JP2016037507A - Epoxy resin composition and cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: an epoxy resin composition for providing a cured product having excellent pot life and excellent transparency; and a cured product thereof.SOLUTION: (1) There is provided an epoxy resin composition comprising an epoxy resin (A) having an isocyanuric ring containing three glycidyl groups in the molecule and a polyvalent carboxylic acid resin (B). (2) There is provided an epoxy resin composition in which the polyvalent carboxylic acid resin (B) is a polyvalent carboxylic acid resin of an addition polymer obtained by reacting at least the following (a) and (b): (a); a polyhydric alcohol compound containing two or more hydroxyl groups in the molecule, (b); a compound containing one or more acid anhydride groups in the molecule.SELECTED DRAWING: None

Description

The present invention relates to an epoxy resin composition suitable for use in a portion requiring high transparency, particularly for optical semiconductor sealing, and a cured product thereof.

Unsaturated hydrocarbon group-containing dimethylpolysiloxane and organohydrogendimethyl as a resin for encapsulating optical semiconductors such as LEDs (Light Emitting Diodes) that emit white light. A silicone resin sealing material using polysiloxane has been used (see Patent Document 1).
Silver plating having high conductivity and high light reflectance is widely used as a lead frame for energization for turning on the LED and improvement of light extraction efficiency. The silver-plated part is covered with the encapsulant, but since the gas permeability of the silicone resin encapsulant is high, sulfur-based gases such as hydrogen sulfide that are present in the air permeate and bond with the silver plating (silver In recent years, it has been regarded as a problem that the lead frame surface is discolored black and the light reflectance is reduced due to the sulfuration of the LED, resulting in a decrease in LED luminance.
Therefore, in order to reduce sulfur-based gas permeability as an improvement in sulfidation resistance, phenyl silicone resin encapsulants with improved sulfidation resistance introduced by introducing phenyl groups into dimethylsilicone resins have been used (patents). Reference 2).
On the other hand, recently, LED packages have been made thinner in order to make liquid crystal displays thinner. In order to reduce the thickness of the LED package, the resin sealing portion is also thinned, and even with a phenyl silicone resin sealing material, satisfactory sulfidation resistance cannot be obtained.
Thus, the epoxy resin composition using a modified epoxy resin having an epoxycyclohexane group introduced into the silicone skeleton and a carboxylic acid anhydride compound has improved sulfidation resistance, but due to volatilization of the carboxylic acid anhydride compound during curing. There is a problem of a dent on the surface of the LED package and a problem that workability is inferior due to a large increase in viscosity (pot life) during storage at room temperature (25 ° C.) (see Patent Document 3).

Japanese Patent No. 4636242 Japanese Patent No. 4676735 JP 2011-109058 A

An object of this invention is to provide the epoxy resin composition which has the outstanding pot life, and gives the hardened | cured material which was further excellent in transparency, and its hardened | cured material.

（式（１）中、Ｒ^１は炭素数１〜６のアルキレン基を表す。式（１）中、複数存在するＲ^１は同一であっても異なっていても構わない。）
（２）式（１）中、Ｒ^１がプロピレン基である、（１）に記載のエポキシ樹脂組成物。
（３）多価カルボン酸樹脂（Ｂ）が、少なくとも次の（ａ）（ｂ）を反応させることによって得られる付加重合体の多価カルボン酸樹脂である、（１）又は（２）のいずれか一項に記載のエポキシ樹脂組成物。
（ａ）；分子内に２つ以上の水酸基を含有する多価アルコール化合物
（ｂ）；分子内に１つ以上の酸無水物基を含有する化合物
（４）多価アルコール化合物（ａ）が下記式（２）〜（６）から選ばれる一種以上、分子内にカルボン酸無水物基を含有する化合物（ｂ）が下記式（７）〜（１８）から選ばれる一種以上である、（３）に記載のエポキシ樹脂組成物。

（式（２）中、Ｒ^２はエーテル結合を介しても良い炭素総数１〜１０アルキレン基を表し、Ｒ^３はメチル基又はフェニル基を表す。また、ｐは繰り返し数であり平均値を意味し、１〜１００である。）

（５）さらにエポキシ樹脂硬化促進剤（Ｃ）を含む（１）〜（４）のいずれか一項に記載のエポキシ樹脂組成物。
（６）（１）〜（５）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。
（７）（１）〜（６）のいずれか一項に記載のエポキシ樹脂組成物からなる、光半導体封止用樹脂組成物。
（８）（７）に記載の光半導体封止用樹脂組成物で光半導体素子を封止した光半導体装置。 As a result of intensive studies in view of the actual situation as described above, the present inventors have found that an epoxy resin composition having an isocyanuric ring and an epoxy resin composition containing a polyvalent carboxylic acid resin solves the above-described problems, and the present invention. It came to complete.
That is, the present invention relates to the following (1) to (8).
(1) An epoxy resin composition containing an epoxy resin (A) represented by the following formula (1) and a polycarboxylic acid resin (B).

(In formula (1), R ¹ represents an alkylene group having 1 to 6 carbon atoms. In formula (1), a plurality of R ¹ may be the same or different.)
(2) The epoxy resin composition according to (1), wherein in formula (1), R ¹ is a propylene group.
(3) Either (1) or (2), wherein the polycarboxylic acid resin (B) is an addition polymer polycarboxylic acid resin obtained by reacting at least the following (a) and (b): The epoxy resin composition according to claim 1.
(A): a polyhydric alcohol compound containing two or more hydroxyl groups in the molecule (b); a compound containing one or more acid anhydride groups in the molecule (4) a polyhydric alcohol compound (a) One or more selected from the formulas (2) to (6), and the compound (b) containing a carboxylic acid anhydride group in the molecule is one or more selected from the following formulas (7) to (18), (3) The epoxy resin composition described in 1.

(In the formula (2), R ² represents an alkylene group having 1 to 10 carbon atoms which may be bonded via an ether bond, R ³ represents a methyl group or a phenyl group, and p is a repeating number and means an average value. 1 to 100.)

(5) The epoxy resin composition according to any one of (1) to (4), further including an epoxy resin curing accelerator (C).
(6) A cured product obtained by curing the epoxy resin composition according to any one of (1) to (5).
(7) A resin composition for encapsulating an optical semiconductor, comprising the epoxy resin composition according to any one of (1) to (6).
(8) An optical semiconductor device in which an optical semiconductor element is sealed with the optical semiconductor sealing resin composition according to (7).

  According to the present invention, an epoxy resin having an isocyanuric ring and an epoxy resin composition containing a polyvalent carboxylic acid resin is excellent in pot life, and provides a cured product having high transparency and excellent mechanical properties. It is extremely useful as a sealing resin for materials requiring high performance, particularly optical semiconductors (LEDs, etc.).

The epoxy resin composition of the present invention is an epoxy resin composition containing an epoxy resin (A) represented by the following formula (1) and a polyvalent carboxylic acid resin (B).
First, the epoxy resin (A) will be described.

In formula (1), R ¹ represents an alkylene group having 1 to 6 carbon atoms.

Specific examples of R ¹ include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, isopropylene group, isobutylene group, isopentylene group, neopentylene group, isohexylene group, cyclohexylene group and the like. However, from the viewpoints of viscosity and heat-resistant transparency of the resulting cured product, an ethylene group and a propylene group are preferable, and a propylene group is particularly preferable.

In the formula (1), a plurality of R ¹ may be the same or different.

  Among the compounds represented by the formula (1), a compound represented by the following formula (19) is particularly preferable.

