阅读说明：本技术 固化性树脂组合物 (Curable resin composition ) 是由 佐藤大河 大桥贤 久保有希 于 2020-03-27 设计创作，主要内容包括：本发明提供可形成适合用于有机EL、高亮度LED、太阳能电池等电子器件的树脂构件的固化体的、耐热性和氧气阻隔性优异的固化性树脂组合物。固化性树脂组合物,其包含下述的(A)～(D)成分：(A)含有氮原子的环氧树脂；(B)含有环氧基的硅氧烷化合物；(C)无机填料；及(D)固化剂。(The invention provides a curable resin composition which can form a cured body suitable for resin members of electronic devices such as organic EL, high-brightness LED, solar battery and the like, and has excellent heat resistance and oxygen barrier property. A curable resin composition comprising the following components (A) to (D): (A) an epoxy resin containing a nitrogen atom; (B) an epoxy group-containing silicone compound; (C) an inorganic filler; and (D) a curing agent.)

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) An inorganic filler, and

(D) and (3) a curing agent.

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

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

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

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

6. The curable resin composition according to any one of claims 1 to 5, wherein the inorganic filler (C) comprises 1 or more selected from synthetic fluorophlogopite, a plate-like glass filler and silica.

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

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

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

Technical Field

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

Background

In electronic devices, particularly in optical devices such as organic EL, high-brightness LED, and solar cell, a resin member formed of a cured product of a resin composition or the like may be used in some cases, such as a sealing portion, an adhesive portion, and a light transmitting portion. Such a resin member is sometimes required to have oxygen gas barrier properties in order to suppress deterioration of internal components of the electronic device and the like due to oxygen in the air. In addition, heat resistance is sometimes required in order to suppress deterioration of internal elements and the like of the electronic device due to outgassing (out gas) generated from the resin member by heat. For example, patent document 1 discloses a resin composition containing a blocked isocyanate obtained by blocking an isocyanate compound with an imidazole, an epoxy resin, and a phenoxy resin, but does not consider heat resistance and oxygen barrier properties. As described above, conventional resin members are not necessarily satisfactory in heat resistance and oxygen barrier properties, and a curable resin composition for resin members satisfying these properties at the same time is required.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2011-84667.

Disclosure of Invention

Problems to be solved by the invention

Accordingly, an object of the present invention is to provide a curable resin composition which can form a cured product suitable for use as a resin member of an electronic device such as an organic EL, a high-brightness LED, or a solar cell, and which has excellent heat resistance and oxygen gas barrier properties.

Means for solving the problems

The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that the above problems can be solved by using a curable resin composition containing the following components (a) to (D), and have completed the present invention. That is, the present invention includes the following.

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

(A) an epoxy resin containing a nitrogen atom;

(B) an epoxy group-containing silicone compound;

(C) an inorganic filler; and

(D) a curing agent;

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

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

[4] the curable resin composition according to any one of [1] to [3], wherein (B) the epoxy group-containing siloxane compound contains a cyclic siloxane skeleton;

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

[6] the curable resin composition according to any one of [1] to [5], wherein the inorganic filler (C) comprises 1 or more selected from synthetic fluorophlogopite, a plate-like glass filler and silica;

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

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

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

ADVANTAGEOUS EFFECTS OF INVENTION

The cured product formed from the curable resin composition of the present invention has a small amount of outgas generation (i.e., has high heat resistance) even when exposed to high temperatures, and also has high oxygen barrier properties. Therefore, the curable resin composition of the present invention is suitably used for resin members of electronic devices such as organic EL, high-brightness LED, and solar cell.

Detailed Description

The present invention will be described below in accordance with preferred embodiments of the present invention.

[ curable resin composition ]

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

< (A) an epoxy resin containing a nitrogen atom

The epoxy resin containing a nitrogen atom (hereinafter, also referred to as the (a) component) used in the present invention is not particularly limited as long as it contains a nitrogen atom in its skeleton. The component (a) is preferably a glycidylamine-type epoxy resin and/or a triazine derivative epoxy resin from the viewpoint of attaining the object of the present invention (particularly, oxygen barrier property) at a high level.

(glycidyl amine type epoxy resin)

The glycidyl amine type epoxy resin is an epoxy resin having a structure in which an amine amino group is glycidylated, and examples thereof include: tetraglycidyl diaminodiphenylmethane, glycidyl compounds of xylylenediamine, triglycidyl aminophenol (triglycidyl p-aminophenol, triglycidyl m-aminophenol, etc.), tetraglycidyl diaminodiphenylmethane, tetraglycidyl diaminodiphenylsulfone, tetraglycidyl diaminodiphenyl ether, tetraglycidyl bisaminomethylcyclohexanone, diglycidyl toluidine, diglycidyl aniline, diglycidyl methoxyaniline, diglycidyl dimethylaniline, diglycidyl trifluoromethylaniline, etc.

Examples of commercially available products include: "630" (triglycidyl p-aminophenol; manufactured by Mitsubishi chemical corporation), "604" (tetraglycidyldiaminodiphenylmethane; manufactured by Mitsubishi chemical corporation), "TETRAD-X" (glycidyl compound of xylylenediamine; manufactured by Mitsubishi gas chemical corporation), "TGDDS" (tetraglycidyldiaminodiphenylsulfone; manufactured by Mitsubishi chemical corporation), "EP-3980S" (diglycidylaniline, manufactured by ADEKA corporation), "GAN" and "GOT" (diglycidylaniline, manufactured by Nippon chemical Co., Ltd.) and the like. From the viewpoint of reactivity, the glycidyl amine epoxy resin preferably has an epoxy equivalent of 50 to 1,000, more preferably 50 to 500, even more preferably 60 to 300, and particularly preferably 80 to 200. The "epoxy equivalent" refers to the number of grams (g/eq) of a resin containing 1 gram equivalent of epoxy groups, and can be measured by a method specified in JIS K7236.

