JP2016079129A - Carboxylic acid anhydride group-containing cyclic siloxane compound, epoxy resin composition containing the same and cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a carboxylic acid anhydride group-containing cyclic siloxane compound that suppresses excessive viscosity increase when used to form an epoxy resin composition, has excellent curability with little volatilization when cured, and gives a cured product excellent in transparency and hardness.SOLUTION: The cyclic siloxane compound (A) is represented by formula (1). For example, it shows an NMR spectrum shown in Fig. 1 (Ris a hydrocarbon group; X is a hydrocarbon group- or carboxylic acid anhydride group-containing organic group; n is an integer of 1 to 3; at least two of a plurality of Xs are a carboxylic acid anhydride group-containing organic group).SELECTED DRAWING: Figure 1

Description

The present invention relates to an epoxy resin curing agent suitable for use in a part requiring high transparency, such as for optical semiconductor sealing, and a part requiring high heat resistance, an epoxy resin composition containing the same, and a cured product thereof.

Epoxy resin compositions are used in the fields of architecture, civil engineering, automobiles, aircraft and the like as resins having excellent heat resistance. In recent years, especially in the field of semiconductor-related materials, products such as mobile phones with cameras, ultra-thin liquid crystals, plasma TVs, and light-weight notebook computers have become a key word. Very high characteristics have been demanded for packaging materials represented by resins.
Furthermore, in recent years, the use in the fields related to optoelectronics has attracted attention. With the advancement of advanced information technology, in order to smoothly transmit and process vast amounts of information, technology that uses optical signals instead of conventional signal transmission using electrical wiring. In the field of optical components such as optical waveguides, blue LEDs, and optical semiconductors, development of a resin composition that gives a cured product having excellent transparency is desired.
An epoxy resin curing agent generally used in the field of optoelectronics includes acid anhydride compounds. In particular, acid anhydrides formed with saturated hydrocarbons are often used because the cured product has excellent light resistance. As these acid anhydrides, alicyclic acid anhydrides such as methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, and tetrahydrophthalic anhydride are generally used. Phthalic anhydride is mainly used because of its ease of handling.
However, when these alicyclic acid anhydrides are used as curing agents for epoxy resins, these compounds have high vapor pressure and partly evaporate during curing. When this is done, the acid anhydride itself volatilizes into the atmosphere. As a result, epoxy resin composition resulting from environmental pollution due to the release of harmful substances to the atmosphere, adverse effects on human bodies, production line contamination, and the absence of a predetermined amount of carboxylic acid anhydride (curing agent) in the cured product Problems such as poor curing occur. Variations in curing conditions due to volatilization of the curing agent result in variations in the physical properties of the cured product, making it difficult to stably obtain a cured product having the intended performance.
In addition, the problem of volatilization is significant when LEDs, particularly SMD (Surface Mount Device) are sealed with a curable resin composition for encapsulating optical semiconductors that is formed using a conventional acid anhydride as a curing agent. Since the amount of resin used is small, dents are generated, and in severe cases, the wires are exposed. Furthermore, there is a problem that it is difficult to endure cracking, peeling, and long-term lighting during solder reflow.
Then, although examination which copes with a dent by mixing and using the polyvalent carboxylic acid compound which has multiple carboxyl groups in a molecule | numerator, and a liquid low molecular acid anhydride compound is also made | formed (patent document 1), this polyvalent A mixture containing a carboxylic acid tends to have a high viscosity, and there is a difficulty in workability in an application where the mixture is used in a liquid state at room temperature (25 ° C.).

Listed Patent WO2010 / 150524

The present invention suppresses excessive viscosity increase when used as an epoxy resin composition, has low volatilization at the time of curing and is excellent in curability, and the cured product has a carboxylic acid anhydride group that provides a cured product with excellent transparency and hardness. It is an object of the present invention to provide a containing cyclic siloxane compound, an epoxy resin composition containing the same, and a cured product thereof.

（式（１）中、Ｒ^１は炭素数１〜１０の炭化水素基を、Ｘは炭素数１〜２０炭化水素基又はカルボン酸無水物基含有の有機基を、ｎは１〜３の整数をそれぞれ表す。式（１）中、複数存在するＲ^１、Ｘはそれぞれ同一であっても異なっていても構わない。ただし、複数存在するＸ中、少なくとも２つはカルボン酸無水物基含有の有機基である。）
（２）カルボン酸無水物基含有の有機基が、下記式（２）〜（５）より選ばれる一種以上である、（１）に記載のカルボン酸無水物基含有環状シロキサン化合物（Ａ）。

（式中、＊で式（１）のＳｉ原子と結合していることを表す。また、Rは水素原子又は炭素数１〜３のアルキル基を表す。）
（３）下記工程を経る、（１）に記載のカルボン酸無水物基含有環状シロキサン化合物（Ａ）の製造方法。
工程１）ハイドロジェンシロキサン化合物とカルボン酸無水物基を有するオレフィン化合物を、ハイドロジェンシロキサン化合物中のＳｉ−Ｈ基１モルに対しカルボン酸無水物基を有するオレフィン化合物を０．２〜０．９モル当量仕込んで付加反応させる工程。
工程２）モノオレフィン化合物を、残存Ｓｉ−Ｈ基１モルに対し、１．１〜２０モル当量仕込み付加反応させる工程。
（４）（１）または（２）に記載のカルボン酸無水物基含有環状シロキサン化合物（Ａ）を含有するエポキシ樹脂硬化剤。
（５）（１）または（２）のいずれか一項に記載のカルボン酸無水物基含有環状シロキサン化合物（Ａ）、または（４）に記載のエポキシ樹脂硬化剤と、エポキシ樹脂（Ｂ）を含有するエポキシ樹脂組成物。
（６）エポキシ樹脂（Ｂ）がシリコーン変性エポキシ樹脂である、（５）に記載のエポキシ樹脂組成物。
（７）シリコーン変性エポキシ樹脂が下記式（６）で表される化合物である、（６）に記載のエポキシ樹脂組成物。

（式（６）中、Ｒ^１、ｎは前記と同じ意味を表し、Ｙは炭素数１〜１０炭化水素基又はエポキシ基含有の有機基をそれぞれ表す。式（６）中、複数存在するＲ^１、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の有機基である。）
（８）さらにエポキシ樹脂硬化促進剤（Ｃ）を含有する、（５）〜（７）のいずれか一項に記載のエポキシ樹脂組成物。
（９）（５）〜（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。
（１０）（５）〜（８）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。
（１１）（９）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 a carboxylic acid anhydride compound containing a cyclic siloxane skeleton, an epoxy resin composition containing the compound, and a cured product thereof solve the above problems. As a result, the present invention has been completed.
That is, the present invention relates to the following (1) to (11).
(1) A carboxylic acid anhydride group-containing cyclic siloxane compound (A) represented by the following formula (1).

