JP6501359B2 - Curable resin composition containing a sulfur-based antioxidant, epoxy resin composition and cured product thereof - Google Patents

Description

The present invention relates to a curable resin composition, an epoxy resin composition, and a cured product obtained by curing the same, which is particularly suitable for use in parts requiring high transparency and low colorability such as optical semiconductor applications.

As thermosetting resins used for optical semiconductor applications, silicone resin compositions and epoxy resin compositions are often used.
When mounting an optical semiconductor, in particular an SMD (Surface Mount Device) among LEDs (Light Emitting Diode), to an equipment, it is exposed to a high temperature such as two hundred and several tens of degrees as a solder reflow process for several tens of seconds.
Although the silicone resin obtained by heat curing the silicone resin composition is excellent in heat-resistant transparency, it has inferior gas barrier properties, and corrosion of members (silver plating, gold wire, etc.) used for optical semiconductors from an external corrosive gas. There is a problem that can not be prevented (Patent Document 1).
On the other hand, although an epoxy resin composition is excellent in gas barrier properties, it is inferior in heat resistance and transparency, and therefore, when used in an optical semiconductor device, there is a problem in that its reliability is inferior.
Then, although heat resistant transparency improvement is performed using a phenolic antioxidant and phosphorus antioxidant, what can not be satisfied yet is obtained (patent document 2).

Patent No. 5678592 JP 2015-117325

The present invention provides an epoxy resin composition and a curable resin composition which give a cured product which is excellent in the transparency of a cured product and also excellent in heat-resistant transparency, particularly when used for SMD type LED sealing materials and the like. The purpose is to

（式（１）中、Ｒ^１は炭素数１〜１０のアルキル基を、Ｒ^２、Ｒ^３は炭素数１〜５のアルキレン基をそれぞれ表す。式中、複数存在するＲ^１〜Ｒ^３はそれぞれ同一であっても異なっていても構わない。）
（２）（Ａ）分子中に二つ以上のカルボキシル基を有する多価カルボン酸化合物が、下記式（２）で表される、（１）に記載の硬化性樹脂組成物。

（式（２）中、Ｘは０〜６の酸素原子、窒素原子、リン原子、ケイ素原子を含んでもよい、炭素数２〜１００の多価アルコールの残基を、Ｒ^４は炭素数２〜２０の脂肪族炭化水素基を、ｍは平均で１〜６を、ｎは平均で２〜６をそれぞれ表す。式中、複数存在するＲ^４はそれぞれ同一であっても異なっていても構わない。）
（３）（Ａ）分子中に二つ以上のカルボキシル基を有する多価カルボン酸化合物が、下記（ａ）の残基及び下記（ｂ）の残基を有し、下記（ａ）及び（ｂ）の各残基はエステル構造で結合されている末端にカルボキシル基を有する化合物である、（１）又は（２）のいずれか一項に記載の硬化性樹脂組成物。

（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の反応残基
（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の反応残基

（４）（Ａ）分子内に一つ以上のカルボン酸無水物基を有する化合物が、下記式（３）〜（５）より選択される一種以上である、（１）〜（３）のいずれか一項に記載の硬化性樹脂組成物。

（５）式（１）中の、Ｒ^１はターシャリーブチル基、Ｒ^２がエチレン基、Ｒ^３がエチレン基である、（１）〜（４）のいずれか一項に記載の硬化性樹脂組成物。
（６）（１）〜（５）の硬化性樹脂組成物に、さらに（Ｃ）エポキシ樹脂を含有することを特徴とするエポキシ樹脂組成物。
（７）（Ｃ）エポキシ樹脂がシリコーン変性エポキシ樹脂である（６）に記載のエポキシ樹脂組成物。
（８）シリコーン変性エポキシ樹脂が下記式（６）で表される（７）に記載のエポキシ樹脂組成物。

（式（６）中、Ｒ^５は炭素数１〜６の炭化水素基を、Ｙ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、ｐは１〜３の整数をそれぞれ表す。式中に複数存在するＲ^５、Ｙ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Ｙ中、２つ以上はエポキシ基含有の有機基である。）
（９）（６）〜（８）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。 In view of the foregoing, the inventors of the present invention conducted intensive studies to find that a polyvalent carboxylic acid compound having two or more carboxyl groups in the molecule and / or one or more carboxylic acid anhydride groups in the molecule. It has been found that a compound having the same, a curable resin composition containing a sulfur-based antioxidant, and an epoxy resin composition solve the above problems, and the present invention has been completed.
That is, the present invention relates to the following (1) to (9).

(1) A curable resin composition containing the following components (A) and (B).
(A) A polyvalent carboxylic acid compound having two or more carboxyl groups in the molecule and / or a compound having one or more carboxylic acid anhydride groups in the molecule (B) represented by the following formula (1) Sulfur-based antioxidant

(In formula (1), R ¹ represents an alkyl group having 1 to 10 carbon atoms, R ² and R ³ each represent an alkylene group having 1 to 5 carbon atoms. In the formula, a plurality of R ^{1 to} R ³ are Each may be the same or different.)
(2) The curable resin composition according to (1), wherein the polyvalent carboxylic acid compound having two or more carboxyl groups in the (A) molecule is represented by the following formula (2).

(In the formula (2), X is 0-6 oxygen atoms, nitrogen atoms, phosphorus atoms which may contain a silicon atom, a residue of a polyhydric alcohol of 2 to 100 carbon atoms, ^{R 4} is 2 carbon atoms 20 aliphatic hydrocarbon groups, m represents an average of 1 to 6 and n represents an average of 2 to 6. In the formula, a plurality of R ⁴ may be the same or different. .)
(3) (A) A polyvalent carboxylic acid compound having two or more carboxyl groups in the molecule has the following residue (a) and the following residue (b), and the following (a) and (b) The curable resin composition as described in any one of (1) or (2) which is a compound which has a carboxyl group at the terminal which each residue of is couple | bonded with ester structure.

(A) Reactive residue of polyhydric alcohol compound having two or more hydroxyl groups in molecule (b) Reactive residue of compound having one or more carboxylic anhydride compounds in molecule

(4) Any one of (1) to (3), wherein the compound having one or more carboxylic acid anhydride groups in the (A) molecule is one or more selected from the following formulas (3) to (5) The curable resin composition according to any one of the preceding claims.

(5) The curable resin according to any one of (1) to (4), wherein in the formula (1), R ¹ is a tertiary butyl group, R ² is an ethylene group, and R ³ is an ethylene group. Composition.
(6) An epoxy resin composition characterized by further containing (C) an epoxy resin in the curable resin composition of (1) to (5).
(7) The epoxy resin composition as described in (6) whose (C) epoxy resin is a silicone modified epoxy resin.
(8) The epoxy resin composition according to (7), wherein the silicone-modified epoxy resin is represented by the following formula (6).

(In the formula (6), R ⁵ represents a hydrocarbon group having 1 to 6 carbon atoms, Y represents an epoxy group-containing organic group or a hydrocarbon group having 1 to 6 carbon atoms, and p represents an integer of 1 to 3) A plurality of R ^{5 's} and Y's in the formula may be the same or different, provided that two or more of the plurality of Y's are epoxy group-containing organic groups)
(9) A cured product obtained by curing the epoxy resin composition according to any one of (6) to (8).

  According to the present invention, a polyvalent carboxylic acid compound having two or more carboxyl groups in the molecule and / or a compound having one or more carboxylic acid anhydride groups in the molecule, and a sulfur-based antioxidant The thermosetting resin composition is very useful as a material for which high transparency and high heat resistance transparency are required, particularly as a resin for optical semiconductors, because it gives a cured product having high transparency and high heat resistance transparency.

The thermosetting resin composition of the present invention contains the following components (A) and (B).
(A) A polyvalent carboxylic acid compound having two or more carboxyl groups in the molecule and / or a compound having one or more carboxylic acid anhydride groups in the molecule (B) represented by the following formula (1) Sulfur-based antioxidant

（式（１）中、Ｒ^１は炭素数１〜１０のアルキル基を、Ｒ^２、Ｒ^３は炭素数１〜５のアルキレン基をそれぞれ表す。式中、複数存在するＲ^１〜Ｒ^３はそれぞれ同一であっても異なっていても構わない。）

(In formula (1), R ¹ represents an alkyl group having 1 to 10 carbon atoms, R ² and R ³ each represent an alkylene group having 1 to 5 carbon atoms. In the formula, a plurality of R ^{1 to} R ³ are Each may be the same or different.)

