WO2011078322A1 - Epoxy resin composition, curable resin composition, and cured object obtained therefrom - Google Patents

Abstract

Disclosed is an epoxy resin composition comprising an epoxy resin obtained by oxidizing an olefin compound represented by formula (1) and an epoxy resin obtained by oxidizing an olefin compound represented by formula (2), wherein the ratio of the epoxy resin derived from the compound of formula (1) to the epoxy resin derived from the compound of formula (2) is 10/90 to 90/10 by weight.

Description

Epoxy resin composition, curable resin composition, and cured product thereof

The present invention relates to an epoxy resin composition suitable for electrical and electronic material applications, particularly for optical semiconductor applications. The present invention also relates to a curable resin composition containing the epoxy resin composition and a cured product thereof. Furthermore, this invention relates to the optical semiconductor device obtained by hardening and sealing with the said curable resin composition.

Epoxy resins are generally cured with various curing agents, resulting in cured products with excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, etc., adhesives, paints, laminates, moldings It is used in a wide range of fields such as materials, casting materials and resists.
Among them, in the field of optoelectronics, especially with the recent advancement of information technology, technology that utilizes optical signals that can smoothly transmit and process huge amounts of information has been developed in place of conventional signal transmission using electrical wiring. Yes. Accordingly, in the field of optical components such as optical waveguides, blue LEDs, and optical semiconductors, development of resins having excellent transparency is desired.

In particular, in the field of optical components such as LED products, a cured product obtained by curing an epoxy resin with a curing agent such as an acid anhydride is often used.
Conventionally, as an epoxy resin used as a sealing material for an optical semiconductor element such as an LED product, a glycidyl ether type typified by a bisphenol A type epoxy resin excellent in balance of heat resistance, transparency and mechanical properties. The epoxy resin composition has been widely used.
However, as a result of the shortening of the emission wavelength of light emitting elements used in LED products (mainly blue emission of 480 nm or less), the sealing material is colored on the LED chip due to the influence of short wavelength light. Problems have been pointed out. When the sealing material is colored, it eventually causes a decrease in illuminance of the LED product.
Therefore, alicyclic epoxy resins represented by 3,4-epoxycyclohexylmethyl-3 ′, 4′epoxycyclohexylcarboxylate are more transparent than glycidyl ether type epoxy resin compositions having an aromatic ring. Therefore, it has been actively studied as an LED sealing material (Patent Documents 1 and 2).

On the other hand, LED products in recent years have been further increased in luminance for lighting, TV backlights, and the like, and have come to generate a lot of heat when the LEDs are turned on. For this reason, even if it is a resin composition which uses this alicyclic epoxy resin, it raise | generates coloring on a LED chip, and it is reported that the illumination intensity fall of an LED product finally arises from this.
Therefore, the alicyclic epoxy resin is required to be improved in terms of durability against light and heat (Patent Document 3).

Japanese Unexamined Patent Publication No. 9-213997 Japanese Patent No. 3618238 International Publication No. 2005/100445

Due to the durability problem of the epoxy resin, a resin having a siloxane skeleton (specifically, a skeleton having a Si—O bond) introduced as a silicone resin or silicone-modified epoxy resin is used as a sealing material. (Patent Document 3).
In general, it is known that a resin having a siloxane skeleton introduced therein is more stable to heat and light than an epoxy resin. Therefore, when applied to the sealing material of LED products, it was said that it was superior to epoxy resin in terms of coloring on the LED chip. However, resins incorporating the siloxane skeleton are inferior in gas permeability resistance compared to epoxy resins. Therefore, when a silicone resin or a silicone-modified epoxy resin is used as the LED sealing material, the color on the LED chip does not matter, but the silver plated on the metal lead frame, which is a component in the LED package. There is a problem that the component (which is silver-plated to increase the reflectance) is discolored or blackened, and ultimately the performance as an LED product is lowered.
Thus, in the market, it is an epoxy resin composition having a structure with no problem in gas permeation resistance, and is more resistant to light and heat than an epoxy resin composition containing a conventional alicyclic epoxy resin. There is a need for epoxy resin compositions that can provide LED products with high durability.

Therefore, in view of the above-mentioned problems of the prior art, an object of the present invention is to provide an epoxy resin composition that provides a cured product having excellent durability against light and heat.

As a result of intensive studies in view of the actual situation as described above, the present inventors have completed the present invention.
That is, the present invention
(1)
An epoxy resin derived from a compound of formula (1) and a formula (2) obtained by oxidizing a mixture of a diolefin compound represented by the following formula (1) and a diolefin compound represented by the following formula (2) An epoxy resin composition characterized in that the ratio of the epoxy resin derived from the compound is 10/90 to 90/10 in weight ratio,

(In the formula, a plurality of R's each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. P represents a cyclohexane ring or a norbornane ring which may have a methyl group as a substituent. Is shown.)