(In the formula (1), the ^{R 1} is a hydrocarbon group having 1 to 10 carbon atoms, X is a number from 1 to 20 hydrocarbon group or carboxylic anhydride group-containing organic group having a carbon, n represents an integer of 1 to 3 In the formula (1), a plurality of R ¹ and X may be the same or different from each other, provided that at least two of the plurality of X contain a carboxylic acid anhydride group. Organic group.)
(2) The carboxylic acid anhydride group-containing cyclic siloxane compound (A) according to (1), wherein the carboxylic acid anhydride group-containing organic group is at least one selected from the following formulas (2) to (5).

(In the formula, * represents bonding to the Si atom of formula (1). R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)
(3) The manufacturing method of the carboxylic acid anhydride group containing cyclic siloxane compound (A) as described in (1) which passes through the following process.
Step 1) An olefin compound having a carboxylic acid anhydride group and a olefin compound having a carboxylic acid anhydride group with respect to 1 mole of Si-H groups in the hydrogen siloxane compound is 0.2 to 0.9. A step of adding a molar equivalent to cause an addition reaction.
Step 2) A step in which a monoolefin compound is charged in an amount of 1.1 to 20 molar equivalents per 1 mol of the remaining Si—H group.
(4) An epoxy resin curing agent containing the carboxylic acid anhydride group-containing cyclic siloxane compound (A) according to (1) or (2).
(5) The carboxylic acid anhydride group-containing cyclic siloxane compound (A) according to any one of (1) or (2), or the epoxy resin curing agent according to (4) and the epoxy resin (B). Contains epoxy resin composition.
(6) The epoxy resin composition according to (5), wherein the epoxy resin (B) is a silicone-modified epoxy resin.
(7) The epoxy resin composition according to (6), wherein the silicone-modified epoxy resin is a compound represented by the following formula (6).

(In Formula (6), R < ¹ >, n represents the same meaning as the above, Y represents a C1-C10 hydrocarbon group or an organic group containing an epoxy group. In Formula (6), multiple R exists. ¹ and Y may be the same as or different from each other, provided that two or more of Y are organic groups of an organic group containing an epoxy group.
(8) The epoxy resin composition according to any one of (5) to (7), further containing an epoxy resin curing accelerator (C).
(9) A cured product obtained by curing the epoxy resin composition according to any one of (5) to (8).
(10) A resin composition for encapsulating an optical semiconductor, comprising the epoxy resin composition according to any one of (5) to (8).
(11) An optical semiconductor device in which an optical semiconductor element is sealed with the optical semiconductor sealing resin composition according to (9).

  According to the present invention, a carboxylic acid anhydride compound containing a cyclic siloxane skeleton and an epoxy resin composition containing the carboxylic acid anhydride compound have excellent workability, low volatilization during curing, and excellent curability. Since the cured product gives a cured product having excellent transparency and hardness, it is required to form a cured product having high transparency and a thin film, and is extremely useful as a sealing resin for materials, particularly optical semiconductors (LEDs, etc.).

  The carboxylic anhydride group-containing cyclic siloxane compound (A) of the present invention is a carboxylic anhydride compound having a cyclic siloxane structure represented by the following formula (1).

In formula (1), R ¹ represents a hydrocarbon group having 1 to 10 carbon atoms, X represents an organic group containing a hydrocarbon group having 1 to 20 carbon atoms or a carboxylic acid anhydride group, and n represents an integer of 1 to 3. Represent each. In the formula (1), a plurality of R ¹ and X may be the same or different. However, in the plurality of Xs, at least two are carboxylic anhydride group-containing organic groups.
As X, 2 to 3 are preferably organic groups containing a carboxylic anhydride group. In X, the ratio of the organic group containing carboxylic anhydride group: the hydrocarbon group having 1 to 20 carbon atoms is preferably 1: 9 to 9: 1 from the viewpoint of the balance between strength and toughness. It is more preferable that it is 3: 7-7: 3.
Moreover, in the composition containing Formula (1), it is good also as two types of compositions from which the value of a carboxylic anhydride group differs, a carboxylic anhydride group number is 2 and a carboxylic anhydride group number is 3. A mixture is preferable, and a compound having 2 carboxylic anhydride groups: a compound having 3 carboxylic anhydride groups is preferably 7: 3 to 3: 7 in area% of LC-MS analysis, and 6: 4 to 4 : 6 is more preferable.

Specific examples of R ¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and a phenyl group. From the viewpoint of transparency, a methyl group and a phenyl group are preferable, and 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 a carboxylic acid anhydride group include cyclohexanedicarboxylic acid anhydride, ethylcyclohexanedicarboxylic acid anhydride, propyl Examples include cyclohexane dicarboxylic acid anhydride, norbornane dicarboxylic acid anhydride, ethyl norbornane dicarboxylic acid anhydride, propyl norbornane dicarboxylic acid anhydride, ethyl succinic acid anhydride, propyl succinic acid anhydride, among which the following formulas (2) to (5) ) Is preferable from the viewpoint of ease of production and compatibility with the epoxy resin (B) described later.

（式中、Rは水素原子又は炭素数１〜３のアルキル基を表す。）

(In the formula, R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)

  In formulas (2) to (5), it represents that it is bonded to the Si atom of formula (1) by *.

In formula (1), specific examples of the hydrocarbon group having 1 to 20 carbon atoms in X include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, Decyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, pentadecyl group, octadecyl group, cyclohexyl group, norbornanyl group, cyclohexaneethyl group, norbornaneethyl group, phenyl group, ethylbenzene group, etc. From the viewpoint of heat-resistant transparency of the product, a methyl group and a phenyl group are preferable, and from the viewpoint of lowering the melting point of the carboxylic anhydride group-containing cyclic siloxane compound (A) or lowering the viscosity of the epoxy resin composition. An octyl group, a hexadecyl group, and an octadecyl group are preferable.
In formula (1), n is preferably 2 in view of the ease of production of the compound.