  First, a polyvalent carboxylic acid compound having two or more carboxyl groups in a molecule (A) will be described.

  Among the polyvalent carboxylic acid compounds having two or more carboxyl groups in the molecule (A), the compound has an ester structure (preferably two or more ester structures) in the molecule represented by the following formula (2), Compounds having a carboxyl group at the end are preferred from the viewpoint of compatibility with the sulfur-based antioxidant.

In the formula (2), X is a residue of a polyhydric alcohol having 2 to 100 carbon atoms which may contain an oxygen atom, a nitrogen atom, a phosphorus atom or a silicon atom of 0 to 50 (preferably 0 to 6); ⁴ represents an aliphatic hydrocarbon group having 2 to 20 carbon atoms, m represents 1 to 6 on average, and n represents 2 to 6 on average. In the formula, a plurality of R ⁴ may be the same or different.

X is a residue of a polyhydric alcohol having 2 to 100 carbon atoms (residue obtained by removing a hydroxyl group from a polyhydric alcohol used in the reaction), preferably a branched crosslinking group, a cycloalkyl group or a polysiloxane group In particular, a divalent to tetravalent crosslinking group as defined in any one or more of the following (I) to (IV) is preferable.
(I) A linear alkylene chain having a branched structure having 6 to 20 carbon atoms, and the linear alkylene chain has a linear chain having 3 to 12 carbon atoms and 2 to 4 side chains, And at least one selected from tricyclodecanedimethanol or pentacyclopentadecanedimethanol, which may have a methyl group on the bridging group (II) cyclo ring in which at least one of its side chains has 2 to 10 carbon atoms Bivalent bridging group (III) from which two hydroxyl groups have been removed from the bridged polycyclic diols (III) is a bivalent bridging group (IV) having at least one hetero ring selected from a triazine ring Here, in (IV), the side chain extending from a silicon atom is preferably a methyl group or a phenyl group. The methyl group or phenyl group of the side chain extending from a plurality of silicon atoms may be the same or different, but the side chain extending from the silicon atoms at both ends is preferably a methyl group.

  Preferred crosslinking group structures in the definitions of (I) to (IV) are shown in formulas (2-I) to (2-V), respectively.

  In formulas (2-I) to (2-V), * represents the bonding position to the oxygen atom next to X in formula (2), and in formulas (2-IV) and (2-V) And q represent 1 to 25 in average value.

The polyvalent carboxylic acid compound having two or more carboxyl groups in the molecule (A) is preferably a compound obtained by the addition reaction of the following (a) and (b) from the viewpoint of compatibility.
(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 The following residues (b) and (b) are obtained, and each residue of the following (a) and (b) is a compound having a carboxyl group at the end which is bound by an ester structure.
(A) Reactive residue of polyhydric alcohol compound having two or more hydroxyl groups in molecule (b) Reactive residue of compound having one or more carboxylic anhydride compounds in molecule (a); The polyhydric alcohol compound containing two or more hydroxyl groups 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, tricyclodecanedimethanol, norbornene diol, 2,2'-bis (4-hydro) Dicyclohexyl) propane, diols such as 2- (1,1-dimethyl-2-hydroxyethyl) -5-ethyl-5-hydroxymethyl-1,3-dioxane, glycerin, trimethylolethane, trimethylolpropane, triyl Triols such as methylol butane and 2-hydroxymethyl-1,4-butanediol, tetraols such as pentaerythritol and ditrimethylolpropane, hexaols such as dipentaerythritol, terminal alcohol polyester, terminal alcohol polycarbonate, terminal alcohol Polyethers, polyhydric alcohols having a siloxane structure, and the like can be mentioned.
Particularly preferred alcohols are those having 5 or more carbon atoms, and in particular 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, 2, 4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecanedimethanol, norbornenediol, 2,2'-bis (4-hydroxycyclohexyl) propane, 2- Compounds such as (1,1-dimethyl-2-hydroxyethyl) -5-ethyl-5-hydroxymethyl-1,3-dioxane can be mentioned, among which 2-ethyl-2-butyl-1,3-propanediol, Neopentyl glycol, 2,4-diethylpentanediol, 1,4-cyclohexene Sandimethanol, tricyclodecanedimethanol, norbornene diol, 2,2'-bis (4-hydroxycyclohexyl) propane, 2- (1,1-dimethyl-2-hydroxyethyl) -5-ethyl-5-hydroxymethyl- Alcohols having a branched structure or a cyclic structure such as a compound such as 1,3-dioxane are more preferable. From the viewpoint of imparting high resistance to sulfurization, compounds such as 2,4-diethylpentanediol, tricyclodecanedimethanol, 2,2'-bis (4-hydroxycyclohexyl) propane and 1,4-cyclohexanedimethanol are particularly preferred. preferable. Among them, particularly in a branched 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 alcohol having a branched structure or a cyclic structure preferably has 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, compounds represented by the following formulas (7) to (12) are preferable.

  Although the polyhydric alcohol which has a siloxane structure is not specifically limited, For example, the silicone oil represented by following formula (13) is preferable.

In formula (13), R ⁵ represents a total of 1 to 10 alkylene groups having a total number of carbon atoms which may be ether-bonded, and R ⁶ represents a methyl group or a phenyl group. Also, r is the number of repetitions and means an average value, which is 1 to 100. Here, r is preferably 1 to 10.

In the formula (13), specific examples of R ⁵ include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, isopropylene group, isobutylene group, isopentylene group, neopentylene group, isohexylene group, cyclohexene group Examples thereof include silene group, heptylene group, octylene group, nonyl group, decyl group, ethyloxyethylene group, ethyloxypropylene group, propyloxyethylene group, propyloxypropylene group and the like, among which viscosity, heat-resistant transparency of cured product From the viewpoint, a propylene group, an ethyloxypropylene group and a propyloxyethylene group are preferable.

  As a silicone oil represented by Formula (13), the following product names can be mentioned. For example, X-22-160 AS, KF-6000, KF-6001, KF-6002, KF-6003 as Shin-Etsu Chemical Co., Ltd., SF8427, BY16-201, Asahi Kasei Wacker Silicone Co., Ltd. as Toray Dow Corning Co. As the product, WACKER IM11, WACKER IM15, as the product of JNC, FM-4411, FM-4421, FM-4425, as the product of Momentive Performance Materials Japan, Inc., XF42-C5277, XF42-B0970, etc. Are all available from the market. These silicone oils can be used alone or in combination 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 compounds containing two or more hydroxyl groups in the molecule may be used alone or in combination of two or more.
In order to impart high gas barrier properties to the cured product by using the curable resin composition obtained in a liquid state, the polyhydric alcohol having the siloxane structure described above and a branched chain structure or cyclic structure having 5 to 25 carbon atoms are used. It is preferable to use a mixture of alcohols and / or polyhydric alcohol compounds having an isocyanuric ring skeleton.
When mixing and using a polyhydric alcohol having a siloxane structure and an alcohol having a branched chain structure having 5 to 25 carbon atoms or a cyclic structure and / or an isocyanuric ring skeleton, the amount used is the mass 0 in all alcohol compounds (polyhydric alcohol having siloxane structure) / (alcohol having branched structure having 5 to 25 carbon atoms or cyclic structure and / or polyhydric alcohol compound having an isocyanuric ring skeleton) as a ratio is 0 2 to 20 are preferable, 0.3 to 15 are preferable from the viewpoint of the heat resistance transparency of the cured product, and the appropriate viscosity of the curable resin composition, and 0.4 to 10 are particularly preferable.

(B); compounds containing one or more acid anhydride groups in the molecule, in particular, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, bicyclo [2,2,1] heptane 2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, glutaric anhydride , 2,4-diethyl glutaric anhydride, succinic anhydride and the like are preferred, among which methyl hexahydrophthalic anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, 2,4- Diethyl glutaric anhydride is preferred. Here, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride is preferable to increase hardness, and methylhexahydrophthalic anhydride is preferable to increase illuminance retention rate. In order to suppress an excessive increase in viscosity of the carboxylic acid resin, 2,4-diethyl glutaric acid and glutaric acid are preferable.

(B) It is preferable to use one or more compounds selected from the compounds represented by the following formulas (14) to (21) as a compound containing one or more acid anhydride groups in the molecule.