(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 preferably an epoxy resin having an isocyanurate ring skeleton. The epoxy resin having an isocyanurate ring skeleton preferably has 2 or more epoxy groups, and more preferably 3 epoxy groups, per 1 isocyanurate ring. Specific examples of the epoxy resin having an isocyanurate ring skeleton include: 1,3, 5-triglycidyl isocyanurate, tris (2, 3-epoxypropyl) isocyanurate, tris (. alpha. -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) -trione, Tris {2, 2-bis [ (oxetan-2-ylmethoxy) methyl ] butyl } -3,3' - [1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione-1, 3, 5-triyl ] tripropionate, and the like.

Examples of commercially available products of triazine derivative epoxy resins (epoxy resins having an isocyanurate ring skeleton) include: TEPIC-G, TEPIC-S, TEPIC-SS, TEPIC-HP, TEPIC-L, TEPIC-PAS, TEPIC-VL, commercially available from Nissan chemical industries, commercially available as 1,3, 5-tris (2, 3-epoxypropyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, TEPIC-VL, commercially available as 1,3, 5-tris (5, 6-epoxybutyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, TEPIC-FL, commercially available from Nissan chemical industries, commercially available as 1,3, 5-tris (5, 6-epoxybutyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, TEPIC-UC manufactured by Nissan chemical industries as a commercial product of tris {2, 2-bis [ (oxetan-2-ylmethoxy) methyl ] butyl } -3,3' - [1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione-1, 3, 5-triyl ] tripropionate.

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

In the present invention, when the triazine derivative epoxy resin has a structure in which an amino group is glycidylated, such a triazine derivative epoxy resin does not belong to the glycidyl amine type epoxy resin described above. That is, in the present invention, the "glycidyl amine type epoxy resin" does not include a triazine derivative.

In the curable resin composition of the present invention, the content of nitrogen atoms in the component (a) is preferably 0.05 to 50%, more preferably 1 to 45%. When the content of nitrogen atoms is in the above 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 a resin can be obtained. The "nitrogen atom content" can be calculated by the following formula (i).

The nitrogen atom content (%) × 100(i) is [ (1 average number of nitrogen atoms in molecule × nitrogen atom amount)/(molecular weight of epoxy resin) ].

In the curable resin composition of the present invention, the average number of epoxy groups in the molecule of the component (a) is preferably 2,3 or 4.

(A) The components may be used alone in 1 kind, or in combination of 2 or more kinds. The content of the component (a) in the curable resin composition is not particularly limited, but is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 3% by mass or more, based on 100% by mass of nonvolatile components in the curable resin composition, from the viewpoint of oxygen barrier properties. From the viewpoint of transparency, the content is preferably 60% by mass or less, more preferably 50% by mass or less, and still more preferably 40% by mass or less, based on 100% by mass of nonvolatile components in the curable resin composition.

In one embodiment of the present invention, the content of the component (a) is preferably 3% by mass or more, more preferably 5% by mass or more, and further preferably 8% by mass or more, based on the total amount (nonvolatile components) of the epoxy resin. The amount of the epoxy resin is preferably 70% by mass or less, more preferably 60% by mass or less, and still more preferably 50% by mass or less, based on the total amount (nonvolatile content) of the epoxy resin.

< (B) an epoxy group-containing siloxane compound

The epoxy group-containing siloxane compound used in the present invention (hereinafter also referred to as component (B)) is a compound having a siloxane bond (Si-O-Si) based skeleton containing an epoxy group in a molecule, and examples of the siloxane skeleton include a cyclic siloxane skeleton, a polysiloxane (silicone) skeleton, and a polysilsesquioxane skeleton. From the viewpoint of achieving heat resistance at a higher level, the siloxane skeleton is preferably a cyclic siloxane skeleton, that is, the component (B) is preferably a cyclic siloxane compound having an epoxy group. The number of Si-O units forming the cyclic siloxane skeleton (the same as the number of silicon atoms forming the siloxane ring) is preferably 2 to 12, more preferably 4 to 8.

The epoxy group-containing silicone compound preferably has 2 or more epoxy groups in 1 molecule. In addition, in the cyclic siloxane compound having an epoxy group, the epoxy group is preferably 2 to 4.

(B) When the component (B) is used in a light-transmitting part or the like, and transparency is required for a resin member, the epoxy group is preferably an alicyclic epoxy group having an epoxy group in an alicyclic skeleton, that is, the component (B) is preferably a siloxane compound containing an alicyclic epoxy group, and more preferably a cyclic siloxane compound having an alicyclic epoxy group. 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, the alicyclic epoxy group is particularly preferably a cyclohexenyl oxide group. (B) The components may be used alone in 1 kind, or in combination of 2 or more kinds.

Specific examples of the component (B) include: 2, 4-bis [2- (3- { oxabicyclo [4.1.0] heptyl }) ethyl ] -2,4,6,6,8, 8-hexamethylcyclotetrasiloxane, 4, 8-bis [2- (3- { oxabicyclo [4.1.0] heptyl }) ethyl ] -2,2,4,6,6, 8-hexamethylcyclotetrasiloxane, 2, 4-bis [2- (3- { oxabicyclo [4.1.0] heptyl }) ethyl ] -6, 8-dipropyl-2, 4,6, 8-tetramethyl-cyclotetrasiloxane, 4, 8-bis [2- (3- { oxabicyclo [4.1.0] heptyl } ethyl ] -2, 6-dipropyl-2, 4,6, 8-tetramethyl-cyclotetrasiloxane, 2, 6-dipropyl-2, 4,6, 8-tetramethyl-cyclotetrasiloxane, 2,4, 8-tris [2- (3- { oxabicyclo [4.1.0] heptyl }) ethyl ] -2,4,6,6, 8-pentamethyl-cyclotetrasiloxane, 2,4, 8-tris [2- (3- { oxabicyclo [4.1.0] heptyl }) ethyl ] -6-propyl-2, 4,6, 8-tetramethyl-cyclotetrasiloxane, 2,4,6, 8-tetrakis [2- (3- { oxabicyclo [4.1.0] heptyl }) ethyl ] -2,4,6, 8-tetramethyl-cyclotetrasiloxane, silsesquioxane having 2 or more epoxy groups in the molecule, and the like.