The carboxylic acid anhydride group-containing cyclic siloxane compound (A) represented by the formula (1) includes a cyclic hydrogen siloxane compound and an olefin compound having a carboxylic anhydride group, and X in the formula (1) has 2 carbon atoms. When -20 hydrocarbon groups are introduced, they can be obtained by a hydrosilylation reaction with a hydrocarbon monoolefin compound having 2 to 20 carbon atoms.
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 a carboxylic acid anhydride group in the molecule include cyclohexene dicarboxylic acid anhydride, methylcyclohexene dicarboxylic acid anhydride, vinylcyclohexanedicarboxylic acid anhydride, allylcyclohexanedicarboxylic acid anhydride, norbornene dicarboxylic acid anhydride, methylnorbornene. Examples thereof include dicarboxylic acid anhydride, vinyl succinic acid, allyl succinic acid and the like, and norbornene dicarboxylic acid anhydride and allyl succinic acid anhydride are preferable from the viewpoint of ease of production and heat-resistant transparency of the cured product.
Examples of the hydrocarbon monoolefin compound having 2 to 20 carbon atoms include ethylene, propene, butene, pentene, hexene, heptene, octene, nonene, decene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, cyclohexene, vinylcyclohexane , Norbornene, vinyl norbornane, styrene and the like. From the viewpoint of lowering the melting point of the carboxylic anhydride group-containing cyclic siloxane compound (A) or lowering the viscosity of the epoxy resin composition, hexene, octene, hexadecene, octadecene Is preferred. Further, hexene and octene are particularly preferred because of their good reactivity and low boiling point.

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, divinyltetramethyldisiloxane platinum complex, tetravinyltetramethylcyclotetrasiloxane platinum complex and the like, and the carboxylic acid anhydride of the present invention. From the viewpoints of the transparency of the group-containing cyclic siloxane compound (A) and the transparency of the cured product, hexachloroplatinic acid hexahydrate, divinyltetramethyldisiloxane platinum complex, and tetravinyltetramethylcyclotetrasiloxane platinum complex are preferred.

The catalyst used for the hydrosilylation reaction can be used without a solvent when the catalyst is in a liquid state, but when the catalyst is a solid, it is preferably used in the form of a solution dissolved in a solvent from the viewpoint of workability. Any solvent can be used as long as it dissolves the catalyst. From the viewpoint of solubility and workability, tetrahydrofuran, toluene, ethanol, and isopropanol are preferable.
When used as a solution, the catalyst is adjusted to 0.05 to 50% by mass and added to the reaction solution.
The addition amount of the catalyst is added in the range of 0.1 to 1000 ppm as the platinum amount. From the viewpoint of the transparency of the carboxylic acid anhydride group-containing cyclic siloxane compound (A) and the transparency of the cured product, 1 to 100 ppm of the raw material mass for producing the carboxylic acid anhydride group-containing cyclic siloxane compound (A) is preferable, 2 to 10 ppm is particularly preferable. If the addition amount is less than 0.1 ppm, there is a concern that the addition reaction will be delayed, and if it is more than 1000 ppm, there is a concern that coloring of the carboxylic acid anhydride group-containing cyclic siloxane compound (A) will be serious.

After the hydrosilylation reaction, it can be purified by known methods such as washing with water, 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.

X in Formula (1) contains a carboxylic anhydride group represented by Formula (1), in addition to an organic group containing a carboxylic anhydride group, including a hydrocarbon group having 1 to 20 carbon atoms. From the viewpoint of production stability of the cyclic siloxane compound (A), it is preferable.
In the case of producing a carboxylic acid anhydride group-containing cyclic siloxane compound (A) represented by the formula (1) wherein all X are carboxylic acid anhydride groups, the Si-H group in the hydrogen siloxane compound Thus, it is necessary to charge an olefin compound having a carboxylic acid anhydride group of 1.0 molar equivalent or more. In order to obtain the carboxylic acid anhydride group-containing cyclic siloxane compound (A) with high purity, it is necessary to remove the olefin compound having an excess of carboxylic acid anhydride group, but generally the olefin compound having a carboxylic acid anhydride group. Many have high boiling points, and it is difficult to remove them easily and completely.

From the above, in the method for producing a carboxylic acid anhydride group-containing cyclic siloxane compound (A) of the present invention, it is preferable to go through the following steps.
Step 1) An olefin compound having a carboxylic acid anhydride group and a olefin compound having a carboxylic acid anhydride group with respect to 1 mole of Si-H groups in the hydrogen siloxane compound is 0.2 to 0.9. A step of adding a molar equivalent to cause an addition reaction.
Step 2) A step in which a monoolefin compound is charged in an amount of 1.1 to 20 molar equivalents per 1 mol of the remaining Si—H group.
By doing in this way, even if the olefin compound which has a carboxylic anhydride group is 1.0 mol or less, the compound obtained from the addition of a monoolefin compound to the remaining Si-H group This is to stabilize. Moreover, it becomes possible to suppress a thickening by making a monoolefin compound react in this way.

Specifically, the olefin having 0.2 to 0.9 mole equivalent, more preferably 0.5 to 0.7 mole equivalent of a carboxylic acid anhydride group with respect to the Si-H group in the hydrogen siloxane compound. After the compound is subjected to an addition reaction (step 1), an excess monoolefin compound is added to the remaining Si-H group (step 2), and after the reaction, the excess monoolefin compound is removed under reduced pressure. This is a preferable production method from the viewpoint of ease of production.
The charged amount of the monoolefin compound at this time may be 1.01 molar equivalent or more with respect to the remaining Si-H group, but 1.1 to 20 molar equivalent is the removal of the monoolefin compound after production. From the easiness of, 1.2-5 molar equivalent is further more preferable, and 1.3-2.0 equivalent is especially preferable.

  In X in the formula (1), the average abundance ratio of the organic group containing a carboxylic acid anhydride group and the hydrocarbon group having 1 to 10 carbon atoms is 20% for the organic group containing a carboxylic acid anhydride group. -95 mol% is preferable, 40-80 mol% is more preferable, 50-70 mol% is more preferable. If it is less than 20 mol%, the mechanical strength of the cured product may be inferior, and if it exceeds 95 mol%, it takes a long time for production, which is not industrially preferable.

