epoxy resin composition

Abstract

To provide an epoxy resin composition that excels in stability during the film production process and storage stability in the film state, as well as in low-temperature curability.SOLUTION: An epoxy resin composition contains (A) an epoxy resin and (B) a curing agent. The (B) curing agent has a hydroxyl value of 50-500 mgKOH / g and an amine value of 50-500 mgKOH / g.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to epoxy resin compositions. [Background technology]

[0002] Traditionally, epoxy resins have been used in a wide range of applications, including insulating materials, sealing materials, adhesives, conductive materials, matrix resins for fiber-reinforced plastics, and impregnation and fixing agents for motor coils in electrical and electronic components.

[0003] The demands on electronic devices today are diverse, encompassing miniaturization, high functionality, weight reduction, and multi-functionality. In semiconductor chip mounting technology, further miniaturization, miniaturization, and density improvements are progressing through the reduction of electrode pad pitch and pad pitch. In particular, with the miniaturization and thinning of electronic materials, the importance of film-shaped epoxy resin compositions is increasing in order to thin adhesive and insulating layers.

[0004] Regarding epoxy resin compositions in film form, for example, Patent Document 1 discloses a dry film using an epoxy resin composition that exhibits excellent thin-film formation properties, storage stability, and curing properties. Furthermore, Patent Document 2 discloses a film-shaped epoxy resin composition using an epoxy resin composition that utilizes a curing agent with excellent curability, solvent resistance, and storage stability, and a microencapsulated curing agent. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2020-152780 [Patent Document 2] Patent No. 6619628 [Overview of the Initiative] [Problems that the invention aims to solve]

[0006] To obtain the epoxy resin composition in the form of a film, a coating solution is prepared by dissolving components such as epoxy resin, a curing agent, a curing accelerator, and a film-forming polymer in a solvent. The coating solution is then applied to a predetermined support, and a drying process is carried out to produce a film. Therefore, the coating solution is required to have strong storage stability as a coating solution, stability during the film manufacturing process when applying and drying the coating solution, and stability in the film state. Furthermore, in order to reduce the impact on semiconductor components, the film is required to have curability at low temperatures, for example, sufficient curability at around 130°C.

[0007] In response to the various requirements for epoxy resin compositions described above, the one-component epoxy resin compositions disclosed in Patent Documents 1 and 2 still have room for improvement in terms of achieving both stability during the film manufacturing process and storage stability in the film state, and also have problems in terms of the curability of films using these epoxy resin compositions at low temperatures, for example, around 130°C.

[0008] Therefore, in view of the problems of the prior art described above, the present invention aims to provide an epoxy resin composition that provides a film that is excellent in stability during the film manufacturing process and in storage stability in the film state, while also exhibiting excellent low-temperature curing properties at around 130°C. [Means for solving the problem]

[0009] As a result of diligent research to solve the above-mentioned problems, the inventors of this invention have found that the above objectives can be achieved by the following technical means, and have completed this invention. In other words, the present invention is as follows:

[0010] [1] (A) Epoxy resin and (B) Hardener and An epoxy resin composition comprising, The epoxy resin composition, wherein the hydroxyl value of the (B) curing agent is 50 to 500 mgKOH / g, and the amine value thereof is 50 to 500 mgKOH / g. [2] The epoxy resin composition according to [1] above, further comprising (C) a reactive diluent. [3] The epoxy resin composition according to [1] or [2] above, wherein the (B) curing agent is a microcapsule-type curing agent in which the surface of a core is covered with a shell. [4] The epoxy resin composition according to any one of [1] to [3] above, which has a viscosity at 25°C of 100 Pa·s or lower. [5] The epoxy resin composition according to any one of [1] to [4] above, wherein the content of the (B) curing agent is 50 to 100 parts by mass relative to 100 parts by mass of the (A) epoxy resin. [6] A paste-like composition comprising the epoxy resin composition according to any one of [1] to [5] above. [7] A film-shaped composition comprising the epoxy resin composition according to any one of [1] to [5] above. [8] An adhesive comprising the epoxy resin composition according to any one of [1] to [5] above. [9] A bonding paste comprising the epoxy resin composition according to any one of [1] to [5] above.

[10] A bonding film comprising the epoxy resin composition according to any one of [1] to [5] above.

[11] A conductive material comprising the epoxy resin composition according to any one of [1] to [5] above.

[12] An anisotropically conductive material comprising the epoxy resin composition according to any one of [1] to [5] above.

[13] An insulating material comprising the epoxy resin composition according to any one of [1] to [5] above.

[14] A sealing material containing the epoxy resin composition described in any one of the above [1] to [5].

[15] A coating material containing the epoxy resin composition described in any one of the above [1] to [5].

[16] A paint composition containing the epoxy resin composition described in any one of the above [1] to [5].

[17] A prepreg containing the epoxy resin composition described in any one of the above [1] to [5].

[18] A thermally conductive material containing the epoxy resin composition described in any one of the above [1] to [5].

[19] A fuel cell separator material containing the epoxy resin composition described in any one of the above [1] to [5]. [Effects of the Invention]

[0011] According to the present invention, it is possible to provide an epoxy resin composition that exhibits excellent stability during the film manufacturing process and storage stability in the film state, as well as excellent low-temperature curing properties. [Modes for carrying out the invention]

[0012] The embodiments for carrying out the present invention (hereinafter referred to as "this embodiment") will be described in detail below. The following embodiments are illustrative examples for explaining the present invention and are not intended to limit the present invention to the following content. The present invention can be implemented by modifying it as appropriate within the scope of its gist.

[0013] [Resin composition] The epoxy resin composition of this embodiment is Ingredients (A): Epoxy resin and Ingredients (B): Hardener and It contains the following, and component (B) the curing agent has a hydroxyl value of 50-500 mgKOH / g and an amine value of 50-500 mgKOH / g. According to this embodiment, an epoxy resin composition is obtained that exhibits excellent stability during the film manufacturing process, storage stability in the film state, and excellent low-temperature curing properties.

[0014] (Component (A): Epoxy resin) The epoxy resin composition of this embodiment includes component (A): epoxy resin (hereinafter, it may be referred to as (A) epoxy resin or component (A)). (A) The epoxy resin is not limited to the following, but examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD ​​type epoxy resin, bisphenol M type epoxy resin, bisphenol P type epoxy resin, tetrabromobisphenol A type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, tetrabromobiphenyl type epoxy resin, diphenyl ether type epoxy resin, benzophenone type epoxy resin, phenylbenzoate type epoxy resin, diphenyl sulfide type epoxy resin, diphenyl sulfoxide type epoxy resin, diphenyl sulfone type epoxy resin, diphenyl disulfide type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, hydroquinone type epoxy resin, methyl hydro Examples include bifunctional epoxy resins such as quinone-type epoxy resins, dibutylhydroquinone-type epoxy resins, resorcinol-type epoxy resins, methylresorcinol-type epoxy resins, and catechol-type epoxy resins; trifunctional epoxy resins such as N,N-diglycidylaminobenzene-type epoxy resins and triazine-type epoxy resins; tetrafunctional epoxy resins such as tetraglycidyldiaminodiphenylmethane-type epoxy resins and diaminobenzene-type epoxy resins; polyfunctional epoxy resins such as phenol novolac-type epoxy resins, cresol novolac-type epoxy resins, triphenylmethane-type epoxy resins, tetraphenylethane-type epoxy resins, dicyclopentadiene-type epoxy resins, naphthol aralkyl-type epoxy resins, and brominated phenol novolac-type epoxy resins; and alicyclic epoxy resins. These can be used individually or in combination of two or more. Furthermore, epoxy resins modified with isocyanates or the like can also be used in combination.

[0015] The epoxy resin composition of this embodiment preferably contains a bisphenol-type epoxy resin from the viewpoint of handling and heat resistance, and preferably contains a bisphenol A-type epoxy resin and / or a bisphenol F-type epoxy resin from the viewpoint of providing storage stability, good reactivity, and sufficient mechanical properties.

[0016] (A) The total amount of chlorine contained in the epoxy resin is preferably 2500 ppm or less, more preferably 2000 ppm or less, even more preferably 1500 ppm or less, and even more preferably 900 ppm or less, from the viewpoint of obtaining an epoxy resin composition that has excellent electrical properties and an excellent balance between curability and storage stability. Furthermore, the lower limit of the total chlorine content in the epoxy resin (A) is not particularly limited, but from the perspective of balancing the effects obtained and economic efficiency, it is preferably 0.01 ppm or more, more preferably 0.02 ppm or more, even more preferably 0.05 ppm or more, even more preferably 0.1 ppm or more, even more preferably 0.2 ppm or more, and especially preferably 0.5 ppm or more.

[0017] Here, (A) the total amount of chlorine contained in the epoxy resin refers to the total amount of organic and inorganic chlorine contained in (A) the epoxy resin, and is a value based on mass relative to (A) the epoxy resin. (A) The total chlorine content of the epoxy resin is measured by the following method. (A) The epoxy resin is washed with xylene, and the washing and filtration process is repeated until no epoxy resin remains in the xylene washing solution. Next, the filtrate is distilled off under reduced pressure at 100°C or below to obtain the epoxy resin. 1 to 10 g of the obtained epoxy resin sample is accurately weighed to obtain a titration volume of 3 to 7 mL, dissolved in 25 mL of ethylene glycol monobutyl ether, and 25 mL of propylene glycol solution with 1 N KOH is added. After boiling for 20 minutes, the titration volume can be calculated from the titration volume obtained by titrating with an aqueous silver nitrate solution.

[0018] Here, of the total chlorine, the chlorine contained in the 1,2-chlorohydrin group is generally called hydrolyzable chlorine. (A) The amount of hydrolyzable chlorine in the epoxy resin is preferably 100 ppm or less, more preferably 50 ppm or less, even more preferably 0.01 to 20 ppm or less, and even more preferably 0.05 to 10 ppm or less. (A) When the amount of hydrolyzable chlorine in the epoxy resin is 100 ppm or less, it is advantageous in the epoxy resin composition of this embodiment to achieve both high curability and storage stability, and the cured product of the epoxy resin composition of this embodiment tends to exhibit excellent electrical properties.

[0019] Here, (A) hydrolyzable chlorine in the epoxy resin is measured by the following method. The titration volume can be calculated by dissolving 3 g of the sample in 50 mL of toluene, adding 20 mL of a 0.1 N KOH methanol solution, boiling for 15 minutes, and then titrating with an aqueous silver nitrate solution.

[0020] When forming a masterbatch-type curing agent for a one-component epoxy resin composition containing component (B), as described later, it is preferable that component (A) is liquid at 25°C from the viewpoint of improving the dispersibility of component (B).

[0021] (Component (B): Hardener) The resin composition of this embodiment includes (B) a curing agent (hereinafter sometimes referred to as component (B)). The hydroxyl value of component (B) is 50 mg KOH / g or more from the viewpoint of improving stability by reducing the basicity of the active amine due to hydrogen bonding at low temperatures. On the other hand, if the hydroxyl value exceeds 500 mg KOH / g, the affinity with epoxy resin (A), which is the curable resin constituting the epoxy resin composition of this embodiment, decreases, making it easier to separate and thus impairing the film strength. From this viewpoint, the hydroxyl value of component (B) is 50 to 500 mg KOH / g, preferably 100 to 300 mg KOH / g, more preferably 160 to 280 mg KOH / g, and even more preferably 220 to 260 mg KOH / g. (B) The hydroxyl value of the curing agent can be controlled to the above-mentioned range by adjusting the temperature conditions and reaction time in the reaction between the epoxy resin and the amine compound during the production of amine adducts.

[0022] The amine value of component (B) is 50 mg KOH / g or higher from the viewpoint of exhibiting sufficient curability. On the other hand, if the amine value of component (B) exceeds 500 mg KOH / g, there will be too many reaction initiation sites, and the stability will be greatly impaired. From this viewpoint, the amine value of component (B) is 50 to 500 mg KOH / g, preferably 100 to 300 mg KOH / g, more preferably 140 to 260 mg KOH / g, and even more preferably 180 to 220 mg KOH / g. (B) The amine value of the curing agent can be controlled to the above-mentioned range by adjusting the ratio of the charges, i.e., the epoxy equivalent and the amine equivalent, in the reaction between the epoxy resin and the amine compound during the production of amine adducts.

[0023] Component (B) is preferably solid at 25°C from the viewpoint of exhibiting curability at relatively low temperatures while maintaining stability against solvents and heat.