From the viewpoint of reactivity, the epoxy equivalent of the epoxy group-containing silicone compound is preferably 50 to 6,000, more preferably 50 to 5,000, even more preferably 60 to 4,000, and particularly preferably 80 to 4,000. The epoxy group-containing silicone compound preferably has a weight average molecular weight of 200 to 8,000, more preferably 200 to 6,000.

Examples of commercially available products of epoxy group-containing silicone compounds include: alicyclic epoxy cyclic polysiloxane oligomer (cyclic siloxane compound having alicyclic epoxy group) "KR-470" (having an epoxy group of 4), "X-40-2670" (having an epoxy group of 4), "X-40-2678" (having an epoxy group of 2) (both manufactured by shin-Etsu chemical Co., Ltd.), modified silicone oil having alicyclic epoxy groups at both terminals "X-22-169B", "X-22-169 AS" (both manufactured by shin-Etsu chemical Co., Ltd.), modified silicone oil having epoxy groups at both terminals "X-22-163", "KF-105", "X-22-163A", "X-22-163B", "X-22-163C", modified silicone oil having alicyclic epoxy groups at side chains "X-22-2046 "KF-102" (all manufactured by shin-Etsu chemical Co., Ltd.), modified silicone oil "X-22-343", "KF-101", "KF-1001" and "X-22-2000" (all manufactured by shin-Etsu chemical Co., Ltd.) having an epoxy group in a side chain.

The content of the component (B) in the curable resin composition of the present invention is not particularly limited, and is preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, and particularly preferably 15% by mass or more, relative to 100% by mass of nonvolatile components in the curable resin composition, from the viewpoint of improving heat resistance. From the viewpoint of reducing the oxygen permeability, the content is preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 75% by mass or less, and particularly preferably 70% by mass or less, relative to 100% by mass of the nonvolatile component of the curable resin composition.

In one embodiment of the present invention, the content of the component (B) is preferably 15% by mass or more, more preferably 20% by mass or more, and further preferably 25% by mass or more, based on the total amount (nonvolatile components) of the epoxy resin. The amount of the epoxy resin is preferably 70% by mass or less, more preferably 60% by mass or less, and still more preferably 50% by mass or less, based on the total amount (nonvolatile content) of the epoxy resin.

(C) inorganic filler

The inorganic filler (hereinafter, also referred to as component (C)) used in the present invention may be used without particular limitation. The inorganic filler may be used alone in 1 kind, or may be used in combination in 2 or more kinds. The inorganic filler is preferably a plate-like filler or silica from the viewpoint of achieving an oxygen barrier property at a higher level. When transparency is required for the resin member to be used in a light-transmitting part or the like, plate glass, a layered silicate mineral (particularly, smectite or synthetic fluorophlogopite), and nano silica are preferable from the viewpoint of excellent transparency. Here, the plate glass and the layered silicate mineral (particularly, smectite and synthetic fluorophlogopite) are both plate-like fillers. In one embodiment of the present invention, the inorganic filler preferably contains 1 or more selected from synthetic fluorophlogopite, plate-like glass filler and silica.

The plate-like filler is not particularly limited as long as the effects of the present invention are exhibited, and examples thereof include plate-like glasses (a glass, C glass, E glass, etc.), layered silicate minerals, and the like. Examples of the layered silicate mineral include kaolinite, halloysite (halloyite), talc, smectite, and mica. Among the mica, synthetic fluorophlogopite is preferable from the viewpoint of excellent transparency. The plate-like filler is particularly preferably a plate-like glass, a smectite, or a synthetic fluorophlogopite, from the viewpoint of excellent transparency. These plate-like fillers may be used alone in 1 kind, or 2 or more kinds may be used in combination.

Synthetic fluorophlogopite is one of synthetic micas, and is different from natural mica and other synthetic micas (K tetrasilicic mica, Na taeniolite, Li taeniolite) in that it is a large crystal having high transparency. On the other hand, as the plate-like glass filler, plate-like glass fillers of various glass compositions typified by a glass, C glass, E glass, and the like can be used.

The plate-like filler preferably has an average particle diameter to thickness ratio (average particle diameter/average thickness) of 1 or more, more preferably 1.5 or more, and still more preferably 2 or more. When the average particle diameter/thickness ratio is 1 or more, sufficient oxygen gas barrier properties tend to be easily obtained. The average particle diameter to thickness ratio is preferably 1000 or less, more preferably 800 or less, and further preferably 500 or less. When the average particle diameter/thickness ratio is 1000 or less, sufficient dispersibility tends to be easily obtained.

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 can be measured by the following method.

The thickness of each of the 100 particles was measured using a Scanning Electron Microscope (SEM), and the measured values were averaged to obtain the thickness. In this case, the measurement may be performed by observing each particle with a scanning electron microscope, or may be performed by filling a resin with a filler (particle group) and molding the resin, and breaking the molded article and observing the broken surface. In all the measurement methods, the specimen stage of the scanning electron microscope is adjusted by the specimen stage fine-adjustment device so that the cross section (thickness plane) of the particle is perpendicular to the irradiation electron beam axis of the scanning electron microscope.