The carboxylic acid anhydride group-containing cyclic siloxane compound (A) of the present invention functions as an epoxy resin curing agent, and can be used by containing other epoxy resin curing agents.
For example, a carboxylic acid anhydride curing agent, an amine-based curing agent, a phenol-based curing agent, and a polyvalent carboxylic acid resin may be mentioned, among which an acid anhydride-based curing agent and a polyvalent carboxylic acid resin are preferable.
Specifically, the acid anhydride curing agent includes phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydro. Phthalic anhydride, a mixture of 3-methyl-hexahydrophthalic anhydride and 4-methyl-hexahydrophthalic anhydride, tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, norbornane-2,3-dicarboxylic anhydride, Examples thereof include methylnorbornane-2,3-dicarboxylic acid anhydride and 2,4-diethylglutaric acid anhydride. Among these, hexahydrophthalic anhydride and derivatives thereof are preferable.

Next, the polyvalent carboxylic acid resin will be described.
The polycarboxylic acid resin 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. A composition is also included, and in the present invention, they are collectively referred to as a polyvalent carboxylic acid resin.

As the polyvalent carboxylic acid resin, a bi- to hexafunctional carboxylic acid is particularly preferable. (A); a polyhydric alcohol compound containing two or more hydroxyl groups in the molecule; and (b); one or more in the molecule. More preferred are compounds obtained by reaction with compounds containing 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-hydroxyethyl) ) Diols such as 5-ethyl-5-hydroxymethyl-1,3-dioxane , Triols such as glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, 2-hydroxymethyl-1,4-butanediol, tetraols such as pentaerythritol and ditrimethylolpropane, hexa such as dipentaerythritol Examples thereof include 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, 2,4-diethylpentanediol, tricyclodecane dimethanol, 2,2'-bis (4-hydroxycyclohexyl) propane, 2- (1,1-dimethyl-2-hydroxy Compounds such as ethyl) -5-ethyl-5-hydroxymethyl-1,3-dioxane are particularly preferred. 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.
Although the polyhydric alcohol which has a siloxane structure is not specifically limited, For example, the silicone oil represented by a following formula can be used.

In the formula (7), A ₁ represents an alkylene group having 1 to 10 carbon atoms that may be bonded via an ether bond, and A ₂ represents a methyl group or a phenyl group. N is the number of repetitions, which means an average value, and is 1 to 100.

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.
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.

  The polycarboxylic acid resin thus obtained is particularly preferably a compound represented by the following formula (8).

In Formula (8), a plurality of A ₃ represent at least one of a hydrogen atom, a methyl group, and a carboxyl group. A ₄ is a polyhydric alcohol compound from 2-20 chain atoms, and a cyclic aliphatic group containing two or more hydroxyl groups in the molecule. m is 2-4.

  The content of the carboxylic acid anhydride group-containing cyclic siloxane compound (A) in the epoxy resin curing agent containing the carboxylic acid anhydride group-containing cyclic siloxane compound (A) is preferably 10% by mass or more, and more preferably 15% by mass or more. More preferred is 20% by mass or more. If the content is less than 10% by mass, the mechanical strength of the cured product may be inferior.

  The compounding amount of the epoxy resin curing agent containing the carboxylic acid anhydride group-containing cyclic siloxane compound (A) is a functional group (acid anhydride curing) having reactivity with the epoxy group with respect to 1 mol in total of all epoxy groups. In the case of an agent, the amount of the acid anhydride group represented by -CO-O-CO-) 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 comprises an epoxy resin curing agent containing a carboxylic acid anhydride group-containing cyclic siloxane compound (A) and / or a carboxylic acid anhydride group-containing cyclic siloxane compound (A), and an epoxy resin (B). Containing.
The epoxy resin (B) includes an epoxy resin that is a glycidyl etherified product of a phenol compound, an epoxy resin that is a glycidyl etherified product of various novolak resins, an alicyclic epoxy resin, an aliphatic epoxy resin, a heterocyclic epoxy resin, and glycidyl. Ester epoxy resins, glycidyl amine epoxy resins, epoxy resins obtained by glycidylation of halogenated phenols, copolymers of polymerizable unsaturated compounds with epoxy groups and other polymerizable unsaturated compounds, epoxy groups Examples thereof include condensates of silicon compounds having other and 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 glycidylating halogenated phenols include brominated bisphenol A, brominated bisphenol F, brominated bisphenol S, brominated phenol novolac, brominated cresol novolac, chlorinated bisphenol S, chlorinated bisphenol A, and the like. An epoxy resin obtained by glycidylating any of the halogenated phenols.

  Examples of the copolymer of the polymerizable unsaturated compound having an epoxy group and other polymerizable unsaturated compound include Marproof G-0115S, G-0130S, G- 0250S, G-1010S, G-0150M, G-2050M (manufactured by NOF Corporation), and the like. Examples of the polymerizable unsaturated compound having an epoxy group include glycidyl acrylate, glycidyl methacrylate, Examples include 4-vinyl-1-cyclohexene-1,2-epoxide. 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 resin containing a silicone skeleton (Si-O skeleton) and two or more epoxy groups in the molecule.

Among the epoxy resins, a silicone-modified epoxy resin represented by the following formula (6) is preferable because of excellent transparency of the cured product.

In formula (6), R < ¹ >, n represents the same meaning as the above, Y represents a C1-C10 hydrocarbon group or an epoxy group containing organic group, respectively. In formula (6), a plurality of R ¹ and Y may be the same or different. However, in the plurality of Y, two or more are organic groups of an organic group containing an epoxy group.

In formula (6), the organic group in Y represents a compound composed of C, H, N, and O atoms, and specific examples of the epoxy group-containing organic group include 2,3-epoxycyclohexylethyl group, 3- A glycidoxypropyl group is mentioned, and 2,3-epoxycyclohexylethyl group is preferable from the viewpoint of heat-resistant transparency of the cured product. 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 10 carbon atoms in Y include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a cyclohexyl group, Examples include norbornanyl group, cyclohexaneethyl group, norbornaneethyl group, phenyl group, ethylbenzene group, etc., but from the viewpoint of heat resistance and transparency of the cured product, methyl group and phenyl group are preferable, and from the viewpoint of heat resistance and transparency of the cured product. A methyl group and a phenyl group are preferred.