[0024] The particle size of component (B) is preferably such that the average particle size (D50), defined by the median diameter, is greater than 0.3 μm and 12 μm or less, more preferably between 1.0 μm and 10 μm, and even more preferably between 1.5 μm and 5.0 μm. Here, the average particle diameter refers to the Stokes diameter measured by laser diffraction / light scattering. When the average particle diameter is 12 μm or less, a homogeneous cured product tends to be obtained, and when the particle diameter exceeds 0.3 μm, aggregation between particles tends to be suppressed.

[0025] Component (B) may have its circularity improved by surface treatment.

[0026] The closer the degree of circularity is to 1, the closer it is to a perfect sphere. Component (B) may be a microencapsulated curing agent having a core-shell structure. In this case, the closer the circularity of the core is to 1, the lower the viscosity of the compound and the better the workability. Furthermore, because a film is formed uniformly during encapsulation, solvent resistance, filler resistance, moisture resistance, and permeability are improved. From the above viewpoint, the closer the circularity of the core is to 1, the more preferably it is 0.93 or higher, even more preferably 0.95 or higher, and even more preferably 0.97 or higher.

[0027] The circularity of the core can be measured by flow-type particle image analysis. More specifically, the sample is flowed through a liquid and the particles are photographed. The particle diameter is determined from the particle projection area, and the circularity can be calculated from the ratio of the perimeter of the particle projection image to the circumference of the circle corresponding to the particle diameter.

[0028] The core can be formed, for example, by treating irregularly shaped particles with hot air, and the circularity can be controlled to the above numerical range by adjusting the processing conditions. Methods for obtaining a core with high circularity include injecting amorphous particles into hot air sprayed from a hot air injection nozzle, and processing the particles by melting their surface upon contact with the hot air.

[0029] The temperature of the hot air used in the hot air treatment is preferably between 100°C and 400°C. A hot air temperature of 100°C or higher allows for sufficient heating of the core surface, enabling control to the desired circularity. A temperature of 400°C or lower suppresses thermal decomposition of the core. From this perspective, the hot air temperature is more preferably between 150°C and 300°C, and even more preferably between 180°C and 250°C.

[0030] Furthermore, it is preferable that component (B) has a weight-average molecular weight of 50 or more and 50,000 or less. In particular, when component (B) is a microencapsulated curing agent with a core-shell structure, if the molecular weight of the core is 50 or more, fusion between particles can be suppressed during the hot air treatment stage, preventing the particle size from becoming too large. If it is 50,000 or less, the softening temperature of the particles does not become too high, making it easier to achieve the desired circularity during the hot air treatment. From the above viewpoint, the weight-average molecular weight range of the core is preferably 50 to 50,000, more preferably 70 to 10,000, even more preferably 100 to 5,000, even more preferably 500 to 4,000, and even more preferably 1,000 to 3,000.

[0031] Here, the weight-average molecular weight can be measured by gel permeation chromatography (GPC).

[0032] The properties of component (B) are not particularly limited, but examples include amine-based curing agents, amide-based curing agents, phenol-based curing agents, acid anhydride-based curing agents, catalytic curing agents, and modified versions thereof. These may be used individually or in combination of two or more. Among these, amine adducts obtained by reacting two or more compounds are preferred from the viewpoint of easy performance adjustment by manufacturing conditions.

[0033] An amine adduct is a compound having an amino group obtained by reacting an amine compound with at least one compound selected from the group consisting of carboxylic acid compounds, sulfonic acid compounds, isocyanate compounds, urea compounds, and epoxy resins.

[0034] The following are carboxylic acid compounds, sulfonic acid compounds, isocyanate compounds, urea compounds, and epoxy resins used as raw materials for amine adducts. Examples of carboxylic acid compounds include, but are not limited to, succinic acid, adipic acid, sebacic acid, phthalic acid, and dimer acid. Examples of sulfonic acid compounds include, but are not limited to, ethanesulfonic acid and p-toluenesulfonic acid. Examples of isocyanate compounds include, but are not limited to, aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, aliphatic triisocyanates, and polyisocyanates. Examples of aliphatic diisocyanates include ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate. Examples of alicyclic diisocyanates include isophorone diisocyanate, 4-4'-dicyclohexylmethane diisocyanate, norbornane diisocyanate, 1,4-isocyanatocyclohexane, 1,3-bis(isocyanatomethyl)-cyclohexane, and 1,3-bis(2-isocyanatopropyl-2yl)-cyclohexane. Examples of aromatic diisocyanates include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylene diisocyanate, and 1,5-naphthalene diisocyanate. Examples of aliphatic triisocyanates include 1,3,6-triisocyanate methylhexane and 2,6-diisocyanatohexanoate-2-isocyanatoethyl. Examples of polyisocyanates include polymethylene polyphenyl polyisocyanate and polyisocyanates derived from the above diisocyanate compounds. Examples of polyisocyanates derived from the above diisocyanates include isocyanurate-type polyisocyanates, burette-type polyisocyanates, urethane-type polyisocyanates, allohanate-type polyisocyanates, and carbodiimide-type polyisocyanates. Examples of urea compounds include, but are not limited to, urea, methylurea, dimethylurea, ethylurea, and t-butylurea.

[0035] The epoxy resin used as a raw material for amine adducts is either a monoepoxy compound, a polyvalent epoxy compound, or a mixture thereof. Examples of monoepoxy compounds include, but are not limited to, butyl glycidyl ether, hexyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, para-tert-butylphenyl glycidyl ether, ethylene oxide, propylene oxide, paraxylyl glycidyl ether, glycidyl acetate, glycidyl butyrate, glycidyl hexoate, and glycidyl benzoate. Polyvalent epoxy compounds are not limited to the following, but include, for example, bisphenol-type epoxy resins obtained by glycidly glyciding bisphenols such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A, and tetrafluorobisphenol A; epoxy resins obtained by glycidly glyciding other divalent phenols such as biphenol, dihydroxynaphthalene, and 9,9-bis(4-hydroxyphenyl)fluorene; epoxy resins obtained by glycidly glyciding trisphenols such as 1,1,1-tris(4-hydroxyphenyl)methane and 4,4-(1-(4-(1-(4-hydroxyphenyl)-1-methylethyl)phenyl)ethylidene)bisphenol; and tetrakisphenols such as 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane. Examples of epoxy resins include glycidyl epoxy resins such as glycidylated epoxy resins obtained by glycidylating novolacs like phenol novolac, cresol novolac, bisphenol A novolac, brominated phenol novolac, and brominated bisphenol A novolac; epoxy resins obtained by glycidylating polyhydric phenols, and aliphatic ether-type epoxy resins obtained by glycidylating polyhydric alcohols such as glycerin and polyethylene glycol; ether ester-type epoxy resins obtained by glycidylating hydroxycarboxylic acids such as p-oxybenzoic acid and β-oxynaphthoic acid; ester-type epoxy resins obtained by glycidylating polycarboxylic acids such as phthalic acid and terephthalic acid; glycidyl epoxy resins such as glycidylated amine compounds like 4,4-diaminodiphenylmethane and m-aminophenol, and triglycidyl isocyanurate, as well as alicyclic epoxides such as 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate.

[0036] As the epoxy resin used as the raw material for the amine adduct, a polyvalent epoxy compound is preferred because it can enhance the storage stability of the epoxy resin composition of this embodiment. As the polyvalent epoxy compound, a glycidyl-type epoxy resin is preferred because it has overwhelmingly high productivity in producing amine adducts, more preferably an epoxy resin in which polyvalent phenols have been glycidylated because the cured product has excellent adhesion and heat resistance, and even more preferably a bisphenol-type epoxy resin. From this viewpoint, an epoxy resin in which bisphenol A has been glycidylated and an epoxy resin in which bisphenol F has been glycidylated are even more preferred, and an epoxy resin in which bisphenol A has been glycidylated is even more preferred.

[0037] Among the carboxylic acid compounds, sulfonic acid compounds, isocyanate compounds, urea compounds, and epoxy resins used as raw materials for amine adducts, epoxy resins are preferred due to their high curability and excellent storage stability.

[0038] (B) The method for producing the amine adduct as a curing agent is not particularly limited, but (B) in order to control the hydroxyl value of the curing agent to a desired range, it is preferable to react the epoxy resin and the amine compound at a temperature of 50°C to 250°C for 20 to 80 hours. From the viewpoint of ensuring a certain level of hydroxyl value, a reaction time of 40 hours or more is preferable. On the other hand, if the reaction time is too long, the hydroxyl value will become too high, so less than 60 hours is preferable.

[0039] Examples of amine compounds that are raw materials for the amine adduct include compounds having at least one primary amino group and / or a secondary amino group but no tertiary amino group; and compounds having at least one tertiary amino group and at least one active hydrogen group. The following are examples of compounds that have at least one primary amino group and / or a secondary amino group but no tertiary amino group: Examples of primary amines that do not have a tertiary amino group include, but are not limited to, methylamine, ethylamine, propylamine, butylamine, ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, ethanolamine, propanolamine, cyclohexylamine, isophoronediamine, aniline, toluidine, diaminodiphenylmethane, and diaminodiphenylsulfone. Examples of secondary amines that do not have a tertiary amino base include, but are not limited to, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, dimethanolamine, diethanolamine, dipropanolamine, dicyclohexylamine, piperidine, piperidone, diphenylamine, phenylmethylamine, and phenylethylamine.

[0040] In a compound having at least one tertiary amino group and at least one active hydrogen group, examples of the active hydrogen group include a primary amino group, a secondary amino group, a hydroxyl group, a thiol group, a carboxylic acid, and a hydrazide group. Compounds having at least one tertiary amino group and at least one active hydrogen group are not limited to the following, but include, for example, amino alcohols such as 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, methyldiethanolamine, triethanolamine, and N-β-hydroxyethylmorpholine; 2-(dimethylaminomethyl)phenol, 2,4,6-tri Aminophenols such as dimethylaminomethylphenol; 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-aminoethyl-2-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazole, 1-( Imidazoles such as 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 Imidazolins such as 1,3-trimethyl-1,4-tetramethylene-bis-imidazoline, 1,3,3-trimethyl-1,4-tetramethylene-bis-imidazoline, 1,1,3-trimethyl-1,4-tetramethylene-bis-4-methylimidazoline, 1,3,3-trimethyl-1,4-tetramethylene-bis-4-methylimidazoline, 1,2-phenylene-bis-imidazoline, 1,3-phenylene-bis-imidazoline, 1,4-phenylene-bis-imidazoline, and 1,4-phenylene-bis-4-methylimidazoline;Examples include tertiary aminoamines such as dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, dipropylaminoethylamine, dibutylaminoethylamine, N-methylpiperazine, N-aminoethylpiperazine, and diethylaminoethylpiperazine; aminomercaptans such as 2-dimethylaminoethanethiol, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptopyridine, and 4-mercaptopyridine; aminocarboxylic acids such as N,N-dimethylaminobenzoic acid, N,N-dimethylglycine, nicotinic acid, isonicotinic acid, and picolinic acid; and aminohydrazides such as N,N-dimethylglycine hydrazide, nicotinic acid hydrazide, and isonicotinic acid hydrazide. As for amine compounds, compounds having at least one tertiary amino group and at least one active hydrogen group are preferred because they offer an excellent balance between storage stability and curability, and imidazoles are more preferred.

[0041] In the production of amine adducts, when reacting an amine compound with an epoxy resin, the ratio of epoxy resin to amine compound is such that (B) in order to control the hydroxyl value and amine value of the curing agent within a desired numerical range, the active hydrogen equivalent of the amine to the epoxy resin is preferably 0.5 or more, more preferably 0.7 or more, and even more preferably 0.9 or more. Furthermore, from the viewpoint of economic efficiency in efficiently recovering any remaining unreacted amine compound, it is preferably 10 or less, more preferably 7 or less, and even more preferably 4 or less.

[0042] In the epoxy resin composition of this embodiment, the content of component (B) is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, and even more preferably 70 parts by mass or more, per 100 parts by mass of component (A), from the viewpoint of exhibiting sufficient curability. Furthermore, from the viewpoint of ensuring ease of handling and manufacturing stability, it is preferably 100 parts by mass or less, more preferably 90 parts by mass or less, and even more preferably 80 parts by mass or less. Furthermore, in the epoxy resin composition of this embodiment, the content of component (B) is preferably 33% by mass or more, and more preferably 40% by mass or more, from the viewpoint of exhibiting low-temperature curability. Furthermore, from the viewpoint of ensuring handling and manufacturing stability, it is preferably 47% by mass or less, and more preferably 45% by mass or less.