The average particle diameter of the plate-like filler is preferably 0.5 μm or more, more preferably 1 μm or more, and further preferably 2 μm or more, from the viewpoint of improving the oxygen barrier property. From the viewpoint of transparency, the thickness is preferably 2000 μm or less, more preferably 1500 μm or less, and still more preferably 1000 μm or less.

The average particle diameter can be determined by a laser diffraction-scattering method based on Mie scattering theory. Specifically, it can be determined by: the particle size distribution of the filler was prepared on a volume basis by using a laser diffraction particle size distribution measuring apparatus, and the median particle size was defined as an average particle size. The measurement sample may preferably be a product obtained by dispersing a filler in water by ultrasonic waves. As the laser diffraction scattering type particle size distribution measuring apparatus, LA-500 manufactured by horiba, Ltd can be used.

The silica is preferably so-called nano silica having a primary particle size of a nanometer order. As the silica, spherical silica is generally used. The silica having a primary particle diameter of 1 to 100nm is preferable, and the silica having a primary particle diameter of 1 to 50nm is more preferable. Since it is difficult to measure the 1 st-order particle diameter of the nano-silica, a converted value from a specific surface area measurement value (according to JIS Z8830) may be used. Among the silica preferred in the present invention, silica more preferred in the present invention can be formed by setting the BET specific surface area to a predetermined value. The preferable BET specific surface area is 2720-27 m²A concentration of 2720 to 54m²/g。

In addition, the inorganic filler may be surface-treated with a surface treatment 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. The surface treatment agent may be used in 1 kind or in combination of 2 or more kinds.

The content of the component (C) in the curable resin composition of the present invention is not particularly limited, and is preferably 1% by mass or more, more preferably 2% by mass or more, further preferably 3% by mass or more, and particularly preferably 5% by mass or more, relative to 100% by mass of nonvolatile components in the curable resin composition, from the viewpoint of improving oxygen barrier properties. From the viewpoint of transparency, the content is preferably 65% by mass or less, more preferably 60% by mass or less, still more preferably 55% by mass or less, and particularly preferably 50% by mass or less, relative to 100% by mass of nonvolatile components in the curable resin composition.

(D) curing agent

The curing agent (hereinafter, also referred to as component (D)) used in the present invention is not particularly limited, as long as it has a function of curing an epoxy resin. Examples thereof include phenol-based curing agents, naphthol-based curing agents, acid anhydride-based curing agents, active ester-based curing agents, benzoxazine-based curing agents, cyanate ester-based curing agents, carbodiimide-based curing agents, imidazole-based curing agents and the like. The component (D) is preferably an acid anhydride curing agent from the viewpoint of heat resistance and transparency. The curing agent may be used alone in 1 kind, or in combination of 2 or more kinds.

Examples of the acid anhydride-based curing agent include a curing agent having 1 or more acid anhydride groups in 1 molecule. Examples of the acid anhydride-based curing agent include phthalic acid anhydride, succinic acid anhydride, maleic acid anhydride, trimellitic acid anhydride, norbornene acid anhydride, and nitrile rubber (nitrile rubber) having an acid anhydride group. Examples of the phthalic acid anhydride include phthalic anhydride, 1,2,3, 6-tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, and 3,3',4,4' -diphenylsulfone tetracarboxylic dianhydride. Examples of the succinic acid anhydride include succinic anhydride, octenylsuccinic anhydride, tetrapropenylsuccinic anhydride, butane-1, 2,3, 4-tetracarboxylic dianhydride, and the like. Examples of the maleic acid anhydride include maleic anhydride and the like. Examples of trimellitic acid anhydrides include ethylene glycol bis-trimellitic anhydride ester, glycerol bis (trimellitic anhydride ester) monoacetate, and the like. Examples of the norbornene acid anhydride include methyl-5-norbornene-2, 3-dicarboxylic anhydride, bicyclo [2.2.1] heptane-2, 3-dicarboxylic anhydride, and methylbicyclo [2.2.1] heptane-2, 3-dicarboxylic anhydride. Examples of the nitrile rubber having an acid anhydride group include a succinic anhydride-modified hydrogenated nitrile rubber, a maleic anhydride-modified hydrogenated nitrile rubber, and the like. A particularly preferred acid anhydride includes a norbornene acid anhydride.

Examples of commercially available acid anhydride curing agents include: rikacid TH (1,2,3, 6-tetrahydrophthalic anhydride), Rikacid HH (hexahydrophthalic anhydride), Rikacid HNA-100 (methyl bicyclo [2.2.1] heptane-2, 3-dicarboxylic anhydride/bicyclo [2.2.1] heptane-2, 3-dicarboxylic anhydride), Rikacid MH-700G (4-methyl hexahydrophthalic anhydride/hexahydrophthalic anhydride-70/30), Rikacid MH (4-methyl hexahydrophthalic anhydride), Rikacid TMEG-S, Rikacid TMEG-100, Rikacid TMEG-200, Rikacid TMEG-500, Rikacid TMEG-600 (ethylene glycol bimetaphthalic anhydride), Rikacid TMTA-C (glycerol bis (trimellitate) monoacetate), Rikacid MTA-15 (glycerol bis (trimellitate) monoacid acetate/alicyclic phthalic anhydride mixture), Rikacid MTA-15 (glycerol bis (trimellitate) and alicyclic phthalic anhydride), manufactured by Nissan-Rikacid, Rikacid DDSA (tetrapropenyl succinic anhydride), Rikacid OSA (octenyl succinic anhydride), Rikacid HF-08 (ester of alicyclic anhydride with polyalkylene glycol), Rikacid SA (succinic anhydride), Rikacid DSDA (3,3',4,4' -diphenylsulfone tetracarboxylic dianhydride), Rikacid dBT-100(1,2,3, 4-butane tetracarboxylic dianhydride), Rikacid TBN series (non-volatile anhydride), and the like.

