Epoxy resin composition, film, method for producing film, and cured product

Abstract

This epoxy resin composition comprises: a component (A) which is an epoxy resin; a component (B) which is a microcapsule-type curing agent; a component (C) which is a reactive diluent; and a component (D) which is a compound represented by formula (1). (In formula (1), X1 has two to five consecutive carbon-carbon bonds, and the substituent of carbon contained in X1, and R1-R5 are each one selected from the group consisting of hydrogen, an alkyl group, an unsaturated aliphatic group, an aromatic group, a heteroatom-containing substituent, a halogen atom-containing substituent, and a halogen atom. The substituent of carbon contained in X1, and R1-R5 may be the same as or different from each other. Moreover, one selected from among R1-R5 may be a fused ring compound present in the same ring.)

Description

[Technical field]

[0001] The present invention relates to an epoxy resin composition, a film, a method for producing the film, and a cured product. [Background technology]

[0002] Epoxy resins have traditionally been used in a wide range of applications, such as insulating materials for electric and electronic components, sealing materials, adhesives, conductive materials, matrix resins for fiber-reinforced plastics, and impregnating and fixing agents for motor coils.

[0003] The demands for electronic devices today are diverse, including miniaturization, high functionality, light weight, and multi-function, and in semiconductor chip mounting technology, the electrode pads and pad pitches are becoming finer, smaller, and more dense, while the semiconductor chips are also becoming larger. In the gap between the semiconductor chip and the substrate, there is an underfill material that protects the bump connections and the circuit surface of the chip, and an epoxy resin composition is used as the underfill material.

[0004] As an epoxy resin composition applicable to an underfill material, for example, a one-liquid type epoxy resin composition containing microencapsulated amine / epoxy adduct particles and a reactive diluent, which is excellent in storage stability, curing characteristics, physical properties of the cured product, and low viscosity, has been disclosed (for example, see Patent Document 1). Furthermore, for example, a one-component epoxy resin composition has been disclosed that includes a microcapsule-type curing agent having an epoxy resin curing agent containing two or more types of amine compounds as a core, and a thermosetting liquid resin having a viscosity at 25°C of 0.03 Pa·s or more and less than 3 Pa·s, and that has excellent storage stability, low-temperature curing property, and gap penetration property (for example, see Patent Document 2). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent No. 3454437 [Patent Document 2] Patent No. 6085130 Summary of the Invention [Problem to be solved by the invention]

[0006] In recent years, the underfill material for the gap between the semiconductor chip and the substrate as described above is required to have low viscosity to enable sufficient penetration in a short time in order to accommodate the larger area of ​​the semiconductor chip due to its larger size and the narrow gap due to the finer pitch of the semiconductor chip. In addition, the underfill material is required to have sufficient hardening properties at low temperatures, for example, at around 100°C, in order to reduce the impact on the components of the semiconductor chip. Furthermore, from the viewpoint of improving productivity, the underfill material is required to be a one-component epoxy resin composition that does not require a mixing step during use. However, since the one-component epoxy resin composition contains an epoxy resin and a curing agent in one body, high storage stability is required. That is, there is a demand for a one-component epoxy resin composition that simultaneously has a high level of low viscosity, sufficient curability at about 100° C., and high storage stability.

[0007] In recent years, with the miniaturization and thinning of electronic materials, the importance of films using epoxy resin compositions has increased in order to make adhesive layers and insulating layers thinner. In order to obtain the film, a coating liquid is prepared by dissolving components such as an epoxy resin, a curing agent, a curing accelerator, and a polymer for film formation in a solvent, and the coating liquid is applied to a predetermined support, followed by drying to produce the film. Therefore, the coating liquid is strongly required to have storage stability as a coating liquid, stability during the film production process when the coating liquid is applied and dried, and stability in the film state.

[0008] With regard to the various requirements for epoxy resin compositions as described above, the one-component epoxy resin compositions disclosed in Patent Documents 1 and 2 have problems in that there is still room for improvement in terms of achieving both curability and storage stability, and there is also still room for improvement in terms of the stability during the production process of films using these epoxy resin compositions and the stability in the film state.

[0009] In view of the above-mentioned problems in the conventional art, the present invention aims to obtain an epoxy resin composition which simultaneously exhibits low viscosity, sufficient curability at about 100°C and excellent storage stability, and also to provide an epoxy resin composition which is excellent in stability during the production process of a film using the epoxy resin composition and in the state of the film. [Means for solving the problem]

[0010] As a result of extensive research, the present inventors have found that the above object can be achieved by the following technical means, and have completed the present invention. That is, the present invention is as follows.

[0011] [1] Component (A): epoxy resin, Component (B): a microcapsule type hardener; Component (C): a reactive diluent; Component (D): a compound represented by the following formula (1), An epoxy resin composition comprising:

[0012] [ka]

[0013] (In formula (1), X1 has 2 to 5 consecutive carbon-carbon bonds, and the carbon substituents included in X1 and R1 to R5 are each one selected from the group consisting of hydrogen, an alkyl group, an unsaturated aliphatic group, an aromatic group, a substituent containing a heteroatom, a substituent containing a halogen atom, and a halogen atom. The carbon substituents included in X1 and R1 to R5 may be the same or different. In addition, the compound may be a fused ring compound in which any one selected from R1 to R5 is present in the same ring.)

[0014] [2] The epoxy resin composition according to the above item [1], wherein the component (D) is a compound represented by the following formula (2):

[0015] [ka]

[0016] (In formula (2), X2 has two or more and four or less consecutive carbon-carbon bonds, and the carbon substituents included in X2 and R1 to R5 are each one selected from the group consisting of hydrogen, an alkyl group, an unsaturated aliphatic group, an aromatic group, a substituent containing a heteroatom, a substituent containing a halogen atom, and a halogen atom. The carbon substituents included in X2 and R1 to R5 may be the same or different. In addition, the compound may be a fused ring compound in which any one selected from R1 to R5 is present in the same ring.)

[0017] [3] The epoxy resin composition according to the above item [1] or [2], wherein the component (D) is a compound represented by the following formula (3):

[0018] [ka]

[0019] In formula (3), R1 to R9 are each one selected from the group consisting of hydrogen, an alkyl group, an unsaturated aliphatic group, an aromatic group, a substituent containing a heteroatom, a substituent containing a halogen atom, and a halogen atom. R1 to R9 may be the same or different. In addition, any one selected from R1 to R5 may be present in the same ring in a fused ring compound.

[0020] [4] The epoxy resin composition according to any one of [1] to [3] above, wherein the component (D) is a compound represented by the following formula (4):

[0021] [ka]

[0022] In formula (4), R1 to R8 are each one selected from the group consisting of hydrogen, an alkyl group, an unsaturated aliphatic group, an aromatic group, a substituent containing a heteroatom, a substituent containing a halogen atom, and a halogen atom. R1 to R8 may be the same or different. In addition, any one selected from R1 to R5 may be present in the same ring in a fused ring compound.

[0023] [5] The epoxy resin composition according to any one of [1] to [4], wherein the component (A) epoxy resin contains at least a bisphenol F type epoxy resin. [6] The epoxy resin composition according to any one of [1] to [5] above, wherein the component (B) microcapsule-type curing agent has a core circularity of 0.93 or more. [7] The epoxy resin composition according to any one of [1] to [6], wherein the component (C) reactive diluent is a compound having an aromatic ring. [8] The epoxy resin composition according to any one of [1] to [7], wherein the component (C) reactive diluent is a monofunctional compound in which the aromatic ring is a monocyclic ring. [9] The epoxy resin composition according to any one of [1] to [8], wherein the content of the component (C) reactive diluent in the epoxy resin composition is 1% by mass or more and 20% by mass or less.

[10] The epoxy resin composition according to any one of [1] to [9], wherein the content of the component (D) in the epoxy resin composition is 0.001% by mass or more and 5% by mass or less.

[11] The epoxy resin composition according to any one of the above [1] to

[10] , wherein R1 to R5 do not contain an epoxy group or a structure of the following formula (5) (terminal diol):

[0024] [ka]

[0025]

[12] A film having a support and a resin composition layer formed on the support, the resin composition layer comprising the epoxy resin composition according to any one of [1] to

[11] .

[13] The film according to

[12] above, wherein the resin composition layer further contains component (E): a film-forming polymer.

[14] The film is The film according to

[12] or

[13] above, which is any one selected from the group consisting of an interlayer insulating film, a film-type solder resist, an encapsulating sheet, a conductive film, an anisotropic conductive film, and a thermally conductive film.

[15] A method for producing a film according to any one of

[12] to

[14] , A method for producing a film, comprising a step of applying a preparation containing at least any one of the epoxy resin compositions [1] to

[11] above and an organic solvent as component (F) onto the support, and then drying the organic solvent as component (F) at a temperature in the range of 50 to 160°C for a time in the range of 1 to 30 minutes.

[16] A cured product of the epoxy resin composition according to any one of [1] to

[11] above.

[17] A cured product of the film according to any one of

[12] to

[14] above. Effect of the Invention

[0026] According to the present invention, it is possible to provide an epoxy resin composition which has low viscosity, sufficient curability at about 100°C, excellent storage stability, and when applied to a film, has excellent stability during the film production process and in the film state. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0027] Hereinafter, an embodiment of the present invention (hereinafter, referred to as "the present embodiment") will be described in detail. The following embodiments are merely illustrative for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be modified appropriately within the scope of the gist thereof.

[0028] [Epoxy resin composition] The epoxy resin composition of the present embodiment comprises: Component (A): epoxy resin, Component (B): a microcapsule type hardener; Component (C): a reactive diluent; Component (D): a compound represented by the following formula (1), Includes.

[0029] [ka]

[0030] In formula (1), X1 has 2 to 5 consecutive carbon-carbon bonds, and the carbon substituents contained in X1 and R1 to R5 are each one selected from the group consisting of hydrogen, an alkyl group, an unsaturated aliphatic group, an aromatic group, a substituent containing a heteroatom, a substituent containing a halogen atom, and a halogen atom. The carbon substituents contained in X1 and R1 to R5 may be the same or different. In addition, it may be a fused ring compound in which any one selected from R1 to R5 is present in the same ring.

[0031] (Component (A): Epoxy resin) The epoxy resin composition of the present embodiment contains component (A): an epoxy resin (hereinafter, may be referred to as (A) epoxy resin or component (A)). Examples of the epoxy resin (A) include, but are not limited to, 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, phenyl benzoate 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 hydrochloride ... bifunctional epoxy resins such as quinone type epoxy resins, dibutylhydroquinone type epoxy resins, resorcin type epoxy resins, methylresorcin 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; multifunctional 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 may be used alone or in combination of two or more thereof. Furthermore, epoxy resins modified with isocyanate or the like may also be used in combination.

[0032] The epoxy resin composition of the present embodiment preferably contains a bisphenol type epoxy resin from the viewpoints of handleability and heat resistance, more preferably contains a bisphenol F type epoxy resin from the viewpoints of imparting storage stability and good reactivity, and further preferably contains a bisphenol A type epoxy resin from the viewpoint of imparting sufficient mechanical properties. Furthermore, by including a bisphenol A type epoxy resin in addition to a bisphenol F type epoxy resin, better storage stability and good reactivity are exhibited. The mechanism is considered to be as follows, although it is not intended to be limiting. By including a bisphenol A type epoxy resin, aggregation between the bisphenol F type epoxy resins is suppressed, so that the uniformity of the epoxy resin composition of this embodiment is improved and storage stability is improved, and at the same time, the reactivity is improved by increasing the diffusivity of the molecules after the start of curing. When bisphenol F type epoxy resin and bisphenol A type epoxy resin are used in combination, the amount of bisphenol F type epoxy resin added is preferably 5 parts by mass or more, more preferably 15 parts by mass or more, even more preferably 25 parts by mass or more, even more preferably 30 parts by mass or more, and even more preferably 40 parts by mass or more, based on 100 parts by mass of the total of bisphenol F type epoxy resin and bisphenol A type epoxy resin, from the viewpoint of fully expressing the above-mentioned effect. Also, from the viewpoint of adding bisphenol A type epoxy resin to express sufficient mechanical properties, the amount of bisphenol F type epoxy resin added is preferably 90 parts by mass or less, more preferably 85 parts by mass or less, and even more preferably 80 parts by mass or less.

