JP6884192B2 - Epoxy resin curing agent composition, epoxy resin composition containing it, cured product thereof - Google Patents

Description

The present invention is a curable resin composition, an epoxy resin composition, and a curing thereof, which are particularly suitable for use in a portion where high transparency, low coloring property, and high ultraviolet absorption are required, such as for opto-semiconductor applications used outdoors. Regarding the cured product.

Silicone resin compositions and epoxy resin compositions are often used as thermosetting resins used in opto-semiconductor applications.
Among optical semiconductors, especially LEDs (Light Emitting Diodes), SMD (Surface Mount Device) is exposed to a high temperature of more than 200 degrees for several tens of seconds as a solder reflow process when it is attached to equipment.
Although the silicone resin obtained by thermosetting the silicone resin composition is excellent in heat resistance and transparency, it is inferior in gas barrier property, and corrosion of members (silver plating, gold wire, etc.) used for optical semiconductors from external corrosive gas. There was a problem that could not be prevented (Patent Document 1).
On the other hand, although the epoxy resin composition is excellent in gas barrier property, it is inferior in heat resistance and transparency, so that when it is used in an optical semiconductor device, there is a problem that its reliability is inferior.
Therefore, although the heat resistance and transparency have been improved by using a phenolic antioxidant and a phosphorus-based antioxidant, no satisfactory one has been obtained yet (Patent Document 2).
Furthermore, among LEDs, LEDs used for LED displays and LED signboards installed outdoors are exposed to sunlight containing ultraviolet rays for a long period of time, causing peeling between the encapsulant and the base material. Therefore, there is a problem that the light extraction efficiency of the LED is lowered.

Japanese Patent No. 5678592 JP 2015-117325

The present invention is an epoxy resin curing agent composition, an epoxy resin composition, which is particularly suitable for use in a portion where high transparency, low coloring property, and high ultraviolet blocking property are required, such as for opto-semiconductor applications used outdoors. It is an object of the present invention to provide a cured product obtained by curing. Another object of the present invention is to provide a cured product in which peeling does not easily occur between the sealing material and the base material even when exposed to sunlight containing ultraviolet rays for a long time, and the light extraction efficiency of the LED does not easily decrease. ..

（３）（１）又は（２）のいずれか一項に記載のエポキシ樹脂硬化剤組成物と、下記Ｅ成分を含有するエポキシ樹脂組成物。
（Ｅ）エポキシ樹脂
（４）（Ａ）多価カルボン酸化合物が、下記（ａ）、（ｂ）の付加反応によって得られる化合物である、（１）〜（３）のいずれか一項に記載のエポキシ樹脂硬化剤組成物および／またはエポキシ樹脂組成物。
（ａ）分子内に二つ以上の水酸基を有する多価アルコール化合物
（ｂ）分子内に一つ以上のカルボン酸無水物化合物を有する化合物
（５）（Ｂ）紫外線吸収剤が下記式（１）で表される、（１）〜（４）のいずれか一項に記載のエポキシ樹脂硬化剤組成物および／またはエポキシ樹脂組成物。

（式（１）中、Ｒ^１は水素原子または塩素原子を表し、Ｒ^２は水素原子または炭素数１〜６の炭化水素基を表す。式中複数存在するＲ^２は同一であっても異なっていても構わない。）
（６）（Ｅ）エポキシ樹脂がシリコーン変性エポキシ樹脂である（３）〜（５）のいずれか一項に記載のエポキシ樹脂組成物。
（７）シリコーン変性エポキシ樹脂が下記式（２）で表される（６）に記載のエポキシ樹脂組成物。

（式（２）中、Ｒ^３は炭素数１〜６の炭化水素基を、Ｘはエポキシ基含有の有機基又は炭素数１〜６の炭化水素基を、ｍは１〜３の整数をそれぞれ表す。式中に複数存在するＲ^３、Ｘはそれぞれ同一であっても異なっていても構わない。ただし、複数存在するＸ中、２つ以上はエポキシ基含有の有機基である。）
（８）（３）〜（７）のいずれか一項に記載のエポキシ樹脂組成物を硬化してなる硬化物。 As a result of diligent studies in view of the above-mentioned actual conditions, the present inventors have obtained (A) a polyvalent carboxylic acid compound, (B) a benzotriazole-based, a salicylate-based or cyanoacrylate-based ultraviolet absorber, and (C) an antioxidant of phenol. We have found that an epoxy resin curing agent composition containing an agent and (D) an antioxidant solves the above problems, and has completed the present invention.
That is, the present invention relates to the following (1) to (8).
(1) An epoxy resin curing agent composition containing the following components (A) to (D).
(A) Polyvalent carboxylic acid compound (B) Benzotriazole-based, salicylate-based or cyanoacrylate-based UV absorber (C) Phenolic antioxidant (D) Antioxidant (2) The (B) UV absorber The epoxy resin curing agent composition according to (1), which is a benzotriazole-based ultraviolet absorber and contains a skeleton represented by the following formula (A).

(3) The epoxy resin curing agent composition according to any one of (1) and (2), and the epoxy resin composition containing the following E component.
(E) Epoxy resin (4) The polyvalent carboxylic acid compound (A) is a compound obtained by the addition reaction of (a) and (b) below, according to any one of (1) to (3). Epoxy resin curing agent composition and / or epoxy resin composition.
(A) Polyhydric alcohol compound having two or more hydroxyl groups in the molecule (b) Compound having one or more carboxylic acid anhydride compounds in the molecule (5) (B) The ultraviolet absorber is the following formula (1). The epoxy resin curing agent composition and / or epoxy resin composition according to any one of (1) to (4) represented by.

(In the formula (1), R ¹ represents a hydrogen atom or a chlorine atom, R ² is R ² that there are a plurality of. Formula represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms be the same or different It doesn't matter if you have it.)
(6) The epoxy resin composition according to any one of (3) to (5), wherein the epoxy resin (E) is a silicone-modified epoxy resin.
(7) The epoxy resin composition according to (6), wherein the silicone-modified epoxy resin is represented by the following formula (2).

(In the formula (2), R ³ is a hydrocarbon group having 1 to 6 carbon atoms, X is an organic group containing an epoxy group or a hydrocarbon group having 1 to 6 carbon atoms, and m is an integer of 1 to 3 carbon atoms. represents. may be different even in R ^3, X are each identical to the plurality present in the formula. However, in X presence of a plurality, two or more is an organic group containing an epoxy group.)
(8) A cured product obtained by curing the epoxy resin composition according to any one of (3) to (7).

According to the present invention, an epoxy resin curing agent composition containing a polyvalent carboxylic acid compound and an ultraviolet absorber and an epoxy resin composition containing the same have high transparency, high heat resistance transparency and high ultraviolet blocking property. Since it gives a cured product, it is extremely useful as a material that requires high transparency and high heat resistance and transparency, especially as a resin for optical semiconductors used outdoors.

9 is a transmittance spectrum of the cured product obtained in Examples 3 to 4 and Comparative Example 1.

The epoxy resin curing agent composition of the present invention contains the following components (A) to (D).
(A) Polyvalent carboxylic acid compound (B) Benzotriazole-based, salicylate-based or cyanoacrylate-based UV absorber (C) Phenolic antioxidant (D) Antioxidant

First, (A) a polyunsaturated carboxylic acid compound will be described.

The (A) polyvalent carboxylic acid compound is a compound having two or more carboxyl groups in the molecule, and is not particularly limited as long as it has an epoxy resin curable ability. For example, succinic acid, maleic acid, glutaric acid, etc. Compounds such as diethylglutaric acid, malic acid, citric acid, itaconic acid, cyclohexanedicarboxylic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, norbornandicarboxylic acid, norbornenedicarboxylic acid, phthalic acid, trimellitic acid, pyromellitic acid, or Examples thereof include compounds obtained by the following addition reactions (a) and (b).
(A) Polyhydric alcohol compound having two or more hydroxyl groups in the molecule (b) Compound having one or more carboxylic acid anhydride compounds in the molecule Among the polyvalent carboxylic acid compounds, (a), ( The compound obtained by the addition reaction of b) is preferable from the viewpoint of the mechanical strength of the obtained cured product.

(A); The polyhydric alcohol compound containing two or more hydroxyl groups in the molecule is not particularly limited as long as it is a compound having two or more alcoholic hydroxyl groups in the molecule, but ethylene glycol, propylene glycol, 1 , 3-Propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl- 2-Butyl-1.3-propanediol, neopentyl glycol, trimethylolpropane dimethanol, norbornenediol, 2,2'-bis (4-hydroxycyclohexyl) propane, 2- (1,1-dimethyl-2-hydroxy) Diols such as ethyl) -5-ethyl-5-hydroxymethyl-1,3-dioxane, triols such as glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, 2-hydroxymethyl-1,4-butanediol Examples include tetraols such as pentaerythritol and ditrimethylolpropane, hexaols such as dipentaerythritol, terminal alcohol polyesters, terminal alcohol polycarbonates, terminal alcohol polyethers, and polyhydric alcohols having a siloxane structure.
Particularly preferable alcohols are alcohols having 5 or more carbon atoms, and particularly 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 2, 4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tris (2-hydroxyethyl) isocyanurate, tricyclodecanedimethanol, norbornenediol, 2,2'-bis Examples thereof include compounds such as (4-hydroxycyclohexyl) propane and 2- (1,1-dimethyl-2-hydroxyethyl) -5-ethyl-5-hydroxymethyl-1,3-dioxane, among which 2-ethyl-2. -Butyl-1,3-propanediol, neopentyl glycol, 2,4-diethylpentanediol, 1,4-cyclohexanedimethanol, tris (2-hydroxyethyl) isocyanurate, tricyclodecanedimethanol, norbornenediol, 2 , 2'-bis (4-hydroxycyclohexyl) propane, 2- (1,1-dimethyl-2-hydroxyethyl) -5-ethyl-5-hydroxymethyl-1,3-dioxane, etc. Alcohols having a structure or a cyclic structure are more preferable. From the viewpoint of imparting high sulfurization resistance, 2,4-diethylpentanediol, tricyclodecanedimethanol, 2,2'-bis (4-hydroxycyclohexyl) propane, 1,4-cyclohexanedimethanol, neopentyl glycol, Compounds such as tris (2-hydroxyethyl) isocyanate, 2- (1,1-dimethyl-2-hydroxyethyl) -5-ethyl-5-hydroxymethyl-1,3-dioxane are particularly preferred. Among them, particularly in the branched chain structure, it is preferable to have two or more branched chains, and it is particularly preferable that the branched chains extend from different carbon atoms. Here, the alcohols having the branched chain structure or the cyclic structure preferably have 5 to 25 carbon atoms, and particularly preferably 5 to 20 carbon atoms.