[0043] Component (B) is preferably a microencapsulated curing agent in which the surface of the core is coated with a shell, from the viewpoint of further improving solvent resistance and thermal stability.

[0044] The microencapsulated curing agent preferably has a structure in which the surface of the core is covered with a shell containing a synthetic resin and / or an inorganic oxide. Among these, from the viewpoint of the stability of the film constituting the shell, its ease of destruction during heating, and the uniformity of the cured product, it is preferable that the shell constituting the microencapsulated curing agent contains a synthetic resin.

[0045] The synthetic resins included in the shell are not limited to the following, but examples include epoxy resins, phenolic resins, polyester resins, polyethylene resins, nylon resins, polystyrene resins, and urethane resins. Among these, epoxy resins, phenolic resins, and urethane resins are preferred.

[0046] The epoxy resin used for the shell is not limited to the following, but examples include epoxy resins having two or more epoxy groups, resins produced by the reaction of an epoxy resin having two or more epoxy groups with a compound having two or more active hydrogens, and reaction products of a compound having two or more epoxy groups, one active hydrogen, and a carbon-carbon double bond. Among these, from the viewpoint of stability, resins produced by the reaction of a compound having two or more epoxy groups with a compound having two or more active hydrogens, particularly reaction products of an amine-based curing agent with an epoxy resin having two or more epoxy groups, are preferred.

[0047] Phenolic resins used for the shell include, but are not limited to, phenol-formaldehyde polycondensates, cresol-formaldehyde polycondensates, resorcinol-formaldehyde polycondensates, bisphenol A-formaldehyde polycondensates, and polyethylene polyamine modified phenol-formaldehyde polycondensates.

[0048] Polyester resins used for the shell are not limited to the following, but examples include ethylene glycol-terephthalic acid-polypropylene glycol polycondensate, ethylene glycol-butylene glycol-terephthalic acid polycondensate, terephthalic acid-ethylene glycol-polyethylene glycol polycondensate, and the like.

[0049] The polyethylene resin used for the shell is not limited to the following, but examples include ethylene-propylene-vinyl alcohol copolymer, ethylene-vinyl acetate copolymer, and ethylene-vinyl acetate-acrylic acid copolymer.

[0050] Examples of nylon-based resins used for the shell include, but are not limited to, adipic acid-hexamethylenediamine polycondensate, sebaciic acid-hexamethylenediamine polycondensate, and p-phenylenediamine-terephthalic acid polycondensate.

[0051] The polystyrene resin used for the shell is not limited to the following, but examples include styrene-butadiene copolymer, styrene-butadiene-acrylonitrile copolymer, acrylonitrile-styrene-divinylbenzene copolymer, and styrene-propenyl alcohol copolymer.

[0052] The urethane resin used for the shell is not limited to the following, but examples include isocyanate monomers such as butyl isocyanate, cyclohexyl isocyanate, octadecyl isocyanate, phenyl isocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tolidine diisocyanate, naphthalene diisocyanate, and triphenylmethane triisocyanate, or their condensates, polymers, and polycondensates of monoalcohols and polyhydric alcohols. Among these, urethane resins that are addition products of monoalcohols or polyhydric alcohols and monoisocyanates or polyhydric isocyanates are preferred.

[0053] The inorganic oxides used for the shell are not limited to the following, but examples include boron compounds such as boron oxide and borate esters, silicon dioxide, and calcium oxide. Among these, boron oxide is preferred from the viewpoint of film stability and ease of breakdown during heating.

[0054] Furthermore, it is preferable that the shell constituting the microencapsulated curing agent contains two or more reaction products selected from the group consisting of isocyanate compounds, active hydrogen compounds, curing agents for epoxy resins, epoxy resins, and amine compounds.

[0055] The isocyanate compound used in the reaction product may be one that is included in the core constituting the microencapsulated curing agent.

[0056] The active hydrogen compounds used in the reaction product are not limited to the following, but examples include water, compounds having at least one primary amino group and / or a secondary amino group, and compounds having at least one hydroxyl group. Furthermore, the active hydrogen compounds may be used individually or in combination of two or more. Examples of compounds having at least one primary amino group and / or secondary amino group include aliphatic amines, alicyclic amines, aromatic amines, and the like. Aliphatic amines include, but are not limited to, alkylamines such as methylamine, ethylamine, propylamine, butylamine, and dibutylamine; alkylenediamines such as ethylenediamine, propylenediamine, butylenediamine, and hexamethylenediamine; polyalkylene polyamines such as diethylenetriamine, triethylenetetramine, and tetraethylenepentamine; and polyoxyalkylene polyamines such as polyoxypropylenediamine and polyoxyethylenediamine. Examples of alicyclic amines include, but are not limited to, cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, and isophoronediamine. Examples of aromatic amines include, but are not limited to, aniline, toluidine, benzylamine, naphthylamine, diaminodiphenylmethane, and diaminodiphenylsulfone.

[0057] Examples of compounds having at least one hydroxyl group include alcohol compounds and phenolic compounds. The alcohol compounds are not limited to the following, but include, for example, methyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, dothyl alcohol, stearyl alcohol, eicosyl alcohol, allyl alcohol, clotyl alcohol, propargyl alcohol, cyclopentanol, cyclohexanol, benzyl alcohol, cinnamyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and di Examples include monoalcohols such as ethylene glycol monobutyl; polyhydric alcohols such as ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-butanediol, 1,4-butanediol, hydrogenated bisphenol A, neopentyl glycol, glycerin, trimethylolpropane, and pentaerythritol; and polyhydric alcohols such as compounds having two or more secondary hydroxyl groups in one molecule, obtained by the reaction of a compound having at least one epoxy group with a compound having at least one hydroxyl group, carboxyl group, primary amino group, secondary amino group, or thiol group. These alcohol compounds may be primary, secondary, or tertiary alcohols. Examples of phenolic compounds include, but are not limited to, monophenols such as carbolic acid, cresol, xylenol, carvacrol, motil, and naphthol, and polyhydric phenols such as catechol, resorcinol, hydroquinone, bisphenol A, bisphenol F, pyrogallol, phloroglucin, 2-(dimethylaminomethyl)phenol, and 2,4,6-tris(dimethylaminomethyl)phenol. These compounds having at least one hydroxyl group are preferably polyhydric alcohols or polyhydric phenols, and more preferably polyhydric alcohols, from the viewpoint of latent properties and solvent resistance.

[0058] The reaction conditions for producing two or more reactants selected from the group consisting of isocyanate compounds, active hydrogen compounds, epoxy resin curing agents, epoxy resins, and amine compounds, which are contained in the shells constituting the microencapsulated curing agent as described above, are not particularly limited, but are usually in the temperature range of -10°C to 150°C and for a reaction time of 10 minutes to 12 hours.

[0059] When using an isocyanate compound and an active hydrogen compound, the mixing ratio is preferably in the range of 1:0.1 to 1:1000, expressed as (isocyanate group in the isocyanate compound):(active hydrogen in the active hydrogen compound)(equivalent ratio).

[0060] The above reaction may be carried out in a predetermined dispersion medium if necessary. Examples of dispersion media include solvents, plasticizers, resins, etc. Examples of solvents, though not limited to the following, include hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirits, and naphtha; ketones such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK); esters such as ethyl acetate, n-butyl acetate, and propylene glycol monomethyl ethyl ether acetate; alcohols such as methanol, isopropanol, n-butanol, butyl cellosolve, and butyl carbitol; and water. Examples of plasticizers include, but are not limited to, phthalate diester plasticizers such as dibutyl phthalate and di(2-ethylhexyl) phthalate; aliphatic dibasic acid ester plasticizers such as di(2-ethylhexyl) adipic acid; phosphate triester plasticizers such as tricresyl phosphate; and glycol ester plasticizers such as polyethylene glycol ester. Examples of resins include, but are not limited to, silicone resins, epoxy resins, and phenolic resins.

[0061] The proportion of the reaction product described above in the shell is usually 1% by mass or more, preferably 50% by mass or more, and may also be 100% by mass.

[0062] In the aforementioned microencapsulated curing agent, examples of methods for forming a shell that covers the surface of the core include the following methods (1) to (3). (1) A method in which the shell components and hardener particles are dissolved and dispersed in a solvent which is a dispersion medium, and then the solubility of the shell components in the dispersion medium is reduced to precipitate the shell on the surface of the hardener particles for epoxy resin. (2) A method of dispersing hardening agent particles in a dispersion medium, adding the above-mentioned shell-forming material to the dispersion medium, and precipitating it on the hardening agent particles for epoxy resin. (3) A method of adding the above-mentioned raw material components for forming the shell to a dispersion medium, and using the surface of the hardening agent particles as the reaction site to produce a shell-forming material. Here, methods (2) and (3) are preferred because they allow the reaction and coating to be carried out simultaneously.

[0063] Examples of dispersion media include solvents, plasticizers, and resins. Furthermore, as solvents, plasticizers, and resins, any two or more of the above-mentioned isocyanate compounds, active hydrogen compounds, curing agents for epoxy resins, epoxy resins, and amine compounds, as listed as examples of solvents, plasticizers, and resins that can be used to obtain reaction products, can be used.

[0064] The method for separating the microencapsulated curing agent from the dispersion medium after forming the shells by the methods described in (2) and (3) above is not particularly limited, but it is preferable to separate and remove the unreacted raw materials together with the dispersion medium after the shells have been formed. One such method is to remove the dispersion medium and the unreacted shell-forming material by filtration. It is preferable to wash the microencapsulated curing agent after removing the dispersion medium. Washing the microencapsulated curing agent removes any unreacted shell-forming material adhering to its surface. The washing method is not particularly limited, but the residue after filtration can be washed using a dispersion medium or a solvent that does not dissolve the microencapsulated curing agent. After filtration and washing, the microencapsulated curing agent can be dried to obtain it in powder form. The drying method is not particularly limited, but it is preferable to dry it at a temperature below the melting point or softening point of the curing agent, for example, by vacuum drying. By making the microencapsulated curing agent into a powder, the compounding process with (A) epoxy resin can be easily applied. Furthermore, using epoxy resin as a dispersion medium is preferable because it is possible to obtain a masterbatch of microencapsulated curing agent integrated with the epoxy resin at the same time as shell formation.

[0065] The shell formation reaction is typically carried out at a temperature range of -10°C to 150°C, preferably 0°C to 100°C, with a reaction time of 10 minutes to 72 hours, preferably 30 minutes to 24 hours.

[0066] Furthermore, the shell is suitable for wavenumbers of 1630-1680 cm, considering the balance between storage stability and reactivity. -1 The urea bond group absorbs infrared radiation, and the wavenumber is 1680-1725 cm. -1 The bilet bond group absorbs infrared radiation, and the wavenumber is 1730-1755 cm. -1 It is preferable that the shell has urethane bonding groups that absorb infrared rays. The urea bonding groups, biuret bonding groups, and urethane bonding groups can be measured using a Fourier transform infrared spectrophotometer (hereinafter sometimes referred to as "FT-IR"). Furthermore, the presence of urea bonding groups, biuret bonding groups, and urethane bonding groups in the shell can be confirmed by microscopic FT-IR. Specifically, a modified aliphatic polyamine curing agent is added to a curable resin composition containing the epoxy resin curing agent and epoxy resin of this embodiment, and the mixture is cured at 40°C for 12 hours. Then, the epoxy resin portion is further cured at 120°C for 24 hours to completely cure it. Subsequently, a sample with a thickness of 5 to 20 μm is prepared from the obtained cured product using an ultramicrotome, and the depth direction of the shell is analyzed by FT-IR. By observing the area near the surface of the shell, the presence of urea bonding groups, biuret bonding groups, and urethane bonding groups can be observed.

[0067] Furthermore, the thickness of the shell constituting the microencapsulated curing agent is preferably 5 nm to 1000 nm, and more preferably 10 nm to 100 nm. By setting the shell thickness to 5 nm or more, the storage stability of the epoxy resin curing agent obtained by the manufacturing method of this embodiment can be further improved. Also, by setting the shell thickness to 1000 nm or less, the curability can be further improved. The thickness referred to here is the average layer thickness and can be measured by a transmission electron microscope.

