KR20210148237A - curable resin composition - Google Patents

Abstract

To provide a curable resin composition excellent in heat resistance and oxygen barrier properties capable of forming a cured body suitable for resin members of electronic devices such as organic EL, high-brightness LED, and solar cell. A curable resin composition comprising the following components (A) to (D): (A) an epoxy resin containing a nitrogen atom; (B) a siloxane compound having an epoxy group; (C) an inorganic filler and (D) a curing agent.

Description

curable resin composition

The present invention relates to a curable resin composition for a resin member characterized by heat resistance and oxygen barrier properties in electronic device applications such as organic EL, high-brightness LED, and solar cell.

A resin member formed of a cured body of a resin composition or the like may be used in electronic devices, particularly in optical devices such as organic EL, high-brightness LED, and solar cells, for sealing, bonding, and light transmission sites. In order to suppress deterioration of the internal elements of an electronic device, etc. by oxygen in air, oxygen barrier property is calculated|required by such a resin member in some cases. Moreover, heat resistance may be calculated|required for deterioration suppression of the internal element of an electronic device, etc. by the outgas which generate|occur|produces from the resin member by heat|fever. For example, Patent Document 1 discloses a resin composition comprising a blocked isocyanate in which an isocyanate compound is blocked with imidazole, an epoxy resin, or a phenoxy resin, but there is no consideration of heat resistance or oxygen barrier properties. . Thus, the conventional resin member is not necessarily satisfactory with respect to heat resistance and oxygen barrier property, and the curable resin composition for resin members which satisfy|fills these performance simultaneously has been calculated|required.

Japanese Patent Laid-Open No. 2011-84667

Accordingly, it is an object of the present invention to provide a curable resin composition excellent in heat resistance and oxygen barrier properties capable of forming a cured body suitable for resin members of electronic devices such as organic EL, high luminance LED, and solar cell.

MEANS TO SOLVE THE PROBLEM The present inventors discovered that the said subject was solved by setting it as curable resin composition containing following (A)-(D) component, as a result of earnestly researching in order to solve the said subject, and came to complete this invention. That is, the present invention includes the following contents.

[1] A curable resin composition comprising the following components (A) to (D):

(A) an epoxy resin containing a nitrogen atom;

(B) a siloxane compound having an epoxy group;

(C) inorganic fillers and

(D) curing agent.

[2] The curable resin composition according to [1], further comprising (E) a curing accelerator.

[3] (A) The curable resin composition according to [1] or [2], wherein the nitrogen atom-containing epoxy resin includes a glycidylamine-type epoxy resin and/or a triazine derivative epoxy resin.

[4] (B) The curable resin composition according to any one of [1] to [3], wherein the siloxane compound having an epoxy group includes a cyclic siloxane skeleton.

[5] (B) The curable resin composition according to any one of [1] to [4], wherein the siloxane compound having an epoxy group contains an alicyclic epoxy group.

[6] (C) The curable resin composition according to any one of [1] to [5], wherein the inorganic filler contains at least one selected from the group consisting of synthetic fluorine phosphite mica, plate-shaped glass filler, and silica.

[7] (D) The curable resin composition according to any one of [1] to [6], wherein the curing agent is an acid anhydride.

[8] The curable resin composition according to any one of [1] to [7], which is for a resin member of an electronic device.

[9] An electronic device comprising the cured product of the curable resin composition according to any one of [1] to [8] as a resin member.

The hardening body formed of the curable resin composition of this invention has little generation|occurrence|production of an outgas even if it exposes to high temperature (that is, it has high heat resistance), and has high oxygen barrier property. Therefore, the curable resin composition of this invention is suitable for resin members of electronic devices, such as organic electroluminescent, high brightness LED, and a solar cell.

Hereinafter, the present invention will be described based on preferred embodiments thereof.

[Curable resin composition]

The curable resin composition of the present invention contains, as essential components, (A) an epoxy resin containing a nitrogen atom, (B) a siloxane compound having an epoxy group, (C) an inorganic filler, and (D) a curing agent.

<(A) Epoxy resin containing nitrogen atom>

The epoxy resin containing a nitrogen atom used in the present invention (hereinafter also referred to as component (A)) can be used without particular limitation as long as it is an epoxy resin containing a nitrogen atom in its skeleton. From the viewpoint of achieving the object of the present invention (particularly, oxygen barrier properties) at a higher level, the component (A) is preferably a glycidylamine type epoxy resin and/or a triazine derivative epoxy resin.

(Glycidylamine type epoxy resin)

The glycidylamine type epoxy resin is an epoxy resin having a structure in which the amino group of an amine is glycidylated, for example, tetraglycidyldiaminodiphenylmethane, a glycidyl compound of xylenediamine, triglycidylamino Phenol (triglycidyl-p-aminophenol, triglycidyl-m-aminophenol, etc.), tetraglycidyldiaminodiphenylmethane, tetraglycidyldiaminodiphenylsulfone, tetraglycidyldiaminodiphenyl Ether, tetraglycidylbisaminomethylcyclohexanone, diglycidyltoluidine, diglycidylaniline, diglycidylmethoxyaniline, diglycidyldimethylaniline, diglycidyltrifluoromethylaniline, etc. can be heard

As a commercial item, "630" (triglycidyl-p-aminophenol; Mitsubishi Chemicals make), "604" (tetraglycidyldiaminodiphenylmethane; Mitsubishi Chemicals make, "TETRAD-X", for example) (Glycidyl compound of xylenediamine; manufactured by Mitsubishi Gas Chemicals), "TGDDS" (tetraglycidyldiaminodiphenylsulfone; manufactured by Konishi Chemicals), "EP-3980S" (diglycidylaniline, manufactured by ADEKA) manufacture), "GAN", "GOT" (diglycidyl aniline, manufactured by Nippon Kayaku Co., Ltd.), etc. are mentioned.

The epoxy equivalent of the glycidylamine-type epoxy resin is preferably 50 to 1,000, more preferably 50 to 500, still more preferably 60 to 300, particularly preferably 80 to 200 from the viewpoint of reactivity and the like. In addition, "epoxy equivalent" is the number of grams (g/eq) of resin containing an epoxy group of 1 gram equivalent, and is measured according to the method prescribed|regulated to JISK7236.