Among the polyhydric alcohol compounds (a) containing two or more hydroxyl groups in the molecule, the compounds represented by the following formulas (3) to (9) are preferable.

The polyhydric alcohol having a siloxane structure is not particularly limited, but for example, a silicone oil represented by the following formula (10) is preferable.

In the formula (10), R ⁴ represents a total number of carbons 1 to 10 alkylene groups which may be via an ether bond, and R ⁵ represents a methyl group or a phenyl group. Further, n is the number of repetitions, which means an average value, and is 1 to 100. Here, n is preferably 1 to 10.

In the formula (10), specific examples of R ⁴ include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, isopropylene group, isobutylene group, isopentylene group, neopentylene group, isohexylene group, cyclohexylene Examples thereof include silene group, heptylene group, octylene group, nonyl group, decyl group, ethyleneoxyethylene group, ethyleneoxypropylene group, propyleneoxyethylene group and propyleneoxypropylene group. From the viewpoint, a propylene group, an ethyleneoxypropylene group, and a propyleneoxyethylene group are preferable.

Examples of the silicone oil represented by the formula (10) include the following product names. For example, X-22-160AS, KF-6000, KF-6001, KF-6002, KF-6003 manufactured by Shin-Etsu Chemical Co., Ltd., SF8427, BY16-201, Asahi Kasei Wacker Silicone Co., Ltd. manufactured by Toray Dow Corning Co., Ltd. WACKER IM11, WACKER IM15, JNC FM-4411, FM-4421, FM-4425, Momentive Performance Materials Japan XF42-C5277, XF42-B0970, etc. All are available from the market. These silicone oils can be used alone or in admixture of two or more. Among these, X-22-160AS, KF6001, KF6002, BY16-201, WACKER IM11, FM-4411, and XF42-B0970 are preferable.

The above-mentioned (a); polyhydric alcohol compound containing two or more hydroxyl groups in the molecule may be used alone or in combination of two or more.
In order to use the obtained curable resin composition in liquid form and impart high gas barrier properties to the cured product, the polyhydric alcohol having the above-mentioned siloxane structure and a branched chain structure or cyclic structure having 5 to 25 carbon atoms are used. It is preferable to mix and use the alcohols having and / or the polyhydric alcohol compound having an isocyanul ring skeleton.
When a polyhydric alcohol having a siloxane structure and an alcohol having a branched chain structure or a cyclic structure having 5 to 25 carbon atoms and / or a polyhydric alcohol compound having an isocyanul ring skeleton are mixed and used, the amount used is mass. As a ratio, 0 in all alcohol compounds (polyhydric alcohol having a siloxane structure) / (alcohols having a branched chain structure or cyclic structure having 5 to 25 carbon atoms and / or a polyhydric alcohol compound having an isocyanul ring skeleton) .2 to 20 is preferable, 0.3 to 15 is preferable, and 0.4 to 10 is particularly preferable from the viewpoint of heat-resistant transparency of the cured product and an appropriate viscosity of the curable resin composition.

(B); Examples of the compound containing one or more acid anhydride groups in the molecule include methyltetrahydroanhydride phthalic acid, hexahydroanhydride phthalic acid, methylhexahydrohydride phthalic acid, and bicyclo [2,2,1] heptane-. 2,3-Dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, glutarate anhydride Preferables, 2,4-diethylglutaric acid anhydride, succinic anhydride and the like, among which methylhexahydrophthalic anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, 2,4- Diethyl glutaric anhydride is preferred. Here, in order to increase the hardness, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride is preferable, and in order to increase the illuminance retention rate, methylhexahydrophthalic anhydride anhydride is preferable, and there are many. 2,4-Diethylglutaric acid and glutaric acid are preferable in order to suppress an excessive increase in viscosity of the valent carboxylic acid resin.

(B); As the compound containing one or more acid anhydride groups in the molecule, it is preferable to use one or more of the compounds represented by the following formulas (11) to (18).

The conditions for the addition reaction are not particularly specified, but one of the specific reaction conditions is (a) a polyhydric alcohol compound having two or more hydroxyl groups in the molecule, and (b) one or more in the molecule. The compound having the carboxylic acid anhydride compound is reacted at 40 to 150 ° C. under the conditions of no catalyst and no solvent, heated, and taken out as it is after the reaction is completed. It is a method called. However, the reaction conditions are not limited to this.
The compound thus obtained has the following residue (a) and the following residue (b), and the following residues (a) and (b) are bonded in an ester structure. It is a compound having a carboxyl group at the end.
(A) Reaction residue of a polyhydric alcohol compound having two or more hydroxyl groups in the molecule (b) Reaction residue of a compound having one or more carboxylic acid anhydride compounds in the molecule

The polyunsaturated carboxylic acid (A) of the present invention may be used alone or in combination of two or more.
Furthermore, it can also be used as a composition with another epoxy resin curing agent.

Examples of other epoxy resin curing agents include amine-based curing agents, phenol-based curing agents, thiol-based curing agents, cationic curing agents, anion curing agents, acid anhydride curing agents, etc., and any epoxy resin curing agent is used. However, an acid anhydride curing agent can be preferably used.
As the acid anhydride curing agent when used in combination, any compound having an acid anhydride group in the molecule can be used, and among them, one or more of the compounds represented by the following formulas (19) to (26) are used. It is preferable to use one or more of the compounds represented by the formulas (19), (20) and (21).

When the polyunsaturated carboxylic acid compound (A) and the acid anhydride compound are used in combination, the usage ratio thereof is preferably in the following range.

W1 / (W1 + W2) = 0.05 to 0.70

However, W1 indicates the compounding mass portion of the polyunsaturated carboxylic acid compound, and W2 indicates the compounding mass portion of the acid anhydride compound. The range of W1 / (W1 + W2) is more preferably 0.05 to 0.60, still more preferably 0.10 to 0.55, and particularly preferably 0.15 to 0.4. If it is less than 0.05, the acid anhydride compound tends to volatilize more during curing, which is not preferable. If it exceeds 0.70, the viscosity becomes high and handling becomes difficult. When no acid anhydride is contained (except when a small amount remains), the shape is solid or close to solid, or crystallized, so that there is no problem.
(A) When the polyvalent carboxylic acid compound and the acid anhydride compound are used in combination, they are produced in the excess acid anhydride compound at the time of producing the polyvalent carboxylic acid compound, and the polyvalent carboxylic acid compound and the acid anhydride compound are produced. The method of making a mixture of the above is also preferable from the viewpoint of ease of operation.

Next, (B) an ultraviolet absorber will be described.
The ultraviolet absorber can be used as long as it absorbs a wavelength of about 400 nm or less and improves the long-term weather resistance and stability of the resin.

Specific examples thereof include ultraviolet absorbers such as benzotriazole type, salicylate type and cyanoacrylate type.

More specifically, as the benzotriazole system, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, 2- (2'-Hydroxy-3', 5'-di tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2 -(2'-Hydroxy-3', 5'-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-ditert-amylphenyl) benzotriazole, 2 -{(2'-Hydroxy-3', 3 "4", 5 ", 6" -tetrahydrophthalimidemethyl) -5'-methylphenyl} benzotriazole, 2- (2H-benzotriazole-2-yl)- 4- (1,1,3,3-tetramethylbutyl) phenol, 2,2'-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethyl) Phenyl) phenol], 2- (2H-benzotriazole-2-yl) -p-cresol, 2- (5-chloro-2H-benzotriazole-2-yl) -6-tert-butyl-4-methylphenol, 2- (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -4,6-di-tert -Pentylphenol and the like are phenylsalicylate, pt-butylphenylsalicylate, p-octylphenylsalicylate and the like as salicylate systems, and 2,2-bis [{2-cyano- (3,3) as the cyanoacrylate system. 3-Diphenylacryloyl) oxy} methyl] Propane-1,3-diyl-bis (2-cyano-3,3-diphenylacryllate), ethyl 2-cyano-3,3-diphenylacrylate, 2-cyano-3 , 3-Diphenylacrylic acid 2-ethylhexyl and the like.