[0068] The method for mixing component (A) and component (B) to obtain a masterbatch-type curing agent for a one-component epoxy resin composition is not particularly limited, but examples include mixing using a general three-roll mixer, a non-bubbling kneader, a planetary mixer, etc.

[0069] The total chlorine content of component (B) is preferably 500 ppm or less, more preferably 450 ppm or less, and even more preferably 400 ppm or less, in order to obtain an epoxy resin composition with a good balance of curability and storage stability.

[0070] ((C) Reactive Diluent) The epoxy resin composition of this embodiment may contain (C) a reactive diluent (hereinafter sometimes referred to as component (C)) from the viewpoint of reducing viscosity. A reactive diluent is a compound that has a reactive functional group that can be incorporated into a curing structure such as an epoxy group. (C) Examples of reactive diluents include epoxy compounds that can reduce viscosity without impairing reactivity. In this specification, the epoxy resins exemplified in component (A) above are excluded, and a compound having a viscosity of 1 mPa·s or more and less than 3 Pa·s at 25°C is defined as the reactive diluent (C). In the resin composition of this embodiment, epoxy compounds are preferred as the reactive diluent (C) from the viewpoint of good compatibility with component (A) and being incorporated into the cured structure after the thermosetting reaction.

[0071] (C) Examples of epoxy compounds used as reactive diluents include, but are not limited to, epoxy compounds without aromatic rings and epoxy compounds having aromatic rings.

[0072] Examples of monofunctional epoxy compounds that do not contain aromatic rings include n-butylglycidyl ether, t-butylglycidyl ether, allylglycidyl ether, and 2-ethylhexylglycidyl ether. Examples of monofunctional epoxy compounds having an aromatic ring include styrene oxide, phenyl glycidyl ether, cresyl glycidyl ether, p-sec-butylphenyl glycidyl ether, t-butylphenyl glycidyl ether, and compounds such as SY-OPG, a product of Sakamoto Pharmaceutical Co., Ltd. Examples of bifunctional epoxy compounds that do not have an aromatic ring include 1,4-cyclohexanedimethanol diglycidyl ether, 1,3-cyclohexanedimethanol diglycidyl ether, (3,4-epoxycyclohexyl)methyl-3,4-epoxycyclohexyl carboxylate, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, dicyclopentadiene dimethanol diglycidyl ether, vinylcyclohexene dioxide, Mitsubishi Chemical Corporation product name: YX-8000, and Sakamoto Pharmaceutical Co., Ltd. product name: SR-8EGS. Examples of difunctional epoxy compounds having one or more aromatic rings include hexahydrophthalate diglycidyl ether, resorcinol diglycidyl ether, tert-butylhydroquinone diglycidyl ether, polyoxyalkylene bisphenol A diglycidyl ether, N,N-diglycidylaniline, and N,N-diglycidyl-o-toluidine. Examples of trifunctional epoxy compounds include trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, and N,N-bis(2,3-epoxypropyl)-4-(2,3-epoxypropoxy)aniline.

[0073] In the resin composition of this embodiment, if component (B) is a microencapsulated curing agent, it is preferable that (C) the reactive diluent has an aromatic ring, from the viewpoint of improving the solvent resistance of the microencapsulated curing agent. Furthermore, it is even more preferable that (C) the reactive diluent is an epoxy compound having the aromatic ring, and that the aromatic ring is monocyclic and monofunctional, from the viewpoint of further improving the solvent resistance of the microencapsulated curing agent. Furthermore, it is even more preferable that the monofunctional group is an epoxy group, as it is incorporated into the cured product after the reaction, thereby exhibiting sufficient mechanical strength. Furthermore, it is even more preferable that the number of carbon atoms in each substituent of the aromatic ring is 3 or less, from the viewpoint of improving penetration into the capsule membrane, which will be described later, and improving solvent resistance.

[0074] (C) The mechanism by which the reactive diluent, as described above, has a monocyclic aromatic ring and is a monofunctional epoxy compound, improves the solvent resistance of the microencapsulated curing agent is thought to be as follows, although this is not intended to be limiting. (C) When the reactive diluent has aromatic rings, the aromatic rings of the reactive diluent incorporated into the shell exhibit a stacking effect and form a network, thereby increasing the cohesive force of the shell. Consequently, a shell that is less prone to swelling in solvents can be constructed, improving the solvent resistance of the microencapsulated curing agent. Furthermore, (C) the reactive diluent has low steric hindrance because the aromatic ring is a monocyclic and monofunctional compound, allowing it to easily penetrate into the shell and form a denser and wider stacking network of aromatic rings. Here, if each substituent of the aromatic ring has 3 or fewer carbon atoms, steric hindrance can be further reduced, penetration into the shell can be increased, and solvent resistance can be further improved. Due to the mechanism described above, solvent resistance is significantly improved compared to conventional microencapsulated curing agents that do not contain reactive diluents. Furthermore, the range of applicable solvents increases, expanding the material options for component (A) or component (B) that can be applied to epoxy resin compositions, making it easier to impart desired physical properties to the epoxy resin composition.

[0075] In the epoxy resin composition of this embodiment, the content of (C) reactive diluent is preferably 3% by mass or more, more preferably 4% by mass or more, even more preferably 5% by mass or more, and even more preferably 6% by mass or more, from the viewpoint of reducing viscosity. Furthermore, from the viewpoint of suppressing excessive viscosity reduction and reduction of mechanical strength of the cured product, it is preferably 15% by mass or less, more preferably 14% by mass or less, even more preferably 13% by mass or less, and even more preferably 12% by mass or less.

[0076] (Viscosity of epoxy resin composition) The epoxy resin composition of this embodiment preferably has a low viscosity at room temperature (25°C) from the viewpoint of ease of handling during work. Specifically, a viscosity of 100 Pa·s or less is preferred, more preferably 80 Pa·s or less, and even more preferably 60 Pa·s or less. On the other hand, from the viewpoint that a viscosity that is too low increases the risk of liquid splashing during work, a viscosity of 0.1 Pa·s or more is preferred, more preferably 0.5 Pa·s or more, and even more preferably 1.0 Pa·s or more. The viscosity of the epoxy resin composition of this embodiment can be controlled to the above numerical range by adjusting the concentrations of components (A) and (C) relative to component (B).

[0077] (Other additives) The resin composition of this embodiment may, if necessary, further contain additives such as organic fillers, inorganic fillers, colorants, defoamers, flow regulators, thickeners, mold release agents, wetting agents, flame retardants, surfactants, and resins, in addition to the components (A) to (C) described above.

[0078] Organic fillers are materials that function as shock absorbers, capable of mitigating stress caused by impact. Examples of organic fillers include, but are not limited to, acrylic resins, silicone resins, butadiene rubber, polyesters, polyurethanes, polyvinyl butyral, polyarylate, polymethyl methacrylate, acrylic rubber, polystyrene, NBR (acrylonitrile-butadiene rubber), SBR (styrene-butadiene rubber), silicone-modified resins, and organic fine particles of copolymers containing these as components. From the viewpoint of improving adhesion, the organic fine particles are preferably, for example, alkyl (meth)acrylate-butadiene-styrene copolymer, alkyl (meth)acrylate-silicone copolymer, silicone-(meth)acrylic copolymer, a composite of silicone and (meth)acrylic acid, a composite of alkyl (meth)acrylate-butadiene-styrene and silicone, and a composite of alkyl (meth)acrylate and silicone. Furthermore, as the organic filler, organic microparticles having a core-shell structure and having different compositions in the core layer and shell layer can also be used. Examples of core-shell type organic microparticles include particles in which acrylic resin is grafted onto a silicone-acrylic rubber core, and particles in which acrylic resin is grafted onto an acrylic copolymer. These organic fillers may be used individually or in combination of two or more.

[0079] Inorganic fillers can improve the physical strength of the resin composition in this embodiment, resulting in superior long-term reliability of the printed circuit board. Inorganic fillers include, but are not limited to, silicates such as talc, calcined clay, uncalcined clay, mica, and glass; oxides such as silica oxides such as titanium dioxide, zinc oxide, zirconium oxide, antimony oxide, aluminum oxide (alumina), fused silica (fused spherical silica, fused crushed silica), synthetic silica, and crystalline silica; carbonates such as calcium carbonate, magnesium carbonate, and hydrotalcite; hydroxides such as aluminum hydroxide, magnesium hydroxide, and calcium hydroxide; sulfates such as barium sulfate, zinc sulfide, and calcium sulfate; sulfites such as calcium sulfite; titanates such as potassium titanate and lead titanate; borates such as zinc borate, barium metaborate, aluminum borate, calcium borate, and sodium borate; and nitrides such as aluminum nitride, boron nitride, and silicon nitride. Among these, for example, titanium dioxide is preferred as an inorganic filler to be included in a resin composition applied to a substrate for mounting light-emitting diodes, from the viewpoint of white appearance and reflectivity. The shape of the inorganic filler is not particularly limited and may be amorphous, spherical, or flaky, for example, and the presence or absence of surface treatment is also not particularly limited. These inorganic fillers may be used individually or in combination of two or more types.

[0080] Examples of colorants include, but are not limited to, phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, leucocrystal violet, carbon black, naphthalene black, and solvent blue. These colorants may be used individually or in combination of two or more.

[0081] Examples of defoaming agents include silicone-based defoaming agents and non-silicone-based defoaming agents. Examples of silicone-based defoaming agents include KS-66 (manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of non-silicone-based defoaming agents include FOAMKILLER NSI-0.00 (manufactured by Aoki Oil & Fat Co., Ltd.). These colorants may be used individually or in combination of two or more.

[0082] Examples of flow regulators include, but are not limited to, organosilane compounds such as silane coupling agents; organotitanium compounds such as titanium tetraisopropoxide and titanium diisopropoxybis(acetylacetonate); and organozirconium compounds such as zirconium tetran-n-butoxide and zirconium tetraacetylacetonate.

[0083] Examples of thickening agents include, but are not limited to, animal-derived thickeners such as gelatin; plant-derived thickeners such as polysaccharides and cellulose; and chemically synthesized thickeners such as polyacrylic thickeners, modified polyacrylic thickeners, polyether thickeners, urethane-modified polyether thickeners, and carboxymethylcellulose.

[0084] Examples of release agents include, but are not limited to, fluorine-based release agents, silicone-based release agents, and acrylic-based release agents consisting of copolymers of glycidyl (meth)acrylate and linear alkyl (meth)acrylate esters having 16 to 22 carbon atoms.

[0085] Examples of wetting agents include, but are not limited to, unsaturated polyester copolymer wetting agents having acidic groups, such as acrylic polyphosphate esters.

[0086] Examples of flame retardants include, but are not limited to, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, halogenated flame retardants such as chlorine compounds and bromine compounds, phosphorus-based flame retardants such as condensed phosphate esters, antimony-based flame retardants such as antimony trioxide and antimony pentoxide, and inorganic oxides such as silica fillers.

[0087] Examples of surfactants include, but are not limited to, anionic surfactants such as alkylbenzene sulfonates and alkyl polyoxyethylene sulfates, cationic surfactants such as alkyldimethylammonium salts, amphoteric surfactants such as alkyldimethylamine oxide and alkyl carboxybetaine, and nonionic surfactants such as linear alcohols with 25 or more carbon atoms and fatty acid esters.

[0088] Examples of resins include, but are not limited to, polyester resins, polyurethane resins, acrylic resins, polyether resins, melamine resins, and modified epoxy resins such as urethane-modified epoxy resins, rubber-modified epoxy resins, and alkyd-modified epoxy resins.

[0089] In addition, antioxidants, thermal polymerization inhibitors, ultraviolet absorbers, antistatic agents, anti-aging agents, antifungal agents, leveling agents, thixotropic agents, photoinitiators, sensitizers, radical polymerization inhibitors, curing accelerators, surface treatment agents, dispersants, dispersion aids, surface modifiers, stabilizers, phosphors, etc., may be added for the purpose of imparting desired physical properties without departing from the effects of the present invention.