The conditions for the addition reaction are not particularly specified, but as one of the specific reaction conditions, acid anhydride and polyhydric alcohol are reacted at 40 to 150 ° C. and heated under non-catalyst, solvent-free conditions. When finished, take out as it is. It is a method called. However, it is not limited to this reaction condition.

(A) The compound having one or more carboxylic acid anhydride groups in the molecule may be a compound having one or more carboxylic acid anhydride groups in the molecule, but the following formulas (3) to (5) It is preferable to use one or more of the compounds represented by

(A) The polyvalent carboxylic acid compound having two or more carboxyl groups in the molecule and the compound having one or more carboxylic acid anhydride groups in the molecule may be used alone or in combination. When used in combination, the use ratio is preferably in the following range.

W1 / (W1 + W2) = 0.05 to 0.70

However, W1 shows the compounding mass part of a polyhydric carboxylic acid compound, W2 shows the compounding mass part of the compound which has a carboxylic acid anhydride group. 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 volatilization of the compound having a carboxylic acid anhydride group tends to increase at the time of curing, which is not preferable. When it exceeds 0.70, the viscosity becomes high and handling becomes difficult. In the case where the acid anhydride is not contained (except when remaining in a small amount), there is no problem because the form becomes solid or near solid, or crystals.
When 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 are used in combination, an excess of molecules may be generated during production of the polyvalent carboxylic acid compound. And a polyvalent carboxylic acid compound having two or more carboxyl groups in the molecule, and one or more carboxylic acid anhydride groups in the molecule. It is also preferable from the viewpoint of the ease of operation to make a mixture of compounds possessed.

Next, the sulfur-based antioxidant (B) represented by the formula (1) will be described.

式（１）中、Ｒ^１は炭素数１〜１０のアルキル基を、Ｒ^２、Ｒ^３は炭素数１〜５のアルキレン基をそれぞれ表す。式中、複数存在するＲ^１〜Ｒ^３はそれぞれ同一であっても異なっていても構わない。

In Formula (1), ^{R 1} is an alkyl group having 1 to 10 carbon ^atoms, R 2, ^{R 3} represent each an alkylene group having 1 to 5 carbon atoms. In the formula, a plurality of R ^{1 to} R ³ may be the same or different.

In formula (1), R ¹ 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., among which methyl group and tertiary group A butyl group is preferable, and in particular, in the formula (1), it is preferable from the viewpoint of the heat resistance transparency of a cured epoxy resin product that any ^one of R ¹ sandwiching a phenolic hydroxyl group is a tertiary butyl group.

In formula (1), R ² and R ³ each represent an alkylene group having 1 to 5 carbon atoms, and specific examples thereof include methylene group, ethylene group, propylene group, butylene group, isobutylene group, pentylene group, isopentylene group, etc. Among them, an ethylene group is preferable from the viewpoint of the heat resistance transparency and the compatibility of the sulfur-based antioxidant represented by the formula (1).

  Among the sulfur-based antioxidants (B) represented by the formula (1), a compound represented by the following formula (22) is particularly preferable.

  A commercial item can be used for the sulfur type antioxidant represented by Formula (1), for example, BASF company make, Irganox1035 etc. are mentioned.

上記式中、Ｒ^７は炭素数１〜３０のアルキル基又は置換基を有しても良いフェニル基を表す。式中、複数存在するＲ^７はそれぞれ同一であっても異なっていても構わない。 The sulfur-based antioxidant represented by the formula (1) is preferably used in combination with a phosphorus-based compound. Although a compound described later can be used as the phosphorus compound, a phosphorus compound which is particularly preferably used in combination is represented by the following formula (23).

In the above formula, R ⁷ 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 ⁷ may be the same or different.

In formula (23), specific examples of the alkyl group having 1 to 30 carbon atoms of R ⁷ include methyl group, ethyl group, propyl group, butyl group, isobutyl group, pentyl group, isopentyl group, nonyl group, decyl group, Undecyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, stearyl group, myristyl group, etc. are mentioned, and a viewpoint of heat-resistant transparency improvement by the synergistic effect with the sulfur type antioxidant represented by Formula (1) among others Decyl and phenyl are preferred.
Further, R ⁷ is more preferably an alkyl group having 8 to 25 carbon atoms.

In the formula (23), specific examples of the substituent of the phenyl group which may have a substituent as R ⁷ include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentyl group and the like.

上記式中、Ｒ^７は炭素数１〜３０のアルキル基又は置換基を有しても良いフェニル基を表す。
式（２３）中、Ｒ^７の炭素数１〜３０のアルキル基の具体例としては、メチル基、エチル基、プロピル基、ブチル基、イソブチル基、ペンチル基、イソペンチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基、ステアリル基、ミリスチル基等が挙げられ、中でも式（１）で表される硫黄系酸化防止剤との相乗効果により耐熱透明性向上の観点からデシル基であることが好ましい。
また、Ｒ^７は炭素数８〜２５のアルキル基がより好ましい。 Among the phosphorus compounds represented by the formula (23), a compound represented by the following formula (24) is particularly preferable.

In the above formula, R ⁷ represents a phenyl group which may have an alkyl group or a substituent having 1 to 30 carbon atoms.
In formula (23), specific examples of the alkyl group having 1 to 30 carbon atoms of R ⁷ include methyl group, ethyl group, propyl group, butyl group, isobutyl group, pentyl group, isopentyl group, nonyl group, decyl group, Undecyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, stearyl group, myristyl group, etc. are mentioned, and a viewpoint of heat-resistant transparency improvement by the synergistic effect with the sulfur type antioxidant represented by Formula (1) among others It is preferable that it is a decyl group.
Further, R ⁷ is more preferably an alkyl group having 8 to 25 carbon atoms.

  The amount of the sulfur based antioxidant, the phosphorus based compound added to the curable resin 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. The addition amount is preferably 0.01% by mass or more from the viewpoint of heat-resistant transparency, and is preferably 10% by mass or less from the viewpoint of excellent transparency of a cured product and curability of a curable resin composition.

In order to use the curable resin composition obtained in a liquid state and to impart high heat resistance to the cured product, it is preferable to use the above-mentioned sulfur-based antioxidant and a phosphorus-based compound in combination.
When a sulfur-based antioxidant and a phosphorus-based compound are mixed and used, the amount of (phosphorus-based compound) / (sulfur-based antioxidant) as the mass ratio is preferably 0.5 to 10, and particularly preferably 1 to 8 preferable.
Further, by using the above formulas (23) to (24) in the above ratio, it is possible to impart high heat resistance and permeability to a more excellent cured product.

(B) The method of adding the sulfur-based antioxidant and the phosphorus-based compound to the curable resin composition can be obtained by uniformly mixing at room temperature or under heating. For example, using an extruder, kneader, triple roll, universal mixer, planetary mixer, homomixer, homodisper, bead mill, etc., mix thoroughly until uniform, and if necessary, perform filtration with a SUS mesh or the like. Be prepared. At this time, the (B) sulfur-based antioxidant or the phosphorus-based compound may be completely dissolved in the polyvalent carboxylic acid compound having two or more carboxyl groups in the (A) molecule, or may not be dissolved. It may be in a dispersed state.

  Next, the epoxy resin composition of the present invention will be described. The epoxy resin composition in the present invention is characterized by containing (A) a polyvalent carboxylic acid compound having two or more carboxyl groups in the molecule, (B) a sulfur-based antioxidant, and an epoxy resin (C). I assume.

  As an epoxy resin (C), for example, an epoxy resin which is a glycidyl ether compound of a phenol compound, an epoxy resin which is a glycidyl ether compound of various novolak resins, an alicyclic epoxy resin, an aliphatic epoxy resin, a heterocyclic epoxy resin, Glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, epoxy resin obtained by glycidylating halogenated phenols, copolymer of polymerizable unsaturated compound having an epoxy group and other polymerizable unsaturated compound, epoxy Examples thereof include condensates of silicon compounds having a group with other silicon compounds, silicone-modified epoxy resins, and the like.

  As an epoxy resin which is a glycidyl etherification thing of the phenols compound, for example, 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, tetramethyl bisphenol A, dimethyl bisphenol A, tetramethyl bisphenol F, dimethyl bisphenol F, tetramethyl bisphenol S, Dimethyl bisphenol 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, resorcinol, hydroquinone, pyrogallol, phlorogricinol, diisopropyl There may be mentioned epoxy resins which are glycidyl ethers of polyphenol compounds having a fluorene skeleton such as phenols having a redenic skeleton, fluorene skeleton such as 1,1-di-4-hydroxyphenyl fluorene, etc.