The epoxy resin represented by the above formula (1) can be obtained as a commercial product. For example, TEPIC, TEPIC-VL, TEPIC-G, TEPIC-S, TEPIC-SP, TEPIC-SS, and TEPIC- It can be obtained as a TEPIC series (manufactured by Nissan Chemical Co., Ltd.) such as HP and TEPIC-L.
Here, as the epoxy resin represented by the above formula (1), it is preferable to use a resin having a chlorine content of 2000 ppm or less, and a chlorine-free resin is particularly preferable from the viewpoint of preventing malfunction of the semiconductor. Moreover, it is suitable that it is liquid from a viewpoint of handling property.

In this invention, content of the epoxy resin represented by this-application formula (1) is the viscosity increase rate 5 hours after the mixing | blending of the epoxy resin composition which does not contain the epoxy resin represented by this-application formula (1). A particularly suitable content can be determined according to (hereinafter referred to as a viscosity increase rate in the absence). Specifically, the epoxy resin of the present formula (1) in the epoxy resin composition is contained so as to be 100 × (thickness increase rate in the absence-1) / 2% by weight or more (theoretical value). Excellent reduction in thickening rate can be achieved. Further, it is optimal that the theoretical value is satisfied. However, it is possible to expect a preferable decrease in the thickening rate even at about ± 5% by weight or more. For example, to explain with a specific example, when the thickening rate in the absence is 1.46, the theoretical value is 23% by weight or more, and the value is optimum, but even if it is 18% by weight or more, a suitable increase is achieved. A decrease in viscosity can be expected.
Moreover, it is preferable to add 20% by weight or more of the epoxy in the epoxy resin composition having a thickening ratio in the absence of 1.45 or more, more preferably 25% by weight or more. Moreover, it is preferable to add 10 weight% or more of the epoxy in the epoxy resin composition whose viscosity increase rate in absence is 1.30 or more, and it is more preferable to add 15 weight% or more. Furthermore, it is preferable to add 5% by weight or more of the epoxy in the epoxy resin composition having a viscosity increase rate in the absence of 1.20 or more, and more preferably 10% by weight or more. By doing in this way, it becomes possible to reduce a viscosity increase rate rapidly.

Next, the polyvalent carboxylic acid resin (B) will be described.
The polyvalent carboxylic acid resin (B) is a compound having at least two or more carboxyl groups and having an aliphatic hydrocarbon group or a siloxane skeleton as a main skeleton. In the present invention, the polyvalent carboxylic acid resin is not only a polyvalent carboxylic acid compound having a single structure, but also a mixture of a plurality of compounds having different substituent positions or different substituents, that is, a polyvalent carboxylic acid. The composition is also included, and in the present invention, they are collectively referred to as a polyvalent carboxylic acid resin (B).

As the polyvalent carboxylic acid resin (B), a bi- to hexafunctional carboxylic acid is particularly preferable. (A): a polyhydric alcohol compound containing two or more hydroxyl groups in the molecule; (b); 1 in the molecule More preferred are compounds obtained by reaction with compounds containing one or more acid anhydride groups. Here, in the reactants (a) and (b), another alcohol compound may be reacted, and two or more compounds corresponding to the component (a) or (b) may be used. .
(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, tricyclodecane dimethanol, norbornenediol, 2,2′-bis (4-hydroxycyclohexyl) propane, 2- (1,1-dimethyl-2-hydroxy) Ethyl) -5-ethyl-5-hydroxymethyl-1,3-dioxane and the like Diols, glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, triols such as 2-hydroxymethyl-1,4-butanediol, tetraols such as pentaerythritol and ditrimethylolpropane, dipentaerythritol, etc. Examples include hexaol, terminal alcohol polyester, terminal alcohol polycarbonate, terminal alcohol polyether, and polyhydric alcohol having a siloxane structure.
Particularly preferred alcohols are alcohols having 5 or more carbon atoms, 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, tricyclodecane dimethanol, norbornenediol, 2,2′-bis (4-hydroxycyclohexyl) propane, 2- And compounds such as (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-cyclohexane Sandimethanol, tricyclodecane dimethanol, norbornenediol, 2,2′-bis (4-hydroxycyclohexyl) propane, 2- (1,1-dimethyl-2-hydroxyethyl) -5-ethyl-5-hydroxymethyl- Alcohols having a branched chain structure or a cyclic structure such as a compound such as 1,3-dioxane are more preferable. From the viewpoint of imparting high sulfidation resistance, compounds such as 2,4-diethylpentanediol, tricyclodecane dimethanol, 2,2′-bis (4-hydroxycyclohexyl) propane, and 1,4-cyclohexanedimethanol are particularly preferred. preferable. Among them, particularly in a 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 alcohol having the branched chain structure or the cyclic structure preferably has 5 to 25 carbon atoms, and particularly preferably 5 to 20 carbon atoms.

  Among the polyhydric alcohol compounds containing two or more hydroxyl groups in the molecule, compounds represented by the following formulas (3) to (6) are preferable.

  Although the polyhydric alcohol which has a siloxane structure is not specifically limited, For example, the silicone oil represented by following formula (2) is preferable.

In the formula (2), R ² represents an alkylene group having 1 to 10 carbon atoms that may be bonded via an ether bond, and R ³ represents a methyl group or a phenyl group. Moreover, p is the number of repetitions and means an average value, and is 1-100. Here, p is preferably 1 to 10.

In formula (2), specific examples of R ² include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, isopropylene group, isobutylene group, isopentylene group, neopentylene group, isohexylene group, cyclohexyl group. Examples include silene group, heptylene group, octylene group, nonyl group, decyl group, ethyloxyethylene group, ethyloxypropylene group, propyloxyethylene group, propyloxypropylene group, etc. Among them, viscosity, heat resistance transparency of cured products From the viewpoint, a propylene group, an ethyloxypropylene group, and a propyloxyethylene group are preferable.

  Examples of the silicone oil represented by the formula (2) include the following product names. For example, as a product made by Shin-Etsu Chemical Co., Ltd., X-22-160AS, KF-6000, KF-6001, KF-6002, KF-6003, and Toray Dow Corning make SF8427, BY16-201, Asahi Kasei Wacker Silicone As manufactured, WACKER IM11, WACKER IM15, as manufactured by JNC, FM-4411, FM-4421, FM-4425, manufactured by Momentive Performance Materials Japan, XF42-C5277, XF42-B0970, etc. All are available from the market. These silicone oils can be used alone or in combination. Among these, X-22-160AS, KF6001, KF6002, BY16-201, WACKER IM11, FM-4411, and XF42-B0970 are preferable.

As described above, (a): the 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 polycarboxylic acid resin in a liquid state and impart high resistance to sulfidation, the polyhydric alcohol having the siloxane structure described above and the alcohol having a branched chain structure or a cyclic structure having 5 to 25 carbon atoms. It is preferable to use a mixture.
When using a mixture of 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, the amount used is in the total alcohol compound (polyhydric alcohol having a siloxane structure). / (Alcohols having a branched chain structure or cyclic structure having 5 to 25 carbon atoms) is preferably 1 to 20, and 5 to 15 from the viewpoint of heat-resistant transparency of the cured product and appropriate viscosity of the polyvalent carboxylic acid resin. Is preferable, and 6 to 10 is particularly preferable.

(B); compounds containing one or more acid anhydride groups in the molecule include, in particular, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butane Tetracarboxylic 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-diethylglutaric anhydride, succinic anhydride and the like are preferred, and among them, methylhexahydrophthalic anhydride, cyclohexane-1,3, 4-tricarboxylic acid-3,4-anhydride, 2,4-diethylglutaric anhydride, 1,2,3,4-butanetetracarboxylic dianhydride Cyclohexane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride is preferred. Here, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride is preferable for increasing hardness, and methylhexahydrophthalic anhydride is preferable for increasing illuminance retention. In order to suppress an excessive increase in viscosity of the polyvalent carboxylic acid resin, 2,4-diethylglutaric acid and glutaric acid are preferable.

(B); It is preferable to use one or more compounds represented by the following formulas (7) to (18) as the compound containing one or more acid anhydride groups in the molecule.

