using the epoxy resin composition for adhesive films as described in any one of Claims 1-13.