  Examples of epoxy resins which are glycidyl ethers of various novolak resins include phenols, cresols, ethylphenols, butylphenols, octylphenols, bisphenols such as bisphenol A, bisphenol F and bisphenol S, and various phenols such as naphthols. And glycidyl ether compounds of various novolak resins such as xylylene skeleton-containing phenol novolac resins, dicyclopentadiene skeleton-containing phenol novolac resins, biphenyl skeleton-containing phenol novolac resins, and fluorene skeleton-containing phenol novolac resins.

The alicyclic epoxy resin is, for example, an alicyclic ring having an aliphatic ring skeleton such as 3,4-epoxycyclohexylmethyl- (3,4-epoxy) cyclohexylcarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, etc. And epoxy resins of the formula.
Examples of the aliphatic epoxy resin include glycidyl ethers of polyhydric alcohols such as 1,4-butanediol, 1,6-hexanediol, polyethylene glycol and pentaerythritol.
As said heterocyclic epoxy resin, the heterocyclic epoxy resin which has heterocyclic rings, such as an isocyanuric ring and a hydantoin ring, is mentioned, for example.
As said glycidyl-ester type epoxy resin, the epoxy resin which consists of carboxylic acid esters, such as hexahydrophthalic-acid diglycidyl ester, is mentioned, for example.
As said glycidyl amine epoxy resin, the epoxy resin which glycidylated amines, such as aniline and toluidine, is mentioned, for example.
Examples of epoxy resins obtained by glycidylating the above-mentioned halogenated phenols include brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolac, brominated cresol novolac, chlorinated bisphenol S, chlorinated bisphenol A, etc. The epoxy resin which glycidylated halogenated phenols of this is mentioned.

  As copolymers of a polymerizable unsaturated compound having an epoxy group and other polymerizable unsaturated compounds, merproof G-0115S, G-0130S, and G-0250S can be used as products available from the market. G-1010S, G- 0150M, G-2050M (manufactured by NOF Corporation) and the like, and examples of the polymerizable unsaturated compound having an epoxy group include glycidyl acrylate, glycidyl methacrylate, 4 And -vinyl-1-cyclohexene-1,2-epoxide and the like. Other polymerizable unsaturated compounds include, for example, 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 combination of two or more.

  The condensation product of the silicon compound having an epoxy group and the other silicon compound is, for example, a hydrolysis condensation product 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 condensation compound obtained by using 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 combination thereof. As the alkoxysilane compound having an epoxy group, for example, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane And 3-glycidoxypropylmethyldimethoxysilane and the like. Examples of alkoxysilane compounds having a methyl group or a phenyl group include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane and the like. . Examples of polydimethyl siloxane having silanol group and polydimethyl diphenyl siloxane having silanol group include X-21-5841 and KF-9701 (manufactured by Shin-Etsu Chemical Co., Ltd.) BY16-873, as products available from the market. PRX 413 (Toray Dow Corning Co., Ltd. product) XC96-723, YF 3804, YF 3800, XF 3905, YF 3057 (Momentive Performance Materials Japan GK) DMS-S12, DMS-S14, DMS-S15, DMS-S21, DMS-S21, DMS-S27, DMS-S31, PDS-0338, PDS-1615 (Gelest company make) etc. are mentioned.

  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 or ladder type. Although the cyclic silicone modified epoxy resin represented by following formula (6) from a viewpoint of transparency of the hardened | cured material obtained and mechanical strength is mentioned as a preferable example especially, it is not limited to this.

In formula (6), R ⁵ represents a hydrocarbon group having 1 to 6 carbon atoms, Y represents an epoxy group-containing organic group or a hydrocarbon group having 1 to 6 carbon atoms, and p represents an integer of 1 to 3 . Plural R ^{5 's} and Y's in the formula may be the same or different. However, in a plurality of Y, two or more are epoxy group-containing organic groups.

Specific examples of R ⁵ 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 transparency of a cured product. Methyl is particularly preferred from the viewpoint of ease of production.
The organic group in Y represents a compound consisting of C, H, N and O atoms, and specific examples of the epoxy group-containing organic group are 2,3-epoxycyclohexylethyl group and 3-glycidoxypropyl group. 2,3-epoxycyclohexylethyl group is preferable from the viewpoint of heat resistance and transparency of the cured product. Here, it is preferable that carbon number in an organic group is 1-20, and it is more preferable that it is 3-15. Moreover, it is preferable that it is a group which the 2,3-epoxycyclohexylethyl group and 3-glycidoxypropyl group add through the C1-C5 alkylene group.
Although a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a phenyl group is mentioned as a specific example of a C1-C6 hydrocarbon group in Y, A heat resistant transparency viewpoint of hardened | cured material Therefore, methyl group and phenyl group are preferable, and methyl group is particularly preferable from the viewpoint of easiness of production.
p is preferably 2 in view of the ease of production of the compound.

The cyclic silicone-modified epoxy resin represented by Formula (6) can be obtained by a hydrosilylation reaction of a cyclic hydrogen siloxane compound and an olefin compound having an epoxy group in the molecule.
Specific examples of cyclic hydrogen siloxane compounds include trimethyltricyclosiloxane, triphenyltricyclosiloxane, tetramethyltetracyclosiloxane, tetraphenyltetracyclosiloxane, pentamethylpentacyclosiloxane, pentaphenylpentacyclosiloxane, etc. Tetramethyltetrasiloxane is preferred because of easiness of production.
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 from the viewpoint of the heat resistance transparency of a cured product, 4-vinyl- 1,2-Epoxycyclohexane is preferred.

In the hydrosilylation reaction, known metal complexes such as rhodium, palladium, platinum and the like can be used as the catalyst. Specifically, tristriphenylphosphine rhodium chloride, hexachloroplatinic acid hexahydrate, divinyl tetramethyl disiloxane platinum complex, tetravinyl tetramethyl cyclotetrasiloxane platinum complex, dichloro bis (triphenyl phosphine) platinum complex, tetrakis ( In addition to triphenylphosphine) platinum complexes etc., platinum catalysts immobilized on a solvent insoluble carrier such as commercially available polyethylene etc., such as FibreCat ^R 4001 and FibreCat ^R 4003 (all manufactured by Wako Pure Chemical Industries) are mentioned. From the viewpoint of the transparency of the resulting cyclic siloxane compound (A) having two or more epoxy groups in the molecule obtained and the transparency of the cured product, hexachloroplatinic acid hexahydrate, divinyl tetramethyl disiloxane platinum co Amplex, tetravinyl tetramethyl cyclotetrasiloxane platinum complex, dichloro bis (triphenyl phosphine) platinum complex, FibreCat ^R 4003 are preferred.

It is preferable from the viewpoint of workability that the catalyst used for the hydrosilylation reaction is dissolved in a solvent to form a solution. As the solvent which can be used, any solvent which can dissolve the catalyst can be used, but from the viewpoint of solubility and workability, tetrahydrofuran and toluene are preferable.
When using as a solution, a catalyst is adjusted to 0.05-50 mass%, and it adds to a reaction liquid.
When using the catalyst fixed to polyethylene etc., it adds to the reaction liquid as it is.
The amount of catalyst added is in the range of 0.1 to 1000 ppm of the reaction substrate as the amount of metal used for the catalyst. From the viewpoint of the transparency of the cyclic siloxane compound (A) having two or more epoxy groups in the molecule to be obtained 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 coloring of the silicone-modified epoxy resin may be aggravated.

After the hydrosilylation reaction, purification can be performed by known methods such as water washing, distillation, recrystallization, column chromatography, adsorption (activated carbon, various minerals) and the like.
The solvent used for the reaction and / or purification can be removed by distillation under reduced pressure or the like.

The epoxy equivalent (measured by the method described in JIS K 7236) of the cyclic silicone-modified epoxy resin represented by the formula (6) is preferably 180 to 400 g / eq, and particularly preferably 190 to 250 g / eq.
The viscosity at 25 ° C. of the epoxy equivalent of the cyclic silicone-modified epoxy resin represented by the above formula (6) is preferably 1,500 to 10,000 mPa · s, more preferably 2,000 to 8,000 mPa · s, and particularly preferably 3,000 to 7,000 mPa · s.