Although there is no particular designation as a condition for the addition reaction, one specific reaction condition is that the acid anhydride and polyhydric alcohol are reacted in a non-catalytic and solvent-free condition at 40 to 150 ° C. and heated to react. After completion, take it out as it is. It is a technique. However, it is not limited to this reaction condition.

A polyvalent carboxylic acid resin and an acid anhydride can be used in combination, and when used in combination, the use ratio is preferably in the following range.

W1 / (W1 + W2) = 0.05-0.70

However, W1 shows the mixing | blending mass part of polyhydric carboxylic acid resin, W2 shows the mixing | blending mass part of an acid anhydride. 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, there is a strong tendency of acid volatilization to increase during curing, which is not preferable. If it exceeds 0.70, the viscosity becomes high and handling becomes difficult. When the acid anhydride is not contained (except when it remains in a small amount), there is no problem because the shape becomes a solid, a solid state or a crystal.
When using polyhydric carboxylic acid resin and acid anhydride in combination, the polyhydric carboxylic acid resin is produced in excess of acid anhydride during production, and the method of making a mixture of polyhydric carboxylic acid resin and acid anhydride is also operated It is preferable from the viewpoint of simplicity.

  The compounding amount of the epoxy resin curing agent (B) is a functional group having reactivity with the epoxy group with respect to a total of 1 mol of all epoxy groups (in the case of an acid anhydride curing agent, -CO-O-CO- Is an amount such that the acid anhydride group is 0.3 to 1.0 mol, preferably 0.4 to 0.8 mol. If the functional group having reactivity with the epoxy group is 0.3 mol or more, the heat resistance and transparency of the cured product are improved, and if it is 1.0 mol or less, the mechanical properties of the cured product are improved. ,preferable. Here, “functional group having reactivity with epoxy group” means an amino group possessed by an amine curing agent, a phenolic hydroxyl group possessed by a phenol curing agent, an acid anhydride group possessed by an acid anhydride curing agent, It is a carboxyl group that the polyvalent carboxylic acid resin has.

The epoxy resin composition of the present invention can be used by mixing an epoxy resin in addition to the epoxy resin (A) described above.
Other epoxy resins that can be used include epoxy resins that are glycidyl etherification products of phenolic compounds, epoxy resins that are glycidyl etherification products of various novolak resins, alicyclic epoxy resins, aliphatic epoxy resins, heterocyclic epoxy resins, Glycidyl ester epoxy resins, glycidyl amine epoxy resins, epoxy resins obtained by glycidylation of halogenated phenols, copolymers of polymerizable unsaturated compounds having an epoxy group with other polymerizable unsaturated compounds, epoxy Examples thereof include condensates of silicon compounds having a group with other silicon compounds, silicone-modified epoxy resins, and the like.

  Examples of the epoxy resin that is a glycidyl etherified product of a phenol 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, tetramethyl bisphenol A, dimethyl bisphenol A, tetramethyl bisphenol F, dimethyl bisphenol F, tetramethyl bisphenol 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, resorcinol, hydroquinone, pyrogallol, phloroglicinol, diisopropyl Examples thereof include phenols having a redene skeleton, phenols having a fluorene skeleton such as 1,1-di-4-hydroxyphenylfluorene, and epoxy resins which are glycidyl etherified products of polyphenol compounds such as phenolized polybutadiene.

  Examples of epoxy resins that are glycidyl etherified products 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 etherified products of various novolac resins such as a novolak resin, a phenol novolac resin containing a xylylene skeleton, a phenol novolak resin containing a dicyclopentadiene skeleton, a phenol novolak resin containing a biphenyl skeleton, and a phenol novolac resin containing a fluorene skeleton.

Examples of the alicyclic epoxy resin include alicyclic rings having an aliphatic ring skeleton such as 3,4-epoxycyclohexylmethyl- (3,4-epoxy) cyclohexylcarboxylate and bis (3,4-epoxycyclohexylmethyl) adipate. An epoxy resin is 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 heterocyclic epoxy resins having a heterocyclic ring such as an isocyanuric 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 epoxy resins obtained by glycidylation of halogenated phenols include brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolak, brominated cresol novolac, chlorinated bisphenol S, chlorinated bisphenol A, and the like. An epoxy resin obtained by glycidylating any of the halogenated phenols.

  As a copolymer of a polymerizable unsaturated compound having an epoxy group and other polymerizable unsaturated compounds, Marproof G-0115S, G-0130S, and G-0250S are commercially available products. G-1010S, G-0150M, G-2050M (manufactured by NOF Corporation), etc., and examples of the polymerizable unsaturated compound having an epoxy group include glycidyl acrylate, glycidyl methacrylate, 4 -Vinyl-1-cyclohexene-1,2-epoxide and the like. Examples of other polymerizable unsaturated compound copolymers include methyl (meth) acrylate, ether (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, and vinylcyclohexane.

  Examples of the condensate of the silicon compound having an epoxy group and another silicon compound include 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 condensate 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-glycidoxypropylmethyldimethoxysilane 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. . As polydimethylsiloxane having a silanol group and polydimethyldiphenylsiloxane having a silanol group, for example, X-21-5841, KF-9701 (manufactured by Shin-Etsu Chemical Co., Ltd.) BY16-873 are available from the market. PRX413 (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 two or more epoxy groups in one molecule. The silicone chain may be linear, branched, cyclic, cage type, or ladder type. A cyclic silicone-modified epoxy resin represented by the following formula (20) is particularly preferred from the viewpoint of the transparency and mechanical strength of the obtained cured product, but is not limited thereto.

In the formula (20), in the formula (1), R ⁴ 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 n represents 1 to 1 Each represents an integer of 3. A plurality of R ⁴ and X present in the formula may be the same or different. However, in the plurality of X, two or more are epoxy group-containing organic groups.

Specific examples of R ⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a phenyl group. From the viewpoint of heat resistance and transparency of the cured product, a methyl group and a phenyl group are preferable. From the viewpoint of ease of production, a methyl group is particularly preferable.
The organic group in X represents a compound composed of C, H, N, and O atoms. Specific examples of the organic group containing an epoxy group include 2,3-epoxycyclohexylethyl group and 3-glycidoxypropyl group. From the viewpoint of heat-resistant transparency of the cured product, 2,3-epoxycyclohexylethyl group is preferable. Here, the number of carbon atoms in the organic group is preferably 1-20, and more preferably 3-15. Further, it is preferably a group to which a 2,3-epoxycyclohexylethyl group or 3-glycidoxypropyl group is 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. From the viewpoint of heat-resistant transparency of the cured product Therefore, a methyl group and a phenyl group are preferred, and a methyl group is particularly preferred from the viewpoint of ease of production.
n is preferably 2 in view of ease of production of the compound.

The cyclic silicone-modified epoxy resin represented by the formula (20) can be obtained by a hydrosilylation reaction between a cyclic hydrogensiloxane compound and an olefin compound having an epoxy group in the molecule.
Specific examples of the cyclic hydrogensiloxane compound include trimethyltricyclosiloxane, triphenyltricyclosiloxane, tetramethyltetracyclosiloxane, tetraphenyltetracyclosiloxane, pentamethylpentacyclosiloxane, pentaphenylpentacyclosiloxane, and the like. Tetramethyltetrasiloxane is preferred because of ease 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 4-vinyl- from the viewpoint of heat-resistant transparency of the cured product. 1,2-epoxycyclohexane is preferred.

In the hydrosilylation reaction, a known metal complex such as rhodium, palladium, or platinum can be used as the catalyst. Specific examples include tristriphenylphosphine rhodium chloride, hexachloroplatinic acid hexahydrate, and the like. Transparency and cured product of cyclic siloxane compound (A) having two or more epoxy groups in the molecule obtained. From the viewpoint of transparency, hexachloroplatinic acid hexahydrate is preferable.