[0033] From the viewpoint of obtaining an epoxy resin composition having excellent electrical properties and an excellent balance between curability and storage stability, the total chlorine content in the epoxy resin (A) is preferably 2500 ppm or less, more preferably 2000 ppm or less, even more preferably 1500 ppm or less, and still more preferably 900 ppm or less. Moreover, from the viewpoint of achieving a predetermined technical significance, the total chlorine content in the epoxy resin (A) is preferably 0.01 ppm or more, more preferably 0.02 ppm or more, even more preferably 0.05 ppm or more, still more preferably 0.1 ppm or more, still more preferably 0.2 ppm or more, and particularly preferably 0.5 ppm or more.

[0034] The total amount of chlorine contained in the epoxy resin (A) refers to the total amount of organic chlorine and inorganic chlorine contained in the epoxy resin (A), and is a value based on the mass of the epoxy resin (A). (A) The total chlorine content of an epoxy resin is measured by the following method. (A) The epoxy resin is washed with xylene, and washing and filtration are repeated until the epoxy resin disappears from the xylene washing solution. Next, the filtrate is distilled under reduced pressure at 100°C or less to obtain the epoxy resin. 1 to 10 g of the obtained epoxy resin sample is precisely weighed out so that the titer is 3 to 7 mL, dissolved in 25 mL of ethylene glycol monobutyl ether, and 25 mL of 1N KOH propylene glycol solution is added to this, boiled for 20 minutes, and then titrated with an aqueous silver nitrate solution to calculate the titer.

[0035] Here, the chlorine contained in the 1,2-chlorohydrin group among the total chlorine is generally called hydrolyzable chlorine. The amount of hydrolyzable chlorine in the (A) epoxy resin is preferably 100 ppm or less, more preferably 50 ppm or less, even more preferably 0.01 to 20 ppm, and even more preferably 0.05 to 10 ppm. When the amount of hydrolyzable chlorine in the (A) epoxy resin is 100 ppm or less, it is advantageous from the viewpoint of achieving both high curability and storage stability in the epoxy resin composition of the present embodiment, and the cured product of the epoxy resin composition of the present embodiment tends to exhibit excellent electrical properties.

[0036] Here, (A) the hydrolyzable chlorine in the epoxy resin is measured by the following method. The titer can be calculated from the amount of titration obtained by dissolving 3 g of a sample in 50 mL of toluene, adding 20 mL of a 0.1 N KOH methanol solution, and boiling for 15 minutes with an aqueous silver nitrate solution.

[0037] (Component (B): Microcapsule type hardener) The epoxy resin composition of the present embodiment contains component (B): a microcapsule-type curing agent (hereinafter, may be referred to as (B) microcapsule-type curing agent or component (B)). The (B) microcapsule type curing agent is a curing agent having at least a core containing a curing agent component and a shell covering the core. Since the component (B) is of microcapsule type, the curing agent component is physically isolated from the above-mentioned (A) epoxy resin, the component (C) (described later): a reactive diluent, and the component (D) (described later): a specific compound, via the capsule membrane, and therefore tends to have excellent storage stability.

[0038] <Core> The core constituting the (B) microcapsule type curing agent may be any curing agent used in epoxy resins, and is not particularly limited, but examples thereof include amine-based curing agents, amide-based curing agents, phenol-based curing agents, acid anhydride-based curing agents, catalyst-based curing agents, and modified products thereof. These may be used alone or in combination of two or more.

[0039] Examples of the amine-based curing agent include, but are not limited to, amine adduct-based, modified polyamine-based, aliphatic polyamine-based, heterocyclic polyamine-based, alicyclic polyamine-based, aromatic amine-based, polyamidoamine-based, ketimine-based, and urethane amine-based agents.

[0040] Examples of the amide-based curing agent include, but are not limited to, dicyandiamide and its derivatives, such as guanidine-based compounds, compounds in which an acid anhydride is added to an amine-based compound, and hydrazide-based compounds. Examples of hydrazide compounds include, but are not limited to, succinic acid dihydrazide, adipic acid dihydrazide, phthalic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, p-oxybenzoic acid hydrazide, salicylic acid hydrazide, phenylaminopropionic acid hydrazide, and maleic acid dihydrazide. Examples of guanidine compounds include, but are not limited to, dicyandiamide, methyl guanidine, ethyl guanidine, propyl guanidine, butyl guanidine, dimethyl guanidine, trimethyl guanidine, phenyl guanidine, diphenyl guanidine, and toluyl guanidine.

[0041] Examples of the phenol-based curing agent include, but are not limited to, phenol novolac resin, cresol novolac resin, phenol aralkyl resin, cresol aralkyl resin, naphthol aralkyl resin, biphenyl-modified phenol resin, biphenyl-modified phenol aralkyl resin, dicyclopentadiene-modified phenol resin, aminotriazine-modified phenol resin, naphthol novolac resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolac resin, and allyl acryl phenol resin.

[0042] Examples of acid anhydride curing agents include, but are not limited to, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride.

[0043] Examples of catalyst-type curing agents include, but are not limited to, cationic thermosetting catalysts, BF3-amine complexes, and the like.

[0044] Among the various curing agents constituting the core described above, an amine-based curing agent containing a low molecular weight amine compound (a1) and an amine adduct is preferred from the viewpoint of having appropriate reactivity.

[0045] Examples of the low molecular weight amine compound (a1) constituting the amine curing agent include a compound having at least one primary amino group and / or secondary amino group but no tertiary amino group, and a compound having at least one tertiary amino group and at least one active hydrogen group.

[0046] Examples of the "compound having at least one primary amino group and / or secondary amino group but no tertiary amino group" include, but are not limited to, primary amines having no tertiary amino group, such as methylamine, ethylamine, propylamine, butylamine, ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, ethanolamine, propanolamine, cyclohexylamine, isophoronediamine, aniline, toluidine, diaminodiphenylmethane, diaminodiphenylsulfone, etc.; secondary amines having no tertiary amino group, such as dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, dimethanolamine, diethanolamine, dipropanolamine, dicyclohexylamine, piperidine, piperidone, diphenylamine, phenylmethylamine, phenylethylamine, etc.

[0047] The "compound having at least one tertiary amino group and at least one active hydrogen group" is not limited to the following, but examples thereof include 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, Aminophenols such as 6-tris(dimethylaminomethyl)phenol; 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-aminoethyl-2-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazole, Imidazoles such as 1-(2-hydroxy-3-butoxypropyl)-2-ethyl-4-methylimidazole; 1-(2-hydroxy-3-phenoxypropyl)-2-phenylimidazoline, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazoline, 2-methylimidazoline, 2,4-dimethylimidazoline, 2-ethylimidazoline, 2-ethyl-4-methylimidazoline, 2-benzylimidazoline, 2-phenylimidazoline, 2-(o-tolyl)-imidazoline, tetramethylene-bis-imidazoline, imidazolines such as 1,1,3-trimethyl-1,4-tetramethylene-bis-imidazoline, 1,3,3-trimethyl-1,4-tetramethylene-bis-imidazoline, 1,1,3-trimethyl-1,4-tetramethylene-bis-4-methylimidazoline, 1,3,3-trimethyl-1,4-tetramethylene-bis-4-methylimidazoline, 1,2-phenylene-bis-imidazoline, 1,3-phenylene-bis-imidazoline, 1,4-phenylene-bis-imidazoline, and 1,4-phenylene-bis-4-methylimidazoline;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.

[0048] Among these low molecular weight amine compounds (a1), imidazoles are preferred from the viewpoint of having appropriate reactivity.

[0049] Next, examples of the amine adduct constituting the amine-based curing agent include compounds having an amino group obtained by reacting each of a carboxylic acid compound, a sulfonic acid compound, a urea compound, an isocyanate compound, and an epoxy resin (e1) with an amine compound (a2).

[0050] Examples of the carboxylic acid compound include, but are not limited to, succinic acid, adipic acid, sebacic acid, phthalic acid, and dimer acid. The sulfonic acid compound is not limited to the following, but examples thereof include ethanesulfonic acid, p-toluenesulfonic acid, and the like. Examples of the urea compound include, but are not limited to, urea, methyl urea, dimethyl urea, ethyl urea, and t-butyl urea.

[0051] The isocyanate compound is not limited to the following, but examples thereof include aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, aliphatic triisocyanates, polyisocyanates, and the like. Examples of the aliphatic diisocyanate include, but are not limited to, ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate. Examples of alicyclic diisocyanates include, but are not limited to, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, norbornane diisocyanate, 1,4-isocyanatocyclohexane, 1,3-bis(isocyanatomethyl)-cyclohexane, and 1,3-bis(2-isocyanatopropyl-2-yl)-cyclohexane. Examples of aromatic diisocyanates include, but are not limited to, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylene diisocyanate, 1,5-naphthalene diisocyanate, and the like. Examples of the aliphatic triisocyanate include, but are not limited to, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyl octane, and 1,3,6-triisocyanate methyl hexane. Examples of the polyisocyanate include, but are not limited to, polymethylene polyphenyl polyisocyanate and polyisocyanates derived from the diisocyanate compounds. Examples of the polyisocyanate derived from the diisocyanate compounds include isocyanurate type polyisocyanate, biuret type polyisocyanate, urethane type polyisocyanate, allophanate type polyisocyanate, carbodiimide type polyisocyanate, etc.

[0052] Examples of the epoxy resin (e1) include the compounds described above in ((A) Epoxy resin).

[0053] As the amine compound (a2), the amine compounds given as examples of the low molecular weight amine compound (a1) constituting the above-mentioned amine-based curing agent can be used.

[0054] Among these amine adducts, those obtained by reacting an epoxy resin (e1) with an amine compound (a2) are particularly preferred. The amine adduct obtained by reacting an epoxy resin (e1) with an amine compound (a2) is also preferred from the viewpoint that the unreacted amine compound (a2) can be reused as the low molecular weight amine compound (a1).

[0055] From the viewpoint of storage stability, it is preferable that the core component of the microcapsule-type hardener (B) contains a hardener that is solid at 25° C. and 1013 hPa. This prevents the core component from leaching out of the capsule even if the capsule is damaged when the components are mixed, and maintains storage stability.

[0056] The average particle diameter of the core constituting the (B) microcapsule type curing agent is preferably greater than 0.3 μm and less than 12 μm. When the average particle diameter of the core is greater than 0.3 μm, the aggregation of the cores can be further prevented, the formation of the (B) microcapsule type curing agent can be further facilitated, and the effect of the epoxy resin composition of this embodiment having sufficient storage stability for practical use can be obtained. When the average particle diameter of the core is less than 12 μm, a homogeneous cured product can be obtained when the epoxy resin composition of this embodiment is cured. In addition, when the average particle diameter of the core is less than 12 μm, the generation of large particle aggregates can be prevented when the epoxy resin composition of this embodiment is blended with a diluent, a filler, a pigment, a dye, a flow control agent, a thickener, a reinforcing agent, a release agent, a wetting agent, a stabilizer, a flame retardant, a surfactant, an organic solvent, a conductive fine particle, a crystalline alcohol, other resins, etc., and the like, and sufficient long-term reliability of the cured product can be obtained. The average particle diameter of the core is preferably greater than 0.3 μm as a lower limit, more preferably 0.4 μm or more, and even more preferably 0.5 μm or more. The upper limit is preferably 12 μm or less, more preferably 10 μm or less, and even more preferably 9 μm or less.