(triazine derivative epoxy resin)

Examples of the triazine derivative epoxy resin include a 1,3,5-triazine derivative epoxy resin, and the 1,3,5-triazine derivative epoxy resin is an epoxy resin having an isocyanurate ring skeleton. is preferable Moreover, it is preferable to have two or more epoxy groups with respect to one isocyanurate ring, and, as for the epoxy resin which has isocyanurate ring skeleton, it is more preferable to have three epoxy groups. As specific examples of the epoxy resin having an isocyanurate ring skeleton, for example, 1,3,5-triglycidyl isocyanurate, tris(2,3-epoxypropyl)isocyanurate, tris(α) -Methylglycidyl)isocyanurate, tris(1-methyl-2,3-epoxypropyl)isocyanurate, 1,3,5-tris(2,3-epoxypropyl)-1,3,5 -Triazine-2,4,6(1H,3H,5H)-trione, 1,3,5-tris(3,4-epoxybutyl)-1,3,5-triazine-2,4,6 (1H,3H,5H)-trione, 1,3,5-tris(5,6-epoxybutyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-tri one, tris {2,2-bis[(oxiran-2-ylmethoxy)methyl]butyl}-3,3',3''-[1,3,5-triazine-2,4,6(1H ,3H,5H)-trione-1,3,5-triyl]tripropanoate and the like.

As a commercial item of a triazine derivative epoxy resin (epoxy resin which has an isocyanurate ring skeleton), For example, 1,3,5-tris(2,3-epoxypropyl)-1,3,5-triazine- 2,4,6(1H,3H,5H) - Trion commercial products manufactured by Nissan Chemical Industry Co., Ltd. TEPIC-G, TEPIC-S, TEPIC-SS, TEPIC-HP, TEPIC-L, TEPIC-PAS, 1, 3,5-tris(3,4-epoxybutyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trion TEPIC-VL manufactured by Nissan Chemical Industry Co., Ltd. , 1,3,5-tris(5,6-epoxybutyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trion, manufactured by Nissan Chemical Industry Co., Ltd. TEPIC-FL, tris{2,2-bis[(oxiran-2-ylmethoxy)methyl]butyl}-3,3',3''-[1,3,5-triazine-2,4,6 (1H,3H,5H)-trion-1,3,5-triyl]tripropanoate, TEPIC-UC manufactured by Nissan Chemical Industry Co., Ltd. which is a commercial item, etc. are mentioned.

The epoxy equivalent of the triazine derivative epoxy resin is preferably 50 to 1,000, more preferably 50 to 500, still more preferably 60 to 300, particularly preferably 80 to 200 from the viewpoint of reactivity.

In the present invention, when the triazine derivative epoxy resin has a structure in which an amino group is glycidylated, the triazine derivative epoxy resin does not belong to the glycidylamine type epoxy resin. That is, in the present invention, the “glycidylamine-type epoxy resin” does not include a triazine derivative.

Curable resin composition of this invention WHEREIN: It is preferable that nitrogen atom content is 0.05 to 50 %, and, as for (A) component, it is more preferable that it is 1-45 %. When the nitrogen atom content is within this range, a cured product having sufficiently high transparency and oxygen barrier properties can be easily obtained, and a curable resin composition having good reactivity in curing the resin can be obtained. In addition, "nitrogen atom content rate" is computed by following formula (i).

Nitrogen atom content (%) = [(average number of nitrogen atoms in one molecule x nitrogen atomic weight)/(molecular weight of epoxy resin)] x 100 (i)

Curable resin composition of this invention WHEREIN: As for (A) component, it is preferable that the average number of the epoxy groups in a molecule|numerator is two, three, or four.

(A) A component may be used individually by 1 type, and may use 2 or more types together. In addition, the content of component (A) in the curable resin composition is not particularly limited, from the viewpoint of oxygen barrier properties, with respect to 100% by mass of the nonvolatile matter in the curable resin composition, preferably 1% by mass or more, and more than 2% by mass or more It is preferable, and 3 mass % or more is more preferable. Moreover, 60 mass % or less is preferable with respect to 100 mass % of non-volatile matter in curable resin composition from a transparency viewpoint, 50 mass % or less is more preferable, 40 mass % or less is still more preferable.

In one embodiment of this invention, 3 mass % or more is preferable, as for content of (A) component, 5 mass % or more is more preferable with respect to the total amount (non-volatile matter) of an epoxy resin, 8 mass % or more This is more preferable. Moreover, 70 mass % or less is preferable with respect to the total amount (non-volatile matter) of an epoxy resin, 60 mass % or less is more preferable, 50 mass % or less is still more preferable.

<(B) Siloxane compound having an epoxy group>

The siloxane compound having an epoxy group used in the present invention (hereinafter also referred to as component (B)) is a compound having a skeleton based on a siloxane bond (Si-O-Si) having an epoxy group in the molecule, and as the siloxane skeleton, for example, For example, cyclic siloxane skeleton, silicone skeleton, polysilsesquioxane skeleton, etc. are mentioned. From the viewpoint of achieving heat resistance at a higher level, the siloxane skeleton is preferably a cyclic siloxane skeleton, that is, as the component (B), it is preferably a cyclic siloxane compound having an epoxy group. 2-12 are preferable and, as for the number of Si-O units (the same as the number of silicon atoms which form a siloxane ring) which form cyclic siloxane skeleton, 4-8 are more preferable.

It is preferable that the siloxane compound which has an epoxy group has two or more epoxy groups in 1 molecule. Moreover, in the cyclic siloxane compound which has an epoxy group, it is preferable that the epoxy groups are 2-4.

The component (B) is preferably an alicyclic epoxy group having an epoxy group on the alicyclic skeleton from the viewpoint of excellent transparency when transparency is required for the resin member, such as for use in a light transmitting site, that is, (B) ) As a component, the siloxane compound which has an alicyclic epoxy group is preferable, and the cyclic siloxane compound which has an alicyclic epoxy group is more preferable. Examples of the alicyclic skeleton include a cyclopropane skeleton, a cyclobutane skeleton, a cyclopentane skeleton, a cyclohexane skeleton, a cycloheptane skeleton, and a cyclooctane skeleton, and a cyclohexane skeleton is particularly preferable. That is, as for the alicyclic epoxy group, a cyclohexene oxide group is especially preferable. (B) A component may be used individually by 1 type, and may use 2 or more types together.