(In the formula, plural Rs each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
(2)
An epoxy resin obtained by oxidizing a diolefin compound represented by the following formula (1):

(In the formula, a plurality of R's each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. P represents a cyclohexane ring or a norbornane ring which may have a methyl group as a substituent. Is shown.)
Epoxy resin obtained by oxidizing the diolefin compound described in the following formula (2)

(In the formula, plural Rs each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
An epoxy resin composition characterized in that the ratio of the epoxy resin derived from the compound of formula (1) and the epoxy resin derived from the compound of formula (2) is 10/90 to 90/10 in weight ratio object,
(3)
The substituent R in the formula (1) and the substituent R in the formula (2) are hydrogen atoms, and the bonding group P is at least one selected from a methylcyclohexane ring, a cyclohexane ring, a methylnorbornane ring, and a norbornane ring. The epoxy resin composition as described in (1) or (2) above,
(4)
The epoxy resin composition according to any one of (1) to (3) above, which is oxidized with hydrogen peroxide,
(5)
A curable resin composition comprising the epoxy resin composition according to any one of (1) to (4) above, a curing agent and / or a curing accelerator,
(6)
The curable resin composition as described in (5) above, wherein the curing agent is an acid anhydride and / or a polycarboxylic acid,

(7)
A cured product obtained by curing the curable resin composition according to (5) or (6),
(8)
An optical semiconductor device obtained by sealing with the curable resin composition according to the above item (5) or (6),
About.

Since the curable resin composition of the present invention is also excellent in resistance to coloring against light and heat, it is extremely useful as an adhesive or sealing material for optical materials, particularly optical semiconductors (LED products, etc.).

Hereinafter, the epoxy resin composition of the present invention will be described.
The epoxy resin composition of the present invention contains, as an essential component, an epoxy resin formed by oxidizing at least two diolefin compounds of the following formulas (1) and (2).

(In the formula, a plurality of R's each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. P represents a cyclohexane ring or a norbornane ring which may have a methyl group as a substituent. Is shown.)
In the formula (1), P means a structure obtained by removing two hydrogen atoms from cyclohexane or norbornane (usually a residue obtained by removing one hydrogen atom from different carbon atoms), and these residues are methyl groups. You may have as a substituent.
Following formula (2)

(In the formula, plural Rs each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

The diolefin compound of the formula (1) can be produced by a known method, and can be obtained, for example, by reacting a dicarboxylic acid form (or a derivative thereof) with a cyclohexene methanol derivative.
Cyclohexene methanol derivatives are not particularly limited, but 3-cyclohexene methanol, 2-methyl-3-cyclohexene-1-methanol, 3-methyl-3-cyclohexene-1-methanol, 3-ethyl- Examples include 3-cyclohexene-1-methanol, 3-methyl-3-cyclohexene-1-methanol, 3-cyclohexyl-3-cyclohexene-1-methanol, and 3-cyclohexenemethanol is preferred. These may be used alone or in combination of two or more.

Dicarboxylic acid compounds (or their derivatives) include cyclohexane-1,2-dicarboxylic acid, cyclohexane-1,2-dicarboxylic anhydride, cyclohexane-1,2-dicarboxylic acid dimethyl ester, and cyclohexane-1,2-dicarboxylic acid diethyl. Ester, cyclohexane-1,2-dicarboxylic acid dipropyl ester, cyclohexane-1,2-dicarboxylic acid dicyclohexyl ester, cyclohexane-1,2-dicarboxylic acid dichloride, cyclohexane-1,2-dicarboxylic acid dibromide, cyclohexane-1, 3-dicarboxylic acid, cyclohexane-1,3-dicarboxylic acid dimethyl ester, cyclohexane-1,3-dicarboxylic acid diethyl ester, cyclohexane-1,3-dicarboxylic acid dipropyl ester, cyclohexane 1,3-dicarboxylic acid dicyclohexyl ester, cyclohexane-1,3-dicarboxylic acid dichloride, cyclohexane-1,3-dicarboxylic acid dibromide, cyclohexane-1,4-dicarboxylic acid, dimethyl cyclohexane-1,2-dicarboxylate Ester, cyclohexane-1,4-dicarboxylic acid diethyl ester, cyclohexane-1,4-dicarboxylic acid dimethyl ester, cyclohexane-1,4-dicarboxylic acid dipropyl ester, cyclohexane-1,4-dicarboxylic acid dicyclohexyl ester, cyclohexane-1 , 4-dicarboxylic acid dichloride, cyclohexane-1,4-dicarboxylic acid dibromide, hydrogenated nadic acid, hydrogenated nadic acid anhydride, hydrogenated nadic acid dimethyl ester, hydrogenated nadic acid diethyl ester Hydrogenated nadic acid dipropyl ester, hydrogenated nadic acid dicyclohexyl ester, hydrogenated nadic acid dichloride, hydrogenated nadic acid dibromide, hydrogenated methyl nadic acid, hydrogenated methyl nadic acid anhydride, hydrogenated methyl nadic acid dimethyl Ester, Hydrogenated methyl nadic acid diethyl ester, Hydrogenated methyl nadic acid dipropyl ester, Hydrogenated methyl nadic acid dicyclohexyl ester, Hydrogenated methyl nadic acid dichloride, Hydrogenated methyl nadic acid dibromide, Norbornane dicarboxylic acid, Norbornane-2, 5-dicarboxylic acid, norbornane-2,5-dicarboxylic acid dimethyl ester, norbornane-2,5-dicarboxylic acid diethyl ester, norbornane-2,5-dicarboxylic acid dipropyl ester, norbornane-2,5-dicarboxylic acid Acid dicyclohexyl ester, norbornane-2,5-dicarboxylic acid dichloride, norbornane-2,5-dicarboxylic acid dibromide, norbornane-2,6-dicarboxylic acid, norbornane-2,6-dicarboxylic acid dimethyl ester, norbornane-2,6 -Dicarboxylic acid diethyl ester, norbornane-2,6-dicarboxylic acid dipropyl ester, norbornane-2,6-dicarboxylic acid dicyclohexyl ester, norbornane-2,6-dicarboxylic acid dichloride, norbornane-2,6-dicarboxylic acid dibromide, etc. However, it is not limited to these. These may be used alone or in combination of two or more.