The catalyst used for the hydrosilylation reaction is preferably dissolved in a solvent and used as a solution from the viewpoint of workability. Any solvent can be used as long as it can dissolve the catalyst. From the viewpoints of solubility and workability, tetrahydrofuran and toluene are preferable.
When used as a solution, the catalyst is adjusted to 0.05 to 50% by weight and added to the reaction solution.

Specific examples of the cyclic silicone-modified epoxy resin represented by the formula (20) include compounds represented by the following formulas (20-1) to (20-6).

  The aforementioned epoxy resins may be used alone or in combination of two or more.

Among the above-mentioned epoxy resins, from the viewpoint of transparency, heat-resistant transparency, and light-resistant transparency, alicyclic epoxy resins, condensates of silicon compounds having an epoxy group with other silicon compounds, and combined use of silicone-modified epoxy resins Is preferred. Among these, a cyclic silicone-modified epoxy resin having an epoxycyclohexane structure in the skeleton is preferable.

  In the present invention, when the epoxy resin (A) and another epoxy resin are used in combination, the ratio of the epoxy resin (A) to the total epoxy resin is preferably 10 to 99 parts by mass, and 60 to 97 parts by mass. Part is particularly preferred. If it is less than 10 parts by mass, the illuminance retention rate during the sulfidation resistance test and the crack resistance during reflow may be inferior.

  In the epoxy resin composition of the present invention, the blending ratio of the total epoxy resin containing the epoxy resin (A) and the epoxy resin curing agent is 0.5 to 1.2 equivalents of curing per 1 equivalent of epoxy groups of all epoxy resins. It is preferable to use an agent. When less than 0.5 equivalent or more than 1.2 equivalent with respect to 1 equivalent of an epoxy group, curing may be incomplete and good cured properties may not be obtained.

Next, the epoxy resin curing accelerator (C) will be described.
As the epoxy resin curing accelerator (C), any one capable of accelerating the curing reaction between the epoxy resin (A) (and the epoxy resin when used together) and the epoxy resin curing agent (B) can be used. However, examples of the curing accelerator (C) 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 include phosphine-based curing accelerators, phosphite-based curing accelerators, and Lewis acid-based curing accelerators.
In the epoxy resin composition of the present invention, the mixing ratio of the epoxy resin curing accelerator (C) 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.

Specific examples of the epoxy resin curing accelerator (C) 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-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, and salts of these imidazoles with polyvalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid and oxalic acid, dicyandiamide, etc. Amides of 1,8-diaza-bicyclo (5.4 0) Diaza compounds such as undecene-7 and salts thereof such as tetraphenylborate and phenol novolac, salts with the above polyvalent carboxylic acids or phosphinic acids, tetrabutylammonium bromide, cetyltrimethylammonium bromide, trioctylmethylammonium bromide Ammonium salts such as triphenylphosphine, tri (toluyl) phosphine, tetraphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate and other phosphines and phosphonium compounds, phenols such as 2,4,6-trisaminomethylphenol, amines Examples thereof include metal compounds such as adducts, tin octylate and the like, and microcapsule type curing accelerators in which these curing accelerators are formed into microcapsules. . Which of these curing accelerators is used is appropriately selected depending on characteristics required for the obtained transparent resin composition, such as transparency, curing speed, and working conditions.

Among these, from the viewpoint of transparency of the cured product and curability of the epoxy resin and the epoxy resin composition of the present invention, the metal soap curing accelerator is excellent, and among the metal soap curing accelerators, a zinc carboxylate compound is particularly preferable.
Examples of the metal soap hardening accelerator include tin octylate, cobalt octylate, zinc octylate, manganese octylate, calcium octylate, sodium octylate, potassium octylate, calcium stearate, zinc stearate, magnesium stearate, stearin Aluminum oxide, barium stearate, lithium stearate, sodium stearate, potassium stearate, 12-hydroxy calcium phosphate, zinc 12-hydroxystearate, magnesium 12-hydroxystearate, aluminum 12-hydroxystearate, 12-hydroxystearic acid 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 , Lithium laurate, zinc undecylate, 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 with excellent transparency and sulfidation resistance, in order to ensure sufficient curability, in particular zinc stearate, zinc montanate, zinc behenate, zinc laurate, zinc undecylenate, zinc ricinoleate, myristic Zinc salts composed of a monocarboxylic acid compound having 10 to 30 carbon atoms and a hydroxyl group such as zinc carboxylate having 10 to 30 carbon atoms such as zinc acid and zinc palmitate and zinc 12-hydroxystearate can be preferably used. Among these, from the viewpoint of excellent pot life and sulfidation resistance, a zinc salt composed of a monocarboxylic acid compound having 10 to 20 carbon atoms such as zinc stearate and zinc undecylenate, and a hydroxyl group such as 12-hydroxyzinc stearate. A zinc salt composed of a monocarboxylic acid compound having 15 to 20 carbon atoms is preferably used, more preferably zinc stearate, zinc undecylenate, zinc 12-hydroxystearate, particularly preferably zinc stearate, 12- Zinc hydroxystearate can be used.

Examples of the ammonium salt curing accelerator include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide. , Trimethylcetylammonium hydroxide, trioctylmethylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate, trioctylmethylammonium acetate and the like. Examples of the phosphonium salt curing accelerator include ethyltriphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, methyltributylphosphonium dimethylphosphate, methyltributylphosphonium diethylphosphate, 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, and heterocyclic compound-based curing accelerators. A phosphine-based curing accelerator, a phosphite-based curing accelerator, a Lewis acid-based curing accelerator, or the like can be used.

  The epoxy resin curing accelerator (C) described above can be used as a solid compound or a liquid compound at room temperature (25 ° C.). When the epoxy resin composition of the present invention is used for optical semiconductor encapsulation, and a solid compound is used as a curing accelerator at room temperature (25 ° C.), it can be used by dissolving it in a resin in advance.

  An acidic curing catalyst can be used as the epoxy resin curing accelerator (C). When curing with an acidic curing catalyst, a photopolymerization initiator or a thermal polymerization initiator is contained. Furthermore, you may contain various well-known compounds, materials, such as a diluent, a polymerizable monomer, a polymerizable oligomer, a polymerization start adjuvant, a photosensitizer. Moreover, you may contain various well-known additives, such as an inorganic filler, a color pigment, a ultraviolet absorber, antioxidant, a stabilizer, as needed.

Among acid curing catalysts, photocationic polymerization is particularly preferred. Examples of cationic catalysts (hereinafter referred to as photocationic polymerization initiators) include onium salts such as iodonium salts, sulfonium salts, and diazonium salts, and these can be used alone or in combination of two or more. The amount of the cationic photopolymerization initiator used is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the epoxy resin composition of the present invention. is there.

Furthermore, it is possible to simultaneously use one or more of these photocationic polymerization initiators, known polymerization initiation assistants and photosensitizers. Examples of polymerization initiators include, for example, benzoin, benzyl, benzoin methyl ether, benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinolpropan-1-one, N, N-dimethylaminoacetophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1- Chloroanthraquinone, 2-amylanthraquinone, 2-isopropylthioxatone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, acetophenone di Chiruketaru, benzophenone, 4-methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bis-diethylamino benzophenone, and a photo-radical polymerization initiator such as Michler's ketone. The usage-amount of polymerization initiation adjuvants, such as radical photopolymerization initiator, is 0.01-30 mass parts with respect to 100 mass parts of resin components, Preferably it is 0.1-10 mass parts.

  Specific examples of the photosensitizer include anthracene, 2-isopropylthioxatone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, acridine orange, acridine yellow, phosphine R, benzo Examples include flavin, cetoflavin T, perylene, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, triethanolamine, triethylamine and the like. The usage-amount of a photosensitizer is 0.01-30 mass parts with respect to 100 mass parts of epoxy resin components, Preferably it is 0.1-10 mass parts.