From the viewpoint of reactivity, 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, and particularly preferably 100 to 700. The "acid anhydride equivalent" refers to the number of grams (g/eq) of the acid anhydride curing agent containing 1 gram equivalent of the acid anhydride group, and can be measured by component analysis using a nuclear magnetic resonance apparatus (NMR), Gas Chromatography (GC), or the like.

Examples of the phenol-based curing agent and the naphthol-based curing agent include a phenol-based curing agent having a phenolic structure (novolac structure), a naphthol-based curing agent having a phenolic structure, a phenol-based curing agent having a triazine skeleton, and a naphthol-based curing agent having a triazine skeleton.

The active ester-based curing agent is generally a compound having 2 or more ester groups having high reactivity in 1 molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxy compounds. The active ester-based curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl 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, resorcinol, bisphenol a, bisphenol F, bisphenol S, phenolphthalin, 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, phloroglucinol, benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac (phenol novolac), and the like. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing 1 molecule of dicyclopentadiene with 2 molecules of phenol.

More specifically, an active ester compound having a dicyclopentadiene type diphenol structure, an active ester compound having a naphthalene structure, an active ester compound having an acetyl compound of a phenol novolac resin, an active ester compound having a benzoyl compound of a phenol novolac resin, and the like can be given.

Examples of the cyanate ester curing agent include 2-functional cyanate ester resins such as bisphenol a dicyanate, polyphenol cyanate ester (oligo (3-methylene-1, 5-phenylene cyanate)), 4 '-methylenebis (2, 6-dimethylphenylcyanate), 4' -ethylenediphenyldicyanate, hexafluorobisphenol a dicyanate, 2-bis (4-cyanate ester) phenylpropane, 1-bis (4-cyanate ester phenylmethane), bis (4-cyanate ester-3, 5-dimethylphenyl) methane, 1, 3-bis (4-cyanate ester-1- (methylethylidene)) benzene, bis (4-cyanate ester phenyl) sulfide, and bis (4-cyanate ester phenyl) ether, and the like, Polyfunctional cyanate ester resins derived from phenol novolac resins, cresol novolac resins, and the like, prepolymers obtained by partially triazinating these cyanate ester resins, and the like.

Examples of the imidazole-based curing agent include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-heptadecylimidazole, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-methylimidazole, 2-heptadecylimidazole, 2-ethylimidazole, 2-ethylmethylimidazole, 2-ethylimidazole, 2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-methylimidazole, and 2-methylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-diamino-6- [2' -methylimidazolyl- (1') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -undecylimidazolyl- (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, imidazole compounds such as 4-diamino-6- [2 '-methylimidazolyl- (1') ] -ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric 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-benzylimidazolium chloride, 2-methylimidazoline and 2-phenylimidazoline, and adducts of imidazole compounds with epoxy resins.

The content of the curing agent (D) in the curable resin composition of the present invention is not particularly limited as long as the effects of the present invention are exhibited, and is preferably 90% by mass or less, more preferably 85% by mass or less, further more preferably 80% by mass or less, and particularly preferably 75% by mass or less with respect to 100% by mass of nonvolatile components in the curable resin composition, from the viewpoint of optical characteristics such as total light transmittance and haze. From the viewpoint of accelerating the curing of the curable resin composition, the content is preferably 2% by mass or more, more preferably 5% by mass or more, and still more preferably 7% by mass or more, relative to 100% by mass of the nonvolatile component of the curable resin composition.

In one embodiment of the present invention, the content of the (D) component is preferably 5% by mass or more, more preferably 7% by mass or more, and still more preferably 10% by mass or more, based on the total amount (nonvolatile components) of the epoxy resin. The amount of the epoxy resin is preferably 150 mass% or less, more preferably 135 mass% or less, and still more preferably 120 mass% or less, based on the total amount (nonvolatile content) of the epoxy resin.

(E) curing Accelerator

The curable resin composition of the present invention may contain a curing accelerator (hereinafter, also referred to as component (E)) for the purpose of improving curability, in addition to the above components (a) to (D). The curing accelerator is not particularly limited, and examples thereof include amine curing accelerators, imidazole curing accelerators, phosphorus curing accelerators, guanidine curing accelerators, and metal curing accelerators. The curing accelerator may be used alone in 1 kind, or in combination of 2 or more kinds.

Examples of the amine-based curing accelerator include aliphatic amine-based curing agents such as triethylamine, tributylamine, 4-Dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, and 1, 8-diazabicyclo [5.4.0] undecene, and examples thereof include 4-dimethylaminopyridine and 1, 8-diazabicyclo [5.4.0] undecene; benzidine, o-tolidine, 4' -diaminodiphenylmethane, 4' -diamino-3, 3' -dimethyldiphenylmethane, 4' -diamino-3, 3' -diethyldiphenylmethane, 4' -diamino-3, 3',5,5' -tetramethyldiphenylmethane, 4' -diamino-3, 3',5,5' -tetraethyldiphenylmethane, 4' -diamino-3, 3' -diethyl-5, 5' -dimethyldiphenylmethane, 4' -diaminodiphenyl ether, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (3-aminophenoxy) benzene, 4-bis (3-aminotoluene), Aromatic amine curing agents such as 1, 4-bis (4-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) neopentane, 4' - [1, 3-phenylenebis (1-methylethylidene) ] dianiline, 4' - [1, 4-phenylenebis (1-methylethylidene) ] dianiline, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane and 4,4' -bis (4-aminophenoxy) biphenyl.

Examples of the imidazole-based curing accelerator include those described in the above imidazole-based curing agent. When the imidazole-based curing agent is used together with another curing agent, the imidazole-based curing agent may function as a curing accelerator.

Examples of the phosphorus-based curing accelerator include triphenylphosphine, a phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, methyltributylphosphonium dimethylphosphate, tetraphenylphosphonium, tetrabutylphosphonium and the like.