A general esterification method can be applied as a reaction of cyclohexene methanol derivative and dicarboxylic acid form (or derivative thereof). Specifically, general esterification reactions can be applied, such as Fischer esterification using acid catalysts, acid halides under basic conditions, alcohol reactions, condensation reactions using various condensing agents (ADVANCED ORGANIC CHEMISTRY) PartB: Reaction and Synthesis p135, 145-147, 151 etc.). Specific examples include esterification reactions between alcohols and carboxylic acids (Tetrahedron vol.36 p.2409 (1980), Tetrahedron Letter p.4475 (1980)), and further ester exchange reactions of carboxylic acid esters ( It can also be produced by using Japanese Unexamined Patent Publication No. 2006-052187).

As the diolefin compound of the formula (1) synthesized in this manner, a compound in which R is either a hydrogen atom or a methyl group in the formula (1) is preferable from the viewpoint of availability. Compounds that are atoms are preferred. Further, P is preferably at least one selected from a methylcyclohexane ring, a cyclohexane ring, a methylnorbornane ring and a norbornane ring, more preferably free of substituents from the viewpoint of availability, and particularly a cyclohexane ring. preferable.

The diolefin compound of the formula (2) can be produced by a known method, for example, dimerization of a cyclohexene aldehyde derivative (Tishenko reaction, patent documents: Japanese Patent Application Publication No. 2003-170059, Japanese Patent Application Publication No. 2004-262871). Obtained by reacting a cyclohexene carboxylic acid derivative with a cyclohexene methanol derivative (reference documents: Tetrahedron vol.36 p.2409 (1980), Tetrahedron Letter p.4475 (1980)) (Methods described in Japanese Unexamined Patent Publication No. 2006-052187) and the like.

Examples of the cyclohexene aldehyde derivative include, but are not limited to, 3-cyclohexene carbaldehyde, 2-methyl-3-cyclohexene carbaldehyde, 4-methyl-3-cyclohexene carbaldehyde and the like. These may be used alone or in combination of two or more.
Specific examples of the cyclohexenecarboxylic acid derivative include cyclohexenecarboxylic acid, methyl cyclohexenecarboxylate, ethyl cyclohexenecarboxylate, propylcyclohexenecarboxylate, butylcyclohexenecarboxylate, hexylcyclohexenecarboxylate, (cyclohexenylmethyl) cyclohexenecarboxylate, and cyclohexenecarboxylate. Octyl acid, cyclohexene carboxylic acid chloride, cyclohexene carboxylic acid bromide, methyl cyclohexene carboxylic acid, methyl methyl cyclohexene carboxylate, ethyl methyl cyclohexene carboxylate, propyl methyl cyclohexene carboxylate, (methyl cyclohexenyl methyl) methyl cyclohexene carboxylate, methyl cyclohexene carboxyl Acid chloride, etc. Including but not limited to. These may be used alone or in combination of two or more.
Moreover, the said compound etc. are mentioned as a cyclohexene methanol derivative.