  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, an alicyclic epoxy resin, a condensate of a silicon compound having an epoxy group and another silicon compound, represented by formula (6) The combined use of a silicone-modified epoxy resin having a cyclic siloxane skeleton is preferred. Among these, a compound having an epoxycyclohexane structure in the skeleton is preferable.

  In the epoxy resin composition of the present invention, when a silicone-modified epoxy resin having a cyclic siloxane skeleton represented by the formula (6) is used, it is preferably used in an amount of 30% by mass or more, more preferably 50% by mass or more. It is particularly preferable to use 70% by mass or more. Although the epoxy resin composition containing the silicone-modified epoxy resin having a cyclic siloxane skeleton represented by the formula (6) has a high viscosity increase rate, the carboxylic acid anhydride group-containing cyclic siloxane represented by the formula (1) of the present invention It becomes possible to suppress thickening by setting it as a composition with a compound. At this time, by adding 0.2 or more of the carboxylic acid anhydride group-containing cyclic siloxane compound represented by the formula (1) by mass ratio with respect to the silicone-modified epoxy resin having a cyclic siloxane skeleton, thickening is effectively performed. It becomes possible to suppress.

The epoxy resin composition can be obtained by uniformly mixing the carboxylic acid anhydride group-containing cyclic siloxane compound (A) and the epoxy resin (B) at room temperature or under heating. For example, mix thoroughly until uniform using a cartridge case, extruder, kneader, three rolls, universal mixer, planetary mixer, homomixer, homodisper, bead mill, etc., and if necessary, filter with SUS mesh etc. It is prepared by doing.
When preparing, you may mix together the other epoxy resin hardening | curing agent mentioned above, the epoxy resin hardening accelerator (C) mentioned later, an adhesion assistant, antioxidant, a light stabilizer, etc. together.

  When the epoxy resin composition of the present invention is used as an LED sealing material, the viscosity is preferably 500 to 10,000 mPa · s, more preferably 1000 to 4000 mPa · s at 25 ° C. When the viscosity at 25 ° C. is less than 500 mPa · s, the phosphor used by mixing with the white LED encapsulant may precipitate in a short time, while when larger than 10000 mPa · s, the size is particularly large. There may be a problem in workability when casting small packages.

The epoxy resin composition of the present invention preferably further contains an epoxy resin curing accelerator (C).
As the epoxy resin curing accelerator (C), any of those capable of accelerating the curing reaction of the carboxylic anhydride group-containing cyclic siloxane compound (A) of the present invention and the epoxy resin (B) can be used. Examples of epoxy resin curing accelerators (C) that can be used include ammonium salt curing accelerators, phosphonium salt curing accelerators, metal soap curing accelerators, imidazole curing accelerators, and amine curing accelerators. Phosphine-based curing accelerators, phosphite-based curing accelerators, Lewis acid-based curing accelerators, and the like.
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, the metal soap curing accelerator is excellent, and among the metal soap curing accelerators, a zinc carboxylate compound is particularly preferable from the viewpoint of transparency of the cured product.
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.
Carbons such as zinc stearate, zinc montanate, zinc behenate, zinc laurate, zinc undecylenate, zinc ricinoleate, zinc myristate, and zinc palmitate are used to obtain cured products with excellent transparency and sulfidation resistance. A zinc salt composed of a monocarboxylic acid compound having 10 to 30 carbon atoms and having a hydroxyl group such as zinc carbonate having several tens to thirty or 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 an application that needs to be liquid at room temperature (25 ° C.), when a solid compound is used as a curing accelerator at room temperature (25 ° C.), the resin is previously added to the resin. It can also be used after being dissolved. Further, it is also possible to use a solid compound dispersed in a resin at room temperature (25 ° C.).

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 weight part normally in the epoxy resin composition of this invention, Preferably 0.1-10 weight part 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. The content of these inorganic fillers is 0 to 95% by weight in the epoxy resin composition of the present invention.

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, the product made from ADEKA, 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 weight of the epoxy resin composition of the present invention. 0.005 to 5.0% by weight.

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 weight, preferably 0.05 to 20 parts per 100 parts by weight of the resin component. Part by weight 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. The content of these inorganic fillers is 0 to 95% by weight in the curable resin composition of the present invention. 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 is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone to obtain a curable resin composition varnish, and glass Curing of the curable resin composition of the present invention by hot press molding a prepreg obtained by impregnating a substrate such as fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. and drying by heating. It can be a thing. The solvent used here is usually 10 to 70% by weight, preferably 15 to 70% by weight 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.

Other uses of optical materials include general uses in which curable resin compositions are used, such as adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), insulation. In addition to materials (including printed circuit boards, wire coatings, etc.), sealants, additives to other resins, and the like. 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.

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.
○ GPC: Gel permeation chromatography (GPC) was measured under the following conditions.
Equipment manufacturer: Waters column: SHODEX GPC LF-G (guard column), KF-603, KF-602.5, KF-602, KF-601 (2)
Flow rate: 0.4 ml / min.
Column temperature: 40 ° C
Solvent: 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 and dissolved in 40 ml of methanol (special grade reagent), and then stirred at 20 to 28 ° C. for 60 minutes to obtain a measurement sample. The measurement sample was titrated with a 0.1N sodium hydroxide solution using a titrator AT-610 manufactured by Kyoto Electronics Industry Co., Ltd., and the value obtained as the acid value was calculated as the functional group equivalent.
○ Melting point using DSC:
It was measured by the method described in JIS K7121, and the peak of the melting peak was defined as the melting point.
Viscosity: Measured at 25 ° C. using an E-type viscometer (TV-20) manufactured by Toki Sangyo Co.
○ Decrease in thermal weight: Using a TG / DTA6200 manufactured by Shimadzu Corporation, the temperature was increased from 30 ° C. at 20 ° C./min. . During the measurement, air was flowed at 200 ml / min.
LC-MS: Liquid chromatography-mass spectrum (LC-MS) was measured under the following conditions after pre-measurement of the measurement sample.
Pretreatment for measurement: 5 mg of a measurement sample was dissolved in 2 mL of ethanol and heated at 70 ° C. for 2 hours.
Equipment manufacturer: Waters Column: BEH Shield RP18
Oven: 40 ° C
Mobile phase: 5 mM ammonium acetate / acetonitrile flow rate: 0.25 ml / min.
Detector: PDA 254 nm, ESI ± (Mass Range 50-2000)
○ ¹ H-NMR: Japan using electronic Ltd. JNM-ECS400, was measured in deuterated chloroform solvent (0.03% by volume tetramethyl silane-containing).
○ Epoxy equivalent: Measured by the method described in JIS K7236.