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

These epoxy resins (C) may be used alone or in combination of two or more.

Among the above-mentioned epoxy resins (C), from the viewpoints of transparency, heat resistance transparency and light resistance transparency, alicyclic epoxy resins, condensates of silicon compounds having an epoxy group with silicon compounds other than these, silicone-modified epoxy resins The combined use of resins is preferred. Among them, cyclic silicone-modified epoxy resins having an epoxycyclohexane structure in the skeleton are preferable.

The epoxy resin (C) is such that the epoxy group is 0.5 to 3.0 equivalents per equivalent of the carboxyl group in the polyvalent carboxylic acid compound (A) having two or more carboxyl groups in the molecule. It is preferred to use. If it is 0.5 equivalent or more, since the heat-resistant transparency of hardened | cured material improves, it is preferable, and if 3.0 or less, since the mechanical physical property of hardened | cured material improves, it is preferable.

The epoxy resin composition of the present invention preferably further contains an epoxy resin curing accelerator (D).
As the epoxy resin curing accelerator (D), any of polyvalent carboxylic acid compounds (A) having two or more carboxyl groups in the molecule and those capable of accelerating the curing reaction of the epoxy resin (C) may be used. Examples of possible curing accelerators (D) that can be used include ammonium salt-based curing accelerators, phosphonium salt-based curing accelerators, metal soap-based curing accelerators, imidazole-based curing accelerators, amine-based curing accelerators Examples thereof include accelerators, phosphine-based curing accelerators, phosphite-based curing accelerators, and Lewis acid-based curing accelerators.
In the epoxy resin composition of the present invention, the compounding ratio of the epoxy resin curing accelerator (D) is preferably 0.001 to 15 parts by mass of the curing accelerator with respect to 100 parts by mass of the epoxy resin composition.

In the epoxy resin composition of the present invention, specific examples of the epoxy resin curing accelerator (D) which can be used include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl -4-Methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecyl Imidazole, 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 ( ')) Ethyl-s-triazine, 2,4-diamino-6 (2'-methylimidazole (1')) ethyl-s-triazine isocyanuric acid adduct, 2: 3 adduct of 2-methylimidazole isocyanuric acid , 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxy Various imidazoles of methylimidazole, salts of such imidazoles with polyphthalic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid, oxalic acid, etc., dicyandiamide, etc. Amides of 1,8-diaza-bicyclo (5.4 0) Diaza compounds such as undecene-7 and salts thereof such as tetraphenylborate, phenol novolac, salts with the polyvalent carboxylic acids or phosphinic acids, tetrabutyl ammonium bromide, cetyltrimethyl ammonium bromide, trioctyl methyl ammonium bromide Ammonium salts such as phosphines, phosphines such as triphenylphosphine, tri (toluyl) phosphine, tetraphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, phosphonium compounds, phenols such as 2,4,6-trisaminomethylphenol, amines Adducts, metal compounds such as tin octylate, etc., and microcapsule type hardening accelerators made by microcapsules of these hardening accelerators etc. can be mentioned. . Which of these curing accelerators is used is appropriately selected according to the properties required of the resulting transparent resin composition, such as transparency, curing speed, and working conditions.

Among these, metal soap curing accelerators are excellent from the viewpoint of the transparency of the cured product, and among the metal soap curing accelerators, zinc carboxylate compounds are 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, zinc stearate, magnesium stearate, stearin. Acid aluminum, barium stearate, lithium stearate, sodium stearate, potassium stearate, calcium 12-hydroxyphosphate, zinc 12-hydroxystearate, magnesium 12-hydroxystearate, aluminum 12-hydroxystearate, 12-hydroxystearate Barium, lithium 12-hydroxystearate, sodium 12-hydroxystearate, calcium montanate, zinc montanate, mon Magnesium phosphate, aluminum montanate, lithium montanate, sodium montanate, calcium behenate, zinc behenate, magnesium behenate, lithium behenate, sodium behenate, silver behenate, calcium laurate, zinc laurate, barium laurate And lithium laurate, zinc undecylenic acid, zinc ricinoleate, barium ricinoleate, zinc myristate, zinc palmitate and the like. These catalysts may be used alone or in combination of two or more.
In order to obtain a cured product excellent in transparency and sulfurization resistance, carbons such as zinc stearate, zinc montanate, zinc behenate, zinc laurate, zinc undecylenate, zinc ricinoleate, zinc myristate, zinc palmitate, etc. A zinc salt composed of a monocarboxylic acid compound having 10 to 30 carbon atoms and having a hydroxyl group such as zinc carboxylate and zinc 12-hydroxystearate of several 10 to 30 can be preferably used. Among them, zinc salts comprising a monocarboxylic acid compound having 10 to 20 carbon atoms such as zinc stearate and zinc undecylenic acid, and hydroxyl groups such as zinc 12-hydroxystearate, from the viewpoint of excellent pot life and sulfuration resistance. Zinc salts composed of monocarboxylic acid compounds having 15 to 20 carbon atoms are preferably used, more preferably zinc stearate, zinc undecylenate and zinc 12-hydroxystearate, and particularly preferably zinc stearate, 12- Zinc hydroxystearate can be used.

Examples of ammonium salt-based curing accelerators include tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, tetrabutyl ammonium hydroxide, trimethylethyl ammonium hydroxide, trimethylpropyl ammonium hydroxide and trimethylbutyl ammonium hydroxide And trimethylcetyl ammonium hydroxide, trioctyl methyl ammonium hydroxide, tetramethyl ammonium chloride, tetramethyl ammonium bromide, tetramethyl ammonium iodide, tetramethyl ammonium acetate, and trioctyl methyl ammonium acetate. Examples of the phosphonium salt-based curing accelerator include ethyl triphenyl phosphonium bromide, tetraphenyl phosphonium tetraphenyl borate, methyl tributyl phosphonium dimethyl phosphate, methyl tributyl phosphonium diethyl phosphate and the like.

In addition to the above-mentioned ammonium salt-based curing accelerators, phosphonium salt-based curing accelerators, metal soap-based curing accelerators, imidazole-based curing accelerators, amine-based curing accelerators, heterocyclic compound-based curing accelerators, for other general-purpose uses. For example, phosphine-based curing accelerators, phosphite-based curing accelerators, and Lewis acid-based curing accelerators can be used.

  The epoxy resin curing accelerator (D) described above can be used as a compound which is solid at room temperature (25 ° C.) or a compound which is liquid. When the epoxy resin composition of the present invention is used for applications requiring a liquid at room temperature (25 ° C.) and a compound which is solid at room temperature (25 ° C.) is used as a curing accelerator, It can also be dissolved and used. Alternatively, a compound which is solid at room temperature (25 ° C.) can be dispersed in a resin and used.

In the curable resin composition or the epoxy resin composition of the present invention, it is possible to complement the viscosity adjustment of the composition and the hardness of the cured product by using a coupling agent as necessary.
As a coupling agent that can be used, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane, N- (2-Aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-Aminoethyl) 3-aminopropylmethyltrimethoxysilane, 3-Aminopropyltriethoxysilane, 3-Mercaptopropyltrithiosilane 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, isopropyl triisostearoyl titanate, titanium di (dioctyl pyrophosphate) oxyacetate, tetraisopropyl di (dioctyl phosphite) titanate Titanium-based coupling agents such as neoalkoxytri (pN- (β-aminoethyl) aminophenyl) titanate; Zr-acetylacetonate, Zr-methacrylate, Zr-propionate, neoalkoxyzirconate, neoalkoxytrisneodeca Noyl zirconate, neoalkoxy tris (dodecanoyl) benzenesulfonyl zirconate, neoalkoxy tris (ethylene diaminoethyl) zirconate, neo alco Examples include xytris (m-aminophenyl) zirconate, ammonium zirconium carbonate, Al-acetylacetonate, zirconium such as Al-methacrylate and Al-propionate, or an aluminum-based coupling agent.
These coupling agents may be used alone or in combination of two or more.
The coupling agent is usually contained in an amount of 0.05 to 20 parts by mass, preferably 0.1 to 10 parts by mass in the curable resin composition or the epoxy resin composition of the present invention as required.