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

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

In the curable resin composition of the present invention, the content of the curing accelerator in the case of using the curing accelerator is usually in the range of 0.05 to 5% by mass relative to the total amount (nonvolatile content) of the epoxy resin contained in the curable resin composition.

Additive (F)

The curable resin composition of the present invention may contain a radical polymerization initiator such as dimethyl 2,2' -azobis (isobutyrate), an organic filler such as rubber particles, silicone powder, nylon powder, or fluororesin powder; silicone, fluorine, or polymer defoaming agents or leveling agents; thickeners such as Orben, Benton, and the like; an antioxidant; a heat stabilizer; light stabilizers and the like.

< use >)

The curable resin composition of the present invention can be used as a resin member such as a sealing portion, an adhesive portion, and a light transmitting portion in an electronic device, particularly an optical device such as an organic EL, a high-luminance LED, and a solar cell.

When the curable resin composition of the present invention is molded into a film shape, for example, a varnish (resin composition varnish) prepared by mixing the components of the curable resin composition and an organic solvent using a kneading roll, a rotary mixer, or the like is applied to a support subjected to a mold release treatment, and the organic solvent is removed from the varnish applied to the support by heating (blowing hot air or the like) and/or pressure reduction treatment using a known machine, whereby a resin composition molded into a film shape (hereinafter, also referred to as a "film-shaped resin composition") can be obtained.

As the support for the release-treated support, for example, polyolefins such as polyethylene, polypropylene, polyvinyl chloride and the like; polyesters such as cycloolefin polymers, polyethylene terephthalate (hereinafter, sometimes abbreviated as "PET") and polyethylene naphthalate; a polycarbonate; plastic films (preferably PET films) such as polyimide, and metal foils such as aluminum foil, stainless steel foil, and copper foil. Examples of the release treatment of the support subjected to the release treatment include release treatment using a release agent such as a silicone resin-based release agent, an alkyd resin-based release agent, or a fluororesin-based release agent.

The solid content of the resin composition varnish is preferably 20 to 80% by mass, and more preferably 30 to 70% by mass.

The heating conditions for removing the organic solvent from the varnish of the resin composition are not particularly limited, and generally, the heating is preferably carried out at about 50 to 130 ℃ for about 2 to 10 minutes.

Examples of the organic solvent include ketones such as acetone, Methyl Ethyl Ketone (MEK) and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolves such as cellosolve, carbitols such as butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide and N-methylpyrrolidone. The organic solvent may be used alone in any 1 kind, or 2 or more kinds may be used in combination.

The thickness of the film-like resin composition varies depending on the apparatus and the application position to which the film-like resin composition is applied, and is preferably in the range of 1 to 1000. mu.m, and more preferably in the range of 2 to 800. mu.m.

The film-like resin composition formed on the support is preferably protected with a protective film in advance in order to protect the resin composition before curing, and for example, a protective film subjected to a release treatment may be laminated on the film-like resin composition formed on the support in advance using a known machine. Examples of the machine for laminating the protective film include a roll laminator, a press machine, and a vacuum pressure type laminator.

As the protective film subjected to the mold release treatment, for example, a film formed of polyolefin such as polyethylene, polypropylene, polyvinyl chloride or the like; polyesters such as cycloolefin polymers, polyethylene terephthalate (hereinafter, sometimes abbreviated as "PET") and polyethylene naphthalate; a polycarbonate; a plastic film (preferably a PET film) such as polyimide, or a support made of a metal foil such as aluminum foil, stainless steel foil, or copper foil, is subjected to a mold release treatment. Examples of the mold release treatment include mold release treatment using a mold release agent such as a silicone resin-based mold release agent, an alkyd resin-based mold release agent, or a fluororesin-based mold release agent.

< cured body >

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

The curing temperature for thermal curing is preferably 70 ℃ or higher, and more preferably 80 ℃ or higher, from the viewpoint of sufficiently advancing the curing reaction. From the viewpoint of preventing coloration of the cured product, the temperature is preferably 180 ℃ or lower, and more preferably 165 ℃ or lower. The heating time is preferably 10 minutes or more, and more preferably 20 minutes or more. Further, it is preferably 150 minutes or less, and more preferably 130 minutes or less.

Examples of the heating means include heating by pressure bonding using a hot air circulation oven, an infrared heater, a Heat gun (Heat gun), a high frequency induction heating device, and a heating tool (Heat tool).

The curable resin composition of the present invention may be applied to a desired position with a liquid resin composition such as varnish and the like to perform a curing reaction, thereby forming a resin member having a desired shape.

Examples

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the following description, "part" in the amount of the component means "part by mass" unless otherwise specified. The materials used in the examples and comparative examples are as follows.

(A) Composition (I)

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

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

"EP 3890S" (manufactured by ADEKA corporation): glycidyl amine type epoxy resin, diglycidyl aniline, epoxy equivalent of 115g/eq, nitrogen content of 6%

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

(B) Composition (I)

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

"X-40-2678" (manufactured by shin-Etsu chemical Co., Ltd.): the cyclic siloxane compound having an alicyclic epoxy group had an epoxy equivalent of 290g/eq, an epoxy group number of 2 and a Si-O unit number of 4.