Example 1 Production of Cyclic Siloxane Compound (A-1) Containing Carboxylic Anhydride Group 20.6 g (0.125 mol) of norbornene dicarboxylic anhydride and divinyl were added to a glass 300 ml four-necked flask while purging with nitrogen. 40 mg of xylene solution of tetramethyldisiloxane-platinum complex (platinum content 2 mass%) and 50 g of toluene were 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 set to 70-80 ° C., and 12.0 g (0.050 mol) of tetramethylcyclotetrasiloxane was added dropwise over 30 minutes.
After the dropping, the internal temperature was kept at 75-80 ° C. and stirred for 5 hours, and then stirred at an internal temperature of 100 ° C. for 5 hours and further at an internal temperature of 120 ° C. for 4 hours. Further, 100 mg of a xylene solution of divinyltetramethyldisiloxane-platinum complex (platinum content 2 mass%) was added, and the mixture was stirred at an internal temperature of 100 ° C. for 8 hours.
After allowing the internal temperature to cool to 50 ° C., 11.4 g (0.135 mol) of hexene was added dropwise over 50 minutes, followed by stirring and reaction for 12 hours.
After the reaction, 3.5 g of activated carbon (CP made by Ajinomoto Fine Techno) was added, and the mixture was stirred at room temperature for 4 hours and filtered. By distilling off the organic solvent in the obtained filtrate, 33.8 g of a carboxylic acid anhydride group-containing cyclic siloxane compound (A-1) having the following formulas (9) and (10) as main components was obtained.
The obtained compound had a GPC purity (GPC area%) of 89%, a functional group equivalent of 178 mgKOH / g, and a white solid in appearance. The melting point (peak peak value) using DSC was 47.6 ° C., and the thermal weight loss was −0.8%. As a result of LC-MS analysis, the peak area ratio of the compound represented by the formula (9) was 44%, the peak area ratio of the compound represented by the formula (10) was 53%, and the formula (11) The peak area ratio of the obtained compound was 3%. A ¹ H-NMR spectrum of the obtained compound is shown in FIG. 1, and a GPC chart is shown in FIG.

Example 2: Production of an epoxy resin curing agent (A-2) containing a carboxylic acid anhydride group-containing cyclic siloxane compound (A-1)
In a glass 30 ml bottle, 3 g of the carboxylic acid anhydride group-containing cyclic siloxane compound (A-1) obtained in Example 1 and 7 g of Ricacid MH-T (4-methylhexahydrophthalic acid manufactured by Shikoku Kasei Kogyo) were charged. A rotor coated with PTFE (polytetrafluoroethylene) was placed, and the mixture was placed on a hot plate with a magnetic stirrer heated to 100 ° C. and stirred while heating. When stirred for 4 hours, A-1 was completely dissolved in Ricacid MH-T, and 10 g of an epoxy resin curing agent (A-2) containing a carboxylic acid anhydride group-containing cyclic siloxane compound (A-1) was obtained. It was. The appearance of A-2 was a colorless transparent liquid, the functional group equivalent was 282 mgKOH / g, the viscosity was 400 mPa · s, and the thermal weight loss was −23.8%.

Example 3 Production of an epoxy resin curing agent (A-3) containing a carboxylic anhydride group-containing cyclic siloxane compound (A-1)
In a glass 30 ml bottle, 4 g of the carboxylic acid anhydride group-containing cyclic siloxane compound (A-1) obtained in Example 1 and 6 g of Ricacid MH-T (4-methylhexahydrophthalic acid manufactured by Shikoku Kasei Kogyo) were charged. A rotor coated with PTFE (polytetrafluoroethylene) was placed, and the mixture was placed on a hot plate with a magnetic stirrer heated to 100 ° C. and stirred while heating. When stirred for 4 hours, A-1 was completely dissolved in Ricacid MH-T, and 10 g of an epoxy resin curing agent (A-3) containing a carboxylic acid anhydride group-containing cyclic siloxane compound (A-1) was obtained. It was. The appearance of A-3 was a colorless transparent liquid, the functional group equivalent was 273 mgKOH / g, the viscosity was 1045 mPa · s, and the thermal weight loss was −23.3%.

Example 4 Production of Epoxy Resin Curing Agent (A-4) Containing Carboxylic Anhydride Group-Containing Cyclic Siloxane Compound (A-1)
A glass 30 ml bottle was charged with 5 g of the carboxylic acid anhydride group-containing cyclic siloxane compound (A-1) obtained in Example 1 and 5 g of Ricacid MH-T (4-methylhexahydrophthalic acid manufactured by Shikoku Kasei Kogyo). A rotor coated with PTFE (polytetrafluoroethylene) was placed, and the mixture was placed on a hot plate with a magnetic stirrer heated to 100 ° C. and stirred while heating. When stirred as it is for 4 hours, A-1 completely dissolves in Ricacid MH-T, and 10 g of an epoxy resin curing agent (A-4) containing a carboxylic acid anhydride group-containing cyclic siloxane compound (A-1) is obtained. It was. The appearance of A-4 was a colorless transparent liquid, the functional group equivalent was 256 mgKOH / g, the viscosity was 3052 mPa · s, and the thermal weight loss was −22.6%.