In the curable resin composition or the epoxy resin composition of the present invention, by using an inorganic filler of nano order level as needed, it is possible to complement mechanical strength etc. without inhibiting transparency. is there. In terms of transparency, it is preferable to use a filler having an average particle size of 500 nm or less, in particular, an average particle size of 200 nm or less. As the inorganic filler, crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, forsterite, steatite, spinel, titania, talc, or a powder thereof And spherical beads, but not limited thereto. These fillers may be used alone or in combination of two or more. The content of these inorganic fillers is used in an amount of 0 to 95% by mass in the epoxy resin composition of the present invention.

The curable resin composition or the epoxy resin composition of the present invention may contain an amine compound as a light stabilizer or a phosphorus compound and / or a phenol compound as an antioxidant 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, tetrakis (2,2,6,6- Totramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and 3 , 9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane mixed ester, bis (2,2,6) decanedioate , 6-Tetramethyl-4-piperidyl) sebacate, bis (1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 2,2,6,6-tetrame Ru-4-piperidyl 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] bu Lumuronate, bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidinyl) ester of decanedioic acid, reaction product of 1,1-dimethylethyl hydroperoxide with octane, N, N ', N ′, N ′ ′-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl)- 4,7-Diazadecane-1,10-diamine, dibutylamine · 1,3,5-triazine · N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexa) Polycondensate of methylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, poly [[6- (1,1,3,3-tetramethylbutyl) amino-1,3 5-triazine- 2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], dimethyl succinate And a polymer of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol, 2,2,4,4-tetramethyl-20- (β-lauryloxycarbonyl) ethyl-7-oxa- 3,20-Diazadispiro [5.1.11.2] heneicosan-2 1-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) pyrrolidine-2,5-dione, 2,2,4,4-tetramethyl-7-oxa 3,20-Diazadispiro [5,1,11] heneicosan-21-one, 2,2,4,4-tetramethyl-21-oxa-3,20-diazadicyclo- [5,1,11] -Henicosan-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-benzenedicarboxamide, N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl) And the like; hindered amines, benzophenone compounds such as octabenzone, 2- (2H-benzotriazol-2-yl) -4- (1,1,3, -Tetramethylbutyl) phenol, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimido-methyl) -5-methylphenyl ] Benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-pentylphenyl) benzotriazole, Reaction product of methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate and polyethylene glycol, 2- (2H-benzotriazol-2-yl)- Benzotriazole compounds such as 6-dodecyl-4-methylphenol, 2,4 Benzoates such as di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- Triazine compounds such as [(hexyl) oxy] phenol and the like can be mentioned, with particular preference given to hindered amine compounds.

The commercial item shown next can be used as an amine compound which is the said light stabilizer.
It does not specifically limit as an amine compound marketed, for example, as product made by Ciba Specialty Chemicals; 62, LA-63P, LA-77Y, LA-81, LA-82, LA-87 and the like.

The phosphorus compound is not particularly limited. For example, 1,1,3-tris (2-methyl-4-ditridecylphosphite-5-tert-butylphenyl) butane, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, Dicyclohexylpentaerythritol diphosphite, tris (diethylphenyl) phosphite, tris (di-isopropylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) Hosf , Tris (2,6-di-tert-butylphenyl) phosphite, Tris (2,6-di-tert-butylphenyl) phosphite, 2,2'-methylenebis (4,6-di-tert-butyl Phenyl) (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'-ethylidene bis (4-methyl-6-tert-butyl Phenyl) (2-tert-butyl-4-methylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4 -Biphenylene diphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylene diphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-bipheny Di-phosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4′-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylene diphospho Knight, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylene diphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis ( 2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butyl) Phenyl) -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 cresyl phosphate, diphenyl mono ortho oxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate and the like

A commercial item can also be used for the said phosphorus compound. It does not specifically limit as a phosphorus system compound marketed, for example, as Adekastab PEP-4C, Adekastab PEP-8, Adekastab PEP-24G, Adekastab PEP-36, Adekastab HP-10, Adekastab HP-2112, Adekastab 260 as Adeka product made, for example. , Adeka stub 522A, Adeka stub 1178, Adeka stub 1500, Adeka stub C, Adeka stub 135A, Adeka stub 3010 and the like.

There is no particular limitation on the phenol compound, and, for example, 2,6-di-tert-butyl-4-methylphenol, 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, pentaery Lytyl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,9-bis- [2- [3- (3-tert-butyl-4-hydroxy-5-) Methylphenyl) -propionyloxy] -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-butylpheno) ), 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -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'-Butylidenebis (3-methyl-6-tert-butylphenol), bis [3,3-Bis- (4'-hydroxy-3'-tert-butylphenyl) -butanolic acid] -glycol ester, 2,4-di-tert-butylphenol, 2,4-di-tert-pentyl Phenol, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, bis- [3,3-bis- (4 ') And -hydroxy-3'-tert-butylphenyl) -butanolic acid] -glycol ester and the like.

A commercial item can also be used for the said phenolic compound. It does not specifically limit as a phenol type compound marketed, For example, as a product made by Ciba Specialty Chemicals, IRGANOX1010, IRGANOX1076, IRGANOX1135, IRGANOX245, IRGANOX259, IRGANOX295, IRGANOX3114, IRGANOX1098, IRGANOX1520L, as an addeca stub AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-60, Adekastab AO-70, Adekastab AO-80, Adekastab AO-90, Adekastab AO-330, made as Sumitomo Chemical Co., Ltd., Sumilizer GA-80, Sumilizer MDP-S, Sumilizer BBM-S, Su Examples include milizer GM, Sumilizer GS (F), Sumilizer GP, and the like.

Besides these, additives commercially available as a resin coloring inhibitor can be used. For example, as Chivas Specialty Chemicals, THINUVIN 328, THINUVIN 234, THINUVIN 326, THINUVIN 120, THINUVIN 477, THINUVIN 479, CHIMASSORB 2020 FDL, CHIMASSORB 119 FL and the like can be mentioned.

It is preferable to contain at least one or more of the above-mentioned phosphorus compounds, amine compounds, and phenol compounds, and the compounding amount thereof is not particularly limited, but it is 0 based on the total mass of the epoxy resin composition of the present invention. It is the range of .005-5.0 mass%.

Furthermore, a binder resin can also be mix | blended with the epoxy resin composition of this invention as needed. Examples of binder resins include butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenol resins, epoxy-NBR resins, polyamide resins, polyimide resins, silicone resins, etc. Not limited to these. The compounding 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 weight are used as necessary.

An inorganic filler can be added to the curable resin composition or the epoxy resin composition of the present invention as required. As the inorganic filler, crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, forsterite, steatite, spinel, titania, talc, or a powder thereof And spherical beads, but not limited thereto. These may be used alone or two or more may be used. The content of these inorganic fillers is used in an amount of 0 to 95% by mass in the curable resin composition of the present invention. Furthermore, to the curable resin composition of the present invention, silane coupling agents, stearic acid, palmitic acid, zinc stearate, mold release agents such as zinc stearate, calcium stearate, various compounding agents such as pigments, various thermosetting resins are added. can do.

The curable resin composition or the epoxy resin composition of the present invention can be obtained by uniformly mixing the above-mentioned components at normal temperature or under heating. For example, using an extruder, kneader, triple roll, universal mixer, planetary mixer, homomixer, homodisper, bead mill, etc., mix thoroughly until uniform, and if necessary, perform filtration with a SUS mesh or the like. Be prepared.

  The curable resin composition or epoxy resin composition of the present invention is a polyvalent carboxylic acid compound having two or more carboxyl groups in the molecule and / or a compound having one or more carboxylic acid anhydride groups in the molecule ((1) A), an epoxy resin composition by sufficiently mixing additives such as a sulfur-based antioxidant (B) and an epoxy resin (C) and / or a curing accelerator (D), an antioxidant, and a light stabilizer It can be prepared and used as an encapsulant. As a mixing method, mixing is carried out at normal temperature or with heating using a medicine bowl, a kneader, a triple roll, a universal mixer, a planetary mixer, a homomixer, a homodisper, a bead mill or the like.

The curable resin composition or 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, dimethyl acetamide, N-methyl pyrrolidone, etc. The composition of the present invention is cured by heat pressing a prepreg obtained as a composition varnish, impregnated with a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper and the like and heat-dried. Can be a cured product of the base resin composition. The solvent used in this case is used in an amount of 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. In addition, it is also possible to obtain an epoxy resin cured product containing carbon fibers by the RTM method as a liquid composition.