(B) Specific examples of the component include, for example, 2,4-di[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-2,4,6,6,8; 8-hexamethyl-cyclotetrasiloxane, 4,8-di[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-2,2,4,6,6,8-hexamethyl- Cyclotetrasiloxane, 2,4-di[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-6,8-dipropyl-2,4,6,8-tetramethyl-cyclotetra Siloxane, 4,8-di[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-2,6-dipropyl-2,4,6,8-tetramethyl-cyclotetrasiloxane, 2,4,8-tri[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-2,4,6,6,8-pentamethyl-cyclotetrasiloxane, 2,4,8 -tri[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-6-propyl-2,4,6,8-tetramethyl-cyclotetrasiloxane, 2,4,6,8- tetra[2-(3-{oxabicyclo[4.1.0]heptyl})ethyl]-2,4,6,8-tetramethyl-cyclotetrasiloxane, silsesquioxane having two or more epoxy groups in the molecule, etc. can be heard

The epoxy equivalent of the siloxane compound having an epoxy group is preferably 50 to 6,000, more preferably 50 to 5,000, still more preferably 60 to 4,000, particularly preferably 80 to 4,000 from the viewpoint of reactivity and the like. Moreover, the weight average molecular weight of the siloxane compound which has an epoxy group becomes like this. Preferably it is 200-8,000, More preferably, it is 200-6,000.

As a commercially available product of the siloxane compound having an epoxy group, for example, an alicyclic epoxy-based cyclic silicone oligomer (a cyclic siloxane compound having an alicyclic epoxy group) “KR-470” (the number of epoxy groups 4), “X-40-2670” (the epoxy group Number 4), "X-40-2678" (number of epoxy groups 2) (both manufactured by Shin-Etsu Chemical Co., Ltd.), modified silicone oils having alicyclic epoxy groups at both terminals "X-22-169B", "X-22-169AS" (All manufactured by Shin-Etsu Chemical), modified silicone oils having an epoxy group at both ends "X-22-163", "KF-105", "X-22-163A", "X-22-163B", "X- 22-163C", modified silicone oil having an alicyclic epoxy group in the side chain "X-22-2046", "KF-102" (all manufactured by Shin-Etsu Chemical Co., Ltd.), modified silicone oil having an epoxy group in the side chain "X-22-343" ', "KF-101", "KF-1001", and "X-22-2000" (all manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

Although content of (B) component in curable resin composition of this invention is not specifically limited, From a viewpoint of improving heat resistance, with respect to 100 mass % of non-volatile matter of curable resin composition, 10 mass % or more is preferable, 15 mass % or more This is more preferable, 20 mass % or more is still more preferable, and 15 mass % or more is especially preferable. Further, from the viewpoint of lowering the oxygen permeability, the content is preferably 90% by mass or less, more preferably 80% by mass, and still more preferably 75% by mass or less, with respect to 100% by mass of the nonvolatile matter of the curable resin composition. and 70 mass % or less is especially preferable.

In one embodiment of this invention, 15 mass % or more is preferable, as for content of (B) component with respect to the total amount (non-volatile matter) of an epoxy resin, 20 mass % or more is more preferable, 25 mass % or more more preferably. Moreover, 70 mass % or less is preferable with respect to the total amount (non-volatile matter) of an epoxy resin, 60 mass % or less is more preferable, 50 mass % or less is still more preferable.

<(C) Inorganic filler>

The inorganic filler (hereinafter also referred to as (C) component) used in the present invention can be used without particular limitation. An inorganic filler may be used individually by 1 type, and may use 2 or more types together. The inorganic filler is preferably a plate-shaped filler or silica from the viewpoint of achieving oxygen barrier properties at a higher level. In addition, when transparency is required for a resin member, such as for use in a light-transmitting site, from the viewpoint of making it excellent in transparency, plate glass, layered silicate minerals (especially smectite, synthetic fluorophorite mica) and nanosilica are preferable. . Here, plate-shaped glass and layered silicate mineral (especially smectite, synthetic fluorine phlogopite) are all plate-shaped fillers.

In one embodiment of the present invention, the inorganic filler preferably includes at least one member selected from the group consisting of synthetic fluorine phosphite mica, plate glass filler, and silica.

A plate-shaped filler will not be specifically limited if the effect of this invention is exhibited, For example, plate-shaped glass (A glass, C glass, E glass, etc.), a layered silicate mineral, etc. are mentioned. As a layered silicate mineral, kaolinite, halloysite, talc, smectite, mica, etc. are mentioned, for example. Among the mica, synthetic fluorine phlogopite mica is preferable from the viewpoint of making it excellent in transparency. As for a plate-shaped filler, from a viewpoint of making it excellent in transparency, plate-shaped glass, smectite, and synthetic|combination fluorophosphite mica are especially preferable. These plate-shaped fillers may be used individually by 1 type, and may use 2 or more types together.

Synthetic fluoride phlogopite mica is a kind of synthetic mica, and in that it is a large, highly transparent crystal, it is different from natural mica and other synthetic mica (K silicon mica, Na silicon mica, Na teniolite, Li teniolite). different. Moreover, the thing of various glass compositions represented by A glass, C glass, E glass, etc. can be used as a plate-shaped glass filler.

An average aspect ratio (average particle diameter/average thickness) of 1 or more is preferable, as for a plate-shaped filler, 1.5 or more are more preferable, and 2 or more are still more preferable. When the average aspect ratio is 1 or more, it tends to be easy to obtain sufficient oxygen barrier properties. Further, the average aspect ratio is preferably 1,000 or less, more preferably 800 or less, and still more preferably 500 or less. If the average aspect ratio is 1,000 or less, it tends to be easy to obtain sufficient dispersibility.

The average thickness of the plate-like filler is preferably 0.01 to 20 µm, more preferably 0.05 to 10 µm. The average thickness is measured by the following method.

Using a scanning electron microscope (SEM), each thickness is measured for 100 particles, and these measurements are averaged to obtain the result. In this case, individual particles may be observed and measured with a scanning electron microscope, or a filler (particle group) may be filled with resin and molded, the molded body may be broken, and the fracture surface may be observed and measured. In any measurement method, the sample stage of a scanning electron microscope is adjusted with the sample stage micro-movement device so that the cross section (thickness surface) of particle|grains may become perpendicular|vertical to the irradiation electron beam axis of a scanning electron microscope.

From a viewpoint of improving oxygen barrier property, 0.5 micrometer or more is preferable, 1 micrometer or more is more preferable, and, as for the average particle diameter of a plate-shaped filler, 2 micrometers or more are still more preferable. Moreover, from a viewpoint of transparency, 2,000 micrometers or less are preferable, 1,500 micrometers or less are more preferable, and 1,000 micrometers or less are still more preferable.