In the epoxy resin composition of the present invention, it is possible to supplement the viscosity adjustment of the composition and the hardness of the cured product by using a coupling agent as necessary.
Examples of coupling agents 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 coupling agents such as propyltrimethoxysilane; isopropyl (N-ethylaminoethylamino) titanate, isopropyl triisostearoyl titanate, titanium di (dioctyl pyrophosphate) oxyacetate, tetraisopropyl di (dioctyl phosphite) titanate, Titanium coupling agents such as neoalkoxytri (pN- (β-aminoethyl) aminophenyl) titanate; Zr-acetylacetonate, Zr-methacrylate, Zr-propionate, neoalkoxyzirconate, neoalkoxytrisneodeca Noyl zirconate, neoalkoxytris (dodecanoyl) benzenesulfonyl zirconate, neoalkoxytris (ethylenediaminoethyl) zirconate, neoalco Examples include zirconium such as xylitol (m-aminophenyl) zirconate, ammonium zirconium carbonate, Al-acetylacetonate, Al-methacrylate, and Al-propionate, or an aluminum coupling agent.
These coupling agents may be used alone or in combination of two or more.
A coupling agent is 0.05-20 mass parts normally in the epoxy resin composition of this invention, Preferably 0.1-10 mass parts is contained as needed.

The epoxy resin composition of the present invention can be supplemented with mechanical strength and the like without impairing transparency by using a nano-order level inorganic filler as necessary. As a standard for the nano-order level, it is preferable from the viewpoint of transparency to use a filler having an average particle size of 500 nm or less, particularly an average particle size of 200 nm or less. Examples of inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, and the like. However, 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.

If necessary, a phosphor can be added to the epoxy resin composition of the present invention. For example, the phosphor has a function of forming white light by absorbing part of blue light emitted from a blue LED element and emitting wavelength-converted yellow light. After the phosphor is dispersed in advance in the curable resin composition, the optical semiconductor is sealed. There is no restriction | limiting in particular as fluorescent substance, A conventionally well-known fluorescent substance can be used, For example, rare earth element aluminate, thio gallate, orthosilicate, etc. are illustrated. More specifically, phosphors such as a YAG phosphor, a TAG phosphor, an orthosilicate phosphor, a thiogallate phosphor, and a sulfide phosphor can be mentioned, and YAlO ₃ : Ce, Y ₃ Al ₅ O ₁₂ : Ce, Y ₄ Al ₂ O ₉ : Ce, Y ₂ O ₂ S: Eu, Sr ₅ (PO ₄ ) ₃ Cl: Eu, (SrEu) O.Al ₂ O _{3 and the} like are exemplified. As the particle size of the phosphor, those having a particle size known in this field are used, and the average particle size is preferably 1 to 250 μm, particularly preferably 2 to 50 μm. When using these fluorescent substance, the addition amount is 1-80 mass parts with respect to 100 mass parts with respect to the resin component, Preferably it is 5-60 mass parts.

  For the purpose of preventing settling of various phosphors during curing, thixotropic imparting agents such as silica fine powder (also referred to as aerosil or aerosol) can be added to the epoxy resin composition of the present invention. Examples of such silica fine powder include Aerosil 50, Aerosil 90, Aerosil 130, Aerosil 200, Aerosil 300, Aerosil 380, Aerosil OX50, Aerosil TT600, Aerosil R972, Aerosil R974, Aerosil R202, Aerosil R202, Aerosil R202, Aerosil R202, Aerosil R202, Aerosil R202, Aerosil R202, Aerosil R202, Aerosil Aerosil R805, RY200, RX200 (made by Nippon Aerosil Co., Ltd.), etc. are mentioned.

For the purpose of preventing coloring, the epoxy resin composition of the present invention may contain an amine compound as a light stabilizer, or a phosphorus compound and a phenol compound as an antioxidant.
Examples of the amine compound include tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (2,2,6,6-6- 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] undecane mixed ester, decanedioic acid bis (2,2,6 , 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 Lumalonate, decanedioic acid bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidinyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide and 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- , 4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], 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] heneicosan-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) pyrrolidine-2,5-dione, 2,2,4,4-tetramethyl-7-oxa 3,20-diazadispiro [5,1,11,2] heneicosane-21-one, 2,2,4,4-tetramethyl-21-oxa-3,20-diazadicyclo- [5,1,11,2] -Heneicosane-20-propanoic acid dodecyl ester / tetradecyl ester, propanedioic acid, [(4-methoxyphenyl) -methylene] -bis (1,2,2,6,6-pentamethyl-4-piperidinyl) ester, 2,2,6,6-tetramethyl-4-piperidinol higher fatty acid ester, 1,3-benzenedicarboxamide, N, N′-bis (2,2,6,6-tetramethyl-4-piperidinyl) Hindered amines such as octabenzone, 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 Benzoate series such as di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5 Examples include triazine compounds such as [(hexyl) oxy] phenol, and hindered amine compounds are particularly preferable.

The following commercially available products can be used as the amine compound that is the light stabilizer.
The commercially available amine compound is not particularly limited, and for example, TINUVIN765, TINUVIN770DF, TINUVIN144, TINUVIN123, TINUVIN622LD, TINUVIN152, CHIMASSORB944, ADEKA manufactured by Ciba Specialty Chemicals, LA-52, LA-57, LA- 62, LA-63P, LA-77Y, LA-81, LA-82, LA-87 and the like.

  The phosphorus compound is not particularly limited, and for example, 1,1,3-tris (2-methyl-4-ditridecyl phosphite-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, phenylbisphenol A pentaerythritol diphosphite, Dicyclohexylpentaerythritol diphosphite, tris (diethylphenyl) phosphite, tris (di-isopropylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) Hosuf Ite, 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′-ethylidenebis (4-methyl-6-tert-butyl) Phenyl) (2-tert-butyl-4-methylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4 -Biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenyl Range 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'-biphenylenediphosphonite, 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 Examples include phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, etc.

  A commercial item can also be used for the said phosphorus compound. It does not specifically limit as a phosphorus compound marketed, For example, as an ADEKA product, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB HP-10, ADK STAB 2112, ADK STAB 260 , Adekas tab 522A, Adekas tab 1178, Adekas tab 1500, Adekas tab C, Adekas tab 135A

  The phenol compound is not particularly limited, and examples thereof include 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, pentaerythrine Lithyl-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-butylphenol) 2), 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) -butanoic 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 ′ -Hydroxy-3'-tert-butylphenyl) -butanoic acid] -glycol ester and the like.

A commercial item can also be used for the said phenolic compound. There are no particular limitations on the commercially available phenolic compounds. For example, IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 245, IRGANOX 259, IRGANOX 295, IRGANOX 3114, IRGANOX 1098, AGANOX 1520L, Adeka 1520L, and AGANOX 1520L manufactured by Ciba Specialty Chemicals , ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-90, ADK STAB AO-330, Sumitizer GA-80 , Sumilizer MDP-S, Sumil zer BBM-S, Sumilizer GM, Sumilizer GS (F), and the like Sumilizer GP.

  In addition, commercially available additives can be used as an anti-coloring agent for the resin. For example, THINUVIN 328, THINUVIN 234, THINUVIN 326, THINUVIN 120, THINUVIN 477, THINUVIN 479, CHIMASSORB 2020FDL, CHIMASSORB 119FL and the like can be cited as those manufactured by Ciba Specialty Chemicals.

  It is preferable to contain at least one of the phosphorus compounds, amine compounds, and phenol compounds, and the amount of the compound is not particularly limited, but is 0 with respect to the total mass of the epoxy resin composition of the present invention. The range is 0.005 to 5.0 mass%.