(C) Composition (I)

"FTD 010 FY-F01" (manufactured by Nippon Banyan Kogyo): plate-like glass filler having an average particle diameter of 10 μm and an average particle diameter to thickness ratio of 25

"MEG 160 FY" (manufactured by japan salted and dried rice): plate-like glass filler having an average particle diameter of 160 μm and an average particle diameter to thickness ratio of 30

"PDM-20L" (manufactured by TOPY INDUSTRIAL CO., LTD.): mica (synthetic fluorophlogopite) with average particle diameter of 20 μm and average particle diameter thickness ratio of 70

"PDM-40L" (manufactured by TOPY INDUSTRIAL CO., LTD.): mica (synthetic fluorophlogopite) with average particle diameter of 40 μm and average particle diameter/thickness ratio of 90

"Y10 SV-AM 1" (manufactured by Admatech corporation): nano silicon dioxide (vinyl silane coupling agent surface treatment), particle size is 10nm, specific surface area is 300m²/g。

(D) Composition (I)

"HNA-100" (manufactured by Nippon chemical and physical Co., Ltd.): norbornene acid anhydride (bicycloheptane anhydride) having an acid anhydride equivalent of 184 g/eq.

(E) Composition (I)

"PX-4 MP" (manufactured by Nippon chemical industries Co., Ltd.): phosphorus-based curing accelerator (methyltributylphosphonium dimethylphosphate).

< example 1 >

An epoxy resin having an isocyanurate ring skeleton ("TEPIC-VL" manufactured by Nissan chemical industries Co., Ltd.), 70 parts of a cyclic siloxane compound having an alicyclic epoxy group ("KR-470" manufactured by shin-Etsu chemical Co., Ltd.), 20 parts of a cyclic siloxane compound having an alicyclic epoxy group ("X-40-2678" manufactured by shin-Etsu chemical Co., Ltd.), 91 parts of norbornene-based acid anhydride ("HNA-100" manufactured by Nippon chemical industries Co., Ltd.), 16 parts of a plate-like glass filler ("FTD 010 FY-F01" manufactured by Nippon Board Nitro Kogyo Co., Ltd.), 4 parts of a plate-like glass filler ("MEG 160 FY" manufactured by Nippon Board Nitro Kogyo Co., Ltd.) and 2.1 parts of a phosphorus-based curing accelerator ("PX-4 MP" manufactured by Nippon chemical industries Co., Ltd.) were mixed and uniformly dispersed by a high-speed rotary mixer to obtain a resin composition.

< example 2 >

A resin composition was obtained in the same manner as in example 1 except that 10 parts of "TEPIC-VL" was changed to 10 parts of "TEPIC-FL" and 91 parts of "HNA-100" was changed to 88 parts of "HNA-FL".

< example 3 >

A resin composition was obtained in the same manner as in example 1 except that 10 parts of "TEPIC-VL" was changed to 10 parts of glycidyl amine type epoxy resin "EP-3980S", 91 parts of "HNA-100" was changed to 93 parts, and 2.1 parts of "PX-4 MP" was changed to 2.2 parts.

< example 4 >

A resin composition was obtained in the same manner as in example 3 except that 10 parts of "EP-3980S" was changed to 10 parts of "630" and 93 parts of "HNA-100" was changed to 95 parts of the resin composition.

< example 5 >

The materials used in example 1 were changed to the compounding ratios shown in table 1, and uniformly dispersed in the same manner as in example 1 to obtain a resin composition of example 5.

< example 6 >

An epoxy resin having an isocyanurate ring skeleton ("TEPIC-VL" manufactured by Nissan chemical industries Co., Ltd.), 80 parts of a cyclic siloxane compound having an alicyclic epoxy group ("KR-470" manufactured by shin-Etsu chemical Co., Ltd.), 20 parts of a cyclic siloxane compound having an alicyclic epoxy group ("X-40-2678" manufactured by shin-Etsu chemical Co., Ltd.), 102 parts of norbornene-based acid anhydride ("HNA-100" manufactured by Nissan chemical industries Co., Ltd.), 16 parts of synthetic fluorophlogopite ("PDM-20L" manufactured by TOPY industries Co., Ltd.), 5 parts of synthetic fluorophlogopite ("PDM-40L" manufactured by TOPY industries Co., Ltd.) and 2.6 parts of a phosphorus-based curing accelerator ("PX-4 MP" manufactured by Nissan chemical industries Co., Ltd.) were mixed and uniformly dispersed in a high-speed rotary mixer to obtain a resin composition.

< example 7 >

An epoxy resin having an isocyanurate ring skeleton ("TEPIC-FL" manufactured by japan chemical industry corporation) 30 parts, a cyclic siloxane compound having an alicyclic epoxy group ("KR-470" manufactured by shin-Etsu chemical corporation) 60 parts, a cyclic siloxane compound having an alicyclic epoxy group ("X-40-2678" manufactured by shin-Etsu chemical corporation) 10 parts, a norbornene-based acid anhydride ("HNA-100" manufactured by shin-Etsu chemical corporation) 94 parts, a plate-like glass filler ("FTD 010 FY-F01" manufactured by japan plate-and-Nitro corporation) 20 parts, a nano silica ("Y10 SV-AM 1" manufactured by Admatech corporation) 50 parts, and a phosphorus-based curing accelerator ("PX-4 MP" manufactured by japan chemical industry corporation) 2.7 parts were mixed and uniformly dispersed by a high-speed rotary mixer to obtain a resin composition.

< example 8 >

An epoxy resin having an isocyanurate ring skeleton ("TEPIC-VL" manufactured by Nissan chemical industries Co., Ltd.), 10 parts of a cyclic siloxane compound having an alicyclic epoxy group ("KR-470" manufactured by shin-Etsu chemical industries Co., Ltd.), 90 parts of a norbornene-based acid anhydride ("HNA-100" manufactured by Nippon chemical industries Co., Ltd.), 96 parts of a plate-like glass filler ("FTD 010 FY-F01" manufactured by Nippon Mitsubishi corporation) and 2.2 parts of a phosphorus-based curing accelerator ("PX-4 MP" manufactured by Nippon chemical industries Co., Ltd.) were mixed and uniformly dispersed by a high-speed rotary mixer to obtain a resin composition.