UV absorbers are available on the market and their product names include, for example, TINUVIN P, TINIVIN 234, TINIVIN 326, TINIVIN 328, TINIVIN 329, TINUVIN 360, TINIVIN 213, TINIVIN 571, TINIVIN 1577ED, CHIMASSORB 81. , Uvinul 3030, Uvinul 3050, Uvinul 3039 (above, manufactured by BASF), Adeka Stub LA-29, Adeka Stub LA-31, Adeka Stub LA-32, Adeka Stub LA-36, Adeka Stub LA-46, Adeka Stab LA-F70 (Adeka Stub LA-F70) As mentioned above, (manufactured by ADEKA Corporation) and the like.

Among the above-mentioned ultraviolet absorbers, benzotriazole-based ultraviolet absorbers are preferable from the viewpoint of excellent heat-resistant transparency and light-transparency of the cured product of the present invention, and among them, tert which may have a substituent in its structure. -Those having a butyl group are more preferable.
Specifically, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (5-chloro-2H-benzotriazole-2-yl)- 6-tert-Butyl-4-methylphenol and 2- (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol are particularly preferred.

上記のような骨格を有することで、長時間太陽光等の光に曝されても、樹脂層と基板材料との剥離を有効に防ぐことが可能となる。
また、下記式（１）で示される化合物が特に好ましい。 As the (B) ultraviolet absorber, a benzotriazole-based ultraviolet absorber containing a skeleton represented by the following formula (A) is preferable.

By having the above-mentioned skeleton, it is possible to effectively prevent the resin layer from peeling off from the substrate material even if it is exposed to light such as sunlight for a long time.
Further, the compound represented by the following formula (1) is particularly preferable.

式（１）中、Ｒ^１は水素原子または塩素原子を表し、Ｒ^２は水素原子または炭素数１〜６の炭化水素基を表す。式中複数存在するＲ^２は同一であっても異なっていても構わない。

In formula (1), R ¹ represents a hydrogen atom or a chlorine atom, and R ² represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R ² is more present in the formula may be different even in the same.

In the formula (1), specific examples of the hydrocarbon having 1 to 6 carbon atoms R ² is a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, and a phenyl group.
The R ^2, a hydrogen atom, a methyl group, the compatibility of the phenyl group to the resin, from the viewpoint of heat transparency of the cured product.

Among the compounds represented by the formula (1), the compounds represented by the following formulas (27) and (28) are particularly preferable.

In the epoxy resin curing agent composition of the present invention, the amount of the (B) ultraviolet absorber added is usually 0.02 to 10% by mass, preferably 0.05 to 5% by mass, and the cured product absorbs ultraviolet rays. From the viewpoint of properties, heat-resistant transparency and solubility in the resin composition, it is particularly preferably 0.1 to 2% by mass.

Further, in the epoxy resin composition described later, the amount of the (B) ultraviolet absorber added is 0.01 to 5% by mass, preferably 0.02 to 3% by mass, and the cured product has ultraviolet absorbability and heat resistance and transparency. From the viewpoint of properties and solubility in the resin composition, it is particularly preferably 0.05 to 1% by mass.

(B) The method of adding the ultraviolet absorber to the epoxy resin curing agent composition is obtained by uniformly mixing at room temperature or under heating. For example, by using an extruder, a kneader, a triple roll, a universal mixer, a planetary mixer, a homomixer, a homodisper, a bead mill, etc., the mixture is sufficiently mixed until it becomes uniform, and if necessary, filtration is performed with a SUS mesh or the like. Prepared. At this time, the (B) ultraviolet absorber may be completely dissolved in the (A) polyunsaturated carboxylic acid compound, or may be in a dispersed state without being dissolved.

Next, (C) a phenol antioxidant will be described.

The phenol antioxidant (C) is not particularly limited as long as it is a phenol compound having an antioxidant function, and is, for example, 2,6-di-tert-butyl-4-methylphenol and n-octadecyl-3- (3). , 5-Di-tert-butyl-4-hydroxyphenyl) propionate, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 2,4-di-tert- Butyl-6-methylphenol, 1,6-hexanediol-bis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], Tris (3,5-di-tert-butyl- 4-Hydroxybenzyl) -isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, pentaerythrityl-tetrakis [3] -(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,9-bis- [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) -propionyl Oxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-) Hydroxyphenyl) propionate], 2,2'-butylidenebis (4,6-di-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4) -Methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methyl) Benzyl) -4-methylphenol acrylate, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 4,4'- Thiobis (3-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 2-tert-butyl-4-methylphenol, 2,4-di-tert- Butylphenol, 2,4-di-tert-pentylphenol, 4,4'-thiobis (3-methyl-6-tert-butylphenol), 4,4'-butyl Redenbis (3-methyl-6-tert-butylphenol), bis- [3,3-bis- (4'-hydroxy-3'-tert-butylphenyl) -butanoic acid] -glycol ester, 2,4- Di-tert-butylphenol, 2,4-di-tert-pentylphenol, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentyl Examples thereof include phenyl acrylate, bis- [3,3-bis- (4'-hydroxy-3'-tert-butylphenyl) -butanoic acid] -glycol ester.

As the above-mentioned phenol antioxidant, a commercially available product can also be used. The commercially available phenolic compounds are not particularly limited. For example, BASF's IRGANOX1010, IRGANOX1035, IRGANOX1076, IRGANOX1135, IRGANOX245, IRGANOX259, IRGANOX295, IRGANOX3114, IRGANOX1098, IRGANOX1520L, ADEKA's ADEKA , Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-60, Adekastab AO-70, Adekastab AO-80, Adekastab AO-90, Adekastab AO-330, Sumitomo Chemical Co., Ltd. 80, Sumilizer MDP-S, Sumilizer BBM-S, Sumilizer GM, Sumilizer GS (F), Sumilizer GP and the like.

Among the above phenolic antioxidants, the compound represented by the following formula (29) is preferable from the viewpoint of heat resistance and transparency of the cured product.

In formula (29), R ⁶ represents an alkyl group having 1 to 10 carbon atoms, and R ⁷ and R ⁸ represent an alkylene group having 1 to 5 carbon atoms, respectively. In the formula, a plurality of R ^{6 to} R ⁸ may be the same or different from each other. )

In the formula (29), R ⁶ represents an alkyl group having 1 to 10 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tertiary butyl group, and a pentyl group. , Isopentyl group, neopentyl group, hexyl group, isohexyl group, heptyl group, isoheptyl group, octyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, cyclohexyl group, etc. preferably butyl groups, in particular in formula (29), it is preferable in view of heat transparency of the cured epoxy resin any one of R ⁶ sandwiching the phenolic hydroxyl group is a tertiary butyl group.

In the formula (29), R ⁷ and R ⁸ represent an alkylene group having 1 to 5 carbon atoms, and specific examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, an isobutylene group, a pentylene group, and an isopentylene group. Among them, an ethylene group is preferable from the viewpoint of compatibility and heat resistance and transparency of the sulfur-based antioxidant represented by the formula (29).

Among the phenolic antioxidants (C) represented by the formula (29), the compound represented by the following formula (30) is particularly preferable.

The (C) phenolic antioxidant is preferably used in combination with the following (D) antioxidant.
The antioxidant (D) is not particularly limited as long as it is a phosphorus compound having an antioxidant function, but for example, 1,1,3-tris (2-methyl-4-ditridecylphosphite-5-tert-). Butylphenyl) butane, distearylpentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) penta Ellisritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite, tris (diethylphenyl) phosphite, tris (di-isopropylphenyl) phosphite, tris (di-n-butylphenyl) phosphite , Tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, 2 , 2'-Methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) (2-tert-Butyl-4-methylphenyl) phosphite, 2,2'-methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2, 2'-Etilidenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4' -Bifenirange phosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-bipheni Range phosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3'-biphenylenediphospho Nite, tetrakis (2,6-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis ( 2,4-Di-tert-butylphenyl) -3- Phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, Bis (2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, tetrakis (2,4-di-tert-butyl-5-methylphenyl) -4,4'-biphenylenediphosphonite, Tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresil phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, trisdecyl Examples include phosphite and bisphenyldecylphosphite.

As the antioxidant, a commercially available product can also be used. The phosphorus compounds on the market are not particularly limited, and for example, ADEKA products such as ADEKA TAB PEP-4C, ADEKA STAB PEP-8, ADEKA STAB PEP-24G, ADEKA STAB PEP-36, ADEKA STAB HP-10, ADEKA STAB 2112, and ADEKA STAB 260. , ADEKA STAB 522A, ADEKA STAB 1178, ADEKA STAB 1500, ADEKA STAB C, ADEKA STAB 135A, ADEKA STAB 3010 and the like.

Among the above-mentioned antioxidants, the compound represented by the following formula (31) is preferable from the viewpoint of heat resistance and transparency of the cured product.

In the above formula (31), R ⁹ represents a phenyl group which may have an alkyl group or a substituent having 1 to 30 carbon atoms. In the formula, a plurality of R ^9s may be the same or different.

Specific examples of the alkyl group having 1 to 30 carbon atoms of R ⁹ include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentyl group, an isopentyl group, a nonyl group, a decyl group, an undecyl group and a dodecyl group. Examples thereof include a tetradecyl group, a hexadecyl group, an octadecyl group, a stearyl group and a myristyl group. Among them, a decyl group and a phenyl group are preferable from the viewpoint of improving heat resistance and transparency due to a synergistic effect with a phenol antioxidant.
Further, R ⁹ is more preferably an alkyl group having 8 to 25 carbon atoms.

Among the phosphorus compounds represented by the formula (31), the compound represented by the following formula (32) is particularly preferable.

In formula (32), R ⁹ has the same meaning as described above.