[0057] The average particle diameter of the cores refers to the average particle diameter defined as the median diameter, more specifically, the Stokes diameter measured by a laser diffraction / light scattering method using a particle size distribution analyzer (HORIBA LA-920, manufactured by HORIBA, Ltd.).

[0058] Methods for controlling the average particle size of the cores to fall within the above-mentioned numerical range include, but are not limited to, a method of precisely controlling the grinding process of the lump hardener, a method of carrying out a coarse grinding process and a fine grinding process as the grinding process of the lump hardener, and further classifying the lump hardener into a desired average particle size using a precise classification device, and a method of spray-drying a solution in which the lump hardener is dissolved in a solvent. As the apparatus used for pulverization, for example, a ball mill, an attritor, a bead mill, a jet mill, etc. can be adopted as necessary, but it is preferable to use an impact type pulverization apparatus. As the impact type pulverization apparatus, for example, jet mills such as a swirling flow powder collision type jet mill and a powder collision type counter jet mill can be mentioned. A jet mill is an apparatus that uses a high-speed jet flow using air or the like as a medium to collide solid materials with each other to make them fine particles. As a method for performing precise control in the pulverization process, a method of controlling the temperature, humidity, pulverization amount per unit time, etc. during pulverization can be mentioned. As a method for obtaining a desired average particle size by classification using a precise classification device after the pulverization process, for example, a method of classifying using a sieve (for example, a standard sieve such as 325 mesh or 250 mesh) or a classifier to obtain a powder or granular material of a predetermined average particle size by classification after pulverization, a method of classifying by wind force according to the specific gravity of the particles, etc. can be mentioned. As the classifier used, a wet classifier or a dry classifier can be mentioned, but in general, a dry classifier is preferable. Examples of such classifiers include the "Elbow Jet" manufactured by Nittetsu Mining Co., Ltd., the "Fine Sharp Separator" manufactured by Hosokawa Micron Corporation, the "Variable Impactor" manufactured by Sankyo Denki Co., Ltd., the "Spedic Classifier" manufactured by Seishin Enterprise Co., Ltd., the "Donaserec" manufactured by Nippon Donaldson Co., Ltd., the "YM Microcassette" manufactured by Yaskawa Shoji Co., Ltd., the "Turbo Classifier" manufactured by Nisshin Engineering Co., Ltd., and various other dry classification devices such as air separators, micron separators, Microbrex, and Accucut, but are not limited to these.

[0059] As a method for directly granulating the hardener particles constituting the core, instead of pulverization, there is a method for spray-drying a solution in which a lump of hardener is dissolved in a solvent. Specifically, there is a method for uniformly dissolving the hardener constituting the core in an appropriate organic solvent, spraying the solution as fine droplets, and then drying with hot air or the like. In this case, a typical spray dryer can be used as the drying device. In addition, as a method for granulating the hardener particles, the hardener constituting the core is uniformly dissolved in a suitable organic solvent, and then, while vigorously stirring the homogeneous solution, a poor solvent for the hardener constituting the core is added to precipitate the hardener constituting the core in the form of fine particles. Next, after filtering and separating the precipitated particles, the solvent is dried and removed at a low temperature below the melting point of the hardener constituting the core. As a method for adjusting the average particle size of the hardener constituting the particulate core by a method other than classification, for example, a method for adjusting the average particle size by mixing a plurality of particles having different average particle sizes can be mentioned. For example, in the case of a hardener having a large particle size that is difficult to crush or classify, a hardener having a small particle size can be added and mixed to obtain a hardener having an average particle size within the above range. The curing agent thus obtained may be further classified as necessary. Examples of mixers used for the purpose of mixing such powders include a container rotation type mixer that rotates the container body containing the powder to be mixed, a container fixed type mixer that does not rotate the container body containing the powder but mixes by mechanical stirring or air current stirring, and a composite type mixer that rotates the container containing the powder and also uses other external forces to mix.

[0060] The shape of the core constituting the (B) microcapsule-type curing agent is not limited to the following, and may be, for example, any of granular, powdery, irregular, and irregular shapes with rounded corners. The closer the shape of the core constituting the (B) microcapsule-type curing agent is to a perfect sphere, the more preferably it is. The closer the core is to a perfect sphere, the more evenly the capsule membrane, which is the shell described below, is formed, and component (B) tends to exhibit low aggregation, excellent storage stability, and excellent solvent resistance. The degree of closeness to a perfect sphere is expressed by circularity, and the circularity of a perfect sphere is 1. The circularity of the core of component (B) is preferably 0.93 or more, more preferably 0.95 or more, and even more preferably 0.98 or more.

[0061] (B) The circularity of the core constituting the microcapsule type curing agent can be measured by a flow type particle image analysis method. More specifically, the circularity can be determined by flowing a measurement sample into a liquid, photographing the particles, determining the particle diameter from the particle projected area, and calculating the ratio of the perimeter of the particle projected image to the circumference of the circle equivalent to the particle diameter.

[0062] The method for controlling the circularity of the core is not particularly limited, but a method for modifying the surface of the curing agent constituting the core is effective. For example, a method for mechanically rounding the particles or a method for subjecting the particles to hot air treatment can be mentioned.

[0063] <shell> The (B) microcapsule type curing agent preferably has a structure in which the surface of a core is covered with a shell containing a synthetic resin and / or an inorganic oxide. Among these, from the viewpoints of the stability of the film constituting the shell, the ease of destruction during heating, and the uniformity of the cured product of the epoxy resin composition of the present embodiment, it is preferable that the shell constituting the (B) microcapsule type curing agent contains a synthetic resin.

[0064] Examples of the synthetic resin contained in the shell include, but are not limited to, epoxy resins, phenol resins, polyester resins, polyethylene resins, nylon resins, polystyrene resins, urethane resins, etc. Among these, the synthetic resin is preferably an epoxy resin, a phenol resin, or a urethane resin from the viewpoint of the balance between the stability of the film constituting the shell and its destructiveness upon heating.

[0065] Examples of epoxy resins used for the shell include, but are not limited to, 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 with a compound having 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 are preferred, and in particular, reaction products of an amine-based curing agent and an epoxy resin having two or more epoxy groups are more preferred.

[0066] Examples of phenol-based resins 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.

[0067] Examples of polyester resins include, but are not limited to, ethylene glycol-terephthalic acid-polypropylene glycol polycondensates, ethylene glycol-butylene glycol-terephthalic acid polycondensates, and terephthalic acid-ethylene glycol-polyethylene glycol polycondensates.

[0068] Examples of polyethylene resins include, but are not limited to, ethylene-propylene-vinyl alcohol copolymers, ethylene-vinyl acetate copolymers, and ethylene-vinyl acetate-acrylic acid copolymers.

[0069] Examples of nylon resins include, but are not limited to, adipic acid-hexamethylenediamine polycondensate, sebacic acid-hexamethylenediamine polycondensate, and p-phenylenediamine-terephthalic acid polycondensate.

[0070] Examples of polystyrene resins include, but are not limited to, styrene-butadiene copolymers, styrene-butadiene-acrylonitrile copolymers, acrylonitrile-styrene-divinylbenzene copolymers, and styrene-propenyl alcohol copolymers.

[0071] Examples of urethane resins include, but are not limited to, 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 condensates thereof, or polycondensates of polymers thereof with monoalcohols or polyhydric alcohols, etc. Among these, urethane resins which are addition polymers of monoalcohols or polyhydric alcohols and monoisocyanates or polyhydric isocyanates are preferred.

[0072] Examples of inorganic oxides include, but are not limited to, boron oxide, boron compounds such as boric acid esters, silicon dioxide, calcium oxide, etc. Among these, boron oxide is preferred from the viewpoints of the stability of the film constituting the shell and the ease of destruction when heated.

[0073] From the viewpoint of the balance between the storage stability and curability of the epoxy resin composition of the present embodiment, the shell preferably contains one or more reaction products selected from the group consisting of an isocyanate compound, an active hydrogen compound, a curing agent for an epoxy resin, an epoxy resin, and an amine compound.

[0074] As the isocyanate compound, the isocyanate compounds given as examples of the raw material of the amine adduct contained in the core described above can be used.

[0075] Examples of the active hydrogen compound include, but are not limited to, water, a compound having at least one primary amino group and / or a secondary amino group, a compound having at least one hydroxyl group, etc. These active hydrogen compounds may be used alone or in combination of two or more.

[0076] Examples of the compound having at least one primary amino group and / or secondary amino group include, but are not limited to, aliphatic amines, alicyclic amines, aromatic amines, and the like. Examples of aliphatic amines include, but are not limited to, alkylamines such as methylamine, ethylamine, propylamine, butylamine, and dibutylamine; alkylene diamines 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, isophoronediamine, and the like. Examples of aromatic amines include, but are not limited to, aniline, toluidine, benzylamine, naphthylamine, diaminodiphenylmethane, and diaminodiphenylsulfone.

[0077] Examples of the compound having at least one hydroxyl group include alcohol compounds and phenol compounds. Examples of the alcohol compound include, but are not limited to, methyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, dodecyl alcohol, stearyl alcohol, eicosyl alcohol, allyl alcohol, crotyl alcohol, propargyl alcohol, cyclopentanol, cyclohexanol, benzyl alcohol, cinnamyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethyl ether, ... Examples of the polyhydric alcohols 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, which are obtained by reacting 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 alcohols, secondary alcohols, or tertiary alcohols. Examples of phenol compounds include, but are not limited to, monophenols such as phenol, cresol, xylenol, carvacrol, motil, and naphthol, and polyphenols such as catechol, resorcinol, hydroquinone, bisphenol A, bisphenol F, pyrogallol, phloroglucinone, 2-(dimethylaminomethyl)phenol, and 2,4,6-tris(dimethylaminomethyl)phenol. From the viewpoints of latency and solvent resistance, these compounds having at least one hydroxyl group are preferably polyhydric alcohols or polyhydric phenols, and more preferably polyhydric alcohols.

[0078] The reaction conditions for preparing one or more reaction products 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 shell constituting the microcapsule-type curing agent (B) as described above, are not particularly limited, but are usually in the temperature range of -10°C to 150°C and the reaction time is 10 minutes to 12 hours.

[0079] When an isocyanate compound and an active hydrogen compound are used to prepare the reaction product contained in the shell, the compounding ratio (isocyanate group in the isocyanate compound):(active hydrogen in the active hydrogen compound) (equivalent ratio) is preferably in the range of 1:0.1 to 1:1000.

[0080] The reaction can be carried out in a predetermined dispersion medium, if necessary. Examples of the dispersion medium include a solvent, a plasticizer, and a resin. Examples of solvents include, but are not limited to, hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirits, naphtha, etc.; ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), etc.; esters such as ethyl acetate, n-butyl acetate, propylene glycol monomethyl ethyl ether acetate, etc.; alcohols such as methanol, isopropanol, n-butanol, butyl cellosolve, butyl carbitol, etc.; water, etc. 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) adipate; phosphate triester plasticizers such as tricresyl phosphate; and glycol ester plasticizers such as polyethylene glycol ester. Examples of the resins include, but are not limited to, silicone resins, epoxy resins, and phenolic resins.