Example 5 Production of Cyclic Siloxane Compound (A-5) Containing Carboxylic Anhydride Group A glass 200 ml four-necked flask was charged with 8.8 g (0.063 mol) of allyl succinic anhydride and divinyltetra with a nitrogen purge. A methyldisiloxane-platinum complex xylene solution (platinum content 2 mass%) 20 mg and toluene 25 g were 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 100 ° C., and 6.0 g (0.025 mol) of tetramethylcyclotetrasiloxane was added dropwise over 40 minutes.
After dropping, the inner temperature was kept at 90-100 ° C. and stirred for 9 hours, and then 20 mg of xylene solution (platinum content 2% by mass) of divinyltetramethyldisiloxane-platinum complex was added, and the inner temperature was 90-100 ° C. For 3 hours.
After allowing the internal temperature to cool to 50 ° C., 5.7 g (0.068 mol) of hexene was added dropwise over 40 minutes, and the reaction was stirred for 3.5 hours after the addition.
After the reaction, 2.0 g of activated carbon (CP made by Ajinomoto Fine Techno) was added, and the mixture was stirred at room temperature for 3 hours and filtered. By distilling off the organic solvent in the obtained filtrate, 16.2 g of a carboxylic acid anhydride group-containing cyclic siloxane compound (A-5) having the following formulas (12) and (13) as main components was obtained.
The obtained compound had a GPC purity (GPC area%) of 92%, a functional group equivalent of 256 mgKOH / g, and an appearance of a pale yellow viscous liquid. The thermogravimetric decrease was -0.9%. As a result of LC-MS analysis, the peak area ratio of the compound represented by formula (12) was 32%, the peak area ratio of the compound represented by formula (13) was 49%, and represented by formula (14). The peak area ratio of the obtained compound was 19%. A ¹ H-NMR spectrum of the obtained compound is shown in FIG. 3, and a GPC chart is shown in FIG.

Comparative Example 1 Production of Epoxy Resin Curing Agent (CA-2) Containing Polyvalent Carboxylic Acid (CA-1) 41.2 g of Tricyclodecane Dimethanol and Ricacid 182.5 g of MH-T (4-methylhexahydrophthalic anhydride manufactured by Shikoku Kasei Kogyo) 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 50 ° C., and the reaction was allowed to proceed for 4 hours. The epoxy resin of the comparative example which is a mixture of polycarboxylic acid (CA-1) and a carboxylic acid anhydride compound represented by the following formula (15) after confirming a peak of 1 area% or less of tricyclodecane dimethanol by GPC 223 g of a curing agent (CA-2) was obtained. The resulting mixture was a colorless and transparent liquid, and the functional group equivalent was 294 g / eq thermal weight loss of -25.5%, but the viscosity was too high to be measured.

(Evaluation test)
Examples 1 to 5, Comparative Example 1 and Comparative Example A as 4-methylhexahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd., Ricacid MH-T), content of each component, functional group equivalent, viscosity, melting point Table 1 summarizes the measurement results of thermal weight loss.

As is apparent from the results in Table 1, the epoxy resin curing agent (A-2 to A-4) containing the carboxylic acid anhydride group-containing cyclic siloxane compound (A-1) has a small weight loss upon heating. The epoxy resin curing agent containing the polyvalent carboxylic acid of Comparative Example 1 has a small weight loss during heating, but the viscosity at 25 ° C. is too high, whereas the viscosity at ° C. is excellent in workability. Inferior workability. Further, 4-methylhexahydrophthalic anhydride of Comparative Example A has a large weight loss. From the above, the epoxy resin curing agent (A-2 to A-4) containing the carboxylic acid anhydride group-containing cyclic siloxane compound (A-1) is used in liquid form at room temperature (25 ° C.). Suitable for use in required applications.

Synthesis Example 1 Production Example of Silicone Modified Epoxy Resin Having Four Epoxy Groups in the Molecule In a 200 ml glass four-necked flask, 33 g of 4-vinyl-1,2-epoxycyclohexane, 1% hexachloroplatinic acid, hexahydrate A 0.03 g 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 g of 1,3,5,7-tetramethyltetracyclosiloxane was added dropwise over 1 hour, and the reaction was allowed to proceed for 1 hour.
Cyclic siloxane having four epoxy groups in the molecule by concentrating under reduced pressure at 110 ° C. while blowing nitrogen gas into the resulting reaction solution to remove tetrahydrofuran and excess 4-vinyl-1,2-epoxycyclohexane. 36 g of compound (B-1) was 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 6: Preparation of epoxy resin composition Epoxy resin curing agent (A-2) obtained in Example 2, silicone-modified epoxy resin (B-1) obtained in Synthesis Example 1 as an epoxy resin, curing accelerator As a U-CAT5003 (manufactured by San Apro, quaternary phosphonium bromide salt) and as an antioxidant, AO-60 (made by ADEKA, hindered phenol antioxidant) are put in a polypropylene container in the quantity ratio shown in Table 2 below. , Mixing and defoaming for 5 minutes to obtain an epoxy resin composition of the present invention.

Example 7: Preparation of epoxy resin composition Example 6 except that the epoxy resin curing agent (A-2) of Example 6 was changed to the epoxy resin curing agent (A-3) obtained in Example 3. It carried out similarly and the epoxy resin composition of this invention was obtained.

Example 8: Preparation of epoxy resin composition Example 6 except that the epoxy resin curing agent (A-2) of Example 6 was changed to the epoxy resin curing agent (A-4) obtained in Example 3 It carried out similarly and the epoxy resin composition of this invention was obtained.

Comparative Example 2 Adjustment of Epoxy Resin Composition Epoxy resin curing agent (CA-2) obtained in Comparative Example 1 as an epoxy resin curing agent, and silicone-modified epoxy resin (B-1) obtained in Synthesis Example 1 as an epoxy resin ), U-CAT5003 (manufactured by San Apro, quaternary phosphonium bromide salt) as a curing accelerator, and AO-60 (manufactured by ADEKA, hindered phenol antioxidant) as an antioxidant in the quantitative ratios shown in Table 2 below. It put into the container made from a polypropylene, mixed and deaerated for 5 minutes, and the epoxy resin composition of the comparative example was obtained.

Comparative Example 3: Preparation of epoxy resin composition Ricacid MH-T (manufactured by Shin Nippon Rika Co., Ltd., 4-methylhexahydrophthalic anhydride) as an epoxy resin curing agent, silicone modified epoxy obtained in Synthesis Example 1 as an epoxy resin The resin (B-1), U-CAT5003 (manufactured by San Apro, quaternary phosphonium bromide salt) as a curing accelerator, and AO-60 (manufactured by ADEKA, hindered phenol antioxidant) as an antioxidant are shown in Table 2 below. It put into the container made from a polypropylene by the described quantity ratio, mixed and defoamed for 5 minutes, and obtained the epoxy resin composition of the comparative example.