The amount of the (C) phenolic antioxidant and (D) phosphoroxidant added to the epoxy resin curing agent composition or the epoxy resin composition is preferably 0.01 to 10% by mass in the composition, and 0. 1 to 2% by mass is more preferable, and 0.15 to 1% by mass is particularly preferable. When the addition amount is 0.01% by mass or more, it is preferable from the viewpoint of heat resistance and transparency, and when it is 10% by mass or less, it is preferable from the viewpoint of excellent transparency of the cured product and curability of the curable resin composition.

In order to use the obtained curable resin composition in a liquid state and impart high heat-resistant permeability to the cured product, it is preferable to use the above-mentioned phenol antioxidant and phosphorylation antioxidant in mixture.
When a phenolic antioxidant and an antioxidant are mixed and used, the mass ratio of (antioxidant) / (phenolic antioxidant) is preferably 0.5 to 10, and 1 to 8 is particularly preferable. preferable.
Further, by using the above formula (31) to the above formula (32) in the above ratio, it is possible to impart high heat resistance permeability to a more excellent cured product.

The method of adding the (C) phenolic antioxidant and (D) phosphoroxidant to the epoxy resin curing agent composition or the epoxy resin composition can be obtained by uniformly mixing at room temperature or under heating. For example, by using an extruder, a kneader, a three-roll, a universal mixer, a planetary mixer, a homomixer, a homodisper, a bead mill, etc., the mixture is sufficiently mixed until it becomes uniform, and if necessary, it is filtered by a SUS mesh or the like. Prepared. At this time, the (B) phenolic antioxidant and (C) antioxidant may be completely dissolved in the epoxy resin curing agent composition or the epoxy resin composition, or may be dispersed without being dissolved. It may be in the state of being.

Next, the epoxy resin composition of the present invention will be described. The epoxy resin composition in the present invention contains (A) a polyvalent carboxylic acid compound, (B) an ultraviolet absorber, (C) a phenolic antioxidant, (D) an antioxidant, and (E) an epoxy resin. It is characterized by that.

Examples of the epoxy resin (E) include an epoxy resin which is a glycidyl etherified product of a phenol compound, an epoxy resin which is a glycidyl etherified product of various novolak resins, an alicyclic epoxy resin, an aliphatic epoxy resin, and a heterocyclic epoxy resin. Glysidyl ester-based epoxy resin, glycidylamine-based epoxy resin, epoxy resin obtained by glycidylizing halogenated phenols, copolymer of polymerizable unsaturated compound having an epoxy group and other polymerizable unsaturated compounds, epoxy Examples thereof include a condensate of a silicon compound having a group and another silicon compound, a silicone-modified epoxy resin, and the like.

Examples of the epoxy resin which is a glycidyl etherified product of the phenolic compound include 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4- (2,3) -Hydroxy) phenyl] ethyl] phenyl] propane, bisphenol A, bisphenol F, bisphenol S, 4,4'-biphenol, tetramethylbisphenol A, dimethylbisphenol A, tetramethylbisphenol F, dimethylbisphenol F, tetramethylbisphenol S, Dimethylbisphenol S, tetramethyl-4,4'-biphenol, dimethyl-4,4'-biphenol, 1- (4-hydroxyphenyl) -2- [4- (1,1-bis- (4-hydroxyphenyl)) Ethyl) phenyl] propane, 2,2'-methylene-bis (4-methyl-6-tert-butylphenol), 4,4'-butylidene-bis (3-methyl-6-tert-butylphenol), trishydroxyphenylmethane , Resolsinol, hydroquinone, pyrogallol, fluoroglycinol, phenols having a diisopropyridene skeleton, phenols having a fluorene skeleton such as 1,1-di-4-hydroxyphenylfluorene, glycidyl ethers of polyphenol compounds such as phenolized polybutadiene. Examples thereof include epoxy resin which is a compound.

Examples of the epoxy resin which is a glycidyl etherified product of the various novolak resins include phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenols such as bisphenol A, bisphenol F and bisphenol S, and various phenols such as naphthols. Examples thereof include glycidyl etherified products of various novolak resins such as novolak resin, xylylene skeleton-containing phenol novolak resin, dicyclopentadiene skeleton-containing phenol novolak resin, biphenyl skeleton-containing phenol novolak resin, and fluorene skeleton-containing phenol novolak resin.

Examples of the alicyclic epoxy resin include an alicyclic having an aliphatic ring skeleton such as 3,4-epoxycyclohexylmethyl- (3,4-epoxy) cyclohexylcarboxylate and bis (3,4-epoxycyclohexylmethyl) adipate. Formula epoxy resin can be mentioned.
Examples of the aliphatic epoxy resin include glycidyl ethers of polyhydric alcohols such as 1,4-butanediol, 1,6-hexanediol, polyethylene glycol, and pentaerythritol.
Examples of the heterocyclic epoxy resin include a heterocyclic epoxy resin having a heterocycle such as an isocyanul ring and a hydantoin ring.
Examples of the glycidyl ester-based epoxy resin include epoxy resins made of carboxylic acid esters such as hexahydrophthalic acid diglycidyl ester.
Examples of the glycidylamine-based epoxy resin include epoxy resins obtained by glycidylating amines such as aniline and toluidine.
Examples of the epoxy resin obtained by glycidylating the halogenated phenols include brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolac, brominated cresol novolac, chlorinated bisphenol S, and chlorinated bisphenol A. An epoxy resin obtained by glycidylating the halogenated phenols of the above can be mentioned.

As a copolymer of a polymerizable unsaturated compound having an epoxy group and another polymerizable unsaturated compound, Marproof G-0115S, G-0130S, and G-0250S are available on the market. , G-1010S, G-0150M, G-2050M (manufactured by Nichiyu Co., Ltd.), and examples of the polymerizable unsaturated compound having an epoxy group include glycidyl acrylate and glycidyl methacrylate, 4 -Vinyl-1-cyclohexene-1,2-epoxide and the like can be mentioned. Examples of other polymerizable unsaturated compounds include methyl (meth) acrylate, ether (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, vinylcyclohexane and the like. These epoxy resins may be used alone or in admixture of two or more.

The condensate of the silicon compound having an epoxy group and the other silicon compound has, for example, a hydrolysis condensate of an alkoxysilane compound having an epoxy group and an alkoxysilane having a methyl group or a phenyl group, or an epoxy group. It is a condensate of an alkoxysilane compound and a polydimethylsiloxane having a silanol group, a polydimethyldiphenylsiloxane having a silanol group, a polyphenylsiloxane having a silanol group, or a condensed compound obtained by using them in combination. Examples of the alkoxysilane compound having an epoxy group include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and 3-glycidoxypropyltrimethoxysilane. , 3-Glysidoxypropylmethyldimethoxysilane and the like. Examples of the alkoxysilane compound having a methyl group or a phenyl group include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, and methylphenyldimethoxysilane. .. Examples of polydimethylsiloxane having a silanol group and polydimethyldiphenylsiloxane having a silanol group include X-21-5841 and KF-9701 (manufactured by Shin-Etsu Chemical Co., Ltd.) BY16-873. PRX413 (manufactured by Toray Dow Corning Co., Ltd.) XC96-723, YF3804, YF3800, XF3905, YF3057 (Momentive Performance Materials Japan GK) DMS-S12, DMS-S14, DMS-S15, DMS-S21, Examples thereof include DMS-S27, DMS-S31, PDS-0338, and PDS-1615 (manufactured by Gelest).

The silicone-modified epoxy resin is a compound having a silicone chain (Si—O chain) as a main skeleton and having two or more epoxy groups in one molecule. The silicone chain may be linear, branched, cyclic, cage-type, or ladder-type. From the viewpoint of transparency and mechanical strength of the obtained cured product, a cyclic silicone-modified epoxy resin represented by the following formula (2) can be mentioned as a particularly preferable example, but the present invention is not limited thereto.

In the formula (2), R ³ represents a hydrocarbon group having 1 to 6 carbon atoms, X represents an epoxy group-containing organic group or a hydrocarbon group having 1 to 6 carbon atoms, and m represents an integer of 1 to 3 carbon atoms. .. May be different even in R ^3, X are each identical to the plurality present in the formula. However, among the plurality of Xs, two or more are organic groups containing an epoxy group.

Specific examples of R ³ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a phenyl group, but a methyl group and a phenyl group are preferable from the viewpoint of heat resistance and transparency of the cured product. A methyl group is particularly preferable from the viewpoint of ease of production.
The organic group in X represents a compound composed of C, H, N, and O atoms, and specific examples of the epoxy group-containing organic group include a 2,3-epoxycyclohexylethyl group and a 3-glycidoxypropyl group. From the viewpoint of heat resistance and transparency of the cured product, a 2,3-epoxycyclohexylethyl group is preferable. Here, the number of carbon atoms in the organic group is preferably 1 to 20, and more preferably 3 to 15. Further, it is preferable that the group has a 2,3-epoxycyclohexylethyl group and a 3-glycidoxypropyl group added via an alkylene group having 1 to 5 carbon atoms.
Specific examples of the hydrocarbon group having 1 to 6 carbon atoms in X include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and a phenyl group. Therefore, a methyl group and a phenyl group are preferable, and a methyl group is particularly preferable from the viewpoint of ease of production.
m is preferably 2.