Furthermore, a binder resin can also be mix | blended with the epoxy resin composition of this invention as needed. Examples of the binder resin include butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenol resins, epoxy-NBR resins, polyamide resins, polyimide resins, and silicone resins. However, it is 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 per 100 parts by mass of the resin component. A mass part is used as needed.

If necessary, an inorganic filler can be added to the epoxy resin composition of the present invention. Examples of inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, and the like. However, the present invention is not limited to these. These 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 curable resin composition of the present invention is used. Furthermore, a silane coupling agent, a release agent such as stearic acid, palmitic acid, zinc stearate, and calcium stearate, various compounding agents such as pigments, and various thermosetting resins are added to the curable resin composition of the present invention. can do.

  The epoxy resin composition of the present invention can be obtained by uniformly mixing the above components at room temperature or under heating. For example, mix thoroughly until uniform using an extruder, kneader, three rolls, universal mixer, planetary mixer, homomixer, homodisper, bead mill, etc., and if necessary, filter with SUS mesh etc. Prepared.

  The epoxy resin composition of the present invention comprises an epoxy resin (A) (another epoxy resin as required), an epoxy resin curing agent (B), a curing accelerator (C), an antioxidant, a light stabilizer and the like. An epoxy resin composition can be prepared by thoroughly mixing the product and used as a sealing material. As a mixing method, a kneader, a three-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 warm.

Further, 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, and the curable resin composition varnish is obtained. A prepreg obtained by impregnating a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. and drying by heating is subjected to hot press molding, whereby the curable resin composition of the present invention is obtained. It can be a cured product. 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. Moreover, the epoxy resin hardened | cured material which contains a carbon fiber by a RTM system with a liquid composition can also be obtained.

Moreover, the epoxy resin composition of this invention can be used also as a modifier of a film type composition. Specifically, it can be used to improve the flexibility of the B-stage. In the case of obtaining such a film-type resin composition, the epoxy resin composition of the present invention is coated with the varnish on a release film, the solvent is removed under heating, and a B-stage adhesive is formed. 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 are mentioned, for example, adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), insulating materials (printed boards, In addition to the encapsulating material, the encapsulating material, a cyanate resin composition for the substrate, and an additive to other resins such as an acrylate-based resin as the curing agent for the resist may be used.

  Examples of the adhesive include civil engineering, architectural, automotive, general office, and medical adhesives, and electronic material adhesives. Among these, adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, BGA reinforcing underfills, anisotropic conductive films ( ACF) and an adhesive for mounting such as anisotropic conductive paste (ACP).

  As sealing agents, potting, dipping, transfer mold sealing for capacitors, transistors, diodes, light-emitting diodes, ICs, LSIs, potting sealings for ICs, LSIs such as COB, COF, TAB, flip chip For example, underfill for QFP, BGA, CSP, etc., and sealing (including reinforcing underfill) can be used.

The cured product obtained in the present invention can be used for various applications including optical component materials. The optical material refers to general materials used for applications in which light such as visible light, infrared light, ultraviolet light, X-rays, and lasers passes through the material. More specifically, in addition to LED sealing materials such as lamp type and SMD type, the following may be mentioned. It is a peripheral material for liquid crystal display devices 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 film for a liquid crystal such as a polarizer protective film in the liquid crystal display field. In addition, color PDP (plasma display) sealing materials, antireflection films, optical correction films, housing materials, front glass protective films, front glass replacement materials, adhesives, and LED displays that are expected as next-generation flat panel displays LED molding materials, LED sealing materials, front glass protective films, front glass substitute materials, adhesives, and substrate materials for plasma addressed 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 substitute material, adhesive, and 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 cards, Pickup lenses, protective films, sealing materials, adhesives and the like.

In the optical equipment field, they are still camera lens materials, finder prisms, target prisms, finder covers, and light receiving sensor sections. It is also a photographic lens and viewfinder for video cameras. Projection lenses for projection televisions, protective films, sealing materials, adhesives, and the like. These include lens materials, sealing materials, adhesives, and films for optical sensing devices. In the field of optical components, they are fiber materials, lenses, waveguides, element sealing materials, adhesives and the like around optical switches in optical communication systems. Optical fiber materials, ferrules, sealing materials, adhesives, etc. around the optical connector. For optical passive components and optical circuit components, there are lenses, waveguides, LED sealing materials, CCD sealing materials, adhesives, and the like. These are substrate materials, fiber materials, device sealing materials, adhesives, etc. around an optoelectronic integrated circuit (OEIC). In the field of optical fiber, it is an optical fiber for lighting, light guides for decorative displays, sensors for industrial use, displays / signs, etc., and for communication infrastructure and home digital equipment connection. As the semiconductor integrated circuit peripheral material, it is a resist material for microlithography for LSI and VLSI material. In the field of automobiles and transport equipment, automotive lamp reflectors, bearing retainers, gear parts, anti-corrosion coatings, switch parts, headlamps, engine internal parts, electrical parts, various interior and exterior parts, drive engines, brake oil tanks, automobile protection Rusted steel plates, interior panels, interior materials, protective / bundling wireness, fuel hoses, automobile lamps, glass replacements. In addition, it is a multilayer glass for railway vehicles. Further, they are toughness imparting agents for aircraft structural materials, engine peripheral members, protective / bundling wireness, and corrosion-resistant coatings. In the construction field, it is interior / processing materials, electrical covers, sheets, glass interlayers, glass substitutes, and solar cell peripheral materials. For agriculture, it is a house covering film. Next-generation optical / electronic functional organic materials include organic EL element peripheral materials, organic photorefractive elements, optical amplification elements that are light-to-light conversion devices, optical arithmetic elements, substrate materials around organic solar cells, fiber materials, elements Sealing material, adhesive and the like.

As sealing agents, potting, dipping, transfer mold sealing for capacitors, transistors, diodes, light-emitting diodes, ICs, LSIs, potting sealings for ICs, LSIs such as COB, COF, TAB, flip chip For example, underfill for sealing, and sealing (reinforcing underfill) when mounting 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. For example, adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), In addition to insulating materials (including printed circuit boards and wire coatings), sealants, additives to other resins and the like can be mentioned. Examples of the adhesive include civil engineering, architectural, automotive, general office, and medical adhesives, and electronic material adhesives. Among these, adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, BGA reinforcing underfills, anisotropic conductive films ( ACF) and an adhesive for mounting such as anisotropic conductive paste (ACP).

  Optical semiconductor elements such as high-intensity white LEDs are generally GaAs, GaP, GaAlAs, GaAsP, AlGa, InP, GaN, InN, AlN, InGaN laminated on a substrate of sapphire, spinel, SiC, Si, ZnO or the like. Such a semiconductor chip is bonded to a lead frame, a heat sink, 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 an epoxy resin in order to protect it from heat and moisture and play a role of a lens. The epoxy resin composition of this invention can be used for this sealing material.

As a molding method of the sealing material, an injection method in which the sealing material is injected into the mold frame in which the optical semiconductor element is fixed is inserted and then heat-cured and then molded, and the sealing material is injected on the mold in advance. A compression molding method is used in which an optical semiconductor element fixed on a substrate is immersed therein and heat-cured and then released from a mold.
Examples of the injection method include a dispenser.
For the heating, methods such as hot air circulation, infrared rays and high frequency can be used. The heating condition is preferably about 80 to 230 ° C. and about 1 minute to 24 hours, for example. For the purpose of reducing internal stress generated during heat curing, for example, after pre-curing at 80 to 120 ° C. for 30 minutes to 5 hours, post-curing is performed at 120 to 180 ° C. for 30 minutes to 10 hours. it can.