[0081] Among the above, the reaction between the epoxy resin and the curing agent for the epoxy resin is usually carried out at a temperature range of -10° C. to 150° C., preferably 0° C. to 100° C., for a reaction time of 1 hour to 168 hours, preferably 2 hours to 72 hours. The dispersion medium is preferably a solvent or a plasticizer.

[0082] The mass % of the reaction product contained in the shell as described above is usually 1 mass % or more, preferably 50 mass % or more, and may be 100 mass %.

[0083] In the (B) microcapsule-type curing agent, examples of a method for forming a shell that covers the surface of the core include the following methods (1) to (3). (1): A method in which the capsule components and hardener particles are dissolved / dispersed in a solvent, which is a dispersion medium, and then the solubility of the capsule components in the dispersion medium is reduced to precipitate the capsules on the surface of the epoxy resin hardener particles. (2) A method in which hardener particles are dispersed in a dispersion medium, and the capsule-forming material is added to the dispersion medium and precipitated on the hardener particles. (3) A method in which capsule-forming raw material components are added to a dispersion medium, and the surface of the hardener particles is used as a reaction site to produce shell-forming materials. Here, the above methods (2) and (3) are preferred because they allow reaction and coating to be carried out simultaneously.

[0084] In the above methods (1) to (3), examples of the dispersion medium include a solvent, a plasticizer, a resin, etc. In addition, examples of the solvent, plasticizer, and resin that can be used include those exemplified as solvents, plasticizers, and resins that can be used when preparing one or more reaction products selected from the group consisting of the above-mentioned isocyanate compounds, active hydrogen compounds, curing agents for epoxy resins, epoxy resins, and amine compounds.

[0085] After forming the shell by the above methods (2) and (3), the method for separating the microcapsule-type curing agent (B) from the dispersion medium is not particularly limited, but it is preferable to separate and remove the unreacted raw materials after the shell is formed together with the dispersion medium. Such a method includes a method of removing the dispersion medium and the unreacted shell-forming materials by filtration. After removing the dispersion medium, it is preferable to wash the microencapsulated curing agent, which can remove unreacted shell-forming material adhering to the surface. The washing method is not particularly limited, but when the residue is filtered, it can be washed with a solvent that does not dissolve the dispersion medium or the microcapsule type curing agent. By drying the microcapsule type curing agent after filtering or washing, the microcapsule type curing agent can be obtained in a powder form. The drying method is not particularly limited, but it is preferable to dry at a temperature below the melting point or softening point of the curing agent, for example, drying under reduced pressure. By making the microcapsule type curing agent into a powder form, it is easy to mix it with the (A) epoxy resin. In addition, it is preferable to use an epoxy resin as a dispersion medium, because a master batch of the microcapsule type curing agent integrated with the epoxy resin can be obtained at the same time as the shell is formed.

[0086] The shell formation reaction is usually carried out at a temperature range of -10°C to 150°C, preferably 0°C to 100°C, for a reaction time of 10 minutes to 72 hours, preferably 30 minutes to 24 hours.

[0087] In addition, the shell constituting the (B) microcapsule-type curing agent has a wave number of 1630 to 1680 cm from the viewpoint of the balance between storage stability and reactivity. -1 The urea bond absorbs infrared radiation with a wave number of 1680 to 1725 cm -1 The biuret bond absorbs infrared radiation at wavenumbers of 1730 to 1755 cm -1 and a urethane bond group that absorbs infrared rays. The urea bonding group, biuret bonding group, and urethane bonding group can be detected by measurement using a Fourier transform infrared spectrophotometer (hereinafter sometimes referred to as "FT-IR"). Furthermore, the presence of a urea bonding group, biuret bonding group, or urethane bonding group in the shell can be confirmed by microscopic FT-IR. Specifically, a modified aliphatic polyamine curing agent is added to the epoxy resin composition of this embodiment, and the composition is cured at 40°C for 12 hours, and then the epoxy resin portion is completely cured at 120°C for another 24 hours. Then, a sample having 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 using a microscopic FT-IR. By observing the vicinity of the surface of the shell, the presence of urea bond groups, biuret bond groups, and urethane bond groups can be observed.

[0088] The thickness of the shell constituting the (B) microcapsule type curing agent is preferably 5 nm or more and 1000 nm or less, more preferably 10 nm or more and 100 nm or less. By making the shell thickness 5 nm or more, the storage stability of the epoxy resin composition of the present embodiment can be further improved. By making the shell thickness 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.

[0089] The content of the microcapsule-type curing agent (B) in the epoxy resin composition of the present embodiment is, from the viewpoint of imparting sufficient reactivity, preferably 1 part by mass or more, more preferably 5 parts by mass or more, even more preferably 10 parts by mass or more, even more preferably 20 parts by mass or more, and even more preferably 30 parts by mass or more, based on 100 parts by mass of the epoxy resin (A). From the viewpoint of suppressing aggregation of the (B) microcapsule-type curing agent, imparting sufficient mechanical strength to the cured product, and imparting sufficient storage stability to the epoxy resin composition, the amount is preferably 100 parts by mass or less, more preferably 90 parts by mass or less, even more preferably 80 parts by mass or less, still more preferably 75 parts by mass or less, and even more preferably 70 parts by mass or less.

[0090] (Component (C): Reactive diluent) The epoxy resin composition of the present embodiment contains component (C): a reactive diluent (hereinafter, may be referred to as (C) reactive diluent or component (C)). The reactive diluent is a compound having an epoxy group or an acrylic group that can be incorporated into a cured structure, and is a compound that, when contained in the epoxy resin composition of the present embodiment, has the effect of reducing the viscosity of the epoxy resin composition.

[0091] (C) The reactive diluent is not limited to the following, but examples thereof include (meth)acrylate compounds and epoxy compounds that can reduce the viscosity without impairing the reactivity. In this specification, the reactive diluent is defined as any compound that excludes the compounds exemplified in the above-mentioned (A) epoxy resin and has a viscosity at 25°C of 1 mPa·s or more and less than 3 Pa·s. In the epoxy resin composition of the present embodiment, the (C) reactive diluent is preferably an epoxy compound from the viewpoints of compatibility with the above-mentioned (A) epoxy resin and (B) microcapsule-type curing agent and of being incorporated into the cured structure after the reaction.

[0092] (C) The (meth)acrylate compound used as the reactive diluent is not limited to the following, but examples thereof include compounds having (meth)acryloyl groups at both ends of polyalkylene oxide, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polybutylene glycol di(meth)acrylate, trimethylolpropane type multifunctional (meth)acrylate, pentaerythritol type multifunctional (meth)acrylate, dipentaerythritol type multifunctional (meth)acrylate, etc. Specifically, examples of bifunctional (meth)acrylate compounds having two or more aromatic rings include compounds in which polyalkylene oxide is added to bisphenol A and both ends have a (meth)acrylate structure, etc., and examples of monofunctional (meth)acrylate compounds having one aromatic ring include phenyl (meth)acrylate, ethylene glycol monophenyl ether (meth)acrylate, etc.

[0093] (C) Epoxy compounds used as reactive diluents include, but are not limited to, the following epoxy compounds having no aromatic ring and epoxy compounds having an aromatic ring. Examples of monofunctional epoxy compounds having no aromatic ring include compounds such as n-butyl glycidyl ether, t-butyl glycidyl ether, allyl glycidyl ether, and 2-ethylhexyl glycidyl ether. Examples of monofunctional epoxy compounds having one or more aromatic rings include styrene oxide, phenyl glycidyl ether, cresyl glycidyl ether, p-sec-butylphenyl glycidyl ether, t-butylphenyl glycidyl ether, and compounds under the trade name SY-OPG manufactured by Sakamoto Yakuhin Kogyo Co., Ltd. Examples of bifunctional epoxy compounds having no 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 (trade name: YX-8000), Sakamoto Yakuhin Kogyo Co., Ltd. (trade name: SR-8EGS), and the like. Examples of bifunctional epoxy compounds having one or more aromatic rings include compounds such as hexahydrophthalic acid diglycidyl ether, resorcinol diglycidyl ether, tert-butylhydroquinone diglycidyl ether, diglycidyl ether of polyoxyalkylene bisphenol A, 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.

[0094] In the epoxy resin composition of the present embodiment, it is preferable that the reactive diluent (C) has an aromatic ring from the viewpoint of enhancing the solvent resistance. In addition, it is more preferable that the reactive diluent (C) has a monocyclic aromatic ring and is monofunctional, particularly a monofunctional compound having either an epoxy group or an acrylic group as a functional group, from the viewpoint of further enhancing the solvent resistance. Furthermore, it is even more preferable that the monofunctional group is an epoxy group, from the viewpoint of exhibiting sufficient mechanical strength by incorporating the component (C) into the cured product of the epoxy resin composition of the present embodiment after the reaction. Furthermore, it is particularly preferable that the carbon number of each substituent of the aromatic ring is 3 or less, from the viewpoint of improving the penetration of the component (B) into the capsule membrane and improving the solvent resistance, as described later. On the other hand, it is preferable that the reactive diluent (C) does not contain a nitrogen atom, from the viewpoints of suppressing the reaction between the reactive diluent (C) and the epoxy resin (A) and enhancing storage stability.

[0095] The mechanism by which the reactive diluent (C) having the above-described structure improves the solvent resistance of the epoxy resin composition of the present embodiment is thought to be as follows, although this is not intended to be limiting. When the (C) reactive diluent has an aromatic ring, the aromatic rings of the reactive diluent incorporated inside the shell of the (B) microcapsule-type curing agent exhibit a stacking effect to form a network, thereby increasing the cohesive force of the shell. Therefore, a shell that is less likely to swell in a solvent can be constructed, and the solvent resistance of the epoxy resin composition of this embodiment can be improved. In addition, the (C) reactive diluent is a monocyclic and monofunctional compound in which the aromatic ring is monocyclic, so that steric hindrance is small, and it is easy to penetrate into the inside of the shell, and it is possible to form a simultaneous stacking network of aromatic rings in a denser and wider area. Here, the number of carbon atoms of each substituent of the aromatic ring is 3 or less, so that steric hindrance is further reduced, the penetration into the inside of the shell is improved, and the solvent resistance can be further improved.

[0096] The amount of the (C) reactive diluent added is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 4% by mass or more, even more preferably 5% by mass or more, and even more preferably 6% by mass or more, based on the entire epoxy resin composition of the present embodiment, from the viewpoint of imparting sufficient solvent resistance. Also, from the viewpoint of preventing excessive viscosity reduction, deterioration of storage stability, and reduction in mechanical strength of the cured product, the amount is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 13% by mass or less, even more preferably 12% by mass or less, and even more preferably 11% by mass or less.

[0097] (Component (D): Compound represented by formula (1)) The epoxy resin composition of the present embodiment contains, as component (D), a compound represented by the following formula (1) (hereinafter sometimes referred to as component (D)). By including component (D), the epoxy resin composition of the present embodiment has improved low viscosity and low-temperature curing properties while maintaining high storage stability, and furthermore, makes it possible to ensure a sufficient curing region even when heat conduction is non-uniform.