The cyclic silicone-modified epoxy resin represented by the formula (2) can be obtained by a hydrosyllation reaction between a cyclic hydrogen siloxane compound and an olefin compound having an epoxy group in the molecule.
Specific examples of the cyclic hydrogen siloxane compound include trimethyltricyclosiloxane, triphenyltricyclosiloxane, tetramethyltetracyclosiloxane, tetraphenyltetracyclosiloxane, pentamethylpentacyclosiloxane, pentaphenylpentacyclosiloxane, and the like. Tetramethyltetrasiloxane is preferred because of its ease of manufacture.
Examples of the olefin compound having an epoxy group in the molecule include 4-vinyl-1,2-epoxycyclohexane, 3-glycidoxy-1,2-propene, and the like, and 4-vinyl- from the viewpoint of heat-resistant transparency of the cured product. 1,2-Epoxycyclohexane is preferred.

For the hydrosyllation reaction, a known metal complex such as rhodium, palladium, or platinum can be used as the catalyst thereof. Specifically, tristriphenylphosphine rhodium chloride, hexachloroplatinic acid / hexahydrate, divinyltetramethyldisiloxane platinum complex, tetravinyltetramethylcyclotetrasiloxane platinum complex, dichlorobis (triphenylphosphine) platinum complex, tetrakis ( In addition to the triphenylphosphine) platinum complex, examples thereof include platinum catalysts immobilized on a commercially available solvent-insoluble carrier such as polyethylene, such as ^{FibreCat R} 4001 and FibreCat ^{R 4003 (both manufactured by Wako Pure Chemical Industries, Ltd.).} From the viewpoint of the transparency of the cyclic siloxane compound (A) having two or more epoxy groups in the obtained molecule and the transparency of the cured product, hexachloroplatinic acid / hexahydrate, divinyltetramethyldisiloxane platinum complex, tetra. Vinyl tetramethylcyclotetrasiloxane platinum complex, dichlorobis (triphenylphosphine) platinum complex, and FiberCat ^R 4003 are preferred.

The catalyst used in the hydrosyllation reaction is preferably used as a solution by dissolving it in a solvent from the viewpoint of workability. The solvent that can be used can be any solvent that dissolves the catalyst, but tetrahydrofuran and toluene are preferable from the viewpoint of solubility and workability.
When used as a solution, the catalyst is adjusted to 0.05-50% by mass and added to the reaction solution.
When a catalyst immobilized on polyethylene or the like is used, it is added to the reaction solution as it is.
The amount of the catalyst added is in the range of 0.1 to 1000 ppm of the reaction substrate as the amount of metal used in the catalyst. From the viewpoint of the transparency of the cyclic siloxane compound (A) having two or more epoxy groups in the obtained molecule and the transparency of the cured product thereof, 1 to 100 ppm is preferable, and 2 to 20 ppm is particularly preferable. If the addition amount is less than 0.1 ppm, the addition reaction may be delayed, and if it is more than 1000 ppm, the silicone-modified epoxy resin may be severely colored.

After the hydrosyllation reaction, it can be purified by a known method such as washing with water, distillation, recrystallization, column chromatography, and adsorption (activated carbon, various minerals).
The solvent used for the reaction and / or purification can be removed by vacuum distillation or the like.

The epoxy equivalent of the cyclic silicone-modified epoxy resin represented by the formula (2) (measured by the method described in JIS K7236) is preferably 180 to 400 g / eq, and particularly preferably 190 to 250 g / eq.
The viscosity of the cyclic silicone-modified epoxy resin represented by the formula (6) at 25 ° C. is preferably 1500 to 10000 mPa · s, more preferably 2000 to 8000 mPa · s, and particularly preferably 3000 to 7000 mPa · s.

Specific examples of the cyclic silicone-modified epoxy resin represented by the formula (2) include compounds represented by the following formulas (2-1) to (2-6).

These (E) epoxy resins may be used alone or in admixture of two or more.

Among the above-mentioned (E) epoxy resins, from the viewpoint of transparency, heat resistance transparency, and light transparency, an alicyclic epoxy resin, a condensate of a silicon compound having an epoxy group and another silicon compound, and a silicone-modified epoxy. The combined use of resin is preferable. Among them, a cyclic silicone-modified epoxy resin having an epoxycyclohexane structure in the skeleton is preferable.

The epoxy resin (E) is preferably used in a range in which the epoxy group is 0.5 to 3.0 equivalents with respect to 1 equivalent of the carboxyl group in the (A) polyvalent carboxylic acid compound. If it is 0.5 equivalent or more, the heat-resistant transparency of the cured product is improved, and if it is 3.0 or less, the mechanical properties of the cured product are improved, which is preferable.

The epoxy resin composition of the present invention preferably further contains an epoxy resin curing accelerator.
As the epoxy resin curing accelerator, both the polyvalent carboxylic acid compound (A) and the one capable of accelerating the curing reaction of the epoxy resin (E) can be used, but as an example of the curing accelerator that can be used, , Ammonium salt-based curing accelerator, phosphonium salt-based curing accelerator, metal soap-based curing accelerator, imidazole-based curing accelerator, amine-based curing accelerator, phosphine-based curing accelerator, phosphite-based curing accelerator, Lewis Acid-based curing accelerators and the like can be mentioned.
In the epoxy resin composition of the present invention, it is preferable to use 0.001 to 15 parts by mass of the curing accelerator with respect to 100 parts by mass of the epoxy resin composition.

Specific examples of the epoxy resin curing accelerator that can be used in the epoxy resin composition of the present invention include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, and 2-phenyl-4-. Methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2 , 4-Diamino-6 (2'-methylimidazole (1')) ethyl-s-triazine, 2,4-diamino-6 (2'-undecylimidazole (1')) ethyl-s-triazine, 2, 4-Diamino-6 (2'-ethyl, 4-methylimidazole (1')) ethyl-s-triazine, 2,4-diamino-6 (2'-methylimidazole (1')) ethyl-s-triazine. Isocyanuric acid adduct, 2-methylimidazole 2: 3 adduct of isocyanuric acid, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5- Various imidazoles of methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, and these imidazoles and phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid , Salts with polyvalent carboxylic acids such as maleic acid and oxalic acid, amides such as dicyandiamide, diaza compounds such as 1,8-diaza-bicyclo (5.4.0) undecene-7 and their tetraphenylborates and phenols. Salts such as novolak, salts with the polyvalent carboxylic acids or phosphinic acids, ammonium salts such as tetrabutylammonium bromide, cetyltrimethylammonium bromide, trioctylmethylammonium bromide, triphenylphosphine, tri (toluyl) phosphine, tetraphenyl. Phosphins and phosphonium compounds such as phosphonium bromide and tetraphenylphosphonium tetraphenylborate, phenols such as 2,4,6-trisaminomethylphenol, metal compounds such as amine adduct and tin octylate, and these curing accelerators Examples include microcapsule type curing accelerators in microcapsules. Be done. Which of these curing accelerators is used is appropriately selected depending on the properties required for the obtained transparent resin composition, such as transparency, curing rate, and working conditions.

Among these, the metal soap curing accelerator is excellent from the viewpoint of the transparency of the cured product, and among the metal soap curing accelerators, the zinc carboxylate compound is particularly preferable from the viewpoint of the transparency of the cured product.
Examples of the metal soap-based curing accelerator include tin octylate, cobalt octylate, zinc octylate, manganese octylate, calcium octylate, sodium octylate, potassium octylate, calcium stearate, zinc stearate, magnesium stearate, and stearate. Aluminum acetate, barium stearate, lithium stearate, sodium stearate, potassium stearate, calcium 12-hydroxystearate, zinc 12-hydroxystearate, magnesium 12-hydroxystearate, aluminum 12-hydroxystearate, 12-hydroxystearic acid Barium, Lithium 12-hydroxystearate, Sodium 12-hydroxystearate, Calcium montanate, Zinc montanate, Magnesium montanate, Aluminum montanate, Lithium montanate, Sodium montanate, Calcium behenate, Zinc behenate, Bechenic acid Magnesium, lithium behate, sodium behenate, silver behate, calcium laurate, zinc laurate, barium laurate, lithium laurate, zinc undecylate, zinc ricinolate, barium ricinate, zinc myristate, zinc palmitate, etc. Can be mentioned. These catalysts may be used alone or in admixture of two or more.
In order to obtain a cured product having excellent transparency and sulfurization resistance, carbons such as zinc stearate, zinc montanate, zinc behenate, zinc laurate, zinc undecylate, zinc ricinoleate, zinc myristate, and zinc palmitate are particularly effective. A zinc salt composed of a monocarboxylic acid compound having 10 to 30 carbon atoms and having a hydroxyl group such as zinc carboxylate of several 10 to 30 and zinc 12-hydroxystearate can be preferably used. Among these, from the viewpoint of excellent pot life and sulfurization resistance, zinc salts composed of monocarboxylic acid compounds having 10 to 20 carbon atoms such as zinc stearate and zinc undecylene, and hydroxyl groups such as zinc 12-hydroxystearate are used. A zinc salt composed of a monocarboxylic acid compound having 15 to 20 carbon atoms can be preferably used, more preferably zinc stearate, zinc undecylene, and zinc 12-hydroxystearate can be used, and particularly preferably zinc stearate, 12-. Zinc hydroxystearate can be used.

Examples of the ammonium salt-based curing accelerator include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylpropylammonium hydroxide, and trimethylbutylammonium hydroxide. , Trimethylacetylammonium hydroxide, trioctylmethylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate, trioctylmethylammonium acetate and the like. Examples of the phosphonium salt-based curing accelerator include ethyltriphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, methyltributylphosphonium dimethyl phosphate, methyl tributylphosphonium diethyl phosphate and the like.

Other general-purpose applications include the above-mentioned ammonium salt-based curing accelerator, phosphonium salt-based curing accelerator, metal soap-based curing accelerator, imidazole-based curing accelerator, amine-based curing accelerator, and heterocyclic compound-based curing accelerator. , A phosphine-based curing accelerator, a phosphite-based curing accelerator, a Lewis acid-based curing accelerator, and the like can be used.