The average particle diameter can be measured by a laser diffraction/scattering method based on the Mie scattering theory. Specifically, it can measure by creating the particle size distribution of a filler on a volume basis with a laser diffraction type particle size distribution measuring apparatus, and making the median diameter into an average particle diameter. As a measurement sample, what disperse|distributed the filler in water by ultrasonic wave can be used preferably. As a laser diffraction scattering type particle size distribution analyzer, Horiba Corporation LA-500 etc. can be used.

As for silica, so-called nano silica whose particle diameter of a primary particle is nano order is preferable. As for silica, a spherical thing is used normally. It is preferable that the particle diameters of a primary particle are 1-100 nm, and it is more preferable that it is 1-50 nm. Since the measurement of the primary particle diameter of nanosilica is relatively difficult, a conversion value from a specific surface area measurement value (based on JIS Z8830) may be used. Also in the silica suitable for this invention, it can be set as the silica more suitable for this invention by making the BET specific surface area into a predetermined value. And appropriate BET specific surface area of 2,720 to about 27m ² / g, more preferably from 2,720 to about 54m ² / g.

In addition, the inorganic filler may be surface-treated with a surface treating agent. Examples of the surface treatment agent include an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, a vinylsilane-based coupling agent, an imidazolesilane-based coupling agent, an organosilazane compound, and a titanate-based coupling agent. have. You may use a surface treatment agent 1 type or in combination of 2 or more type.

Although there is no restriction|limiting in particular content of (C) component in curable resin composition of this invention, 1 mass % or more is preferable with respect to 100 mass % of non-volatile matter of curable resin composition from a viewpoint of improving oxygen barrier property, 2 mass % or more is more preferable, 3 mass % or more is still more preferable, and 5 mass % or more is especially preferable. Further, from the viewpoint of transparency, the content is preferably 65% by mass or less, more preferably 60% by mass, still more preferably 55% by mass or less, with respect to 100% by mass of the nonvolatile matter of the curable resin composition, 50 % by mass or less is particularly preferred.

<(D) curing agent>

The curing agent used in the present invention (hereinafter, also referred to as component (D)) can be used without particular limitation as long as it has a function of curing the epoxy resin. For example, a phenol-based curing agent, a naphthol-based curing agent, an acid anhydride-based curing agent, an active ester-based curing agent, a benzoxazine-based curing agent, a cyanate ester-based curing agent, a carbodiimide-based curing agent, and an imidazole-based curing agent may be mentioned. From a viewpoint of heat resistance and transparency, it is preferable that (D) component is an acid anhydride type hardening|curing agent. A hardening|curing agent may be used individually by 1 type, and may be used in combination of 2 or more type.

As an acid anhydride type hardening|curing agent, the hardening|curing agent which has one or more acid anhydride groups in 1 molecule is mentioned. Examples of the acid anhydride curing agent include phthalic acid anhydride, succinic acid anhydride, maleic acid anhydride, trimelliic acid anhydride, norbornene acid anhydride, and nitrile rubber having an acid anhydride group. As phthalic acid anhydride, phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 3 3',4,4 '-diphenylsulfonetetracarboxylic dianhydride etc. are mentioned. Examples of the succinic acid anhydride include succinic anhydride, octenyl succinic anhydride, tetrapropenyl succinic anhydride, and butane-1,2,3,4-tetracarboxylic dianhydride. Maleic anhydride etc. are mentioned as maleic anhydride. Examples of the trimelliic acid-based acid anhydride include ethylene glycol/bisanhydrotrimellitate and glycerinbis/anhydrotrimellitate/monoacetate. Examples of the norbornene acid anhydride include methyl-5-norbornene-2,3-dicarboxylic acid anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, and bicyclo[2.2.1]heptane-2,3- dicarboxylic acid anhydride, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid anhydride, and the like. Examples of the nitrile rubber having an acid anhydride group include succinic anhydride-modified hydrogenated nitrile rubber, maleic anhydride-modified hydrogenated nitrile rubber, and the like. A norbornene-type acid anhydride is mentioned as an especially preferable acid anhydride.

As a commercially available acid anhydride type hardening|curing agent, For example, Rikasiddo TH (1,2,3,6-tetrahydrophthalic anhydride), Rikasiddo HH (hexahydrophthalic anhydride), manufactured by Shin Nippon Rica Co., Ltd. Casiddo HNA-100 (methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid anhydride/bicyclo[2.2.1]heptane-2,3-dicarboxylic acid anhydride), Ricasiddo MH-700, Li Cassiddo MH-700G (4-methylhexahydrophthalic anhydride/hexahydrophthalic anhydride = 70/30), Rikasiddo MH (4-methylhexahydrophthalic anhydride), Rikasiddo TMEG-S, Rikasiddo TMEG- 100, Rikasido TMEG-200, Rikasiddo TMEG-500, Rikasiddo TMEG-600 (ethylene glycol bisanhydrotrimellitate), Rikasiddo TMTA-C (glycerin bisanhydrotrimellitate) Monoacetate), Rikasiddo MTA-15 (a mixture of glycerin bis anhydrotrimellitate monoacetate and alicyclic dicarboxylic anhydride), Rikasiddo DDSA (tetrapropenyl succinic anhydride), Rikasiddo OSA (octenyl succinic anhydride), Rikasiddo HF-08 (esters of alicyclic acid anhydrides and polyalkylene glycols), Rikasiddo SA (succinic anhydride), Rikasiddo DSDA (3,3',4,4) '-diphenylsulfone tetracarboxylic dianhydride), Rikasido BT-100 (1,2,3,4-butanetetracarboxylic dianhydride), and Ricasiddo TBN series (nonvolatile acid anhydride).

The acid anhydride equivalent of the acid anhydride curing agent is preferably 70 to 1,000, more preferably 80 to 900, still more preferably 90 to 800, particularly preferably 100 to 700 from the viewpoint of reactivity and the like. In addition, "acid anhydride equivalent" is the number of grams (g/eq) of an acid anhydride-based curing agent containing 1 gram equivalent of an acid anhydride group, and is used for component analysis by nuclear magnetic resonance (NMR), gas chromatography (GC), etc. is measured by

Examples of the phenol-based curing agent and the naphthol curing agent include a phenol-based curing agent having a novolak structure or a naphthol curing agent having a novolak structure, a triazine skeleton-containing phenolic curing agent or a triazine skeleton-containing naphthol curing agent.