[0090] [Paste-like compositions, film-like compositions, adhesives, bonding pastes, bonding films] The paste-like composition, adhesive, and bonding paste of this embodiment contain the epoxy resin composition of this embodiment described above. The film-like composition and bonding film of this embodiment may include the epoxy resin composition of this embodiment described above, and may be in the form of having a layer of the epoxy resin composition on a predetermined substrate. The adhesive, bonding paste, and bonding film of this embodiment are useful as liquid adhesives, film adhesives, die bonding materials, and the like. The adhesive, bonding paste, and bonding film of this embodiment can be manufactured by methods described, for example, in Japanese Patent Publication No. 62-141083 and Japanese Patent Publication No. 5-295329. More specifically, a solution is prepared by dissolving, mixing, and dispersing a solid epoxy resin, a liquid epoxy resin, and a solid urethane resin in toluene to a concentration of about 50% by mass. To this solution, the epoxy resin composition of this embodiment is added and dispersed to the solution at a concentration of about 30% by mass to prepare a varnish for use as an adhesive and bonding paste. This varnish is applied to, for example, a polyethylene terephthalate substrate for release with a thickness of about 50 μm, so that after the toluene has dried, the varnish reaches a thickness of about 30 μm. By drying the toluene, a bonding film can be obtained that is inert at room temperature and exhibits adhesive properties through the action of a latent curing agent when heated. The adhesive, bonding paste, and bonding film of this embodiment are cured products with excellent adhesion, heat resistance, and elongation at break.

[0091] [Conductive materials, anisotropic conductive materials, anisotropic conductive films] The conductive material and anisotropic conductive material of this embodiment contain the epoxy resin composition of this embodiment described above. Examples of conductive materials include conductive films and conductive pastes. Examples of anisotropic conductive materials include anisotropic conductive films and anisotropic conductive pastes. The conductive material of this embodiment can be manufactured, for example, by the method described in Japanese Patent Application Publication No. 1-113480. More specifically, for example, in the manufacture of the bonding film described above, it can be manufactured by mixing and dispersing a conductive material or an anisotropic conductive material when preparing the varnish, applying it to a release substrate, and then drying it. Examples of conductive particles that make up conductive materials and anisotropic conductive materials include metal particles such as solder particles, nickel particles, nano-sized metal crystals, particles with a metal surface coated with another metal, and copper and silver gradient particles, as well as resin particles such as styrene resin, urethane resin, melamine resin, epoxy resin, acrylic resin, phenolic resin, and styrene-butadiene resin, coated with a conductive thin film of gold, nickel, silver, copper, solder, etc. Generally, the conductive particles that make up conductive materials and anisotropic conductive materials are spherical fine particles of about 1 to 20 μm in size. Examples of substrates used when producing an anisotropic conductive film using the aforementioned conductive material or anisotropic conductive material include polyester, polyethylene, polyimide, and polytetrafluoroethylene. The film can be manufactured by applying the conductive material or anisotropic conductive material to the substrate and then drying the solvent. The conductive material, anisotropic conductive material, and anisotropic conductive film of this embodiment exhibit excellent adhesion, heat resistance, and elongation at break, and therefore have excellent conductivity and connection reliability.

[0092] [Insulating materials] The insulating material of this embodiment contains the epoxy resin composition of this embodiment described above. Examples of insulating materials include insulating adhesive films and insulating adhesive pastes. The insulating material of this embodiment can be used as the bonding film described above to obtain an insulating adhesive film, which is an insulating material. In addition to using a sealing material, an insulating adhesive paste can be obtained by incorporating an insulating filler from among the fillers described above. The insulating material of this embodiment has excellent adhesive properties, heat resistance, and elongation at break, and therefore exhibits excellent insulating properties.

[0093] [Sealing material] The sealing material of this embodiment contains the epoxy resin composition of this embodiment described above. The sealing material of this embodiment is useful as a solid sealing material, a liquid sealing material, a film-like sealing material, etc. When the sealing material of this embodiment is a liquid sealing material, it is useful as an underfill material, potting material, dam material, etc. The sealing material of this embodiment can be manufactured by methods described in, for example, Japanese Patent Publication No. 5-43661 and Japanese Patent Publication No. 2002-226675 as methods for manufacturing molding materials for sealing and impregnating electrical and electronic components. More specifically, a sealing material can be obtained by uniformly mixing a bisphenol A type epoxy resin, an acid anhydride curing agent such as methylhexahydrophthalic acid anhydride, and spherical fused silica powder, and then uniformly mixing the epoxy resin composition of this embodiment. The sealing material of this embodiment results in a cured product with excellent adhesion, heat resistance, and elongation at break.

[0094] [Materials for coating] The coating material of this embodiment contains the epoxy resin composition of this embodiment described above. Examples of coating materials include coating materials for electronic materials, overcoat materials for covering printed circuit boards, and resin compositions for interlayer insulation of printed circuit boards. The coating material of this embodiment can be manufactured by various methods described in, for example, Japanese Patent Publication No. 4-6116, Japanese Patent Application Publication No. 7-304931, Japanese Patent Application Publication No. 8-64960, Japanese Patent Application Publication No. 2003-246838, etc. Specifically, silica or the like is selected as a filler, and as a filler, phenoxy resin, rubber-modified epoxy resin, etc., in addition to bisphenol A type epoxy resin, are blended, and the epoxy resin composition of this embodiment is further blended, and a solution of about 50% is prepared with methyl ethyl ketone (MEK) to obtain the coating material. This is coated onto a polyimide film to a thickness of about 50 μm, copper foil is placed on top and laminated at 60 to 150°C, and the laminate is heat-cured at 180 to 200°C to obtain a laminate in which the interlayers are coated with the epoxy resin composition, which is the coating material of this embodiment. The coating material of this embodiment is easy to handle and forms a cured product with excellent adhesion, heat resistance, and elongation at break.

[0095] [Paint composition] The paint composition of this embodiment contains the epoxy resin composition of this embodiment described above. The paint composition of this embodiment can be manufactured by methods described, for example, in Japanese Patent Publication No. 11-323247 and Japanese Patent Publication No. 2005-113103. Specifically, titanium dioxide, talc, etc. are blended with a bisphenol A type epoxy resin, and a 1:1 mixed solvent of methyl isobutyl ketone (MIBK) / xylene is added, stirred, and mixed to form the main component. The epoxy resin composition of this embodiment is then added to this and uniformly dispersed to obtain the paint composition of this embodiment. The coating composition of this embodiment results in a cured product that is easy to handle and has excellent adhesion, heat resistance, and elongation at break.

[0096] [Prepreg] The prepreg of this embodiment contains the epoxy resin composition of this embodiment described above. The prepreg of this embodiment can be manufactured by impregnating a reinforcing substrate with the epoxy resin composition of this embodiment and heating it, as described in, for example, Japanese Patent Publication No. 9-71633, International Publication No. 98 / 44017, etc. Examples of solvents for the impregnation varnish include methyl ethyl ketone, acetone, ethyl cellsolve, methanol, ethanol, isopropyl alcohol, etc., and it is preferable that these solvents do not remain in the prepreg. The type of reinforcing substrate is not particularly limited, but examples include paper, glass cloth, glass nonwoven fabric, aramid cloth, liquid crystal polymer, etc. The ratio of epoxy resin composition to reinforcing substrate is also not particularly limited, but it is generally preferable to adjust it so that the resin content in the prepreg is 20 to 80% by mass. The prepreg of this embodiment becomes a cured product with excellent heat resistance and elongation at break.

[0097] [Thermal conductive materials] The thermally conductive material of this embodiment contains the epoxy resin composition of this embodiment described above. The thermally conductive material of this embodiment can be manufactured, for example, by the methods described in Japanese Patent Publication No. 6-136244, Japanese Patent Publication No. 10-237410, and Japanese Patent Publication No. 2000-3987. Specifically, an epoxy resin is used as the thermosetting resin, a phenol novolac curing agent is used as the curing agent, and graphite powder is used as the thermally conductive filler is blended and kneaded uniformly. By blending the epoxy resin composition of this embodiment with this mixture, the thermally conductive material of this embodiment can be obtained. Examples of thermally conductive fillers include silica particles, alumina particles, and boron nitride particles. The thermally conductive material of this embodiment results in a cured product with excellent heat resistance and elongation at break.

[0098] [Fuel cell separator material] The fuel cell separator material of this embodiment contains the epoxy resin composition of this embodiment described above. The fuel cell separator material of this embodiment can be manufactured, for example, by the methods described in Japanese Patent Publication No. 11-154521, Japanese Patent Publication No. 2000-239488, and Japanese Patent Publication No. 2021-106111. Specifically, it can be obtained by uniformly kneading a composition in which an epoxy resin is used as a thermosetting resin, an amine-based curing agent is used as a curing agent, and conductive particles are used as a filler, pouring this composition into a mold for forming a separator, and then heat-pressing it. Examples of conductive particles include graphite particles and metal oxide particles. Additionally, release agents and lubricants may be added to the filler as appropriate. The fuel cell separator material of this embodiment hardens to a product with excellent heat resistance and elongation at break. [Examples]

[0099] The present invention will be described below with reference to specific examples and comparative examples, but the present invention is not limited to the following examples and comparative examples. In the following, "parts" and "%" refer to mass unless otherwise specified.

[0100] [Ingredients listed] The components (A) to (C) used in the examples and comparative examples are shown below in Tables 1 and 2. Component (B): The hardening agent was manufactured as follows.

[0101] ((B) Example of manufacturing of hardener) (B-1) Hardener One equivalent of bisphenol A type epoxy resin (epoxy equivalent 184 g / eq, total chlorine content 300 ppm, hydrolyzable chlorine content 30 ppm) and 1.2 equivalents of 2-methylimidazole were reacted in a 1:1 mixed solvent of n-butanol and toluene at 80°C for 48 hours to obtain the reaction product, amine adduct. Subsequently, the excess amine was removed along with the solvent under reduced pressure, and a solid block-type epoxy resin curing agent was obtained at 25°C. Next, the block-shaped epoxy resin curing agent is pulverized with a jet mill, resulting in a specific surface area of ​​3.56 m². 2 A curing agent for epoxy resin (B'-1) was obtained, consisting of particles (pulverized product) with a particle size of / g, an average particle size D50 under sieving of 2.30 μm, and a D99 / D50 of 8.5. The epoxy resin curing agent (B'-1) prepared as described above was fed using a Cryptron Orb manufactured by Earth Technica Co., Ltd., under conditions of 10°C, 30% humidity, a rotation speed of 13500 rpm, a supply speed of 10 kg / hr, and an airflow of 3 m³. 3 Shape correction treatment was performed at / min to produce surface-modified product (B'-1). A cyclone-type collector and bag filter were attached to adjust the specific surface area value, and epoxy resin curing agent (B-1) with a circularity of 0.97 and an average particle size of 2.6 μm was produced by classification using a classifier.

[0102] (B-2) Hardener One equivalent of bisphenol A type epoxy resin (epoxy equivalent 184 g / eq, total chlorine content 300 ppm, hydrolyzable chlorine content 30 ppm) and 0.75 equivalents of 2-methylimidazole were reacted in a 1:1 mixed solvent of n-butanol and toluene at 80°C for 20 hours to obtain the reaction product, amine adduct. Subsequently, the excess amine was removed along with the solvent under reduced pressure, and a solid block-type epoxy resin curing agent was obtained at 25°C. Subsequently, the block-shaped curing agent for epoxy resin is pulverized with a jet mill to obtain a specific surface area value of 3.63 m 2 / g, a curing agent for epoxy resin (B'-2) which is particles (pulverized product) having an under-sieve average particle diameter D50 of 2.40 µm and a D99 / D50 of 8.6 was obtained. The epoxy resin curing agent (B'-2) produced as described above was processed using a Kryptron Orb manufactured by Earth Technica Co., Ltd. under an environment of a temperature of 10°C and a humidity of 30%, at a rotation speed of 13,500 rpm, a feeding speed of 10 kg / hr, and an air volume of 3 m 3 / min, shape correction treatment was performed to prepare a surface-modified product of (B'-2). A cyclone type collector and a bag filter were attached to adjust the specific surface area value, and the curing agent for epoxy resin (B-2) having a circularity of 0.97 and an average particle diameter of 2.5 µm was prepared by classification operation using a classifier.