The epoxy resin curing accelerator described above can be used as either a solid compound or a liquid compound at room temperature (25 ° C.). When the epoxy resin composition of the present invention is used for applications that require liquidity at room temperature (25 ° C.) and a solid compound at room temperature (25 ° C.) is used as a curing accelerator, the resin is previously prepared. It can also be dissolved and used. Further, a solid compound can be dispersed in a resin at room temperature (25 ° C.) and used.

By using a coupling agent in the curable resin composition or epoxy resin composition of the present invention, if necessary, it is possible to adjust the viscosity of the composition and supplement the hardness of the cured product.
Examples of the coupling agent that can be used include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyl. Trimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltri Methoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxysilane hydrochloride, 3-methacryloxypropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloro Silane-based coupling agents such as propyltrimethoxysilane; isopropyl (N-ethylaminoethylamino) titanate, isopropyltriisostearoyl titanate, titaniumdi (dioctylpyrrofostate) oxyacetate, tetraisopropyldi (dioctylphosphite) titanate, Titanium-based coupling agents such as neoalkoxytri (p-N- (β-aminoethyl) aminophenyl) titanate; Zr-acetylacetonate, Zr-methacrylate, Zr-propionate, neoalkoxyzirconate, neoalkoxytris neodeca Noylzirconate, neoalkoxytris (dodecanoyl) benzenesulfonylzirconate, neoalkoxytris (ethylenediaminoethyl) zirconate, neoalkoxytris (m-aminophenyl) zirconate, ammonium zirconium carbonate, Al-acetylacetonate, Al-methacrylate, Examples thereof include zirconium such as Al-propionate, and aluminum-based coupling agents.
These coupling agents may be used alone or in admixture of two or more.
The coupling agent is usually contained in the epoxy resin curing agent composition or the epoxy resin composition of the present invention in an amount of 0.05 to 20 parts by mass, preferably 0.1 to 10 parts by mass, if necessary.

By using a nano-order level inorganic filler as necessary for the epoxy resin curing agent composition or epoxy resin composition of the present invention, it is possible to supplement mechanical strength and the like without impairing transparency. Is. As a guideline for the nano-order level, it is preferable to use a filler having an average particle size of 500 nm or less, particularly an average particle size of 200 nm or less, from the viewpoint of transparency. Examples of the inorganic filler include powders such as crystalline silica, molten silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, and talc, or these. Spherical beads and the like can be mentioned, but the present invention is not limited to these. These fillers may be used alone or in combination of two or more. As the content of these inorganic fillers, an amount occupying 0 to 95% by mass in the epoxy resin composition of the present invention is used.

The epoxy resin curing agent composition or the epoxy resin composition of the present invention may contain an amine compound as a light stabilizer for the purpose of preventing coloration.
Examples of the amine compound include tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate and tetrakis (2,2,6,6-totramethyl). -4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3, 9-Bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-Tetraoxaspiro [5.5] A mixed esterified product with undecane, bisdecanedioate (2,2,6) 6-Tetramethyl-4-piperidyl) sebacate, bis (1-undecaneoxy-2,2,6,6-tetramethylpiperidine-4-yl) carbonate, 2,2,6,6, -tetramethyl-4-yl Piperidine methacrylate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 4-benzoyloxy-2,2 , 6,6-tetramethylpiperidine, 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di) -Tert-Butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethyl-4-piperidinyl-methacrylate, bis (1,2) , 2,6,6-pentamethyl-4-piperidinyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butylmalonate, bisdecanedioate (2,2,6) , 6-Tetramethyl-1 (octyloxy) -4-piperidinyl) ester, 1,1-dimethylethylhydroperoxide and octane reaction product, N, N', N ", N"'-tetrakis- (4, 6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidine-4-yl) amino) -triazine-2-yl) -4,7-diazadecan-1,10-diamine, Dibutylamine 1,3,5-triazine N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6) Polycondensate of 6-tetramethyl-4-piperidyl) butylamine, poly [[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-tria Jin-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] Hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], Polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, 2,2,4,4-tetramethyl-20- (β-lauryloxycarbonyl) ethyl-7 -Oxa-3,20-diazadispiro [5.1.11.2] heneikosan-21-one, β-alanine, N,-(2,2,6,6-tetramethyl-4-piperidinyl) -dodecyl ester / Tetradecyl ester, N-acetyl-3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidinyl) pyrridine-2,5-dione, 2,2,4,4-tetramethyl-7 -Oxa-3,20-diazazispiro [5,1,11,2] heneikosan-21-one, 2,2,4,5-tetramethyl-21-oxa-3,20-diazadicyclo-[5,1,11] , 2] -Heneicosan-20-propanoic acid dodecyl ester / tetradecyl ester, propanedioic acid, [(4-methoxyphenyl) -methylene] -bis (1,2,2,6,6-pentamethyl-4-piperidinyl) ) Ester, higher fatty acid ester of 2,2,6,6-tetramethyl-4-piperidinol, 1,3-benzenedicarboxyamide, N, N'-bis (2,2,6,6-tetramethyl-4) -Hindertamine-based compounds such as piperidinyl), benzophenone-based compounds such as octabenzone, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- ( 2-Hydroxy-5-methylphenyl) benzotriazole, 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimide-methyl) -5-methylphenyl] benzotriazole, 2- (3-tert -Butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-pentylphenyl) benzotriazole, methyl 3- (3- (2H-benzo) Triazole-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate and polyethylene glycol reaction products, 2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol, etc. Bentotriazole compounds , 2,4-Di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate and other benzoate compounds, 2- (4,6-diphenyl-1,3,5-triazine-2-) Il) -5-[(Hexyl) oxy] Phenol and other triazine compounds can be mentioned, but hindered amine compounds are particularly preferable.

As the amine compound which is the light stabilizer, the following commercially available products can be used.
The commercially available amine compounds are not particularly limited, and for example, TINUVIN765, TINUVIN770DF, TINUVIN144, TINUVIN123, TINUVIN622LD, TINUVIN152, CHIMASSORB944, and ADEKA, LA-52, LA-57, LA- 62, LA-63P, LA-77Y, LA-81, LA-82, LA-87 and the like can be mentioned.

The blending amount of the amine compound is not particularly limited, but is in the range of 0.005 to 5.0% by mass with respect to the total mass of the epoxy resin curing agent composition or the epoxy resin composition of the present invention.

Further, a binder resin can be added to the epoxy resin curing agent composition or the epoxy resin composition of the present invention, if necessary. Examples of the binder resin include butyral resin, acetal resin, acrylic resin, epoxy-nylon resin, NBR-phenol resin, epoxy-NBR resin, polyamide resin, polyimide resin, silicone resin and the like. , Not limited to these. The blending amount of the binder resin is preferably in a range that does not impair the flame retardancy and heat resistance of the cured product, and is usually 0.05 to 50 parts by mass, preferably 0.05 to 20 parts by mass with respect to 100 parts by mass of the resin component. Parts by mass are used as needed.

An inorganic filler can be added to the epoxy resin curing agent composition or the epoxy resin composition of the present invention, if necessary. Examples of the inorganic filler include powders such as crystalline silica, molten silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, and talc, or these. Spherical beads and the like can be mentioned, but the present invention is not limited to these. These may be used alone or two or more kinds may be used. As the content of these inorganic fillers, an amount occupying 0 to 95% by mass in the curable resin composition of the present invention is used. Further, to the curable resin composition of the present invention, a silane coupling agent, a mold release agent such as stearic acid, palmitic acid, zinc stearate, calcium stearate, various compounding agents such as pigments, and various thermosetting resins are added. can do.

The epoxy resin curing agent composition or epoxy resin composition of the present invention can be obtained by uniformly mixing the above components at room temperature or heating. For example, by using an extruder, a kneader, a triple roll, a universal mixer, a planetary mixer, a homomixer, a homodisper, a bead mill, etc., the mixture is sufficiently mixed until it becomes uniform, and if necessary, filtration is performed with a SUS mesh or the like. Prepared.

The epoxy resin curing agent composition or epoxy resin composition of the present invention comprises a polyvalent carboxylic acid compound (A), an ultraviolet absorber (B), a phenol antioxidant (C), an antioxidant (D) and an epoxy resin. An epoxy resin composition can be prepared by sufficiently mixing additives such as (E), an antioxidant, and a light stabilizer, and can be used as a sealing material. As a mixing method, a spatula, a kneader, a triple roll, a universal mixer, a planetary mixer, a homomixer, a homodisper, a bead mill or the like is used to mix at room temperature or by heating.

The epoxy resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. to obtain a curable resin composition varnish, which is made into glass. A cured product of the epoxy resin composition of the present invention is obtained by hot-press molding a prepreg obtained by impregnating a base material such as fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper and heating and drying. Can be. The solvent used in this case is usually 10 to 70% by mass, preferably 15 to 70% by mass in the mixture of the epoxy resin composition of the present invention and the solvent. It is also possible to obtain a cured epoxy resin containing carbon fibers by the RTM method as it is in the liquid composition.

The epoxy resin composition of the present invention can also be used as a modifier for a film-type composition. Specifically, it can be used to improve the flexibility and the like in the B-stage. In order to obtain such a film-type resin composition, the epoxy resin composition of the present invention is coated on a release film with the varnish, the solvent is removed under heating, and B-stage is performed to form a sheet-like adhesive. To get. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.