[0098] [ka]

[0099] In formula (1), X1 has 2 to 5 consecutive carbon-carbon bonds. The carbon substituents included in X1 and R1 to R5 are each one selected from the group consisting of hydrogen, an alkyl group, an unsaturated aliphatic group, an aromatic group, a substituent containing a heteroatom, a substituent containing a halogen atom, and a halogen atom. The carbon substituents included in X1 and R1 to R5 may be the same or different. In addition, the compound may be a fused ring compound in which any one selected from R1 to R5 is present in the same ring.

[0100] Examples of the compound represented by the formula (1) include, but are not limited to, 3-phenoxy-1-propanol, 3-phenoxy-1,2-propanediol, 3-phenoxy-1,3-propanediol, mephenesin (3-(ortho-toluoxy-1,2-propanediol), guaifenesin (3-(2-methoxyphenoxy)propane-1,2-diol), bisphenol A (3-hydroxypropyl) glycidyl ether, bisphenol A (2,3-dihydroxypropyl) glycidyl ether, and the following compounds 1, 2, and 3.

[0101] [ka]

[0102] [ka]

[0103] [ka]

[0104] The mechanism by which component (D) improves the low viscosity and low-temperature curing properties of the epoxy resin composition of the present embodiment and is effective in improving the cured region is thought to be as follows, although this is not intended to be limiting. Interactions between (A) epoxy resins, such as aromatic ring stacking and hydrogen bonding, are replaced by interactions between (A) epoxy resin and component (D) by aromatic groups and hydroxyl groups of component (D), eliminating interactions between (A) epoxy resins, and facilitating molecular movement in the epoxy resin composition as a whole, resulting in a low viscosity. In addition, during curing, a coordinate bond is formed between the hydroxyl group of component (D) and the curing agent component in the (B) microcapsule-type curing agent, thereby increasing the compatibility of the curing agent component and (A) epoxy resin, improving the diffusibility of the curing agent in the epoxy resin composition, and enabling a steep reaction at a lower temperature. Furthermore, since the epoxy resin composition of this embodiment contains (C) reactive diluent, it is believed that the viscosity of the epoxy resin composition is further reduced and the diffusibility is dramatically improved. Furthermore, according to the above mechanism, when the compatibility of component (D), (A) epoxy resin, and (C) reactive diluent is good, it is believed that a particularly excellent improvement in reactivity is exhibited. In this mechanism, component (D) acts as a catalyst in the reaction between the curing agent and the epoxy group until it is incorporated into the polymer. The improvement of the curing region is also due to the improved compatibility between the curing agent and the epoxy resin (A) and the reactive diluent (C) after the coordination of the above-mentioned component (D), as well as the improved component diffusion. The effects on the interaction, coordination, and compatibility are greatly influenced by the molecular structure. Therefore, in the epoxy resin composition of this embodiment, component (D) contains a compound represented by the above formula (1).

[0105] Component (D) is preferably a compound represented by the following formula (2), from the viewpoint of suppressing steric hindrance during the formation of a coordinate bond with the curing agent component in the microcapsule-type curing agent (B) and exhibiting good curing properties.

[0106] [ka]

[0107] In formula (2), X2 has 2 to 4 consecutive carbon-carbon bonds, and the carbon substituents included in X2 and R1 to R5 are each one selected from the group consisting of hydrogen, an alkyl group, an unsaturated aliphatic group, an aromatic group, a substituent containing a heteroatom, a substituent containing a halogen atom, and a halogen atom. The carbon substituents included in X2 and R1 to R5 may be the same or different. In addition, it may be a fused ring compound in which any one selected from R1 to R5 is present in the same ring.

[0108] It is more preferable that component (D) is a compound having two consecutive carbon-carbon bonds, as represented by the following formula (3), from the viewpoint of good diffusibility into the epoxy resin after forming a coordinate bond with the curing agent component in the microcapsule-type curing agent (B).

[0109] [ka]

[0110] In formula (3), R1 to R9 are each one selected from the group consisting of hydrogen, an alkyl group, an unsaturated aliphatic group, an aromatic group, a substituent containing a heteroatom, a substituent containing a halogen atom, and a halogen atom. R1 to R9 may be the same or different, and may be a fused ring compound in which any one selected from R1 to R5 is present on the same ring.

[0111] It is further preferable that component (D) is a compound represented by the following formula (4), in which R9 in the above formula (3) is a hydroxyl group, from the viewpoint of improving solvent resistance, film production stability, and film storage stability.

[0112] [ka]

[0113] In formula (4), R1 to R8 are each one selected from the group consisting of hydrogen, an alkyl group, an unsaturated aliphatic group, an aromatic group, a substituent containing a heteroatom, a substituent containing a halogen atom, and a halogen atom. R1 to R8 may be the same or different, and may be a fused ring compound in which any one selected from R1 to R5 is present on the same ring.

[0114] From the viewpoint of reducing steric hindrance to enhance coordination with the curing agent component, R6, R7, and R8 in the compounds represented by the formulae (3) and (4) as component (D) are preferably hydrogen atoms.

[0115] From the viewpoint of allowing component (D) to act efficiently, it is preferable that R1 to R5 in the compounds of component D represented by the above formulas (1) to (4) do not contain an epoxy group or a structure of the following formula (5) (terminal diol structure).

[0116] [ka]

[0117] The compounds represented by the formulas (1) to (4) as component (D) do not have epoxy groups in R1 to R5, and therefore are able to act for a long period of time without being incorporated into the curing reaction system. In addition, when R1 to R5 have the structure of the formula (5), two or more functional groups capable of forming coordinate bonds with a curing agent are present in the molecule of the compound of the formulas (1) to (4) in a positional relationship that reduces the effect of steric hindrance, and as a result, coordinate bonds are formed between multiple molecules, resulting in reduced molecular mobility. Therefore, it is preferable that R1 to R5 in the compound of the formulas (1) to (4) do not include the structure of the formula (5) (terminal diol structure).

[0118] The sp value (δ) is used as an index of compatibility, and when the difference in sp value between compounds is small, the compounds show good compatibility. Since the compatibility of component (D) with the epoxy resin (A) and the reactive diluent (C) is excellent, and the coordination compound formed by coordination of component (D) with the curing agent has excellent compatibility with the epoxy resin (A) and the reactive diluent (C), the effects of lowering the viscosity, improving the low-temperature curing property, and improving the curing range in the epoxy resin composition of the present embodiment are more effectively exhibited, and therefore it is preferable that the sp value of component (D) is close to the sp values ​​of the epoxy resin (A) and the reactive diluent (C). The sp value of each compound at 25° C. was calculated by Fedors' calculation method (formula (i)) using the values ​​described in ROBERT F. FEDORS, POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1974, Vol. 14, No. 2. In the following formula, δ represents the sp value. δ = (ΣΔe / ΣΔv) 1 / 2 Formula (i) Δe represents the cohesive energy for each substituent, and Δv represents the molar volume. [Component (A)] Bisphenol A type epoxy resin (n=0) δ=10.9 (cal / cm 3 ) 1 / 2 Bisphenol F type epoxy resin (n=0) δ=12.1(cal / cm 3 ) 1 / 2 1,6-bis(2,3-epoxypropoxy)naphthalene δ=13.1(cal / cm 3 ) 1 / 2 [Component (C)] Phenyl glycidyl ether δ=10.6(cal / cm 3 ) 1 / 2 Ortho-cresyl glycidyl ether δ=9.7(cal / cm 3 ) 1 / 2 1,6-Hexanediol diglycidyl ether δ=9.8(cal / cm 3 ) 1 / 2 [Component (D)] 3-Phenoxy-1-propanol δ=12.0(cal / cm 3 ) 1 / 2 3-Phenoxy-1,2-propanediol δ=14.3(cal / cm 3 ) 1 / 2 Mephenesin δ=13.0(cal / cm 3 ) 1 / 2 Guaifenesin δ=13.0(cal / cm 3 ) 1 / 2 Bisphenol A (3-hydroxypropyl) glycidyl ether δ=11.6(cal / cm 3 ) 1 / 2 Bisphenol A (2,3-dihydroxypropyl) glycidyl ether δ=12.9(cal / cm 3 ) 1 / 2 Compound 1...δ=12.0(cal / cm 3 ) 1 / 2 Compound 2...δ=12.0(cal / cm 3 ) 1 / 2 Compound 3...δ=12.6(cal / cm 3 ) 1 / 2

[0119] In order to further exert the effects of lowering the viscosity of the epoxy resin composition of the present embodiment, improving the low-temperature curing property, and improving the curing range, it is preferable that the epoxy resin (A) and / or the reactive diluent (C) have an sp value of 9 to 14 (cal / cm 3 ) 1 / 2 In the case where the epoxy resin is contained, the sp value of component (D) is 7 (cal / cm 3 ) 1 / 2 More than 8 (cal / cm 3 ) 1 / 2 More preferably, 9 (cal / cm 3 ) 1 / 2More preferably, 10 (cal / cm 3 ) 1 / 2 More preferably, 11 (cal / cm 3 ) 1 / 2 More preferably, the upper limit is 20 (cal / cm 3 ) 1 / 2 Less than 18 (cal / cm 3 ) 1 / 2 Less than 16 (cal / cm 3 ) 1 / 2 Even more preferred is the following:

[0120] From the viewpoint of fully exerting the effects of lowering the viscosity and improving the catalytic reactivity of the epoxy resin composition of this embodiment, the amount of component (D) added is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, even more preferably 0.01% by mass or more, and even more preferably 0.012% by mass or more, based on the total epoxy resin composition. Also, from the viewpoint of suppressing deterioration of storage stability due to excessive addition, the amount is preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 2.5% by mass or less, and even more preferably 2% by mass or less.

[0121] Component (D) may be added when mixing with the other components, or may be generated in the system after mixing. Alternatively, component (D) may be generated in the system when producing (A) the epoxy resin, (B) the microcapsule-type curing agent, and (C) the reactive diluent.

[0122] (Other additives) The epoxy resin composition of the present embodiment may further contain, in addition to the above-mentioned components, (B) a curing agent other than the microcapsule-type curing agent, and additives such as organic fillers, inorganic fillers, pigments, dyes, flow control agents, thickeners, release agents, wetting agents, flame retardants, surfactants, and resins, as necessary.

[0123] (B) Examples of the curing agent other than the microcapsule type curing agent include the curing agents exemplified as the core component of the microcapsule type curing agent described above, active ester compounds, and the like.

[0124] The organic filler functions as a shock mitigating agent, capable of mitigating stress caused by impact. By containing an organic filler, the epoxy resin composition of the present embodiment can further improve the adhesion to various connecting members. In addition, the occurrence and progression of fillet cracks tends to be suppressed. Examples of the organic filler include, but are not limited to, organic fine particles of acrylic resin, silicone resin, butadiene rubber, polyester, polyurethane, polyvinyl butyral, polyarylate, polymethyl methacrylate, acrylic rubber, polystyrene, NBR, SBR, silicone-modified resin, and copolymers containing these as components. From the viewpoint of improving adhesion, examples of organic fine particles include alkyl (meth)acrylate-butadiene-styrene copolymers, alkyl (meth)acrylate-silicone copolymers, silicone-(meth)acrylic copolymers, complexes of silicone and (meth)acrylic acid, complexes of alkyl (meth)acrylate-butadiene-styrene and silicone, and complexes of alkyl (meth)acrylate and silicone. The organic fine particles may have a core-shell structure, and the core layer and shell layer may have different compositions. Examples of the core-shell organic fine particles include particles having a silicone-acrylic rubber core and an acrylic resin grafted thereto, and particles having an acrylic resin grafted to an acrylic copolymer. These organic fillers may be used alone or in combination of two or more kinds.