Example 6-8, blending ratio and viscosity of epoxy resin compositions obtained in Comparative Examples 2 and 3, viscosity increase after standing at 25 ° C. for 5 hours, weight loss at curing, cured product permeability, cured product Table 2 shows the results of the hardness and the presence or absence of gold wire exposure. The test in Table 2 was performed as follows.
Viscosity after adjustment After adjusting the epoxy resin compositions obtained in Examples 6 to 8 and Comparative Examples 2 and 3, using an E-type viscometer (TV-20) manufactured by Toki Sangyo Co., Ltd. within 25 minutes, 25 ° C. Measured with
After leaving the mixture at 25 ° C. for 5 hours, the thickened resin compositions obtained in Examples 6 to 8 and Comparative Examples 2 and 3 were prepared, and then allowed to stand at 25 ° C. for 5 hours. Using a viscometer (TV-20), the viscosity was measured at 25 ° C., and the increase in viscosity from the adjusted viscosity obtained in (1) was calculated.
Weight reduction during curing After the epoxy resin compositions obtained in Examples 6 to 8 and Comparative Examples 2 and 3 were vacuum degassed for 5 minutes, the mass was weighed in advance, 30 mm × 20 mm × height 0. It was gently cast on a glass substrate on which a dam was created with a heat-resistant tape so as to be 8 mm, and the mass after casting was weighed. The casting was cured at 120 ° C. for 3 hours after pre-curing at 120 ° C. for 1 hour, the mass after curing was weighed, and the weight reduction rate during curing of the epoxy resin composition during curing was calculated. .
Cured product transmittance After carrying out the vacuum defoaming for 5 minutes with the epoxy resin compositions obtained in Examples 6 to 8 and Comparative Examples 2 and 3, a dam was formed with a heat-resistant tape so as to be 30 mm × 20 mm × height 0.8 mm The casting was gently performed on the prepared 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 taken out from the glass substrate, and the light transmittance at 450 nm was measured under the following conditions.
<Spectrophotometer measurement conditions>
Manufacturer: Hitachi High-Technologies Corporation Model: U-3300
Slit width: 2.0nm
Scanning speed: 120 nm / min Hardness of cured product The durometer hardness was measured by the method described in JIS K6253.

As is apparent from the results in Table 2, the compositions of Examples 6 to 8 have an appropriate viscosity for use as an LED sealing material, and are excellent in workability because of little viscosity increase after standing at 25 ° C. for 5 hours. . In addition, these cured products had high cured product transmittance and hardness without decreasing the thermogravimetricity at the time of curing, whereas they were cured using CA-2 which is an epoxy resin curing agent containing polyvalent carboxylic acid. Comparative Example 2 had high cured product transmittance and hardness, but in addition to high viscosity after adjustment, the viscosity increased after standing at 25 ° C. for 5 hours was inferior in workability. Further, Comparative Example 3 cured with only 4-methylhexahydrophthalic anhydride had a significant weight loss upon curing. From the above, the epoxy resin composition using the carboxylic anhydride group-containing cyclic siloxane compound of the present invention is particularly suitable as a curable resin composition for optical semiconductor encapsulation.

1 is a ¹ H-NMR spectrum of a carboxylic acid anhydride group-containing cyclic siloxane compound (A-1) obtained in Example 1. 2 is a GPC chart of a carboxylic acid anhydride group-containing cyclic siloxane compound (A-1) obtained in Example 1. 3 is a ¹ H-NMR spectrum of a carboxylic acid anhydride group-containing cyclic siloxane compound (A-5) obtained in Example 5. 4 is a GPC chart of a carboxylic acid anhydride group-containing cyclic siloxane compound (A-5) obtained in Example 5.

Claims (11)

Carboxylic anhydride group-containing cyclic siloxane compound (A) represented by the following formula (1).

(In the formula (1), the ^{R 1} is a hydrocarbon group having 1 to 10 carbon atoms, X is a number from 1 to 20 hydrocarbon group or carboxylic anhydride group-containing organic group having a carbon, n represents an integer of 1 to 3 In the formula (1), a plurality of R ¹ and X may be the same or different from each other, provided that at least two of the plurality of X contain a carboxylic acid anhydride group. Organic group.) The carboxylic acid anhydride group-containing cyclic siloxane compound (A) according to claim 1, wherein the carboxylic acid anhydride group-containing organic group is at least one selected from the following formulas (2) to (5).

(In the formula, * represents bonding to the Si atom of formula (1). R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.) The manufacturing method of the carboxylic acid anhydride group containing cyclic siloxane compound (A) of Claim 1 which passes through the following process.
Step 1) An olefin compound having a carboxylic acid anhydride group and a olefin compound having a carboxylic acid anhydride group with respect to 1 mole of Si-H groups in the hydrogen siloxane compound is 0.2 to 0.9. A step of adding a molar equivalent to cause an addition reaction.
Step 2) A step in which a monoolefin compound is charged in an amount of 1.1 to 20 molar equivalents per 1 mol of the remaining Si—H group. An epoxy resin curing agent containing the carboxylic acid anhydride group-containing cyclic siloxane compound (A) according to claim 1 or 2.   The epoxy resin composition containing the carboxylic acid anhydride group containing cyclic siloxane compound (A) as described in any one of Claim 1 or 2, or the epoxy resin hardening | curing agent of Claim 4, and an epoxy resin (B). object.   The epoxy resin composition according to claim 5, wherein the epoxy resin (B) is a silicone-modified epoxy resin. The epoxy resin composition according to claim 6, wherein the silicone-modified epoxy resin is a compound represented by the following formula (6).

(In Formula (6), R < ¹ >, n represents the same meaning as the above, Y represents a C1-C10 hydrocarbon group or an organic group containing an epoxy group. In Formula (6), multiple R exists. ¹ and Y may be the same as or different from each other, provided that two or more of Y are organic groups of an organic group containing an epoxy group.   Furthermore, the epoxy resin composition as described in any one of Claims 5-7 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 5-8.   The resin composition for optical semiconductor sealing which consists of an epoxy resin composition as described in any one of Claims 5-8.   The optical semiconductor device which sealed the optical semiconductor element with the resin composition for optical semiconductor sealing of Claim 9.

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