The epoxy resin composition of the present invention can also be used as a film type composition modifier. Specifically, it can be used to improve the flexibility and the like in the B-stage. When such a film-type resin composition is obtained, the epoxy resin composition of the present invention is coated on a release film with the varnish, the solvent is removed under heating, and a sheet-like adhesive is obtained by B-stage formation. Get This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.

Furthermore, general applications in which a thermosetting resin such as an epoxy resin is used include an adhesive, a paint, a coating agent, a molding material (including sheet, film, FRP, etc.), an insulating material (printed substrate, In addition to wire coverings and the like), sealing materials, as well as sealing materials, cyanate resin compositions for substrates, acrylic resin based resins as resist curing agents, additives to other resins, etc. may be mentioned.

Examples of the adhesive include adhesives for electronic materials, in addition to adhesives for civil engineering, construction, automobiles, general office work, and medical use. Among these, as adhesives for electronic materials, interlayer adhesives for multilayer substrates such as buildup substrates, die bonding agents, adhesives for semiconductors such as underfills, underfills for BGA reinforcement, anisotropic conductive films ( Examples of the adhesive include mounting adhesives such as ACF) and anisotropic conductive paste (ACP).

As a sealant, potting for capacitors, transistors, diodes, light emitting diodes, ICs, LSIs, etc., dipping, transfer mold sealing, pots for IC, LSIs such as COB, COF, TAB, etc., flip chip And under-fill for packaging, and sealing (including underfill for reinforcement) at the time of mounting of IC packages such as QFP, BGA, and CSP.

The cured product obtained by the present invention can be used in various applications including optical component materials. The optical material refers to a general material used for passing light such as visible light, infrared light, ultraviolet light, X-rays, and laser through the material. More specifically, in addition to sealing materials for LEDs such as lamp types and SMD types, the following may be mentioned. It is a liquid crystal display peripheral material such as a substrate material in the liquid crystal display field, 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 addition, sealing materials for color PDPs (plasma displays) expected as next-generation flat panel displays, antireflection films, optical correction films, housing materials, protective films for front glass, front glass alternative materials, adhesives, and LED displays LED molding materials used in devices, LED sealing materials, front glass protective films, front glass alternatives, adhesives, and substrate materials for plasma addressed liquid crystal (PALC) displays, light guide plates, prism sheets, deflection plates , Retardation plate, viewing angle correction film, adhesive, polarizer protective film, protective film of front glass in organic EL (electroluminescence) display, front glass alternative material, adhesive, various in field emission display (FED) Film substrate Front glass protective films, front glass substitute material, an adhesive. In the optical recording field, VD (video disc), CD / CD-ROM, CD-R / RW, DVD-R / DVD-RAM, MO / MD, PD (phase change disc), disc substrate material for optical card, Pick-up lenses, protective films, encapsulants, adhesives and the like.

In the field of optical instruments, it is a lens material for a still camera, a finder prism, a target prism, a finder cover, and a light receiving sensor portion. Also, it is a shooting lens of a video camera and a finder. In addition, they are a projection lens of a projection television, a protective film, a sealing material, an adhesive, and the like. Materials for lenses of light sensing devices, encapsulants, adhesives, films, and the like. In the optical component field, fiber materials, lenses, waveguides, sealing materials for elements, adhesives, etc. in the vicinity of an optical switch in an optical communication system. Optical fiber material around the optical connector, ferrules, sealants, adhesives, etc. Examples of optical passive components and optical circuit components include lenses, waveguides, LED sealing materials, LED packaging materials, LED reflectors, CCD sealing materials, adhesives, and the like. Substrate materials around an optoelectronic integrated circuit (OEIC), fiber materials, sealing materials for devices, adhesives, etc. In the field of optical fiber, they are sensors for industrial applications such as illuminations and light guides for decorative displays, indicators and signs, etc., 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 automotive and transport sector, lamp reflectors, bearing retainers, gear parts, corrosion resistant coats, switch parts, headlamps, engine internal parts, electrical parts, various internal and external parts, drive engines, brake oil tanks, automotive protection Rust steel plate, interior panel, interior material, wire for protection and binding, fuel hose, car lamp, glass substitute. In addition, it is a multilayer glass for railway vehicles. In addition, they are toughness imparting agents for structural materials of aircraft, engine peripheral members, wireness for protection and binding, and corrosion resistant coat. In the construction field, materials for interior and processing, electric covers, sheets, glass interlayers, glass substitutes, solar cell peripheral materials. For agriculture, it is a film for house coating. Organic EL element peripheral materials, organic photorefractive elements, light amplification elements that are light-light conversion devices, optical calculation elements, substrate materials around organic solar cells, fiber materials, elements as next-generation photo / electronic functional organic materials Sealing materials, adhesives and the like.

As a sealant, potting for capacitors, transistors, diodes, light emitting diodes, ICs, LSIs, etc., dipping, transfer mold sealing, pots for IC, LSIs such as COB, COF, TAB, etc., flip chip And under-fill for packaging, and sealing (reinforcing under-fill) at the time of mounting of IC packages such as BGA and CSP.

Other uses of the optical material include general uses in which the curable resin composition A is used, and examples thereof include adhesives, paints, coatings, molding materials (including sheets, films, FRPs, etc.), In addition to insulating materials (including printed circuit boards, wire coatings and the like), sealants, additives to other resins and the like can be mentioned. Examples of the adhesive include adhesives for electronic materials, in addition to adhesives for civil engineering, construction, automobiles, general office work, and medical use. Among these, as adhesives for electronic materials, interlayer adhesives for multilayer substrates such as buildup substrates, die bonding agents, adhesives for semiconductors such as underfills, underfills for BGA reinforcement, anisotropic conductive films ( Examples of the adhesive include mounting adhesives such as ACF) and anisotropic conductive paste (ACP).

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

As a molding method of the sealing material, a molding method in which the sealing material is injected into the mold in which the substrate on which the optical semiconductor element is fixed is inserted and then heat curing is performed to form the molding material. A compression molding method or the like is used in which the optical semiconductor element fixed on the substrate is immersed therein and heat-cured, and then released from the mold.
A dispenser etc. are mentioned as an injection method.
For heating, a method such as hot air circulation, infrared, high frequency, etc. can be used. The heating conditions are preferably, for example, 80 to 230 ° C. and about 1 minute to 24 hours. In order to reduce the internal stress generated during heat curing, for example, after precuring at 80 to 120 ° C. for 30 minutes to 5 hours, post curing at 120 to 180 ° C. for 30 minutes to 10 hours it can.

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

Hereinafter, the present invention will be described in more detail by way of synthesis examples and examples. The present invention is not limited to these synthesis examples and examples. In addition, each physical-property value in a synthesis example and an Example was measured with the following method. Here, parts represent parts by mass unless otherwise specified.
○ GPC: GPC was measured under the following conditions.
Various conditions maker of GPC: Waters column: SHODEX GPC LF-G (guard column), KF-603, KF-602.5, KF-602, KF-601 (two)
Flow rate: 0.4 ml / min.
Column temperature: 40 ° C
Solvent used: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)
○ Functional group equivalent: Measured by the following method.
About 0.15 g of the polyvalent carboxylic acid composition was weighed, dissolved in 40 ml of methanol (special grade reagent), and stirred at 20-28 ° C. for 10 minutes to prepare a measurement sample. The measurement sample was titrated using a 0.1 N sodium hydroxide solution using a titration apparatus AT-610 manufactured by Kyoto Denshi Kogyo Co., Ltd., 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: Preparation 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 Agitator, reflux condenser, stirrer 15 g of tricyclodecanedimethanol, 70 g of methylhexahydrophthalic anhydride (manufactured by Shin Nippon Chemical Co., Ltd., Rikasid MH), and cyclohexane-1,2,4-tricarboxylic acid while nitrogen purge is performed in a flask equipped with After adding 15 g of 1,2-anhydride (H-TMAn manufactured by Mitsubishi Gas Chemical Co., Ltd.) and reacting at 40 ° C. for 3 hours, the mixture was heated and stirred at 70 ° C. for 1 hour. 1 area% or less of tricyclodecane dimethanol was confirmed by GPC, and 100 g of mixtures (A-1) of polyhydric carboxylic acid resin and a carboxylic anhydride compound were obtained. The obtained mixture is a colorless liquid, and the purity by GPC is 42% by area of polyvalent carboxylic acid resin (the following formula A-1), cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride There were 11 area% and 47 area% of methylhexahydrophthalic anhydride. Moreover, a functional group equivalent is 171 g / eq. Met.