[0125] The inorganic filler can adjust the thermal expansion coefficient of the epoxy resin composition of the present embodiment, and therefore, by containing the inorganic filler, there is a tendency that the heat resistance and moisture resistance of the epoxy resin composition of the present embodiment are improved when the epoxy resin composition is used as an underfill material. Examples of inorganic fillers include, but are not limited to, silicates such as talc, calcined clay, uncalcined clay, mica, and glass; oxides such as titanium oxide, aluminum oxide (alumina), fused silica (e.g., fused spherical silica and 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 and calcium sulfate; sulfites such as calcium sulfite; 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, from the viewpoint of improving heat resistance, moisture resistance, and strength, fused silica, crystalline silica, and synthetic silica powder are preferred, and aluminum oxide and boron nitride are also preferred. By using these, the coefficient of linear thermal expansion can be suppressed, which is expected to improve thermal cycle tests. The shape of the inorganic filler is not particularly limited, and may be, for example, any of amorphous, spherical, and flaky shapes. These inorganic fillers may be used alone or in combination of two or more kinds.

[0126] Examples of pigments include, but are not limited to, kaolin, aluminum oxide trihydrate, aluminum hydroxide, chalk powder, gypsum, calcium carbonate, antimony trioxide, pentone, silica, aerosol, lithopone, baryte, titanium dioxide, and the like.

[0127] Dyes include, but are not limited to, natural dyes such as dyes derived from plants such as madder and indigo, dyes derived from minerals such as yellow ocher and red clay, synthetic dyes such as alizarin and indigo, and fluorescent dyes.

[0128] Examples of flow control agents include, but are not limited to, organic silane compounds such as silane coupling agents; organic titanium compounds such as titanium tetraisopropoxide and titanium diisopropoxybis(acetylacetonate); and organic zirconium compounds such as zirconium tetra-n-butoxide and zirconium tetraacetylacetonate.

[0129] Examples of thickeners include, but are not limited to, animal-based thickeners such as gelatin; vegetable-based thickeners such as polysaccharides and cellulose; and chemically synthesized thickeners such as polyacrylic thickeners, modified polyacrylic thickeners, polyether thickeners, urethane-modified polyether thickeners, and carboxymethyl cellulose.

[0130] Examples of the release agent include, but are not limited to, fluorine-based release agents, silicone-based release agents, and acrylic release agents made of a copolymer of glycidyl (meth)acrylate and linear alkyl (meth)acrylate having 16 to 22 carbon atoms.

[0131] Examples of wetting agents include, but are not limited to, unsaturated polyester copolymer wetting agents having an acidic group, such as acrylic polyphosphate ester.

[0132] Examples of flame retardants include, but are not limited to, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, halogen-based flame retardants such as chlorine compounds and bromine compounds, phosphorus-based flame retardants such as condensed phosphate esters, antimony-based flame retardants such as antimony trioxide and antimony pentoxide, and inorganic oxides such as silica fillers.

[0133] 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 oxides and alkylcarboxybetaines, and nonionic surfactants such as linear alcohols and fatty acid esters having 25 or more carbon atoms.

[0134] Examples of the resins include, but are not limited to, silicone resins, phenol resins, phenoxy resins, polyvinyl butyral resins, polyvinyl acetal resins, polyacrylic resins, polyimide resins, and elastomers having functional groups such as a carboxyl group, a hydroxyl group, a vinyl group, and an amino group.

[0135] [Method for producing epoxy resin composition] The method for producing an epoxy resin composition according to the present embodiment includes a step of mixing the above-mentioned (A) epoxy resin, (B) microcapsule-type curing agent, (C) reactive diluent, and a compound of component (D) to obtain an epoxy resin composition. The method of producing the epoxy resin composition of this embodiment includes the steps of mixing (A) epoxy resin, (C) reactive diluent, and the compound of component (D) in advance, and then adding (B) microcapsule type curing agent, mixing (B) microcapsule type curing agent, (C) reactive diluent, and the compound of component (D), and then adding (A) epoxy resin, and also adding (A) epoxy resin, (B) microcapsule type curing agent, (C) reactive diluent, and the compound of component (D) to a master batch in which (A) epoxy resin and (B) microcapsule type curing agent are integrated. The mixing method is not particularly limited, and can be appropriately selected from, for example, a method using a planetary mixer or a method using a three-roll mill. The (B) microcapsule type curing agent may be produced by any of the methods described above.

[0136] [Method for producing curable resin composition] The epoxy resin composition of the present embodiment can also be used as a masterbatch type epoxy resin curing agent to produce a curable resin composition. That is, a curable resin composition can be produced by adding an epoxy resin and other curing agents to the epoxy resin composition of the present embodiment. In such a case, the curable resin composition is also included in the embodiment of the present invention. The curable resin composition can be obtained by thoroughly mixing the epoxy resin composition of the present embodiment with the (A) epoxy resin, the (B) curing agent exemplified as the core component of the microcapsule-type curing agent, and other additives exemplified therein, until the mixture is homogeneous, using a mixing roll such as a three-roll mixer, a dissolver, a planetary mixer, a kneader, an extruder, or the like.

[0137] The epoxy resin composition of the present embodiment, the curable resin composition, and the epoxy resin composition preparation liquid for film described below may be subjected to a heat treatment for 1 to 168 hours at a temperature of 30° C. to 80° C. The heating method is not particularly limited, and examples thereof include heating methods using an oven, an incubator, a water bath, an oil bath, etc. The temperature history is also not particularly limited, and for example, the temperature may be raised stepwise or all at once. The heat treatment can terminate the reaction of excess functional groups that react at low temperatures.

[0138] [Specific embodiments of the epoxy resin composition and the curable resin composition] The epoxy resin composition of the present embodiment and the curable resin composition using the same are suitable for, but not limited to, sealing materials for electric and electronic components such as underfill materials and relay sealing materials, insulating materials, adhesives, conductive materials, matrix resins for fiber-reinforced plastics, impregnation and fixing materials for motor coils, and the like. For example, underfill materials are required to have low viscosity for rapid penetration between the semiconductor chip and the substrate, stability against heat during penetration, and excellent curing properties at temperatures of 100° C. or higher, and the epoxy resin composition of this embodiment combines all of these properties. Furthermore, the epoxy resin composition of this embodiment is also suitable for increasing the area of ​​semiconductor chips, since it can ensure a sufficient curing area even when heat is not uniformly conducted. Furthermore, matrix resins for fiber-reinforced plastics and impregnating adhesives for motor coils are required to have the ability to penetrate into gaps in fine fibers or coils, stability during penetration, and curing properties; the epoxy resin composition of the present embodiment is suitable because it has all of these properties. A curable resin composition using the epoxy resin composition of the present embodiment has similar properties and is therefore suitable for the above-mentioned embodiment.

[0139] (Film Containing the Epoxy Resin Composition of the Present Embodiment) The film of the present embodiment has a resin composition layer containing the epoxy resin composition of the present embodiment. In this case, the epoxy resin composition can also function as an epoxy resin curing agent or curing accelerator. The epoxy resin composition of the present embodiment has low viscosity, excellent solvent resistance, storage stability, and curing properties, and is suitable for films. The film of the present embodiment has, for example, a predetermined support and a resin composition layer formed on the support from an epoxy resin composition preparation liquid described below, and may have a protective layer on the surface of the resin composition layer opposite the support, as necessary.

[0140] <Method for preparing epoxy resin composition for film> An example of a method for preparing an epoxy resin composition liquid preparation for forming a resin composition layer of a film is a method in which the epoxy resin composition of the present embodiment is mixed with (A) an epoxy resin, (B) a curing agent exemplified as a core component of the microcapsule-type curing agent, other additives, component (E): a film-forming polymer, etc., and then component (F): an organic solvent is added, followed by mixing using a planetary mixer or the like. As the (E) film-forming polymer, any polymer that has the effect of suppressing cracking, cissing, and excessive flow when the epoxy resin composition preparation liquid is applied and then dried to form a film, and that has the effect of maintaining the film shape, can be used. Examples of such component (E) include, but are not limited to, phenoxy resin, polyvinyl butyral resin, polyvinyl acetal resin, polyacrylic resin, polyimide resin, and elastomers having functional groups such as carboxyl group, hydroxyl group, vinyl group, and amino group. (E) The film-forming polymer is sometimes called a binder polymer. (F) The organic solvent is not particularly limited, and known organic solvents can be used. Examples of the organic solvent include, but are not limited to, hydrocarbons such as toluene, xylene, cyclohexane, mineral spirits, and solvent 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 amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.

[0141] <Support> The support is preferably a material that can withstand the temperature during drying of the organic solvent, and examples of such supports include, but are not limited to, polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, and cellulose derivative film. These films may be stretched as necessary.

[0142] <Protective layer> The protective layer is preferably made of a material capable of sufficiently maintaining the smoothness of the surface of the resin composition layer. As such a protective layer, a polyethylene film, a polypropylene film, a polyethylene terephthalate film treated for easy peeling, an oriented polypropylene film, etc. can be preferably used, but is not limited to the following.

[0143] <Film manufacturing method> The film of the present embodiment can be produced by sequentially laminating a support, a resin composition layer, and, if necessary, a protective layer. As a method for laminating the support, the resin composition layer, and the protective layer, a known method can be adopted. For example, a preparation containing the epoxy resin composition of this embodiment and (F) an organic solvent is prepared, and first, the mixture is applied to a support using a known method such as an applicator or a bar coater, and then dried to form a resin composition layer on the support. The drying method is not particularly limited, and examples thereof include an oven and hot air blowing. In addition, there are no particular limitations on the drying temperature and time, but from the viewpoint of sufficiently removing the solvent and suppressing deformation of the support due to excessive heating and excessive reaction of the resin composition layer during drying, it is preferable to dry at a temperature range of 50°C to 160°C within a drying time of 1 minute to 30 minutes, and more preferably at 80°C to 150°C for 3 minutes to 25 minutes. The drying temperature may be a constant temperature or may be a temperature gradient. Next, if necessary, a protective layer may be laminated on the formed resin composition layer to produce a film.

[0144] <Specific embodiment of the film> The film of the present embodiment can be used as, for example, an interlayer insulating film, a film-type solder resist, a sealing sheet, a conductive film, an anisotropic conductive film, a thermally conductive film, and the like, although not limited thereto. Since the epoxy resin composition of the present embodiment has excellent solvent resistance and storage stability, it is possible to extend the coating time of an epoxy resin composition preparation for film containing the composition, and also to extend the storage period of the obtained film. In particular, it is possible to store films at temperatures ranging from refrigeration to room temperature, which have traditionally been stored in a freezer. In addition, since the epoxy resin composition of the present embodiment has a low viscosity, it is easy to control the viscosity of a preparation containing the composition, and the composition also has excellent applicability onto a support. Furthermore, the resin composition layer containing the epoxy resin composition of this embodiment has a sufficiently low viscosity due to heating during film attachment, and has excellent stability during the film preparation process and during storage, so that the reaction of the epoxy compound after film preparation is suppressed and the low viscosity can be maintained for a long period of time. Due to these properties, the film of this embodiment has excellent conformability to unevenness and can be attached to a substrate without gaps. Furthermore, since the epoxy resin composition of the present embodiment has excellent curability at around 100° C., the film of the present embodiment also has excellent curability. The above-mentioned properties are commonly required for interlayer insulating films, film-type solder resists, sealing sheets, conductive films, anisotropic conductive films, and thermally conductive films, and therefore the film of this embodiment is suitable for these applications.