As the active ester curing agent, generally a compound having two or more ester groups in one molecule with high reaction activity, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. can be heard It is preferable that an active ester type hardening|curing agent is obtained by the condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound, and a hydroxy compound and/or a thiol compound. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac, etc. are mentioned. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol to one molecule of dicyclopentadiene.

More specifically, it includes an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and a benzoyl product of phenol novolac. and active ester compounds.

Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis(2,6) -Dimethylphenylcyanate), 4,4'-ethylidenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4 -Cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4- Bifunctional cyanate resins such as cyanate phenyl) thioether and bis (4-cyanate phenyl) ether, polyfunctional cyanate resins derived from phenol novolac and cresol novolac, etc., these cyanate resins are partially triazined A prepolymer etc. are mentioned.

Examples of the imidazole-based curing agent include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl. Midazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole Sol, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl- 4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium tri melitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimida Zolyl-(1′)]-ethyl-s-triazine, 2,4-diamino-6-[2′-ethyl-4′-methylimidazolyl-(1′)]-ethyl-s-triazine , 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl- (1')]-ethyl-s-triazineisocyanuric acid adduct, 2-phenylimidazoleisocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl -4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzyl imida imidazole compounds, such as zolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and adduct bodies of an imidazole compound and an epoxy resin.

The content of the curing agent (D) in the curable resin composition of the present invention is not particularly limited as long as the effect of the present invention is exhibited, but from the viewpoint of optical properties such as total light transmittance and ductility, the content is With respect to 100 mass % of non-volatile matter of a resin composition, 90 mass % or less is preferable, 85 mass % or less is more preferable, 80 mass % or less is still more preferable, 75 mass % or less is especially preferable. In addition, from the viewpoint of accelerating curing of the curable resin composition, the content is preferably 2% by mass or more, more preferably 5% by mass or more, more preferably 7% by mass or more, with respect to 100% by mass of the nonvolatile matter of the curable resin composition. desirable.

In one embodiment of this invention, 5 mass % or more is preferable, as for content of (D)component, 7 mass % or more is more preferable with respect to the total amount (non-volatile matter) of an epoxy resin, 10 mass % or more This is more preferable. Moreover, 150 mass % or less is preferable with respect to the total amount (non-volatile matter) of an epoxy resin, 135 mass % or less is more preferable, and its 120 mass % or less is still more preferable.

<(E) curing accelerator>

The curable resin composition of this invention may contain the hardening accelerator (henceforth (E) component) for the purpose of improving sclerosis|hardenability other than the said (A)-(D) component. Although it does not specifically limit as a hardening accelerator, For example, an amine type hardening accelerator, an imidazole type hardening accelerator, a phosphorus type hardening accelerator, a guanidine type hardening accelerator, a metal type hardening accelerator, etc. are mentioned. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the amine curing accelerator include triethylamine, tributylamine, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-dia Java bicyclo [5.4.0] undecene, etc. are mentioned, Aliphatic amine type hardening|curing agents, such as 4-dimethylamino pyridine and 1,8- diazabicyclo [5.4.0] undecene; Benzidine, o-trizine, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-di Ethyldiphenylmethane, 4,4'-diamino-3,3',5,5'-tetramethyldiphenylmethane, 4,4'-diamino-3,3',5,5'-tetraethyldi Phenylmethane, 4,4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane, 4,4'-diaminodiphenyl ether, 1,3-bis(3-aminophenoxy) C)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 1,3- Bis(4-aminophenoxy)neopentane, 4,4'-[1,3-phenylenebis(1-methyl-ethylidene)]bisaniline, 4,4'-[1,4-phenylenebis( 1-Methyl-ethylidene)bisaniline, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane and aromatic amine curing agents such as 4,4'-bis(4-aminophenoxy)phenyl.

Examples of the imidazole-based curing accelerator include those described in the above-mentioned imidazole-based curing agent. The imidazole-based curing agent may function as a curing accelerator when used in combination with other curing agents.

Examples of the phosphorus-based curing accelerator include triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphoniumdecanoate, (4-methylphenyl)triphenyl Phosphonium thiocyanate, tetraphenyl phosphonium thiocyanate, butyl triphenyl phosphonium thiocyanate, methyl tributyl phosphonium dimethyl phosphate, tetraphenyl phosphonium, tetrabutyl phosphonium, etc. are mentioned.

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, and diphenylguanidine. , trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]deca-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1, 1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, etc. are mentioned.

Examples of the metal-based curing accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese and tin. Specific examples of the organometallic complex include organocobalt complexes such as cobalt(II)acetylacetonate and cobalt(III)acetylacetonate, organocopper complexes such as copper(II)acetylacetonate, and zinc(II)acetylacetonate. organic zinc complexes, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organometallic salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like.

In the curable resin composition of the present invention, the content of the curing accelerator in the case of using a curing accelerator is usually in the range of 0.05 to 5 mass % with respect to the total amount (non-volatile matter) of the epoxy resin contained in the curable resin composition. .

<(F) additive>

In the curable resin composition of the present invention, radical polymerization initiators such as 2,2'-azobis(isobutyric acid)dimethyl, rubber particles, silicone powder, nylon powder, fluororesin powder, within the range not impairing the effects of the present invention organic fillers such as; silicone-based, fluorine-based, polymer-based defoaming agents or leveling agents; thickeners such as orben and bentone; antioxidants; heat stabilizer; Additives, such as a light stabilizer, can be mix|blended.

<Use>

Curable resin composition of this invention is used as a resin member, such as a sealing site|part, an adhesion|attachment site|part, and a light transmission site|part in an electronic device, especially optical devices, such as organic electroluminescent, high brightness LED, and a solar cell, for example.

When the curable resin composition of the present invention is molded into a film, for example, a varnish (resin composition varnish) prepared by mixing the components of the curable resin composition and an organic solvent using a kneading roller or a rotary mixer, etc. is subjected to a release treatment. A resin composition molded into a film is obtained by applying on a support and removing the organic solvent from the varnish applied on the support by heating (hot air spraying, etc.) and/or reduced pressure treatment using a known device (hereinafter, Also referred to as "film-like resin composition").