[0103] (B-3) Curing agent 1 equivalent of bisphenol A type epoxy resin (epoxy equivalent: 186 g / eq, total chlorine content: 1700 ppm, hydrolyzable chlorine content: 300 ppm) and 1.2 equivalents of 2-methylimidazole were reacted in a 1:1 mixed solvent of n-butanol and toluene at 80°C for 48 hours to obtain an amine adduct as a reaction product. Thereafter, excess amine was distilled off together with the solvent under reduced pressure to obtain a solid block-shaped curing agent for epoxy resin at 25°C. Subsequently, the block-shaped curing agent for epoxy resin is pulverized with a jet mill to obtain a specific surface area value of 3.57 m 2 / g, a curing agent for epoxy resin (B'-3) which is particles (pulverized product) having an under-sieve average particle diameter D50 of 2.31 µm and a D99 / D50 of 8.5 was obtained. The epoxy resin curing agent (B'-3) produced as described above was processed using a Kryptron Orb manufactured by Earth Technica Co., Ltd. under an environment of a temperature of 10°C and a humidity of 30%, at a rotation speed of 13,500 rpm, a feeding speed of 10 kg / hr, and an air volume of 3 m 3 / min, shape correction treatment was performed to prepare a surface-modified product of (B'-3). A cyclone type collector and a bag filter were attached to adjust the specific surface area value, and the curing agent for epoxy resin (B-3) having a circularity of 0.98 and an average particle diameter of 2.6 µm was prepared by classification operation using a classifier.

[0104] (B-4) Hardener One equivalent of bisphenol A type epoxy resin (epoxy equivalent 184 g / eq, total chlorine content 300 ppm, hydrolyzable chlorine content 30 ppm) and 20.0 equivalents of triethylenetetramine were reacted in a 1:1 mixed solvent of n-butanol and toluene at 80°C for 48 hours to obtain the reaction product, amine adduct. Subsequently, the excess amine was removed along with the solvent under reduced pressure, and a solid block-type epoxy resin curing agent was obtained at 25°C. Next, the block-shaped epoxy resin curing agent is pulverized with a jet mill, resulting in a specific surface area of ​​3.57 m². 2 A curing agent for epoxy resin (B'-4) was obtained, consisting of particles (pulverized) with a particle size of / g, an average particle size D50 under sieving of 2.42 μm, and a D99 / D50 ratio of 8.2. The epoxy resin curing agent (B'-4) prepared as described above was fed using a Cryptron Orb manufactured by Earth Technica Co., Ltd., under conditions of 10°C, 30% humidity, a rotation speed of 13500 rpm, a supply speed of 10 kg / hr, and an airflow of 3 m³. 3 Shape correction treatment was performed at / min to produce surface-modified product (B'-4). A cyclone-type collector and bag filter were attached to adjust the specific surface area value, and epoxy resin curing agent (B-4) with a circularity of 0.98 and an average particle size of 2.9 μm was produced by classification using a classifier.

[0105] (B-5) Hardener One equivalent of bisphenol A type epoxy resin (epoxy equivalent 184 g / eq, total chlorine content 300 ppm, hydrolyzable chlorine content 30 ppm) and 0.2 equivalents of 2-methyl-4-ethylimidazole were reacted in a 1:1 mixed solvent of n-butanol and toluene at 80°C for 48 hours to obtain the reaction product, amine adduct. Subsequently, the excess amine was removed along with the solvent under reduced pressure, and a solid block-type epoxy resin curing agent was obtained at 25°C. Next, the block-shaped epoxy resin curing agent is pulverized with a jet mill, resulting in a specific surface area of ​​3.62 m². 2A curing agent for epoxy resin (B'-5) was obtained, consisting of particles (pulverized) with a particle size of / g, an average particle size D50 under sieving of 2.18 μm, and a D99 / D50 ratio of 8.7. The epoxy resin curing agent (B'-5) prepared as described above was fed using a Cryptron Orb manufactured by Earth Technica Co., Ltd., under conditions of 10°C, 30% humidity, a rotation speed of 13500 rpm, a supply speed of 10 kg / hr, and an airflow of 3 m³. 3 Shape correction treatment was performed at / min to produce surface-modified product (B'-5). A cyclone-type collector and bag filter were attached to adjust the specific surface area value, and epoxy resin curing agent (B-5) with a circularity of 0.98 and an average particle size of 2.2 μm was produced by classification using a classifier.

[0106] (B-6) Hardener One equivalent of bisphenol A type epoxy resin (epoxy equivalent 184 g / eq, total chlorine content 300 ppm, hydrolyzable chlorine content 30 ppm) and 0.5 equivalents of 2-methylimidazole were reacted in a 1:1 mixed solvent of n-butanol and toluene at 80°C for 90 hours to obtain the reaction product, amine adduct. Subsequently, the excess amine was removed along with the solvent under reduced pressure, and a solid block-type epoxy resin curing agent was obtained at 25°C. Next, the block-shaped epoxy resin curing agent is pulverized with a jet mill, resulting in a specific surface area of ​​3.24 m². 2 A curing agent for epoxy resin (B'-6) was obtained, consisting of particles (pulverized) with a particle size of / g, an average particle size D50 under sieving of 2.58 μm, and a D99 / D50 ratio of 8.4. The epoxy resin curing agent (B'-6) prepared as described above was fed using a Cryptron Orb manufactured by Earth Technica Co., Ltd., under conditions of 10°C, 30% humidity, a rotation speed of 13500 rpm, a supply speed of 10 kg / hr, and an airflow of 3 m³. 3 Shape correction treatment was performed at / min to produce surface-modified product (B'-6). A cyclone-type collector and bag filter were attached to adjust the specific surface area value, and epoxy resin curing agent (B-6) with a circularity of 0.98 and an average particle size of 2.5 μm was produced by classification using a classifier.

[0107] (B-7) Hardener Powdered 2-heptadecylimidazole (Shikoku Chemicals Co., Ltd.: C17Z) was pulverized using a jet mill to obtain a specific surface area of ​​3.14 m². 2 A curing agent for epoxy resin (B'-7) was obtained, consisting of particles (pulverized) with a particle size of / g, an average particle size D50 under sieving of 2.68 μm, and a D99 / D50 ratio of 8.4. The epoxy resin curing agent (B'-7) prepared as described above was fed using a Cryptron Orb manufactured by Earth Technica Co., Ltd., under conditions of 10°C, 30% humidity, a rotation speed of 13500 rpm, a supply speed of 10 kg / hr, and an airflow of 3 m³. 3 Shape correction treatment was performed at / min to produce surface-modified product (B'-7). A cyclone-type collector and bag filter were attached to adjust the specific surface area value, and epoxy resin curing agent (B-7) with a circularity of 0.98 and an average particle size of 2.4 μm was produced by classification using a classifier.

[0108] (B-1-M) Microencapsulated hardener To 100 parts by mass of bisphenol A type epoxy resin (epoxy equivalent 186 g / eq, total chlorine content 600 ppm, hydrolyzable chlorine content 50 ppm), 100 parts by mass of curing agent core (B-1) and 5 parts by mass of encapsulating agent (Tosoh Corporation, Coronate T100) were added, and after complete dispersion and mixing, the mixture was reacted at 45°C for 10 hours. Subsequently, the epoxy resin, which was the dispersion medium, was washed with toluene to obtain microencapsulated curing agent (B-1-M).

[0109] (B-2-M) Microencapsulated hardener To 100 parts by mass of bisphenol A type epoxy resin (epoxy equivalent 186 g / eq, total chlorine content 600 ppm, hydrolyzable chlorine content 50 ppm), 100 parts by mass of curing agent core (B-2) and 5 parts by mass of encapsulating agent (Tosoh Corporation, Coronate T100) were added, and after complete dispersion and mixing, the mixture was reacted at 45°C for 10 hours. Subsequently, the epoxy resin, which was the dispersion medium, was washed with toluene to obtain a microencapsulated curing agent (B-2-M).

[0110] (B-3-M) Microencapsulated hardener To 100 parts by mass of bisphenol A type epoxy resin (epoxy equivalent 186 g / eq, total chlorine content 600 ppm, hydrolyzable chlorine content 50 ppm), 100 parts by mass of curing agent core (B-3) and 5 parts by mass of encapsulating agent (Tosoh Corporation, Coronate T100) were added, and after complete dispersion and mixing, the mixture was reacted at 45°C for 10 hours. Subsequently, the epoxy resin, which was the dispersion medium, was washed with toluene to obtain a microencapsulated curing agent (B-3-M).

[0111] (B-4-M) Microencapsulated hardener To 100 parts by mass of bisphenol A type epoxy resin (epoxy equivalent 186 g / eq, total chlorine content 600 ppm, hydrolyzable chlorine content 50 ppm), 100 parts by mass of curing agent core (B-4) and 5 parts by mass of encapsulating agent (Tosoh Corporation, Coronate T100) were added, and after complete dispersion and mixing, the mixture was reacted at 45°C for 10 hours. Subsequently, the epoxy resin, which was the dispersion medium, was washed with toluene to obtain a microencapsulated curing agent (B-4-M).

[0112] (B-5-M) Microencapsulated hardener To 100 parts by mass of bisphenol A type epoxy resin (epoxy equivalent 186 g / eq, total chlorine content 600 ppm, hydrolyzable chlorine content 50 ppm), 100 parts by mass of curing agent core (B-5) and 5 parts by mass of encapsulating agent (Tosoh Corporation, Coronate T100) were added, and after complete dispersion and mixing, the mixture was reacted at 45°C for 10 hours. Subsequently, the epoxy resin, which was the dispersion medium, was washed with toluene to obtain a microencapsulated curing agent (B-5-M).

[0113] (B-6-M) Microencapsulated hardener To 100 parts by mass of bisphenol A type epoxy resin (epoxy equivalent 186 g / eq, total chlorine content 600 ppm, hydrolyzable chlorine content 50 ppm), 100 parts by mass of curing agent core (B-6) and 5 parts by mass of encapsulating agent (Tosoh Corporation, Coronate T100) were added, and after complete dispersion and mixing, the mixture was reacted at 45°C for 10 hours. Subsequently, the epoxy resin, which was the dispersion medium, was washed with toluene to obtain a microencapsulated curing agent (B-6-M).

[0114] (B-7-M) Microencapsulated hardener To 100 parts by mass of bisphenol A type epoxy resin (epoxy equivalent 186 g / eq, total chlorine content 600 ppm, hydrolyzable chlorine content 50 ppm), 100 parts by mass of curing agent core (B-7) and 5 parts by mass of encapsulating agent (Tosoh Corporation, Coronate T100) were added, and after complete dispersion and mixing, the mixture was reacted at 45°C for 10 hours. Subsequently, the epoxy resin, which was the dispersion medium, was washed with toluene to obtain a microencapsulated curing agent (B-7-M).

[0115] (Component (A): Epoxy resin) jER828 (manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin, epoxy equivalent: 186 g / eq)

[0116] (Component (B): Hardener) B-1 (Hydroxyl value: 230 mg KOH / g, Amine value: 200 mg KOH / g, Total chlorine content: 200 ppm) B-1-M (Hydroxyl value: 230 mg KOH / g, Amine value: 200 mg KOH / g, Total chlorine content: 200 ppm) B-2-M (Hydroxyl value: 200 mg KOH / g, Amine value: 150 mg KOH / g, Total chlorine content: 200 ppm) B-3-M (Hydroxyl value: 230 mg KOH / g, Amine value: 200 mg KOH / g, Total chlorine content: 1000 ppm) B-4-M (Hydroxyl value: 200 mg KOH / g, Amine value: 600 mg KOH / g, Total chlorine content: 200 ppm) B-5-M (Hydroxyl value: 200 mg KOH / g, Amine value: 20 mg KOH / g, Total chlorine content: 200 ppm) B-6-M (Hydroxyl value: 700 mg KOH / g, Amine value: 220 mg KOH / g, Total chlorine content: 200 ppm) B-7-M (Hydroxyl value: 0 mg KOH / g, Amine value: 183 mg KOH / g, Total chlorine content: 10 ppm)

[0117] (Component (C): Reactive diluent) PGE: Phenylglycidyl ether (viscosity at 25°C: 7 mPa·s)

[0118] [Preparation of epoxy resin composition] (Example 1) 130 parts by mass of component (A), 100 parts by mass of component (B-1-M), and 20 parts by mass of component (C) were stirred in a planetary mixer at 25°C for 30 minutes to obtain an epoxy resin composition.

[0119] (Example 2) 130 parts by mass of component (A), 100 parts by mass of component (B-2-M), and 20 parts by mass of component (C) were stirred in a planetary mixer at 25°C for 30 minutes to obtain an epoxy resin composition.

[0120] (Example 3) 130 parts by mass of component (A), 100 parts by mass of component (B-1), and 20 parts by mass of component (C) were stirred in a planetary mixer at 25°C for 30 minutes to obtain an epoxy resin composition.

[0121] (Example 4) 150 parts by mass of component (A) and 100 parts by mass of component (B-1-M) were stirred in a planetary mixer at 25°C for 30 minutes to obtain an epoxy resin composition.