[0145] [Cured product] The cured product of this embodiment is a cured product of the above-mentioned epoxy resin composition of this embodiment and the film of this embodiment. The cured product of the present embodiment can be produced by subjecting the epoxy resin composition and film of the present embodiment to a heat treatment. The heat treatment can be carried out, for example, by heat treatment in a heating furnace such as an oven, thermocompression bonding, etc. The heating conditions are not particularly limited and can be appropriately selected depending on the composition of the epoxy resin composition and the heat treatment device. The cured product of this embodiment has excellent mechanical strength. EXAMPLES

[0146] Hereinafter, the present embodiment will be described with reference to specific examples and comparative examples, but the present embodiment is not limited to the following examples and comparative examples. In the following, "parts" and "%" are by weight unless otherwise specified.

[0147] [Method for producing microcapsule-type curing agent] (Production Example 1) 50 parts by mass of bisphenol A type epoxy resin A-1 (epoxy equivalent 186g / eq, total chlorine content 600ppm, hydrolyzable chlorine content 50ppm, hereinafter referred to as "epoxy resin A-1"), 50 parts by mass of bisphenol F type epoxy resin A-2 (epoxy equivalent 172g / eq, total chlorine content 500ppm, hydrolyzable chlorine content 100ppm, hereinafter referred to as "epoxy resin A-2"), 100 parts by mass of hardener core component b-1 (manufactured by Asahi Kasei Corporation, solid amine adduct with circularity of 0.93, hereinafter referred to as "core b-1"), and 10 parts by mass of encapsulating agent c-1 (manufactured by Nippon Polyurethane Co., Ltd.: MR-400) were added, dispersed and mixed, and then reacted at 55°C for 5 hours to obtain a microcapsule type hardener B-1 dispersed in the epoxy resin.

[0148] (Production Example 2) 50 parts by mass of "epoxy resin A-1", 50 parts by mass of "epoxy resin A-2", 100 parts by mass of "core b-1", and 10 parts by mass of encapsulating agent c-2 (T-80 manufactured by Tosoh Corporation) were added, dispersed and mixed, and then reacted at 55°C for 5 hours to obtain a microcapsule-type curing agent B-2 dispersed in the epoxy resin.

[0149] (Production Example 3) 50 parts by mass of "epoxy resin A-1", 50 parts by mass of "epoxy resin A-2", 100 parts by mass of "core component b-1", 7 parts by mass of encapsulating agent c-3 (Tosoh Corporation: Coronate 1391), and 3 parts by mass of encapsulating agent c-4 (Asahi Kasei Corporation: Duranate TUL-100) were added, dispersed and mixed, and then reacted at 55°C for 5 hours to obtain a microcapsule-type curing agent B-3 dispersed in the epoxy resin.

[0150] [Preparation of Epoxy Resin Composition] (A) epoxy resin, (B) microcapsule-type curing agent, (C) reactive diluent, and component (D): a compound represented by formula (1) were weighed and mixed in the amounts shown in the component tables in Tables 1 to 3 below, and then filtered at 55°C for 48 hours to obtain an epoxy resin composition. The number of parts of (A) epoxy resin listed in Tables 1 to 3 below is the amount of epoxy resin in the entire epoxy resin composition, including the epoxy resin that is added at the same time when the "microencapsulated curing agent dispersed in epoxy resin" prepared in Production Examples 1, 2, and 3 is added. Therefore, the number of parts of "(B) microencapsulated curing agent" listed in Tables 1 to 3 below is the number of parts of the microencapsulated curing agent itself consisting of a core and a shell.

[0151] [Methods for measuring and evaluating characteristics] (Initial Viscosity Measurement of Epoxy Resin Composition) The viscosity (initial viscosity) of the epoxy resin composition immediately after preparation was measured at room temperature (25° C.) using an E-type viscometer (TVE-35H, manufactured by Toki Sangyo Co., Ltd.). From the viewpoint of sufficient gap permeability and manufacturability of the resin composition layer constituting the film, the initial viscosity was evaluated as preferably 4500 mPa·s or less, more preferably 3500 mPa·s or less, and even more preferably 3000 mPa·s or less.

[0152] (Storage stability: Storage stability viscosity magnification) The initial viscosity immediately after the preparation of the epoxy resin composition and the viscosity after leaving the epoxy resin composition at 40°C for 7 days were measured at room temperature (25°C) using an E-type viscometer, and the storage stability viscosity ratio was calculated using the following formula (1). Storage stability viscosity ratio = viscosity after 7 days at 40°C / initial viscosity Formula (1) The storage stability viscosity factor was evaluated as being preferably 1.2 or less, more preferably 1.1 or less, and even more preferably 1.0.

[0153] (The temperature at which the dynamic viscosity reaches a specified value as measured by a rheometer (curability at around 100°C)) The dynamic viscosity η'-temperature curve was obtained when the epoxy resin composition was heated from 25°C to 200°C at a heating rate of 5°C / min in oscillation mode (f=1 Hz) using a rheometer (HAAKE MARS, manufactured by Thermo Scientific). From the obtained dynamic viscosity-temperature curve, the dynamic viscosity was found to be 10 5 The temperature at which the value becomes mPa s: T (℃) was confirmed. The following evaluations were made according to the temperature: T (° C.). T≦95℃...◎ 95℃ <T≦105℃ ····〇 105℃ <T≦110℃ ···△ 110℃ <T ·····×

[0154] (hardened area) The epoxy resin composition was poured thoroughly into a Teflon (registered trademark) mold measuring 550 mm in length, 350 mm in width, and 2 mm in thickness, up to the opening, and heated in a heating furnace at a set temperature of 100° C. for 25 minutes. After the heating was completed, the volume of the cured body removed from the Teflon (registered trademark) mold was designated as Vc, and the volume of the epoxy resin composition poured in was designated as V0, and the cured area was calculated using the following formula (2). Hardened area (%) = 100 × Vc / V0 Formula (2) The evaluation was carried out according to the following criteria, depending on the percentage of hardened area. ◎ Cured area: 100% Hardened area: 80% or more but less than 100% △ Hardened area: 50% to less than 80% × Hardened area: Less than 50% It was evaluated that the larger the cured region when the epoxy resin composition was cured, the better it was in terms of being able to ensure a sufficient cured region even when heat transfer to the cured region was insufficient. That is, the order of the evaluations from best to worst is shown in the table as ., .smallcircle., .smallcircle., .DELTA., and x.

[0155] (Solvent resistance stability) Samples were prepared by mixing 80 parts by mass of the epoxy resin compositions of Examples 1 to 19 and Comparative Example 2 with 20 parts by mass of MEK (methyl ethyl ketone) as a solvent. The obtained sample was heated at 50° C., and the time (h) until the fluidity disappeared was measured. The time until fluidity disappeared was evaluated as being preferably 0.5 hours (h) or more, more preferably 1 hour (h), and even more preferably 2 hours (h) or more.

[0156] (Stability during preparation of film using epoxy resin composition) A solution was obtained by mixing and dissolving 50 parts by mass of a phenoxy resin (manufactured by InChem Corporation, product name "PKHB"), 50 parts by mass of a bisphenol A type liquid epoxy resin (manufactured by Mitsubishi Chemical Corporation, product name "jER828"), and 100 parts by mass of MEK. 20 parts by mass of the epoxy resin composition of any one of Examples 1 to 19 and Comparative Example 2 was mixed with 100 parts by mass of this solution to prepare a mixed liquid for an epoxy resin composition for use in a film. This preparation was applied onto a polyethylene terephthalate film (thickness 50 μm) as a support so that the dry film thickness was 40 μm, and then the film was dried by heating for 5 minutes in an oven preheated to 120° C., and the surface opposite the support was protected with a polyethylene terephthalate film that had been treated to be easily peeled, to obtain a film. These are the films of Examples 20 to 38 and Comparative Example 4, respectively. The FT-IR spectrum of the obtained film was measured using a Fourier transform infrared spectrophotometer (FT / IR-6600, manufactured by JASCO Corporation). The 2920cm methylene group-derived epoxide resin and phenoxy resin have no change in strength due to heat drying. -1 Based on the absorption P1 near the 915 cm -1 The intensity ratio P2 / P1 of the absorption peak P2 near the center of the film was calculated by subtracting the intensity ratio P20 / P10 (P10 is 2920 cm) from the intensity ratio P20 / P10 (P10 is 2920 cm) when a film was produced in the same manner but with a composition that excluded the microcapsule-type hardener component in the epoxy resin composition, which is the hardener component. -1 Absorption near 915 cm -1 The epoxy consumption rate was calculated using the following formula (3) by comparing with the absorption rate (absorption near the Epoxy consumption rate = 100 - [(P2 / P1) / (P20 / P10)] × 100... Equation (3) The epoxy consumption rate was evaluated according to the following criteria. 0%≦Epoxy consumption rate<10% ◎ 10%≦Epoxy consumption rate<15%... 〇 15%≦Epoxy consumption rate<20%...△ 20% or less epoxy consumption rate × The evaluations are shown in the table in order from best to worst: ◎, ◯, △, ×.

[0157] (Storage stability of film using epoxy resin composition) A film was prepared by the same method as described above (Film stability during preparation) using any of the epoxy resin compositions of Examples 1 to 19 and Comparative Example 2. The film was then stored in an oven at 40° C. for 7 days. The FT-IR spectrum of the film after storage was measured by the same method as described above (Film stability during preparation), and the epoxy consumption rate after storage was calculated by adopting the value after storage as the value of P2 / P1 in the formula (3). The epoxy consumption rate after storage was evaluated according to the following criteria. 0%≦Epoxy consumption rate<10% ◎ 10%≦Epoxy consumption rate<15%... 〇 15%≦Epoxy consumption rate<20%...△ 20% or less epoxy consumption rate × The evaluations are shown in the table in order from best to worst: ◎, ◯, △, ×.

[0158] (Stability during production of films using epoxy resin composition as a curing accelerator) A solution was obtained by mixing and dissolving 50 parts by mass of phenoxy resin (manufactured by InChem, product name "PKHB"), 50 parts by mass of bisphenol A type liquid epoxy resin (manufactured by Mitsubishi Chemical Corporation, product name "jER828"), and 100 parts by mass of MEK. To 100 parts by mass of this solution, 2.5 parts by mass of dicyandiamide (DICY) as a curing agent component and 2 parts by mass of the epoxy resin composition of Examples 1, 5, 10 and 15 as a curing accelerator were added to prepare a mixed liquid for an epoxy resin material for films. This prepared solution was used to prepare films for determining the P20 / P10 ratio. Except for this, the films of Examples 39 to 42 were prepared in the same manner as described above (film preparation stability), except that the composition used was one that did not contain the curing agent dicyandiamide and the microcapsule-type curing agent, and the epoxy consumption rate was measured and evaluated. The epoxy consumption rate was evaluated according to the following criteria. 0%≦Epoxy consumption rate<10% ◎ 10%≦Epoxy consumption rate<15%... 〇 15%≦Epoxy consumption rate<20%...△ 20% or less epoxy consumption rate × The evaluations are shown in the table in order from best to worst: ◎, ◯, △, ×.

[0159] (Storage stability of film when epoxy resin composition is used as a curing accelerator) Using the epoxy resin compositions of Examples 1, 5, 10, and 15, films were produced in the same manner as described above (Stability during film production when the epoxy resin composition was used as a curing accelerator). Thereafter, the film was stored in an oven at 40° C. for 7 days. For the film after storage, the FT-IR spectrum was measured in the same manner as described above (Stability during production of film using epoxy resin composition as curing accelerator), and the epoxy consumption rate after storage was calculated by adopting the value after storage as the value of P2 / P1 in the above formula (3). The epoxy consumption rate after storage was evaluated according to the following criteria. 0%≦Epoxy consumption rate<10% ◎ 10%≦Epoxy consumption rate<15%... 〇 15%≦Epoxy consumption rate<20%...△ 20% or less epoxy consumption rate × The evaluations are shown in the table in order from best to worst: ◎, ◯, △, ×.