Synthesis example 2; Production example of cyclic siloxane compound having four epoxy groups in molecule using Fibrecat ^R 4003 (made by Wako Pure Chemical Industries, Ltd.) which is a platinum fixed catalyst as a hydrosilylation catalyst 200 ml of glass A three-necked flask is charged with 32.3 parts of 4-vinyl-1,2-epoxycyclohexane, 0.023 parts of Fibrecat ^R 4003 (platinum content of 3.4 to 4.5%), and 50 parts of toluene. A stirrer, a thermometer was installed, and the flask was immersed in an oil bath. The oil bath was heated, the internal temperature was kept at 80 ° C., 12 parts of 1,3,5,7-tetramethyltetracyclosiloxane was added dropwise over 1 hour, and the reaction was allowed to react for 10 hours. When the ¹ H-NMR measurement of the reaction liquid was carried out, the proton peak derived from hydrogen siloxane had 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 The reaction solution is concentrated under reduced pressure at 60 ° C. to remove toluene and excess 4-vinyl-1,2-epoxycyclohexane to obtain 36.7 g of a cyclic siloxane compound (C-1) having four epoxy groups in the molecule. The The epoxy equivalent of the obtained compound was 184.3 g / eq, the viscosity was 5601 mPa · s, and the appearance was a colorless and transparent liquid.

Example 1;
A-1 obtained in Synthesis Example 1, Irganox 1035 manufactured by BASF as the sulfur-based antioxidant, C-1 obtained in Synthesis Example 2 as the sulfur-based antioxidant, C-A obtained as a curing accelerator, manufactured by San Apro U-CAT 5003 and Adeka Stub 135A manufactured by ADEKA as a phosphorus-based antioxidant are weighed into a polyethylene container at a quantitative ratio described in Table 1 below, mixed well with a medical spoon, and stirred for 2 minutes with a vacuum stirring defoamer The epoxy resin composition of the present invention was obtained.

Comparative example 1;
A-1 obtained in Synthesis Example 1, AO-60 manufactured by ADEKA described in the following formula (25) as an antioxidant, C-1 obtained in Synthesis Example 2 as a curing accelerator, U manufactured by San-Apro Co., Ltd. -CAT 5003, ADEKA adekastab 135A manufactured by ADEKA as a phosphorus-based antioxidant was weighed into a polyethylene container at a quantitative ratio described in Table 1 below, mixed well with a medical spoon, and then stirred for 2 minutes with a vacuum stirring defoamer The epoxy resin composition of the comparative example was obtained.

The compounding ratio of the epoxy resin composition obtained in Example 1 and Comparative Example 1 and the viscosity thereof, the mass decrease at curing, the cured product transmittance, the transmittance after heat resistance test, the results of the glass transition temperature (Tg) are shown in Table 1 Shown in. The tests in Table 1 were performed as follows.
Viscosity Viscosity was measured at 25 ° C. using an E-type viscometer (TV-20) manufactured by Toki Sangyo Co., Ltd.
Hardened material permeability After implementing vacuum degassing for 5 minutes for the epoxy resin composition obtained in Example 1 and Comparative Example 1, a glass substrate was prepared with a heat resistant tape so as to be 30 mm × 20 mm × height 0.8 mm. I cast it quietly on top. The cast material was cured at 150 ° C. for 3 hours after pre-curing at 120 ° C. for 1 hour to obtain a 0.8 mm thick specimen for transmittance. The obtained test piece was taken out from the glass substrate, and the light transmittance of 400 nm was measured under the following conditions.
<Spectrophotometer measurement conditions>
Manufacturer: Hitachi High-Technologies Inc. Model: U-3300
Slit width: 2.0 nm
Scan rate: 120 nm / min. Permeability after heat resistance test (2) Permeability of cured product The sample whose transmittance is measured is left in an oven at 180 ° C for 72 hours (in the air) The same condition as (2) for the test piece The light transmittance of 400 nm was measured by
Glass transition temperature (Tg)
After carrying out vacuum degassing for 5 minutes for the epoxy resin composition obtained in Example 1 and Comparative Example 1, quietly on a glass substrate on which a dam was made with a heat-resistant tape so as to be 30 mm × 20 mm × 0.8 mm in height. I cast it. The cast material was cured at 150 ° C. for 3 hours after pre-curing at 120 ° C. for 1 hour to obtain a 0.8 mm thick specimen for transmittance.
The obtained cured product was molded into a width of 5 mm and a length of 25 mm, DMA (Dynamic Mechanical Analysis) was measured under the following conditions, and Tg (glass transition temperature) was read.
<DMA measurement conditions>
Manufacturer: Seiko Instruments Inc. Model: Viscoelastic spectrometer EXSTAR DMS6100
Measurement temperature: -50 ° C to 150 ° C
Heating rate: 2 ° C / min
Frequency: 10Hz
Measurement mode: Glass transition temperature (Tg) measured by tensile vibration DMA method:
The temperature at the maximum point of the loss coefficient (tan δ = E ′ ′ / E ′) represented by the quotient of the storage elastic modulus (E ′) and the loss elastic modulus (E ′ ′) when the DMA was measured was read.

  As apparent from the results in Table 1, the epoxy resin composition of Example 1 has an appropriate viscosity to be used as an LED sealing material, and is excellent also in the transmittance of the cured product and the transmittance after the heat test. . On the other hand, although the epoxy resin composition of the comparative example 1 is a moderate viscosity and the transmittance | permeability of the hardened | cured material is excellent, it is inferior to the transmittance | permeability after a heat test. From the above, the epoxy resin composition of the present invention using a polyvalent carboxylic acid, an acid anhydride compound and a sulfur-based antioxidant is suitable for the field requiring transparency and heat-resistant transparency.

Claims (8)

The epoxy resin composition containing following (A), (B) component, and (C) epoxy resin .
(A) A polyvalent carboxylic acid compound having two or more carboxyl groups in the molecule represented by the following formula (2)

(In the formula (2), X is 0-6 oxygen atoms, nitrogen atoms, phosphorus atoms which may contain a silicon atom, a residue of a polyhydric alcohol of 2 to 100 carbon atoms, ^{R 4} is 2 carbon atoms 20 aliphatic hydrocarbon groups, m represents an average of 1 to 6 and n represents an average of 2 to 6. In the formula, a plurality of R ⁴ may be the same or different. .)
(B) Sulfur-based antioxidant represented by the following formula (1)

(In formula (1), R ¹ represents an alkyl group having 1 to 10 carbon atoms, R ² and R ³ each represent an alkylene group having 1 to 5 carbon atoms. In the formula, a plurality of R ^{1 to} R ³ are Each may be the same or different.) (A) A polyvalent carboxylic acid compound having two or more carboxyl groups in the molecule has the following residue (a) and the following residue (b), and each of the following (a) and (b) The epoxy resin composition according to claim 1 , wherein the residue is a compound having a carboxyl group at the end bonded with an ester structure.
(A) Reactive residue of polyhydric alcohol compound having two or more hydroxyl groups in molecule (b) Reactive residue of compound having one or more carboxylic anhydride compounds in molecule The epoxy resin composition according to claim 1, further comprising a compound having one or more carboxylic acid anhydride groups in the molecule. The epoxy resin composition according to claim 3 , wherein the compound having one or more carboxylic acid anhydride groups in the molecule is one or more selected from the following formulas (3) to (5).

The epoxy resin composition according to any one of claims 1 to 4, wherein in the formula (1), R ¹ is a tertiary butyl group, R ² is an ethylene group, and R ³ is an ethylene group. (C) The epoxy resin is a silicone modified epoxy resin, The epoxy resin composition as described in any one of Claims 1-5 . The epoxy resin composition according to claim 6, wherein the silicone-modified epoxy resin is represented by the following formula (6).

(In the formula (6), R ⁵ represents a hydrocarbon group having 1 to 6 carbon atoms, Y represents an epoxy group-containing organic group or a hydrocarbon group having 1 to 6 carbon atoms, and p represents an integer of 1 to 3) A plurality of R ^{5 's} and Y's in the formula may be the same or different, provided that two or more of the plurality of Y's are epoxy group-containing organic groups) The hardened | cured material formed by hardening | curing the epoxy resin composition as described in any one of Claims 1-7 .