< example 9 >

A resin composition was obtained in the same manner as in example 8 except that 90 parts of "KR-470" was changed to 90 parts of "X-40-2678", 96 parts of "HNA-100" was changed to 71 parts of "HNA-100", and 2.2 parts of "PX-4 MP" was changed to 1.9 parts of "PX-4 MP".

< comparative example 1 >

A resin composition was obtained by mixing 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 Co., Ltd.), 83 parts of a norbornene-based acid anhydride (HNA-100, manufactured by Nippon chemical Co., Ltd.) and 1.9 parts of a phosphorus-based curing accelerator (PX-4 MP, manufactured by Nippon chemical industry Co., Ltd.), followed by uniformly dispersing the mixture in a high-speed rotary mixer.

< comparative example 2 >

A resin composition was obtained by mixing 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 Co., Ltd.), 83 parts of a norbornene-based acid anhydride (HNA-100, manufactured by Nippon chemical Co., Ltd.), 16 parts of a plate-like glass filler (FTD 010FY-F01, manufactured by Nippon Kagaku Co., Ltd.), 4 parts of a plate-like glass filler (MEG 160FY, manufactured by Nippon Kagaku Kogyo Co., Ltd.), and 2.1 parts of a phosphorus-based curing accelerator (PX-4 MP, manufactured by Nippon chemical industry Co., Ltd.), followed by uniform dispersion in a high-speed rotary mixer.

< comparative example 3 >

100 parts of p-aminophenol type epoxy resin "630", 184 parts of norbornene type acid anhydride ("HNA-100" manufactured by Nippon chemical Co., Ltd.), 16 parts of plate-like glass filler ("FTD 010 FY-F01" manufactured by Nippon Kayaku Co., Ltd.), 4 parts of plate-like glass filler ("MEG 160 FY" manufactured by Nippon Kayaku Co., Ltd.) and 3.1 parts of phosphorus type curing accelerator ("PX-4 MP" manufactured by Nippon chemical industry Co., Ltd.) were mixed and uniformly dispersed by a high-speed rotary mixer to obtain a resin composition.

< comparative example 4 >

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

< Heat resistance test >

The resin compositions prepared in examples and comparative examples were heated at 90 ℃ for 2 hours and then at 150 ℃ for 2 hours to prepare cured bodies, and the thermogravimetric reduction (%) at 380 ℃ upon heating was measured using a differential heat-thermogravimetric simultaneous measurement device ("TG/DTA STA7200 RV" manufactured by Hitachi High-Tech Science Corporation). This evaluation was performed in the following manner: in the aluminum sample tray, weighing each 10mg cured product sample, in the open state without lid, in the air, with 20 degrees C/min heating rate from 25 degrees C to 400 degrees C under the condition of temperature. The heat weight loss rate was calculated by the following formula (ii).

The thermogravimetric decrease rate (%) (100 × (mass before heating (μ g) — mass at a predetermined temperature (μ g))/mass before heating (μ g) (ii).

For the heat resistance test, the following criteria were used for evaluation:

good quality: less than 20 percent

Poor x: more than 20 percent.

< determination of oxygen Transmission Rate >

(1) A frame (frame planar shape: 10 cm. times.10 cm, planar area: 100 cm) was formed on a polyimide film (UPILEX (product of UK Seisakusho Co., Ltd., thickness: 75 μm)) with a 200 μm thick tape²) The resin composition was poured into the frame, bar-coated with a glass bar, heated at 90 ℃ for 2 hours in a thermal cycle oven, and then heated at 150 ℃ for 2 hours to obtain a cured product (test piece) having a thickness of about 200 μm. The thickness of the obtained cured product was measured by a micrometer (manufactured by Mitutoyo Co., Ltd.) to a unit of 1 μm.

(2) The oxygen permeability of the test piece in an environment of 23 ℃ and 50% RH (relative humidity) was measured using an oxygen permeability measuring apparatus (product name: OX-TRAN 2/22L, manufactured by MOCON Co., Ltd.) (unit: ml. 200 μm/m)²Day atm) using the following criteria;

good quality: less than 500ml 200 μm/m²·day·atm

Poor x: 500ml 200 μm/m²Day atm or more.

< measurement of Total light transmittance >

(1) A resin composition was poured into a frame of boat glass (boat glass having a length of 8mm, a width of 6mm and a thickness of 200 μm), and then the resin composition was cured by heating at 90 ℃ for 2 hours and then at 150 ℃ for 2 hours in a thermal cycle oven, thereby obtaining a laminate having a cured product of the resin composition (sample for evaluation, thickness of cured product: 200 μm).

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

The light transmittance spectrum of the obtained evaluation sample was measured using a fiber-optic spectrophotometer (MCPD-7700, model 311C, made by Otsuka electronics, external light source unit: halogen lamp MC-2564(24V, 150W standard)) equipped with a phi 80mm integrating sphere (model SRS-99-010, reflectance 99%), with the distance between the integrating sphere and the evaluation sample being 0mm and the distance between the light source and the evaluation sample being 48 mm. The reference material was glass similar to the above. The total light transmittance (%) at 400nm was determined from the obtained light transmittance spectrum.

The compositions and test results of the resin compositions of examples and comparative examples are shown in table 1 below. As is clear from table 1, the curable resin compositions of the examples can form cured products having both high heat resistance and high oxygen barrier property. Further, it is found that the curable resin compositions of the examples are further excellent in transparency.

[ Table 1]

Industrial applicability

The cured product of the curable resin composition of the present invention is less in the amount of outgas generation even when exposed to high temperatures, and is excellent in heat resistance. Further, the resin member is excellent in oxygen gas barrier property, and is suitably used for a sealing portion, an adhesive portion, a light transmitting portion, and the like in an electronic device, particularly an optical device such as an organic EL, a high-luminance LED, and a solar cell.

The present application is based on Japanese laid-open application No. 2019-068248, the entire contents of which are incorporated herein by reference.