Further, general applications in which thermosetting resins such as epoxy resins are used include, for example, adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), insulating materials (printed substrates, printed substrates, etc.). (Including wire coating, etc.), encapsulant, encapsulant, cyanate resin composition for substrate, acrylic acid ester resin, additive to other resins, etc. as a curing agent for resist.

Examples of the adhesive include adhesives for civil engineering, construction, automobiles, general office work, medical use, and adhesives for electronic materials. Among these, adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, adhesives for semiconductors such as underfills, underfills for BGA reinforcement, and anisotropic conductive films (an anisotropic conductive film). ACF), adhesives for mounting such as anisotropic conductive paste (ACP) and the like can be mentioned.

Sealants include potting, dipping, transfer mold encapsulation for capacitors, transistors, diodes, light emitting diodes, ICs, LSIs, etc., potting encapsulation for ICs, LSIs such as COB, COF, TAB, etc., and flip chips. Examples include underfilling for such as, sealing (including reinforcing underfilling) when mounting IC packages such as QFP, BGA, and CSP.

The cured product obtained in the present invention can be used for various purposes including optical component materials. The optical material refers to a general material used for passing light such as visible light, infrared rays, ultraviolet rays, X-rays, and lasers through the material. More specifically, in addition to the sealing material for LEDs such as lamp type and SMD type, the following can be mentioned. It is a peripheral material for a liquid crystal display device such as a substrate material, a light guide plate, a prism sheet, a deflection plate, a retardation plate, a viewing angle correction film, an adhesive, and a liquid crystal film such as a polarizer protective film in the liquid crystal display field. In addition, color PDP (plasma display) encapsulants, antireflection films, optical correction films, housing materials, front glass protective films, front glass substitute materials, adhesives, and LED displays, which are expected as next-generation flat panel displays. LED mold materials used in equipment, LED encapsulants, front glass protective films, front glass substitute materials, adhesives, substrate materials for plasma address liquid crystal (PALC) displays, light guide plates, prism sheets, deflection plates. , Phase difference plate, viewing angle correction film, adhesive, polarizer protective film, front glass protective film in organic EL (electroluminescence) display, front glass alternative material, adhesive, and various types in field emission display (FED). A film substrate, a protective film for the front glass, a substitute material for the front glass, and an adhesive. In the field of optical recording, VD (video disc), CD / CD-ROM, CD-R / RW, DVD-R / DVD-RAM, MO / MD, PD (phase change disc), disc substrate material for optical cards, Pickup lenses, protective films, encapsulants, adhesives, etc.

In the field of optical equipment, it is a material for a lens of a steel camera, a finder prism, a target prism, a finder cover, and a light receiving sensor unit. It is also a shooting lens and viewfinder for video cameras. It also includes projection lenses for projection televisions, protective films, encapsulants, and adhesives. Materials for lenses of optical sensing equipment, encapsulants, adhesives, films, etc. In the field of optical components, there are fiber materials around optical switches in optical communication systems, lenses, waveguides, element encapsulants, adhesives, and the like. Optical fiber materials, ferrules, encapsulants, adhesives, etc. around optical connectors. Optical passive components and optical circuit components include lenses, waveguides, LED encapsulants, LED packaging materials, LED reflector materials, CCD encapsulants, adhesives, and the like. Substrate materials, fiber materials, element encapsulants, adhesives, etc. around optoelectronic integrated circuits (OEICs). In the field of optical fibers, sensors for industrial applications such as lighting and light guides for decorative displays, displays and signs, and optical fibers for communication infrastructure and for connecting digital devices in homes. The semiconductor integrated circuit peripheral material is a resist material for microlithography for LSI and VLSI materials. In the field of automobiles and transport equipment, lamp reflectors for automobiles, bearing retainers, gear parts, corrosion-resistant coats, switch parts, headlamps, engine internal parts, electrical components, various interior and exterior parts, drive engines, brake oil tanks, automobile protection Rusted steel plate, interior panel, interior material, wireness for protection and binding, fuel hose, automobile lamp, glass substitute. It is also a double glazing for railway vehicles. In addition, it is a toughness-imparting agent for aircraft structural materials, engine peripheral members, wireness for protection and binding, and corrosion-resistant coating. In the field of construction, it is a material for interior / processing, an electric cover, a sheet, a glass interlayer film, a glass substitute, and a peripheral material for a solar cell. For agriculture, it is a film for covering houses. Next-generation optical and electronic functional organic materials include organic EL element peripheral materials, organic photorefractive elements, optical amplification elements that are optical-optical conversion devices, optical arithmetic elements, substrate materials around organic solar cells, fiber materials, and elements. Encapsulant, adhesive, etc.

Sealants include potting for capacitors, transistors, diodes, light emitting diodes, ICs, LSIs, dipping, transfer mold encapsulation, potting encapsulation for ICs, LSIs COB, COF, TAB, etc., and flip chips. Examples include underfilling for such purposes, sealing (reinforcing underfilling) when mounting IC packages such as BGA and CSP, and the like.

Other uses of optical materials include general uses where curable resin compositions are used, such as adhesives, paints, coatings, molding materials (including sheets, films, FRP, etc.), insulation. In addition to materials (including printed circuit boards, wire coatings, etc.) and encapsulants, additives to other resins and the like can be mentioned. Examples of the adhesive include adhesives for civil engineering, construction, automobiles, general office work, medical use, and adhesives for electronic materials. Among these, adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, adhesives for semiconductors such as underfills, underfills for BGA reinforcement, and anisotropic conductive films (an anisotropic conductive film). ACF), adhesives for mounting such as anisotropic conductive paste (ACP) and the like can be mentioned.

Optical semiconductor devices such as high-brightness white LEDs generally include GaAs, GaP, GaAlAs, GaAsP, AlGa, InP, GaN, InN, AlN, and InGaN laminated on a substrate such as sapphire, spinel, SiC, Si, and ZnO. A semiconductor chip such as the above is adhered to a lead frame, a heat radiating plate, or a package using an adhesive (die bond material). There is also a type in which a wire such as a gold wire is connected to pass an electric current. The semiconductor chip is sealed with a sealing material such as epoxy resin in order to protect it from heat and humidity and to play a role of a lens function. The epoxy resin composition of the present invention can be used for this encapsulant.

The encapsulant molding method includes an injection method in which the encapsulant is injected into a mold in which a substrate on which an optical semiconductor element is fixed is inserted and then heat-cured to form the encapsulant. Then, a compression molding method or the like is used in which an optical semiconductor element fixed on a substrate is immersed therein, heat-cured, and then separated from a mold.
Examples of the injection method include a dispenser and the like.
For heating, a hot air circulation method, infrared rays, high frequency, or the like can be used. The heating conditions are preferably, for example, 80 to 230 ° C. for about 1 minute to 24 hours. For the purpose of reducing the internal stress generated during heat curing, for example, pre-curing at 80 to 120 ° C. for 30 minutes to 5 hours and then post-curing at 120 to 180 ° C. for 30 minutes to 10 hours. it can.

In the present specification, ratios, percentages, parts, etc. are based on mass unless otherwise specified. In the present specification, the expression "X to Y" indicates a range from X to Y, and the range includes X and Y.

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples and Examples. The present invention is not limited to these synthetic examples and examples. The physical property values in the synthetic examples and the examples were measured by the following methods. Here, the part represents a mass part unless otherwise specified.
-Gel permeation chromatography (GPC): GPC was measured under the following conditions.
Various conditions of GPC Manufacturer: Waters column: SHODEX GPC LF-G (guard column), KF-603, KF-602.5, KF-602, KF-601 (2)
Flow velocity: 0.4 ml / min.
Column temperature: 40 ° C
Solvent used: THF (tetrahydrofuran)
Detector: RI (Differential Refractometer)
○ Functional group equivalent: Measured by the following method.
Approximately 0.15 g of the polyunsaturated carboxylic acid composition was weighed, dissolved in 40 ml of methanol (special grade reagent), and then stirred at 20 to 28 ° C. for 10 minutes to prepare a measurement sample. The measurement sample was titrated using a titrator AT-610 manufactured by Kyoto Electronics Industry Co., Ltd. using a 0.1N sodium hydroxide solution, and the value obtained as the acid value was calculated as the functional group equivalent.
○ Viscosity: Measured at 25 ° C. using an E-type viscometer (TV-20) manufactured by Toki Sangyo Co., Ltd.
○ Epoxy equivalent: Measured by the method described in JIS K7236.

Synthesis Example 1: Production of a mixture of a polyvalent carboxylic acid compound having two or more carboxyl groups in the molecule and a compound having one or more carboxylic acid anhydride groups in the molecule Stirrer, reflux cooling tube, stirrer Tricyclodecanedimethanol 15 g, methylhexahydrophthalic anhydride (manufactured by Shin Nihon Rika Co., Ltd., Ricacid MH) 70 g, cyclohexane-1,2,4-tricarboxylic acid- 15 g of 1,2-anhydride (H-TMAn manufactured by Mitsubishi Gas Chemicals, Inc.) was added, and the reaction was carried out at 40 ° C. for 3 hours, followed by heating and stirring at 70 ° C. for 1 hour. 1 area% or less of tricyclodecanedimethanol was confirmed by GPC, and 100 g of a mixture (A-1) of a polyunsaturated carboxylic acid resin and a carboxylic acid anhydride compound was obtained. The obtained mixture is a colorless liquid, and the purity according to GPC is 42 area% of polyvalent carboxylic acid resin (formula A-1 below) and cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride. 11 area% and 47 area% of methylhexahydrophthalic anhydride. The functional group equivalent is 171 g / eq. Met.