[0122] (Example 5) 130 parts by mass of component (A), 100 parts by mass of component (B-3-M), and 20 parts by mass of component (C) were stirred in a planetary mixer at 25°C for 30 minutes to obtain an epoxy resin composition.

[0123] (Example 6) 130 parts by mass of component (A), 100 parts by mass of component (B-1-M), and 5 parts by mass of component (C) were stirred in a planetary mixer at 25°C for 30 minutes to obtain an epoxy resin composition.

[0124] (Example 7) 130 parts by mass of component (A), 50 parts by mass of component (B-1-M), and 20 parts by mass of component (C) were stirred in a planetary mixer at 25°C for 30 minutes to obtain an epoxy resin composition.

[0125] (Comparative Example 1) 130 parts by mass of component (A), 100 parts by mass of component (B-4-M), and 20 parts by mass of component (C) were stirred in a planetary mixer at 25°C for 30 minutes to obtain an epoxy resin composition.

[0126] (Comparative Example 2) 130 parts by mass of component (A), 100 parts by mass of component (B-5-M), and 20 parts by mass of component (C) were stirred in a planetary mixer at 25°C for 30 minutes to obtain an epoxy resin composition.

[0127] (Comparative Example 3) 130 parts by mass of component (A), 100 parts by mass of component (B-6-M), and 20 parts by mass of component (C) were stirred in a planetary mixer at 25°C for 30 minutes to obtain an epoxy resin composition.

[0128] (Comparative Example 4) 130 parts by mass of component (A), 100 parts by mass of component (B-7-M), and 20 parts by mass of component (C) were stirred in a planetary mixer at 25°C for 30 minutes to obtain an epoxy resin composition.

[0129] (Example 8) [Fabrication of conductive films] Fifteen parts by mass of bisphenol F type epoxy resin (Mitsubishi Chemical Corporation: jER YL983U), six parts by mass of phenol novolac resin (Showa Polymer Co., Ltd., trade name "BRG-558"), and four parts by mass of synthetic rubber (Nipol 1072, Nippon Zeon Co., Ltd., weight-average molecular weight 300,000) were dissolved in 20 parts by mass of a 1:1 (by mass ratio) mixed solvent of methyl ethyl ketone and butyl cellosolve acetate to obtain a solution. Seventy-four parts by mass of silver powder were mixed into this solution and further kneaded using a three-roller mixer. To this, 30 parts by mass of the epoxy resin composition obtained in (Example 1) was added and further mixed uniformly to obtain a conductive adhesive. Using the obtained conductive adhesive, it was cast onto a 40 μm thick polypropylene film and dried and semi-cured at 80°C for 60 minutes to obtain a conductive film having a 35 μm thick conductive adhesive layer. Using this conductive film, a conductive adhesive layer was transferred to the back surface of a silicon wafer on an 80°C heat block. Furthermore, the silicon wafer was fully diced, and the semiconductor chip with conductive adhesive was bonded and cured to a lead frame on the heat block at 200°C for 2 minutes. It was found that there were no conductivity issues with the chip.

[0130] (Example 9) [Preparation of conductive paste] 100 parts by mass of bisphenol F type epoxy resin (manufactured by Mitsubishi Chemical Corporation: jER YL983U), 30 parts by mass of the epoxy resin composition obtained in (Example 1), 150 g of flake-shaped silver powder with an average particle size of 14 μm and an aspect ratio of 11 (manufactured by Tokuriki Chemical Research Institute Co., Ltd.), and 60 g of flake-shaped nickel powder with an average particle size of 10 μm and an aspect ratio of 9 (manufactured by Kojunkagaku Co., Ltd., trade name "NI110104") were added, and after stirring until homogeneous, the mixture was uniformly dispersed using a three-roll machine to obtain a conductive paste. The obtained conductive paste was screen printed onto a 1.4 mm thick polyimide film substrate and then heat-cured at 200°C for 1 hour. The conductivity of the resulting wiring board was measured, and the results showed that it was a useful conductive paste.

[0131] (Example 10) [Fabrication of anisotropic conductive films] 40 parts by mass of bisphenol F type epoxy resin (manufactured by Mitsubishi Chemical Corporation: jER YL983U) and 30 parts by mass of phenoxy resin (manufactured by Toto Kasei, YP-50) were dissolved in 30 parts by mass of ethyl acetate. To this, 30 parts by mass of the epoxy resin composition obtained in (Example 1) and 5 parts by mass of conductive particles with a particle size of 8 μm (gold-plated cross-linked polystyrene) were added and mixed uniformly to obtain a one-component epoxy resin composition. This was coated onto a polyester film, and the ethyl acetate was dried off at 70°C to obtain an anisotropic conductive film. The resulting anisotropic conductive film is sandwiched between the IC chip and the electrode, and heated on a hot plate at 200°C at a rate of 30 kg / cm². 2 After performing thermocompression bonding for 20 seconds, the electrodes joined together, electrical conductivity was achieved, and the material proved useful as an anisotropic conductive material.

[0132] (Example 11) [Preparation of anisotropic conductive paste] 100 parts by mass of bisphenol F type epoxy resin (Mitsubishi Chemical Corporation: jER YL983U) and 5 parts by mass of Micropearl Au-205 (Sekisui Chemical Co., Ltd., specific gravity 2.67) as conductive particles were mixed. Then, 30 parts by mass of the epoxy resin composition obtained in (Example 1) were added and further mixed uniformly to obtain an anisotropic conductive paste. The obtained anisotropic conductive paste was applied to a low-alkali glass having ITO electrodes. The paste was bonded to a test TAB (Tape Automated Bonding) film by pressing it with a ceramic tool at 230°C under a pressure of 2 MPa for 30 seconds. When the resistance value between adjacent ITO electrodes was measured, it was found to be useful as an anisotropic conductive paste.

[0133] (Example 12) [Preparation of insulating paste] 100 parts by mass of bisphenol F type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., trade name "YL983U"), 4 parts by mass of dicyandiamide, 100 parts by mass of silica powder, 10 parts by mass of phenyl glycidyl ether as a diluent, and 1 part by mass of organic phosphate ester (manufactured by Nippon Kayaku Co., Ltd., trade name "PM-2") were thoroughly mixed and then kneaded using a three-roll mill. Furthermore, 30 parts by mass of the epoxy resin composition obtained in (Example 1) were added and further mixed uniformly, and then degassed under reduced pressure and centrifugal degassing were performed to produce an insulating paste. When a semiconductor chip was bonded to a resin substrate by heating and curing the resulting insulating paste at 200°C for 1 hour, it proved to be useful as an insulating paste.

[0134] (Example 13) [Fabrication of insulating film] 180 parts by mass of phenoxy resin (manufactured by Toto Kasei Co., Ltd., trade name "YP-50"), 40 parts by mass of cresol novolac type epoxy resin (epoxy equivalent 200 g / eq, manufactured by Nippon Kayaku Co., Ltd., trade name "EOCN-1020-80"), 300 parts by mass of spherical silica (average particle size: 2 μm, manufactured by Admatec Co., Ltd., trade name SE-5101), and 200 parts by mass of methyl ethyl ketone were mixed and uniformly dispersed. Then, 250 parts by mass of the epoxy resin composition obtained in (Example 1) were added to this mixture and further stirred and mixed to obtain a solution containing the epoxy resin composition. The obtained solution was applied to mold-release treated polyethylene terephthalate so that the thickness after drying would be 50 μm, and heated and dried in a hot air circulating dryer to obtain an insulating film for semiconductor bonding. The obtained insulating film for semiconductor bonding was cut larger than the 5-inch wafer size, along with the support substrate, and the resin film was aligned with the electrode side of a wafer with bump electrodes. Next, a support substrate with a release treatment was placed on top, and the wafer was heated and pressed in a vacuum at 70°C, 1 MPa, and a pressurization time of 10 seconds to obtain a wafer with adhesive resin. Subsequently, using a dicing saw (DISCO DAD-2H6M), the individual pieces were cut and separated at a spindle rotation speed of 30,000 rpm and a cutting speed of 20 mm / sec, and it was observed that there was no resin peeling of the semiconductor elements with adhesive film. The obtained film was useful as an insulating film.

[0135] (Example 14) [Examples of sealing material production] 100 parts by mass of bisphenol F type epoxy resin (manufactured by Mitsubishi Chemical Corporation: jER YL983U), 40 parts by mass of HN-2200 (manufactured by Hitachi Chemical Co., Ltd.), which mainly consists of phthalic anhydride, and 80 parts by mass of spherical fused silica with an average particle size of 16 μm were uniformly dispersed and blended. 5 parts by mass of the epoxy resin composition obtained in (Example 1) were added to this to obtain another epoxy resin composition. The obtained epoxy resin composition was applied to a printed circuit board in a 1 cm square area to a thickness of 60 μm and heated in an oven at 110°C for 10 minutes to partially cure it. Then, a 370 μm thick, 1 cm square silicon chip was placed on top of the partially cured epoxy resin composition, and while applying a load to bring the bump and the chip electrodes into contact and hold them, a complete curing treatment was performed at 220°C for 1 hour. The resulting epoxy resin composition was a useful encapsulant with no problems regarding appearance or electrical conductivity of the chip.

[0136] (Example 15) [Examples of coating material preparation] A solution was prepared by adding 30 parts by mass of epoxy resin, 30 parts by mass of YP-50 as phenoxy resin (manufactured by Toto Chemical Co., Ltd.), 50 parts by mass of a methyl ethyl ketone solution of methoxy group-containing silane-modified epoxy resin (manufactured by Arakawa Chemical Industries, Ltd., trade name "Compocelan E103"), and 30 parts by mass of the epoxy resin composition obtained in (Example 1) above, and then diluting and mixing with methyl ethyl ketone to 50% by mass. The prepared solution was applied to a release PET (polyethylene terephthalate) film (SG-1 manufactured by Panac Co., Ltd.) using a roll coater, and dried and cured at 150°C for 15 minutes to produce a semi-cured resin (dry film) with a release film and a film thickness of 100 μm. The dry film was heated and pressed onto the copper-clad laminate at 120°C for 10 minutes at 6 MPa, then allowed to return to room temperature to remove the release film, and cured at 200°C for 2 hours. This yielded a material useful as an interlayer insulating coating.

[0137] (Example 16) [Preparation of paint composition] 50 parts by mass of bisphenol F type epoxy resin (manufactured by Mitsubishi Chemical Corporation: jER YL983U) was mixed with 30 parts by mass of titanium dioxide and 70 parts by mass of talc. 140 parts by mass of a 1:1 mixed solvent of MIBK / xylene was added as a mixed solvent, stirred, and mixed to form the main component. 30 parts by mass of the epoxy resin composition obtained in (Example 1) were added to this mixture and uniformly dispersed to obtain a useful epoxy paint composition.

[0138] (Example 17) [Prepreg preparation] In a flask in an oil bath at 130°C, 15 parts by mass of novolac-type epoxy resin (EPICLON N-740, manufactured by Dainippon Ink and Chemicals), 40 parts by mass of bisphenol F-type epoxy resin (Epikote 4005, manufactured by JER), and 30 parts by mass of bisphenol A-type liquid epoxy resin (AER2603, manufactured by Asahi Kasei Chemicals) were dissolved and mixed, and then cooled to 80°C. Furthermore, 15 parts by mass of the epoxy resin composition obtained in (Example 1) were added, and the mixture was thoroughly stirred and mixed. The resin composition, cooled to room temperature, was then applied to release paper using a doctor knife, resulting in a resin basis of 162 g / m². 2 It was then coated to form a resin film. Next, on this resin film, a Mitsubishi Rayon CF cloth (model number: TR3110, basis weight 200g / m²) made of carbon fibers with an elastic modulus of 24 tons / mm² woven at a density of 12.5 strands / inch was applied. 2 A resin composition was impregnated into a carbon fiber cloth by layering it with polypropylene film, and then the cloth was passed between a pair of rolls at a surface temperature of 90°C to produce a cloth prepreg. The resin content was 45% by mass. The obtained prepreg was further laminated with the fiber direction aligned, and molded under curing conditions of 150°C for 1 hour to obtain an FRP molded article with carbon fibers as reinforcing fibers, and the produced prepreg proved to be useful.