Examples of the support of the support subjected to the release treatment include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride; polyesters such as cycloolefin polymer, polyethylene terephthalate (hereinafter, may be abbreviated as "PET"), and polyethylene naphthalate; polycarbonate; A plastic film (preferably PET film), such as polyimide, and metal foil, such as aluminum foil, stainless foil, and copper foil, are used. As a mold release process of the support body which carried out the mold release process, the mold release process by mold release agents, such as a silicone resin mold release agent, an alkyd resin mold release agent, and a fluororesin mold release agent, is mentioned, for example.

Solid content of the resin composition varnish becomes like this. Preferably it is 20-80 mass %, More preferably, it is 30-70 mass %.

Although there is no restriction|limiting in particular in the heating conditions for removing the organic solvent from the resin composition varnish, Usually, about 2 to 10 minutes at about 50-130 degreeC is suitable.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; Cellosolves, such as cellosolve, carbitols, such as butylcarbitol, aromatic hydrocarbons, such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. are mentioned. Any 1 type may be used for these organic solvents, and may use 2 or more types together.

Although the thickness of the film-form resin composition also changes with the apparatus which applies the film-form resin composition, and an application site|part, Preferably it is 1-1,000 micrometers, More preferably, it is the range of 2-800 micrometers.

The film-form resin composition formed on the support is preferably protected with a protective film for protection until the resin composition is cured, for example, using a known device for the film-form resin composition formed on the support, and releasing the resin composition. The treated protective film can be laminated. As an apparatus used for lamination|stacking of a protective film, a roll laminator, a press machine, a vacuum pressure laminator etc. are mentioned, for example.

The protective film to which the release process was carried out, For example, Polyolefin, such as polyethylene, a polypropylene, and polyvinyl chloride; polyesters such as cycloolefin polymer, polyethylene terephthalate (hereinafter, may be abbreviated as "PET"), and polyethylene naphthalate; polycarbonate; A plastic film (preferably a PET film) such as polyimide, or a support made of a metal foil such as aluminum foil, stainless foil, or copper foil, which has been subjected to a release treatment is used. As a mold release process, the mold release process by mold release agents, such as a silicone resin mold release agent, an alkyd resin mold release agent, and a fluororesin mold release agent, is mentioned, for example.

<hardening body>

The cured product of the present invention is obtained by thermosetting the curable resin composition of the present invention, and can be used as a resin member of an electronic device. When the film-form resin composition is cured, a film-form cured body is obtained, which can be a film-form resin member.

From a viewpoint of fully advancing hardening reaction, 70 degreeC or more is preferable, and, as for the hardening temperature of thermosetting, 80 degreeC or more is more preferable. Moreover, from a viewpoint of coloring prevention of a hardening body, 180 degrees C or less is preferable, and 165 degrees C or less is more preferable. Moreover, 10 minutes or more are preferable and, as for heating time, 20 minutes or more are more preferable. Moreover, 150 minutes or less are preferable and 130 minutes or less are more preferable.

Examples of the heating means include a hot air circulation type oven, an infrared heater, a heat gun, a high-frequency induction heating device, and heating by pressing a heat tool.

The curable resin composition of this invention can apply|coat liquid resin compositions, such as a varnish, to a desired part, and can also perform hardening reaction and form the resin member of a desired shape.

Example

Hereinafter, the present invention will be described in more detail by disclosing Examples, but the present invention is not limited to these Examples. In addition, in the following description, "part" in the quantity of a component means "part by mass" unless otherwise specified.

Materials used in Examples and Comparative Examples are shown below.

(A) component

"TEPIC-VL" (manufactured by Nissan Chemical Industry Co., Ltd.): epoxy resin having an isocyanurate ring skeleton, 1,3,5-triglycidyl isocyanurate, epoxy equivalent 135 g/eq, nitrogen content 12%

"TEPIC-FL" (manufactured by Nissan Chemical Industry Co., Ltd.): an epoxy resin having an isocyanurate ring skeleton, 1,3,5-triglycidyl isocyanurate, an epoxy equivalent of 175 g/eq, a nitrogen content of 9%

"EP3890S" (manufactured by ADEKA Corporation): glycidylamine-type epoxy resin, diglycidylaniline, epoxy equivalent 115 g/eq, nitrogen content 6%

"630" (manufactured by Mitsubishi Chemical): p-aminophenol type epoxy resin, triglycidyl-p-aminophenol, epoxy equivalent 95 g/eq, nitrogen content 5%

(B) component

"KR-470" (manufactured by Shin-Etsu Chemical Co., Ltd.): cyclic siloxane compound having an alicyclic epoxy group, epoxy equivalent 200 g/eq, number of epoxy groups 4, number of Si-O units 4

"X-40-2678" (manufactured by Shin-Etsu Chemical Co., Ltd.): cyclic siloxane compound having an alicyclic epoxy group, epoxy equivalent 290 g/eq, number of epoxy groups 2, number of Si-O units 4

(C) component

"FTD010FY-F01" (manufactured by Nihon Ita Glass): plate-shaped glass filler, average particle diameter of 10 µm, average aspect ratio 25

"MEG160FY" (manufactured by Nippon Ita Glass): plate-shaped glass filler, average particle diameter of 160 µm, average aspect ratio of 30

"PDM-20L" (manufactured by Topico Corporation): mica (synthetic fluoride phlogopite mica), average particle diameter of 20 µm, average aspect ratio of 70

"PDM-40L" (manufactured by Topico Corporation): mica (synthetic fluoride phosphite mica), average particle diameter of 40 µm, average aspect ratio of 90

"Y10SV-AM1" (manufactured by Adomatex): Nanosilica (vinyl silane coupling agent surface treatment) particle diameter 10 nm, specific surface area 300 m ² /g

(D) component

"HNA-100" (manufactured by New Japan Rica): norbornene-based acid anhydride (bicycloheptane dicarboxylic acid anhydride), acid anhydride equivalent 184 g/eq

(E) component

"PX-4MP" (manufactured by Nippon Chemical Co., Ltd.): phosphorus-based curing accelerator (methyltributylphosphonium dimethyl phosphate)

<Example 1>

10 parts of an epoxy resin having an isocyanurate ring skeleton ("TEPIC-VL" manufactured by Nissan Chemical Industry Co., Ltd.), 70 parts of a cyclic siloxane compound having an alicyclic epoxy group ("KR-470" manufactured by Shin-Etsu Chemical), an alicyclic 20 parts of a cyclic siloxane compound having an epoxy group ("X-40-2678" manufactured by Shin-Etsu Chemical Co., Ltd.) 91 parts of norbornene-based acid anhydride ("HNA-100" manufactured by Shin-Nippon Rica) 16 parts of manufactured "FTD010FY-F01"), 4 parts of plate-shaped glass filler ("MEG160FY" manufactured by Nippon Ita Glass Co., Ltd.) and 2.1 parts of a phosphorus curing accelerator ("PX-4MP" manufactured by Nippon Chemical Co., Ltd.) 2.1 parts are mixed, and then, It disperse|distributed uniformly with a high-speed rotation mixer, and obtained the resin composition.