Synthesis Example 2; Production example of a cyclic siloxane compound having four epoxy groups in the molecule using ^{Flaskrat R} 4003 (manufactured by Wako Pure Chemical Industries, Ltd.), which is a platinum-immobilized catalyst, as a hydrosyllation catalyst 200 ml of glass In a two-necked flask, 32.3 parts of 4-vinyl-1,2-epoxycyclohexane ^{, 0.023 parts of Fibercat R} 4003 (platinum content 3.4 to 4.5%), and 50 parts of toluene were charged, and a Jimroth condenser was charged. , A stirrer and a thermometer were installed, and the flask was immersed in an oil bath. The oil bath was heated to maintain the internal temperature at 80 ° C., and 12 parts of 1,3,5,7-tetramethyltetracyclosiloxane was added dropwise thereto over 1 hour, and the reaction was carried out as it was for 10 hours. ^{When 1} H-NMR measurement of the reaction solution was carried out, the proton peak derived from hydrogen siloxane disappeared.
To the reaction solution, activated carbon (manufactured by Ajinomoto Fine-Techno Co., Inc.) was added, After stirring for 3 hours at room temperature (20 to 30 ° C.), was removed by filtration with activated carbon and FibreCAT ^R 4003, while blowing nitrogen gas into the resulting filtrate , 60 ° C. and concentrated under reduced pressure to remove toluene and excess 4-vinyl-1,2-epoxycyclohexane to obtain 36.7 g of a cyclic siloxane compound (E-1) having four epoxy groups in the molecule. It was. The epoxy equivalent of the obtained compound was 184.3 g / eq, the viscosity was 5601 mPa · s, and the appearance was a colorless transparent liquid.

Example 1;
A-1 obtained in Synthesis Example 1, TINUVIN 234 manufactured by BASF described in the above formula (27) as an ultraviolet absorber (B), and BASF described in the above formula (30) as a phenol antioxidant (C). Irganox 1035 manufactured by Irganox 1035 and Trisdecylphosphite (Adecastab 3010 manufactured by ADEKA) as an antioxidant (D) are weighed in a polyethylene container at the ratio shown in Table 1 below, mixed well with a spoon, and then vacuumed. The epoxy resin curing agent composition of the present invention was obtained by stirring with a stirring defoaming device for 2 minutes.

Example 2;
A-1 obtained in Synthesis Example 1, TINUVIN 326 manufactured by BASF, which is described in the above formula (28) as an ultraviolet absorber (B), and BASF, which is described in the above formula (30) as a phenol antioxidant (C). Irganox 1035 manufactured by Irganox 1035 and Trisdecylphosphite (Adecastab 3010 manufactured by ADEKA) as an antioxidant (D) are weighed in a polyethylene container at the ratio shown in Table 1 below, mixed well with a spoon, and then vacuumed. The epoxy resin curing agent composition of the present invention was obtained by stirring with a stirring defoaming device for 2 minutes.

Example 3;
In the epoxy resin curing agent composition obtained in Example 1, E-1 obtained in Synthesis Example 2 as the epoxy resin (E) and U-CAT5003 manufactured by San-Apro Co., Ltd. as the curing accelerator are shown in Table 1 below. The epoxy resin composition of the present invention was obtained by weighing the mixture in a polyethylene container at the ratio of the above amount, mixing well with a spoon, and then stirring for 2 minutes with a vacuum stirring defoaming device.

Example 4;
In the epoxy resin curing agent composition obtained in Example 2, E-1 obtained in Synthesis Example 2 as the epoxy resin (E) and U-CAT5003 manufactured by San-Apro Co., Ltd. as the curing accelerator are shown in Table 1 below. The epoxy resin composition of the present invention was obtained by weighing the mixture in a polyethylene container at the ratio of the above amount, mixing well with a spoon, and then stirring for 2 minutes with a vacuum stirring defoaming device.

Comparative Example 1;
A-1 obtained in Synthesis Example 1, Irganox 1035 manufactured by BASF according to the above formula (30) as the phenolic antioxidant (C), and trisdecylphosphite (manufactured by ADEKA) as the phosphoroxidant (D). Adecastab 3010), E-1 obtained in Synthesis Example 2 as the epoxy resin (E), and U-CAT5003 manufactured by San-Apro Co., Ltd. as the curing accelerator were weighed in a polyethylene container in the amount ratios shown in Table 1 below. After mixing well with a spoon, the mixture was stirred with a vacuum stirring defoaming device for 2 minutes to obtain an epoxy resin composition of Comparative Example.

The results of the compounding ratio and viscosity of the epoxy resin compositions obtained in Examples 3 to 4 and Comparative Example 1, the mass reduction during curing, the transmittance of the cured product, the transmittance after the heat resistance test, and the glass transition temperature (Tg) are shown. It is shown in Table 1. The tests in Table 1 were performed as follows.
Viscosity Measured at 25 ° C. using an E-type viscometer (TV-20) manufactured by Toki Sangyo Co., Ltd.
Cured product transmittance The epoxy resin compositions obtained in Example 1 and Comparative Example 1 were vacuum defoamed for 5 minutes, and then a dam was formed with heat-resistant tape so as to have a size of 30 mm × 20 mm × height 0.8 mm. Gently cast on top. The cast product was pre-cured at 120 ° C. for 1 hour and then cured at 150 ° C. for 3 hours to obtain a transmittance test piece having a thickness of 0.8 mm. The obtained test piece was taken out from the glass substrate, and the light transmittance at 450 nm was measured under the following conditions.
<Spectrophotometer measurement conditions>
Manufacturer: Hitachi High-Technologies Corporation Model: U-3300
Slit width: 2.0 nm
Scanning speed: 120 nm / min Transmittance after heat resistance test (2) The test piece after the sample whose transmittance was measured by the cured product transmittance was left in an oven at 180 ° C. for 72 hours (in the air) under the same conditions as (2). The light transmittance at 450 nm was measured.
Transmittance after heat resistance test (2) The light transmittance of the sample whose transmittance was measured by the cured product transmittance was measured under the same conditions as in (2) after the light resistance test was performed under the following conditions.
<Light resistance test conditions>
Manufacturer: Iwasaki Electric Co., Ltd. Model: Eye Super UV Tester SUV-W161
Light source; Metal halide lamp irradiation energy; 90 mW / cm2
Environmental temperature and humidity; 60 ° C, 60% RH
Test time; 168 hours

＊図１に硬化物透過率スペクトルを示した。

* Fig. 1 shows the cured product transmittance spectrum.

As is clear from the cured product transmittance spectra in Table 1 and FIG. 1, the epoxy resin compositions of Examples 3 and 4 have an appropriate viscosity for use as an LED encapsulant, and the cured product transmittance, In addition to being excellent in transmittance after the heat resistance test, it is also excellent in transmittance after the light resistance test, does not transmit short wavelength light rays, and is excellent in ultraviolet blocking property, whereas the cured product of Comparative Example 1 is inferior in ultraviolet blocking property. .. From the above, the epoxy resin curing agent composition of the present invention using the polyvalent carboxylic acid compound and the ultraviolet absorber gives a cured product having excellent ultraviolet blocking property, heat resistance transparency, and light transparency transparency, and is particularly ultraviolet. It is suitable as an LED encapsulant exposed to light.

Claims (7)

An epoxy resin curing agent composition containing the following components (A) to (D), wherein the mass ratio of the following (C) phenolic antioxidant and the following (D) antioxidant is (antioxidant) /. An epoxy resin curing agent composition of 0.5 to 10 (phenolic antioxidant).
(A) Polyunsaturated carboxylic acid compound (B) Benzotriazole-based ultraviolet absorber, which contains a skeleton represented by the following formula (A).

(C) Phenolic antioxidant represented by the following formula (30)

(D) Antioxidant represented by the following formula (31)

(In the formula (31), R ⁹ is optionally substituted by one or more identical each R ⁹ there are multiple in. Formula, which represents a phenyl group which may have an alkyl group or a substituent having 1 to 30 carbon atoms It doesn't matter.) (B) The epoxy resin curing agent composition according to claim 1, wherein the ultraviolet absorber is represented by the following formula (1).

(In the formula (1), R ¹ represents a hydrogen atom or a chlorine atom, R ² is R ² that there are a plurality of. Formula represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms be the same or different It doesn't matter if you have it.)
The epoxy resin curing agent composition according to claim 1 or 2, and the epoxy resin composition containing the following E component.
(E) Epoxy resin
The epoxy resin curing agent composition or epoxy resin according to any one of claims 1 to 3, wherein the polyunsaturated carboxylic acid compound is a compound obtained by the addition reaction of the following (a) and (b). Composition.
(A) Polyhydric alcohol compound having two or more hydroxyl groups in the molecule (b) Compound having one or more carboxylic acid anhydride compounds in the molecule
(E) The epoxy resin composition according to any one of claims 3 or 4, wherein the epoxy resin is a silicone-modified epoxy resin.
The epoxy resin composition according to claim 5, wherein the silicone-modified epoxy resin is represented by the following formula (2).

(In the formula (2), R ³ is a hydrocarbon group having 1 to 6 carbon atoms, X is an organic group containing an epoxy group or a hydrocarbon group having 1 to 6 carbon atoms, and m is an integer of 1 to 3 carbon atoms. represents. may be different even in R ^3, X are each identical to the plurality present in the formula. However, in X presence of a plurality, two or more is an organic group containing an epoxy group.)
A cured product obtained by curing the epoxy resin composition according to any one of claims 3 to 6.

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