  When the epoxy resin of the present invention is used as a resin composition for encapsulating an optical semiconductor, the refractive index of the cured product is preferably 1.35 to 1.53, more preferably 1.42 to 1.50, and 1.45. ˜1.49 is particularly preferred. If the refractive index is less than 1.35, the gas barrier property of the cured product may be inferior. If it is greater than 1.53, the illuminance of the optical semiconductor (for example, LED) encapsulated with the curable resin composition for encapsulating an optical semiconductor is increased. May be inferior.

  In this specification, ratios, percentages, parts and the like 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 synthesis examples and examples. In addition, each physical-property value in a synthesis example and an Example was measured with the following method. Here, a part represents a mass part unless otherwise specified.
○ Gel permeation chromatography (GPC): GPC was measured under the following conditions.
Manufacturer: Shimadzu Corporation Column: SHODEX GPC LF-G (guard column), LF-804 (three)
Flow rate: 1.0 ml / min.
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Detector: RI (differential refraction detector)
○ Epoxy equivalent: Measured by the method described in JIS K-7236.
○ Acid value: measured by the following method.
About 0.15 g of the sample is weighed and dissolved in 20 ml of methyl ethyl ketone and 20 ml of ethanol, and then titrated with a 0.1N sodium hydroxide solution using a titrator AT-610 manufactured by Kyoto Electronics Industry, and the acid value is measured. did.
Viscosity: Measured at 25 ° C. using an E-type viscometer (TV-20) manufactured by Toki Sangyo Co., Ltd. according to JIS K7233.

Synthesis Example 1 Synthesis of an epoxy resin which is a condensate of a silicon compound having an epoxy group and another silicon compound. 394 parts of 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, having a molecular weight of 1700 (measured by GPC) A reaction vessel was charged with 475 parts of polydimethyldiphenylsiloxane having a silanol group, 4 parts of a 5% KOH methanol solution, and 36 parts of isopropyl alcohol, and the temperature was raised to 75 ° C. After raising the temperature, the reaction was carried out under reflux for 10 hours. After the reaction, after adding 656 parts of methanol, 172.8 parts of a 50% distilled water methanol solution was added dropwise over 60 minutes, and the mixture was further reacted for 10 hours under reflux. After completion of the reaction, the reaction mixture was neutralized with 5% aqueous sodium hydrogen phosphate solution, and methanol was recovered by distillation at 80 ° C. Thereafter, 780 parts of methyl isobutyl ketone (MIBK) was added for washing, and washing with water was repeated three times. Subsequently, 731 parts of epoxy resins (A-1) were obtained by removing a solvent at 100 degreeC under pressure reduction of the organic phase. The epoxy equivalent of the obtained compound was 491 g / eq, the weight average molecular weight in terms of polystyrene by GPC measurement was 2090, the viscosity was 3328 mPa · s, and the appearance was colorless and transparent.

Synthesis Example 2: Synthesis of epoxy resin which is a condensate of a silicon compound having an epoxy group and another silicon compound. 111 parts of 2- (3,4 epoxy cyclohexyl) ethyltrimethoxysilane, molecular weight 1700 (measured by GPC) 100 parts of polydimethyldiphenylsiloxane having silanol groups, 1 part of 5% KOH methanol solution, and 8 parts of isopropyl alcohol were charged into a reaction vessel, and the temperature was raised to 75 ° C. After raising the temperature, the reaction was carried out under reflux for 10 hours. After the reaction, 120 parts of methanol was added, 48.6 parts of 50% distilled water methanol solution was added dropwise over 60 minutes, and the mixture was further reacted for 10 hours under reflux. After completion of the reaction, the reaction mixture was neutralized with 5% aqueous sodium hydrogen phosphate solution, and methanol was recovered by distillation at 80 ° C. Thereafter, 174 parts of MIBK was added for washing, and washing with water was repeated three times. Subsequently, 174 parts of epoxy resins (A-2) were obtained by removing a solvent at 100 degreeC under pressure reduction of the organic phase. The obtained compound had an epoxy equivalent of 411 g / eq, a polystyrene-equivalent weight average molecular weight of 3200, a viscosity of 15140 mPa · s as measured by GPC, and the appearance was colorless and transparent.

Synthesis Example 3: (a) As a polyhydric alcohol compound containing two or more hydroxyl groups in the molecule, both terminal carbinol-modified silicone oil and 2,2′-bis (4-hydroxycyclohexyl) propane are used, (b) Example of synthesis of polyvalent carboxylic acid resin using methylhexahydrophthalic anhydride and glutaric anhydride as a compound containing one or more acid anhydride groups in the molecule Into a 500 ml separable flask made of glass, Ricabinol HB (new Nippon Rika Co., Ltd., 2,2′-bis (4-hydroxycyclohexyl) propane) 18.2 g, glutaric anhydride 20.1 g, KF-6000 (manufactured by Shin-Etsu Chemical Co., Ltd., both-end carbinol-modified silicone oil, the above formula (2) a middle ^{R 2} is propyloxy ethylene group, ^{R 3} is a methyl group, p is a 7.5) 122.7 g, RIKACID H-T (manufactured by New Japan Chemical Co., Ltd., 4-methylhexahydrophthalic anhydride) were charged 39.0 g, toluene 200 g, Dimroth condenser, stirrer, thermometer assembled and the flask was placed in an oil bath. The oil bath was heated at 130 ° C. and reacted for 8 hours while toluene was refluxing. When the reaction solution was confirmed by GPC after completion of the reaction, the peaks of 4-methylhexahydrophthalic anhydride, glutaric anhydride, and 2,2′-bis (4-hydroxycyclohexyl) propane disappeared. Toluene was distilled off from the resulting reaction solution under reduced pressure to obtain 195 g of a polycarboxylic acid resin (B-1). The polyvalent carboxylic acid resin (B-1) had an acid value of 113.4 mgKOH / g, a viscosity of 2780 mPa · s, a polystyrene-reduced weight average molecular weight of 1264 by GPC measurement, and the appearance was a colorless transparent liquid.

Synthesis Example 4 Production Example of Cyclic Siloxane Compound Having Four Epoxy Groups in the Molecule In a 200 ml glass four-necked flask, 33 parts of 4-vinyl-1,2-epoxycyclohexane, 1% hexachloroplatinic acid hexahydrate A 0.03 part tetrahydrofuran solution was charged, a Dimroth condenser, a stirrer, and a thermometer were installed, and the flask was immersed in an oil bath. The oil bath was heated, the internal temperature was kept at 80 ° C., and 12 parts of 1,3,5,7-tetramethyltetracyclosiloxane was added dropwise over 1 hour, and the reaction was allowed to proceed for 1 hour.
Cyclic silicone having four epoxy groups in the molecule by concentrating under reduced pressure at 110 ° C. while blowing nitrogen gas into the resulting reaction solution, and removing tetrahydrofuran and excess 4-vinyl-1,2-epoxycyclohexane. 36 parts of modified epoxy resin (A-3) were obtained. The epoxy equivalent of the obtained compound was 190 g / eq, the viscosity was 2800 mPa · s, and the appearance was a colorless transparent liquid.

Example 1: Preparation of epoxy resin composition TEPIC-VL (manufactured by Nissan Chemical Industries, 1,3,5-isocyanuric acid tris (3-carboxypropyl)) as the epoxy resin, polyvalent carboxylic acid obtained in Synthesis Example 3 Acid resin (B-1) and zinc octylate as a curing accelerator are placed in a polypropylene container at the quantitative ratio shown in Table 1 below, mixed and degassed for 5 minutes to obtain the epoxy resin composition of the present invention. It was.

Example 2 Preparation of Epoxy Resin Composition The present invention was carried out in the same manner as in Example 1 except that the epoxy resins A-1 and A-2 obtained in Synthesis Examples 1 and 2 were added as the epoxy resin of Example 1. An epoxy resin composition was obtained.

Examples 3 and 4; Preparation of epoxy resin composition The epoxy resin composition of the present invention was the same as in Example 1 except that the epoxy resin A-3 obtained in Synthesis Example 4 was added as the epoxy resin of Example 1. I got a thing.