<Example 2>

Except having changed 10 parts of "TEPIC-VL" into 10 parts of "TEPIC-FL", and having changed 91 parts of "HNA-100" into 88 parts, it carried out similarly to Example 1, and obtained the resin composition.

<Example 3>

Changed 10 parts of "TEPIC-VL" to 10 parts of glycidylamine type epoxy resin "EP-3980S", changed 91 parts of "HNA-100" to 93 parts, and changed 2.1 parts of "PX-4MP" to 2.2 parts. It carried out similarly to Example 1, and obtained the resin composition.

<Example 4>

Except having changed 10 parts of "EP-3980S" into 10 parts of "630" and having changed 93 parts of "HNA-100" into 95 parts, it carried out similarly to Example 3, and obtained the resin composition.

<Example 5>

Each material used in Example 1 was changed to the compounding ratio shown in Table 1, it disperse|distributed uniformly similarly to Example 1, and the resin composition of Example 5 was obtained.

<Example 6>

30 parts of an epoxy resin having an isocyanurate ring skeleton ("TEPIC-VL" manufactured by Nissan Chemical Corporation), 80 parts of a cyclic siloxane compound having an alicyclic epoxy group ("KR-470" manufactured by Shin-Etsu Chemical), alicyclic 20 parts of a cyclic siloxane compound having an epoxy group (“X-40-2678” manufactured by Shin-Etsu Chemical Co., Ltd.), 102 parts of norbornene-based acid anhydride (“HNA-100” manufactured by Shin-Nippon Rica), 102 parts of synthetic fluorine phosphite mica (Topico Co., Ltd.) Manufactured "PDM-20L") 16 parts, synthetic fluorine phosphite mica ("PDM-40L" manufactured by Topico Co., Ltd.) 5 parts and phosphorus-based curing accelerator ("PX-4MP" manufactured by Nippon Chemical Co., Ltd.) 2.6 parts were mixed, and the Then, it was uniformly dispersed with a high-speed rotary mixer to obtain a resin composition.

<Example 7>

30 parts of an epoxy resin having an isocyanurate ring skeleton ("TEPIC-FL" manufactured by Nissan Chemical Industries, Ltd.), 60 parts of a cyclic siloxane compound having an alicyclic epoxy group ("KR-470" manufactured by Shin-Etsu Chemical), alicyclic 10 parts of a cyclic siloxane compound having an epoxy group ("X-40-2678" manufactured by Shin-Etsu Chemical Co., Ltd.) 94 parts of norbornene-based acid anhydride ("HNA-100" manufactured by Shin-Nippon Rica), plate-shaped glass filler (Nippon Itagas Co., Ltd.) 20 parts of manufactured "FTD010FY-F01"), 50 parts of nanosilica ("Y10SV-AM1" manufactured by Adomatex Co., Ltd.), and 2.7 parts of a phosphorus curing accelerator ("PX-4MP" manufactured by Nippon Chemical Industries, Ltd.) are mixed, and then It disperse|distributed uniformly with a high-speed rotation mixer, and obtained the resin composition.

<Example 8>

10 parts of an epoxy resin having an isocyanurate ring skeleton ("TEPIC-VL" manufactured by Nissan Chemical Industry Co., Ltd.), 90 parts of a cyclic siloxane compound having an alicyclic epoxy group ("KR-470" manufactured by Shin-Etsu Chemical), Norbor 96 parts of nene-based acid anhydride (“HNA-100” manufactured by Shin-Nippon Rika Co., Ltd.), 20 parts of plate glass filler (“FTD010FY-F01” manufactured by Nippon Ita Glass Co., Ltd.), and a phosphorus-based curing accelerator (“PX-4MP” manufactured by Nippon Chemical Co., Ltd.) ') 2.2 parts were mixed, and then uniformly dispersed with a high-speed rotary mixer to obtain a resin composition.

<Example 9>

In the same manner as in Example 8, except that 90 parts of “KR-470” were changed to 90 parts of “X-40-2678”, 96 parts of “HNA-100” were changed to 71 parts, and 2.2 parts of “PX-4MP” were changed to 1.9 parts. Thus, a resin composition was obtained.

<Comparative Example 1>

70 parts of a cyclic siloxane compound having an alicyclic epoxy group (“KR-470” manufactured by Shin-Etsu Chemical Co., Ltd.) 30 parts of a cyclic siloxane compound having an alicyclic epoxy group (“X-40-2678” manufactured by Shin-Etsu Chemical) 30 parts, norbornene-based acid 83 parts of anhydride (“HNA-100” manufactured by Shin-Nippon Rica Co., Ltd.) and 1.9 parts of a phosphorus curing accelerator (“PX-4MP” manufactured by Nippon Chemical Co., Ltd.) are mixed, and then uniformly dispersed with a high-speed rotary mixer to obtain a resin composition got it

<Comparative Example 2>

70 parts of a cyclic siloxane compound having an alicyclic epoxy group (“KR-470” manufactured by Shin-Etsu Chemical Co., Ltd.) 30 parts of a cyclic siloxane compound having an alicyclic epoxy group (“X-40-2678” manufactured by Shin-Etsu Chemical) 30 parts, norbornene-based acid 83 parts of anhydride (“HNA-100” manufactured by Nippon Rica Co., Ltd.), 16 parts of plate-shaped glass filler (“FTD010FY-F01” manufactured by Nippon Ita Glass), 4 parts of plate-shaped glass filler (“MEG160FY” manufactured by Nippon Ita Glass), and 2.1 parts of phosphorus curing accelerators ("PX-4MP" manufactured by Nippon Chemical Industry Co., Ltd.) were mixed, and then, uniformly dispersed with a high-speed rotary mixer to obtain a resin composition.