[0160] (Film hardening) A film was produced by the method described above in (Stability during production of film using epoxy resin composition) and (Stability during production of film using epoxy resin composition as curing accelerator). Then, the epoxy resin composition layer was transferred onto aluminum foil and cured in an oven at 180°C for 1 hour. The appearance and cross section of the resulting cured product were observed to determine whether or not it had cured.

[0161] [Ingredients] Components (C) and (D) in Tables 1 to 3 below are shown below. The viscosity of component (C) was measured in the same manner as in measuring the initial viscosity of the epoxy resin composition. Ingredients (C): PGE: Phenyl glycidyl ether (viscosity 6 mPa·s at 25°C) (Tokyo Chemical Industry Co., Ltd.) o-CGE: ortho-cresyl glycidyl ether (viscosity 7 mPa·s at 25°C) (Sigma-Aldrich Japan) tBPGE: t-butylphenyl glycidyl ether (viscosity 20 mPa s at 25°C) (Tokyo Chemical Industry Co., Ltd.) YED216D: 1,6-Hexanediol diglycidyl ether (viscosity at 25°C: 121 mPa·s) (product name manufactured by Mitsubishi Chemical Corporation) Ingredients (D): 3-Phenoxy-1,2-propanediol (Tokyo Chemical Industry Co., Ltd.) Mephenesin (Tokyo Chemical Industry Co., Ltd.) 3-Phenoxy-1-propanol (Tokyo Chemical Industry Co., Ltd.) Other Ingredients: Newpol BPE-20: A polyol compound in which ethylene oxide is added to bisphenol A (product name manufactured by Sanyo Chemical Industries, Ltd.)

[0162] [Examples 1 to 19], [Comparative Examples 1 to 3] The components were mixed in the proportions shown in Tables 1 to 3, and epoxy resin compositions were prepared by the method described above. The properties of the prepared epoxy resin composition were measured by the above-mentioned methods.

[0163] [Table 1]

[0164] [Table 2]

[0165] [Table 3]

[0166] Comparing the Examples with Comparative Examples 1 and 2, it was found that by adding component (C) and component (D), it was possible to obtain an epoxy resin composition having a good balance of properties, which lowers the viscosity and improves the reactivity while maintaining excellent storage stability. Comparing Example 1 with Comparative Example 3, it was found that the compound having the structure of component (D) was effective in all respects: storage stability, low viscosity, and improved reactivity. Comparing Examples 1 and 4, it was found that the component (C) PGE exhibited a better balance of properties in terms of low viscosity and reactivity. Comparing Examples 5, 10, and 11, it was found that the greater the amount of component (D), the better the low viscosity, and the smaller the amount of component (D), the better the storage stability. Comparing Examples 10, 15, and 16, it was found that the more the amount of component (C) increased, the more excellent the curability and storage stability. On the other hand, when comparing Example 1 and Example 5, the more the amount of component (C) increased, the lower the storage stability. However, this is because the amount of component (D) contained in Examples 10, 15, and 16 was more appropriate, so the effect of component (D) on storage stability was small, and the effect of improving storage stability due to stacking in the shell of component (C) was imparted. In addition, since the viscosity decreased with the increase in the amount of component (C), the diffusibility of component (D) and that of the component (D) coordinated to the curing agent during the curing reaction improved, and excellent curability was expressed. In addition, comparing Example 15 with Comparative Example 1, it was found that even a small amount of component (D) had an effect of improving reactivity, and it was found that this was due to component (D) acting as a catalyst. Comparing Examples 5, 13, and 14, it was found that an epoxy resin composition having an excellent balance of properties can be obtained even if the ratio of bisphenol A type epoxy resin to bisphenol F type epoxy resin in component (A) is changed. It was also found that the lower the viscosity and the better the storage stability, the higher the ratio of bisphenol F type epoxy resin in component (A).

[0167] Table 4 shows the evaluation results of the hardening range test.

[0168] [Table 4]

[0169] It was found that the hardening region was improved by adding components (C) and (D).

[0170] Tables 5 and 6 show the evaluation results of the solvent resistance test.

[0171] [Table 5]

[0172] [Table 6]

[0173] Comparing the Example and Comparative Example 2, it was found that the addition of component (C) improved the solvent resistance. Comparing Example 1 and Example 5, it was found that the solvent resistance improved with an increase in the amount of component (C) added. In addition, when Examples 5, 6, and 7 were compared with Example 18, it was found that compounds in which component (C) had an aromatic ring had better solvent resistance. Furthermore, when Examples 5, 6 and 7 were compared with Example 7, it was found that compounds in which component (C) was PGE and / or o-CGE showed better solvent resistance than tBPGE. This is thought to be because aromatic ring substituents with less steric hindrance easily penetrate into the capsule membrane and form a denser aromatic ring stacking network. Furthermore, when Examples 5 and 12 are compared with Example 19, it is found that the compound in which the terminal of component (D) is a diol structure has better solvent resistance.

[0174] Tables 7 and 8 show the results of tests on stability during film production and storage stability for the films of Examples 20 to 38 and Comparative Example 4, which used the epoxy resin compositions of Examples 1 to 19 and Comparative Example 2.

[0175] [Table 7]

[0176] [Table 8]

[0177] Comparing Examples 20 to 38 with Comparative Example 4, it was found that the addition of component (C) resulted in excellent stability during film production and excellent storage stability of the film. Comparing Example 20 with Example 24, it was found that increasing the amount of component (C) added improved the stability during film production and the storage stability of the film. Comparing Examples 24, 25, and 26 with Example 37, it was found that compounds having an aromatic ring as component (C) had better stability during film preparation. In addition, comparing Examples 24, 25 with Example 26, it was found that when component (C) was PGE and / or o-CGE, it was better than tBPGE in both stability during film preparation and storage stability. Comparing Examples 24, 32, and 33, it was found that the greater the amount of bisphenol F type epoxy resin, the more excellent the stability during film production and the storage stability of the film tended to be.

[0178] Table 9 shows the evaluation results of the film stability during film production and the storage stability test for the films of Examples 39 to 42, in which the epoxy resin compositions of Examples 1, 5, 10 and 15 were used as the curing accelerator.

[0179] [Table 9]

[0180] Examples 39 to 42 showed excellent stability during film preparation and excellent film storage stability.

[0181] Tables 10 and 11 show the evaluation results of the curing test for the films of Examples 20 to 42.

[0182] [Table 10]

[0183] [Table 11]

[0184] All of the films of Examples 20 to 42 exhibited excellent curability.

[0185] Although the present embodiment has been described above, the present invention is not limited to this embodiment, and can be modified as appropriate without departing from the spirit of the invention.

[0186] This application is based on a Japanese patent application (Patent Application No. 2021-114776) filed with the Japan Patent Office on July 12, 2021, and a Japanese patent application (Patent Application No. 2021-133229) filed with the Japan Patent Office on August 18, 2021, the contents of which are incorporated herein by reference. [Industrial Applicability]

[0187] The epoxy resin composition of the present invention has industrial applicability in insulating materials for electric and electronic components such as underfills, sealing materials, adhesives, conductive materials, matrix resins for fiber-reinforced plastics, impregnation fixing agents for motor coils, and the like. It also has industrial applicability in films such as interlayer insulating films, film-type solder resists, sealing sheets, conductive films, anisotropic conductive films, and thermally conductive films, which use the epoxy resin composition of the present invention as a curing agent or curing accelerator, as well as in various paste materials such as insulating adhesive pastes, conductive pastes, anisotropic conductive pastes, and thermally conductive pastes, as well as various coating materials, paints, and the like, which can take advantage of the excellent solvent resistance.

Claims

1. Component (A): an epoxy resin, Component (B): a microcapsule type curing agent; Component (C): a reactive diluent; Component (D): a compound represented by the following formula (3), Including, The component (A) has an sp value at 25° C. calculated by the following formula (i) of 9 to 14 (cal / cm 3 ) 1 / 2 The epoxy resin is The sp value of the compound (D) at 25° C., calculated by the following formula (i), is 11 to 16 (cal / cm 3 ) 1 / 2 The epoxy resin composition according to claim 1, δ = (ΣΔe / ΣΔv) 1 / 2 ・・・・・ Equation (i) (In formula (i), δ represents the sp value, Δe represents the cohesive energy for each substituent, and Δv represents the molar volume.) 【Chemistry 1】 (In formula (3), R 1 ~R 9 are each one selected from the group consisting of hydrogen, an alkyl group, an unsaturated aliphatic group, an aromatic group, a substituent containing a hetero atom, a substituent containing a halogen atom, and a halogen atom. R 1 ~R 9 may be the same or different. 1 ~R 5 may be a condensed ring compound in which any one selected from the following is present in the same ring.)

2. The component (D) is a compound represented by the following formula (4): The epoxy resin composition according to claim 1. 【Chemistry 2】 (In formula (4), R 1 ~R 8 are each one selected from the group consisting of hydrogen, an alkyl group, an unsaturated aliphatic group, an aromatic group, a substituent containing a hetero atom, a substituent containing a halogen atom, and a halogen atom. R 1 ~R 8 may be the same or different. 1 ~R 5 may be a condensed ring compound in which any one selected from the following is present in the same ring.)

3. The component (A) epoxy resin is Contains at least bisphenol F type epoxy resin; The epoxy resin composition according to claim 1 or 2.

4. The component (B) microcapsule-type curing agent has a core circularity of 0.93 or more. The epoxy resin composition according to claim 1 or 2.

5. The component (C) reactive diluent is a compound having an aromatic ring. The epoxy resin composition according to claim 1 or 2.

6. The component (C) reactive diluent is a compound in which the aromatic ring is a monocyclic ring and is monofunctional. The epoxy resin composition according to claim 5.

7. The content of the component (C) reactive diluent is In the epoxy resin composition, the content is 1% by mass or more and 20% by mass or less. The epoxy resin composition according to claim 1 or 2.

8. The content of the component (D) is In the epoxy resin composition, the content is 0.001% by mass or more and 5% by mass or less. The epoxy resin composition according to claim 1 or 2.

9. The content of the component (D) is In the epoxy resin composition, the content is 0.001% by mass or more and 5% by mass or less. The epoxy resin composition according to claim 5.

10. The R 1 ~R 5 does not contain an epoxy group or a structure of the following formula (5) (terminal diol): The epoxy resin composition according to claim 1 or 2. 【Chemistry 3】

11. A support; A resin composition layer comprising the epoxy resin composition according to claim 1 or 2 formed on the support; A film having

12. The resin composition layer further contains component (E): a film-forming polymer; The film of claim 11.

13. The film is any one selected from the group consisting of an interlayer insulating film, a film-type solder resist, an encapsulating sheet, a conductive film, an anisotropic conductive film, and a thermally conductive film; The film of claim 11.

14. A method for producing the film according to claim 11, comprising the steps of: The method includes a step of applying a preparation containing at least the epoxy resin composition of claim 1 or 2 and component (F) an organic solvent onto the support, and then drying the component (F) organic solvent at a temperature in the range of 50 to 160° C. for a time in the range of 1 to 30 minutes. A method for manufacturing a film.

15. A cured product of the epoxy resin composition according to claim 1 or 2.

16. A cured product of the film according to claim 11.

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