[0139] (Example 18) [Preparation of thermally conductive epoxy resin compositions] 100 parts by mass of bisphenol F type epoxy resin (Mitsubishi Chemical Corporation: jER YL983U), 40 parts by mass of a 50% methyl ethyl ketone solution of phenol novolac resin (Arakawa Chemical Industries, Ltd., trade name "Tamanol 759") as a curing agent for epoxy resins, and 15 parts by mass of flake-shaped graphite powder (Union Carbide Corporation, trade name HOPG) were mixed until homogeneous and then uniformly dispersed using a three-roll roller. To this, 15 parts by mass of the epoxy resin composition obtained in (Example 1) was added and thoroughly mixed to form a conductive paste. A semiconductor chip (1.5 mm square, 0.8 mm thick) was mounted on a Cu lead frame using the obtained conductive paste, and the paste was heat-cured at 150°C for 30 minutes to obtain an evaluation sample. The thermal conductivity of the obtained sample was measured using the laser flash method. Specifically, the thermal conductivity K was calculated from the measured thermal diffusivity α, specific heat Cp, and density σ using the following formula: K = α × Cp × σ, and the result was K = 5 × 10⁻⁶ -3 It had a thermal conductivity of over cal / cm·sec·℃, making it useful as a thermally conductive paste.

[0140] (Example 19) [Manufacturing of sealing materials for fuel cells] A raw material consisting of 100 parts by mass of biphenyl-type epoxy resin 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenylglycidyl ether (Epicoat YX-4000, manufactured by Japan Epoxy Resin, epoxy equivalent 195), 60 parts by mass of phenol novolac resin (TD-2131, manufactured by Dainippon Ink), 10 parts by mass of bisphenol F-type epoxy resin (JER YL983U, manufactured by Mitsubishi Chemical Corporation), 800 parts by mass of artificial graphite (SGP, manufactured by SEC, average particle size 75 μm), a mold release agent (calcium stearate), and a lubricant (carnauba wax) was mixed in a mixer. Then, 10 parts by mass of the epoxy resin composition obtained in (Example 1) was added and the mixture was uniformly mixed using a three-roll mixer. The obtained material was pressure-molded in a mold for fuel cell separator material at a molding pressure of 25 MPa, a molding temperature of 150°C, and a molding time of 15 minutes to obtain an evaluation sample. The bending strength of the obtained fuel cell separator material was measured in accordance with JIS K 7203 and showed a bending strength of 50 MPa. Furthermore, when gas permeability was measured using nitrogen gas according to the JIS K7126A method, the gas permeability was 0.6 cm². 3 / m 2 It had a 24-hour atm rating and was useful as a separator material for fuel cells.

[0141] [Methods for measuring and evaluating characteristics] (Viscosity of epoxy resin composition) The viscosity of the epoxy resin compositions prepared according to Examples 1-7 and Comparative Examples 1-4 described above was measured using an E-type viscometer at a temperature of 25°C.

[0142] (Evaluation of varnish storage stability) A solution was prepared by mixing and dissolving 50 parts by mass of phenoxy resin (InChem, trade name "PKHB"), 50 parts by mass of bisphenol A type liquid epoxy resin (Mitsubishi Chemical Corporation, trade name "jER828"), 30 parts by mass of phenol curing agent (UBE, trade name "HF-1M"), 10 parts by mass of epoxy resin compositions prepared according to Examples 1-7 and Comparative Examples 1-4 described above, and 100 parts by mass of MEK (methyl ethyl ketone). The viscosity of the mixture immediately after preparation (n1) and the viscosity after the mixture was placed in a sealed container and left to stand at 25°C for 5 days (n2) were measured using an E-type viscometer at 25°C. The viscosity ratio (n2 / n1) was calculated by comparing the two viscosities (n1) and (n2). The viscosity ratio was evaluated according to the following criteria based on the viscosity ratio. <Evaluation Criteria> Thickening ratio <1.3 times ····◎ 1.3 times ≤ Thickening ratio < 1.5 times ····〇 1.5 times ≤ Thickening ratio < 1.7 times ····△ 1.7 times ≤ Thickening ratio ····×

[0143] (Evaluation of film storage stability) A solution was prepared by mixing and dissolving 50 parts by mass of phenoxy resin (manufactured by InChem, trade name "PKHB"), 50 parts by mass of bisphenol A type liquid epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name "jER828"), 30 parts by mass of phenol curing agent (manufactured by UBE, trade name "HF-1M"), and 100 parts by mass of MEK. A curable resin composition was prepared by mixing 2 parts by mass of the epoxy resin composition prepared according to Examples 1 to 7 and Comparative Examples 1 to 4 described above with 100 parts by mass of this solution. This curable resin composition was coated onto an easily peelable polyethylene terephthalate film (50 μm thick) to a dry film thickness of 40 μm, and then heated and dried in an oven preheated to 120°C for 5 minutes to obtain a film-type epoxy resin composition. Subsequently, the film-type epoxy resin composition was stored in an incubator at 40°C for 7 days. The FT-IR spectra of the film-type epoxy resin composition before and after storage were measured using a Fourier transform infrared spectrophotometer (FT / IR-6600, manufactured by JASCO Corporation). Epoxy resins and phenoxy resins that do not change in strength upon heat drying have methylene groups derived from 2920 cm². -1 Using the nearby absorption P1 as a reference, the epoxy group-derived 915 cm⁻¹ -1 The strength ratio P2 / P1 with the nearby absorbent P2 was compared before and after storage, and the epoxy consumption rate was calculated using the following formula. Note that P10 and P20 in the following formula represent the strength after storage. Epoxy consumption rate = 100 - [(P20 / P10) / (P2 / P1)] × 100 The following criteria were used to evaluate the epoxy consumption rate after storage. <Evaluation Criteria> Epoxy consumption rate <20% ····◎ 20% ≤ Epoxy consumption rate < 35% ····〇 35% ≤ Epoxy consumption rate < 50% ····△ 50% or less epoxy consumption rate ····×

[0144] (Evaluation of film curing properties) A solution was prepared by mixing and dissolving 50 parts by mass of phenoxy resin (manufactured by InChem, trade name "PKHB"), 50 parts by mass of bisphenol A type liquid epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name "jER828"), 30 parts by mass of phenol curing agent (manufactured by UBE, trade name "HF-1M"), and 100 parts by mass of MEK. A curable resin composition was prepared by mixing 2 parts by mass of the epoxy resin composition prepared according to Examples 1 to 7 and Comparative Examples 1 to 4 described above with 100 parts by mass of this solution. This curable resin composition was coated onto an easily peelable polyethylene terephthalate film (50 μm thick) to a dry film thickness of 40 μm, and then heated and dried in an oven preheated to 120°C for 5 minutes to obtain the film. After curing the aforementioned film in an oven at 130°C for 30 minutes, the epoxy reaction rate was evaluated using a differential scanning calorimetry system (DSC7020, manufactured by Hitachi High-Tech Science Corporation) by measuring the change in total heat generated when the sample amount of 10 mg was heated from 30°C to 250°C at a heating rate of 10°C / min. The epoxy reaction rate relative to the total heat generated before curing was evaluated according to the following criteria. <Evaluation Criteria> 90% epoxy reaction rate ···◎ 70% < Epoxy reaction rate ≤ 90% ···〇 50% < Epoxy reaction rate ≤ 70% ···△ Curing rate ≦50% ···×

[0145] (Evaluation of film strength) A solution was prepared by mixing and dissolving 50 parts by mass of phenoxy resin (manufactured by InChem, trade name "PKHB"), 50 parts by mass of bisphenol A type liquid epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name "jER828"), and 100 parts by mass of MEK. A curable resin composition was prepared by mixing 15 parts by mass of the epoxy resin composition prepared according to Examples 1 to 7 and Comparative Examples 1 to 4 described above with 100 parts by mass of this solution. This curable resin composition was coated onto an aluminum film (100 μm thick) to a dry film thickness of 200 μm, and then heated and dried in an oven preheated to 120°C for 5 minutes to obtain a film. The aforementioned film was heated for 1 hour in a small high-temperature chamber "ST-110B2" manufactured by ESPEC Corporation, which maintains a stable internal temperature of 150°C, to obtain a test specimen for measuring film strength. After cooling to room temperature, the maximum load at which the film broke and separated was measured using a Shimadzu AGX-5kNX load cell at a speed of 5 mm / min with a load cell of 5 kN. The film strength was defined as the maximum load at which separation occurred divided by the film's cross-sectional area. The film strength was evaluated according to the following criteria. <Evaluation Criteria> Film strength > 50 MPa ····◎ 30 MPa ≤ Film Strength < 50 MPa ····〇 10 MPa ≤ Film Strength ≤ 30 MPa ····△ 10 MPa ≤ Film Strength ····×

[0146] The evaluation results for Examples 1 to 7 are shown in Table 1 below.

[0147] [Table 1]

[0148] As shown in Table 1, Example 1, which used a microencapsulated curing agent, was found to have better film storage stability and varnish storage stability compared to Comparative Example 3. Furthermore, Example 1, which included component (C), showed increased varnish storage stability and film storage stability compared to Example 4, which did not include component (C). Example 1, in which the chlorine content of component (B) was 500 ppm or less, showed increased stability and curability compared to Example 5, in which the chlorine content exceeded 500 ppm. Example 1, which had a viscosity of less than 100 Pa·s at 25°C, showed increased stability and film strength compared to Example 6, which had a viscosity of 100 Pa·s or more. Example 1, in which component (B) was present in an amount of 50 parts by mass or more and 100 parts by mass or less per 100 parts by mass of component (A), showed increased curability and film strength compared to Example 7, in which component (B) was present in an amount of less than 50 parts by mass.

[0149] The evaluation results for Comparative Examples 1-4 are shown in Table 2 below.

[0150] [Table 2]

[0151] As shown in Table 2, Comparative Example 1, which had a high amine value, showed significantly worse stability compared to Example 1. Comparative Example 2, which had a lower amine value, showed significantly worse curability and film strength compared to Example 1. Comparative Example 3, which had a high hydroxyl value, showed significantly worse stability compared to Example 1. Comparative Example 4, which had a lower hydroxyl value, exhibited worse varnish storage stability, film storage stability, and film strength compared to Example 1. [Industrial applicability]

[0152] The epoxy resin composition of the present invention has industrial applicability as various film materials and paste materials such as insulating adhesive films or pastes, sealing sheets, conductive films or pastes, anisotropic conductive films or pastes, and thermally conductive films or pastes, as well as various coating materials and paints.

Claims

1. (A) Epoxy resin and (B) An epoxy resin composition comprising a curing agent, The curing agent (B) has a hydroxyl value of 50 to 500 mg KOH / g and an amine value of 180 to 500 mg KOH / g. The epoxy resin (A) includes a bisphenol-type epoxy resin, The curing agent (B) comprises an amine adduct, The content of the curing agent (B) is 50 to 100 parts by mass per 100 parts by mass of the epoxy resin (A). Epoxy resin composition.

2. (C) Further comprising a reactive diluent, The epoxy resin composition according to claim 1.

3. The curing agent (B) is a microencapsulated curing agent in which the surface of the core is covered with a shell. The epoxy resin composition according to claim 1.

4. The viscosity at 25°C is 100 Pa·s or less. The epoxy resin composition according to claim 1.

5. A composition containing the epoxy resin composition according to any one of claims 1 to 4, A paste-like composition.

6. A composition containing the epoxy resin composition according to any one of claims 1 to 4, A film-like composition.

7. A composition containing the epoxy resin composition according to any one of claims 1 to 4, glue.

8. A composition containing the epoxy resin composition according to any one of claims 1 to 4, Bonding paste.

9. A composition containing the epoxy resin composition according to any one of claims 1 to 4, Bonding film.

10. A composition containing the epoxy resin composition according to any one of claims 1 to 4, Conductive material.

11. A composition containing the epoxy resin composition according to any one of claims 1 to 4, Anisotropic conductive material.

12. A composition containing the epoxy resin composition according to any one of claims 1 to 4, Insulating material.

13. A composition containing the epoxy resin composition according to any one of claims 1 to 4, Sealing material.

14. A composition containing the epoxy resin composition according to any one of claims 1 to 4, Coating material.

15. A composition containing the epoxy resin composition according to any one of claims 1 to 4, Paint composition.

16. A composition containing the epoxy resin composition according to any one of claims 1 to 4, Prepreg.

17. A composition containing the epoxy resin composition according to any one of claims 1 to 4, Thermally conductive material.

18. A composition containing the epoxy resin composition according to any one of claims 1 to 4, Separator material for fuel cells.

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