Comparative Example 1; Preparation of epoxy resin composition TEPIC-VL (manufactured by Nissan Chemical Industries, Ltd., 1,3,5-isocyanuric acid tris (3-carboxypropyl)) as an epoxy resin, and Rikacid MH-T (New Japan) as a curing agent Rika Co., Ltd., 4-methylhexahydrophthalic anhydride), and Hicocorin PM4ET (manufactured by Nippon Kagaku Kogyo Co., Ltd., tetrabutylphosphonium diethyl phosphorodithioate) as a curing accelerator in a quantity ratio shown in Table 1 below in a polypropylene container The mixture was mixed and degassed for 5 minutes to obtain a comparative epoxy resin composition.

Comparative Example 2 Adjustment of Epoxy Resin Composition An epoxy resin composition of a comparative example was obtained in the same manner as in Comparative Example 1, except that the curing accelerator of Comparative Example 1 was replaced with zinc octylate.

Comparative Example 3; Preparation of Epoxy Resin Composition The epoxy resin of Comparative Example 1 was changed from TEPIC-VL to the epoxy resins A-1 and A-2 obtained in Synthesis Examples 1 and 2, and the curing agent was Ricacid MH-T. From the above, a comparative epoxy resin composition was obtained in the same manner as in Comparative Example 1 except that the polyvalent carboxylic acid resin B-1 obtained in Synthesis Example 3 was used.

Comparative Example 4 Preparation of Epoxy Resin Composition The epoxy resin of Comparative Example 1 was replaced with the epoxy resin A-3 obtained in Synthesis Example 4 from TEPIC-VL, and the curing agent was obtained in Synthesis Example 3 from Ricacid MH-T. A comparative epoxy resin composition was obtained in the same manner as in Comparative Example 1 except that the polyvalent carboxylic acid resin B-1 was replaced.

(Evaluation test)
Table 1 shows the blending ratios of the epoxy resin compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 4 and their viscosities, the viscosity increase rate after 5 hours, the refractive index of the cured product, and the transmittance of the cured product. Shown in The test in Table 1 was performed as follows.
○ Viscosity immediately after blending: Within 10 minutes after blending the blended epoxy resin, the viscosity was measured at 25 ° C. using an E-type viscometer (TV-20) manufactured by Toki Sangyo Co., Ltd. according to JIS K7233.
○ Viscosity increase rate after 5 hours after blending: After leaving the blended epoxy resin at 25 ° C for 5 hours, using an E-type viscometer (TV-20) manufactured by Toki Sangyo Co., Ltd. according to JIS K7233 at 25 ° C The viscosity was measured. From the viscosity at that time and the viscosity immediately after blending, the rate of increase in viscosity was calculated.
○ Refractive index of cured product: After carrying out the vacuum defoaming for 5 minutes with the epoxy resin compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 4, with a heat-resistant tape so as to be 30 mm x 20 mm x height 0.8 mm The dam was gently cast on the glass substrate. The cast was cured at 120 ° C. for 3 hours after pre-curing at 120 ° C. for 1 hour to obtain a test piece for transmittance having a thickness of 0.8 mm. The obtained test piece was measured for a refractive index of 633 nm under the following conditions.
<Refractive index measurement conditions>
Manufacturer: Metricon Model: Model PC2010
Temperature: 25 ° C
Wavelength: 663nm
○ Cured product transmittance: After carrying out vacuum defoaming for 5 minutes with the epoxy resin compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 4, with a heat-resistant tape so as to be 30 mm × 20 mm × height 0.8 mm The dam was gently cast on the glass substrate. The cast was cured at 120 ° C. for 3 hours after pre-curing at 120 ° C. for 1 hour to obtain a test piece for transmittance having a thickness of 0.8 mm. The obtained specimen was measured for light transmittance at 400 nm under the following conditions.
<Spectrophotometer measurement conditions>
Manufacturer: Hitachi High-Technologies Corporation Model: U-3300
Slit width: 2.0nm
Scan speed: 120 nm / min

＊１；日産化学工業社製、１，３，５−イソシアヌル酸トリス（３−カルボキシプロピル）
＊２；新日本理化者製、４−メチルヘキサヒドロ無水フタル酸
＊３；日本化学工業社製、テトラブチルホスホニウムジエチルホスホロジチオエート
＊４；前記屈折率計では、屈折率が測定できなかった。
＊５；比較例２のエポキシ樹脂組成物は硬化しなかった。

* 1; manufactured by Nissan Chemical Industries, Ltd., 1,3,5-isocyanuric acid tris (3-carboxypropyl)
* 2; New Nippon Rika, 4-methylhexahydrophthalic anhydride * 3; Nippon Chemical Industry Co., Ltd., tetrabutylphosphonium diethyl phosphorodithioate * 4; The refractive index could not be measured with the refractometer .
* 5: The epoxy resin composition of Comparative Example 2 was not cured.

  As is clear from the results in Table 1, the rate of increase in viscosity 5 hours after mixing of Comparative Examples 1 and 2 was small, but the cured product transmittance of Comparative Example 1 was low. Moreover, the epoxy resin composition of Comparative Example 2 was not cured. In Comparative Example 3, the viscosity increase rate after 5 hours was large and the workability was poor. On the other hand, the epoxy resin compositions of Examples 1 and 2 have a small increase in viscosity after 5 hours after compounding, and further the transmittance of the cured product is excellent. In particular, optical semiconductor encapsulation is required. It is suitable as a resin composition.

よって、本願発明は特に増粘上昇率を抑えることができることが確認された。
(Thickening rate measurement)
The rate of increase in viscosity was measured by the following formula. The viscosity increase rate after 5 hours of blending was measured by the same method as the viscosity increase rate after 5 hours of blending.

Viscosity increase rate (%) = 100 × (Viscosity increase rate after 5 hours of each Example or Comparative Example 4-1) / (Viscosity increase rate after 5 hours of Comparative Example 4) -1

As a result of calculating the rate of increase in viscosity, it was as follows.

Therefore, it was confirmed that the present invention can particularly suppress the rate of increase in viscosity.

Claims (8)

An epoxy resin composition containing an epoxy resin (A) represented by the following formula (1) and a polyvalent carboxylic acid resin (B).

(In formula (1), R ¹ represents an alkylene group having 1 to 6 carbon atoms. In formula (1), a plurality of R ¹ may be the same or different.) The epoxy resin composition of Claim ¹ whose R < ¹ > is a propylene group in Formula (1). The polyvalent carboxylic acid resin (B) is a polyvalent carboxylic acid resin of an addition polymer obtained by reacting at least the following (a) and (b): 3. Epoxy resin composition.
(A): a polyhydric alcohol compound containing two or more hydroxyl groups in the molecule (b); a compound containing one or more acid anhydride groups in the molecule The polyhydric alcohol compound (a) is one or more selected from the following formulas (2) to (6), and the compound (b) containing a carboxylic acid anhydride group in the molecule is selected from the following formulas (7) to (18). The epoxy resin composition according to claim 3, wherein the epoxy resin composition is one or more of the above.

(In the formula (2), R ² represents an alkylene group having 1 to 10 carbon atoms which may be bonded via an ether bond, R ³ represents a methyl group or a phenyl group, and p is a repeating number and means an average value. 1 to 100.)

  Furthermore, the epoxy resin composition as described in any one of Claims 1-4 containing an epoxy resin hardening accelerator (C).   Hardened | cured material formed by hardening | curing the epoxy resin composition as described in any one of Claims 1-5.   The resin composition for optical semiconductor sealing which consists of an epoxy resin composition as described in any one of Claims 1-6.   An optical semiconductor device in which an optical semiconductor element is sealed with the resin composition for sealing an optical semiconductor according to claim 7.