<Comparative Example 3>

100 parts of p-aminophenol type epoxy resin "630", 184 parts of norbornene-based acid anhydride ("HNA-100" manufactured by Nippon Rica), 16 parts of plate glass filler ("FTD010FY-F01" manufactured by Nippon Ita Glass) , 4 parts of plate glass filler (“MEG160FY” manufactured by Nippon Ita Glass) and 3.1 parts of a phosphorus curing accelerator (“PX-4MP” manufactured by Nippon Chemical Co., Ltd.) are mixed, and then uniformly dispersed with a high-speed rotary mixer to form a resin composition got

<Comparative Example 4>

10 parts of an epoxy resin having an isocyanurate ring skeleton ("TEPIC-FL" manufactured by Nissan Chemical Industries, Ltd.), 70 parts of a cyclic siloxane compound having an alicyclic epoxy group ("KR-470" manufactured by Shin-Etsu Chemical), alicyclic 20 parts of a cyclic siloxane compound having an epoxy group ("X-40-2678" manufactured by Shin-Etsu Chemical Co., Ltd.), 88 parts of norbornene-based acid anhydride ("HNA-100" manufactured by Shin-Nippon Rica), and a phosphorus-based curing accelerator (Nippon Chemical Co., Ltd.) 1.9 parts of "PX-4MP" manufactured by Kyoyo Co., Ltd.) were mixed, and then uniformly dispersed with a high-speed rotary mixer to obtain a resin composition.

<Heat resistance test>

The resin composition prepared in Examples and Comparative Examples was heated at 90° C. for 2 hours and then heated at 150° C. for 2 hours to prepare a cured body, and the amount of thermal weight loss (%) at 380° C. It measured with the measuring apparatus ("TG/DTA STA7200RV" manufactured by Hitachi High-Tech Sciences). In this evaluation, 10 mg of each sample of the cured product was weighed in a sample pan made of aluminum, and in an open state without a lid, in the atmosphere, from 25°C to 400°C, the temperature increase rate was 20°C/min. The thermogravimetric reduction rate was calculated by the following formula (ii).

Thermogravimetric reduction rate (%) = 100 x (mass before heating (μg) - mass when reaching a predetermined temperature (μg)) / mass before heating (μg) (ii)

The heat resistance test was evaluated using the following criteria.

Good ○: less than 20%

Bad ×: 20% or more

<Measurement of oxygen transmittance>

^{(1) A frame (flat shape of border: 10cm×10cm, planar area: 100cm 2} ) is formed on a polyimide film (Upirex (manufactured by Ubeko San Co., Ltd., thickness 75 μm) with a 200 μm thick tape), and within the frame The resin composition was poured, bar-coated with a glass bar, heated at 90° C. for 2 hours in a thermal cycle oven, and then heated at 150° C. for 2 hours to obtain a cured body (test piece) having a thickness of around 200 μm. It measured down to the unit of 1 micrometer with a micrometer (made by Mitutoyo).

(2) Using an oxygen permeability measuring device (manufactured by Mocon, trade name “OX-TRAN 2/22L”), the oxygen permeability of the test piece under an environment at 23° C. and 50% RH (relative humidity) (unit: ml·200) μm/m ² ·day·atm) was measured and evaluated using the following criteria.

Good ○: less than 500ml·200㎛/m ² ·day·atm

Defect ×: 500ml·200㎛/m ² ·day·atm or more

<Measurement of total light transmittance>

(1) After pouring the resin composition into the teddy of boat glass (mold glass with a length of 8 mm, a width of 6 mm and a thickness of 200 μm), heated at 90° C. The resin composition was hardened by heating for 2 hours, and the laminated body (sample for evaluation, thickness of a hardening body: 200 micrometers) which has the hardening body of the resin composition was obtained.

(2) Evaluation of light absorption capacity in short wavelength region (measurement of total light transmittance at 400 nm)

Fiber-type spectrophotometer (MCPD-7700, model 311C, manufactured by Otsuka Denshi Corporation, external light source unit: halogen lamp MC-2564 (24V, 150W specification)) equipped with a φ80 mm integrating sphere (model SRS-99-010, reflectance 99%) ) was used, the distance between the integrating sphere and the evaluation sample was set to 0 mm, and the distance between the light source and the evaluation sample was set to 48 mm, and the light transmittance spectrum of the obtained evaluation sample was measured. The reference was made into the same glass as above. The total light transmittance (%) of 400 nm was calculated|required from the obtained light transmittance spectrum.

Table 1 below shows the composition and test results of the resin compositions of Examples and Comparative Examples.

From Table 1, it turns out that the curable resin composition of an Example can form the hardening body which has high heat resistance and high oxygen barrier property. In addition, it can be seen that the curable resin composition of Examples is also excellent in transparency.

[Table 1]

Even if the hardening body of curable resin composition of this invention is exposed to high temperature, there is little amount of generation of an outgas, and it is excellent in heat resistance. Moreover, it is excellent also in oxygen barrier property, and it is suitable for resin members, such as a sealing site|part, a bonding site|part, and a light transmission site|part in electronic devices, especially optical devices, such as organic electroluminescent, high-brightness LED, and a solar cell.

This application is based on Japanese Patent Application No. 2019-068248 filed in Japan, the contents of which are all incorporated herein.

Claims (9)

Curable resin composition containing the following components (A) to (D):
(A) an epoxy resin containing a nitrogen atom;
(B) a siloxane compound having an epoxy group;
(C) inorganic fillers and
(D) curing agent. The curable resin composition according to claim 1, further comprising (E) a curing accelerator. The curable resin composition according to claim 1 or 2, wherein the (A) nitrogen atom-containing epoxy resin includes a glycidylamine-type epoxy resin and/or a triazine derivative epoxy resin. The curable resin composition according to any one of claims 1 to 3, wherein (B) the siloxane compound having an epoxy group includes a cyclic siloxane skeleton. The curable resin composition according to any one of claims 1 to 4, wherein (B) the siloxane compound having an epoxy group contains an alicyclic epoxy group. The curable resin composition according to any one of claims 1 to 5, wherein (C) the inorganic filler contains at least one member selected from the group consisting of synthetic fluorine phosphite mica, plate-shaped glass filler, and silica. The curable resin composition according to any one of claims 1 to 6, wherein (D) the curing agent is an acid anhydride. The curable resin composition according to any one of claims 1 to 7, which is for a resin member of an electronic device. The electronic device which contains the hardening body of curable resin composition in any one of Claims 1-8 as a resin member.