The epoxy resin composition of the present invention is obtained by oxidizing the mixture of the compounds of the formulas (1) and (2) to epoxidize or separately oxidizing the compounds of the formulas (1) and (2). It can be obtained by mixing the epoxy resin. Examples of the oxidation method include, but are not limited to, a method of oxidizing with a peracid such as peracetic acid, a method of oxidizing with a hydrogen peroxide solution, and a method of oxidizing with air (oxygen).
Specific examples of the epoxidation method with peracid include the methods described in Japanese Patent Publication No. 2007-510772 and Japanese Patent Application Laid-Open No. 2006-52187.
Various methods can be applied to the epoxidation method using hydrogen peroxide solution. Specifically, Japanese Patent Application Laid-Open No. 59-108793, Japanese Patent Application Laid-Open No. 62-234550, Japanese Patent Application Laid-Open No. No. 5-291919, Japanese Patent Application Laid-Open No. 11-349579, Japanese Patent Publication No. 1-33341, Japanese Patent Publication No. 2001-17864, Japanese Patent Publication No. 3-57102, etc. Various methods can be applied.
In the present invention, it is more preferable to use hydrogen peroxide because of the low viscosity of the product.
An example of the epoxidation method using hydrogen peroxide is described below.

First, the diolefin compound of the formula (1) and the diolefin compound of the formula (2) are used alone or as a mixture (hereinafter collectively referred to simply as a diolefin compound), polyacids and quaternary ammonium salts are mixed with an organic solvent, The reaction is carried out in an emulsion state of hydrogen oxide water. A buffer solution can also be used for the reaction.
The polyacid used in the present invention is not particularly limited as long as it is a compound having a polyacid structure, but polyacids containing tungsten or molybdenum are preferable, polyacids containing tungsten are more preferable, and tungstate is particularly preferable.

Specific polyacids include tungsten acids selected from tungstic acid, 12-tungstophosphoric acid, 12-tungstoboric acid, 18-tungstophosphoric acid and 12-tungstosilicic acid, their salts, molybdic acid or phosphomolybdic acid, etc. And molybdenum-based acids selected from the above and their salts.
Examples of the counter cation of these salts include ammonium ions, alkaline earth metal ions, and alkali metal ions.

Specific examples include, but are not limited to, alkaline earth metal ions such as calcium ions and magnesium ions, and alkali metal ions such as sodium ions, potassium ions and cesium ions. Particularly preferred counter cations are sodium ion, potassium ion, calcium ion and ammonium ion.

The amount of polyacid used is 0.5 to 20 mmol, preferably 1.0 to 20 mmol, in terms of metal element (moles of tungsten atoms for tungstic acid and molybdenum atoms for molybdic acid) per mol of diolefin compound. More preferably 2.5 to 15 mmol.

As the quaternary ammonium salt, a quaternary ammonium salt having a total carbon number of 10 or more, preferably 25 to 100, more preferably 25 to 55 can be preferably used, and in particular, the alkyl chain is preferably an aliphatic chain. .
Specifically, tridecanylmethylammonium salt, dilauryldimethylammonium salt, trioctylmethylammonium salt, trialkylmethyl (a mixed type of a compound in which the alkyl group is an octyl group and a compound in which the decanyl group is a compound) ammonium salt, trihexa Examples include decylmethylammonium salt, trimethylstearylammonium salt, tetrapentylammonium salt, cetyltrimethylammonium salt, benzyltributylammonium salt, dicetyldimethylammonium salt, tricetylmethylammonium salt, and di-cured tallow alkyldimethylammonium salt. It is not limited to.

There are no particular limitations on the anion species of these salts, and specific examples include halide ions, nitrate ions, sulfate ions, hydrogen sulfate ions, acetate ions, carbonate ions, etc., but acetate ions are particularly preferred. .
When the number of carbon atoms exceeds 100, the hydrophobicity becomes too strong, and the solubility of the quaternary ammonium salt in the organic layer may deteriorate. When the number of carbon atoms is less than 10, the hydrophilicity is increased, and the compatibility of the quaternary ammonium salt with the organic layer is similarly deteriorated.
The amount of the quaternary ammonium salt used is 0.01 to 10 times equivalent, more preferably 0.05 to 6.0 times equivalent, more preferably 0.05 to 4.5 times the valence of the polyacids used. It is a double equivalent.

For example, since tungstic acid is divalent with H ₂ WO ₄ , the quaternary ammonium carboxylate is 0.02 to 1.6 mol, or 2.2 to 20 mol per mol of tungstic acid. A range is preferred. In addition, since tungstophosphoric acid is trivalent, it is similarly 0.03 to 2.4 mol, or 3.3 to 30 mol, and in the case of silicotungstic acid, it is tetravalent, so 0.04 to 3.2. Mole or 4.4 to 40 mol is preferred.
When the amount of the quaternary ammonium carboxylate is lower than 0.01 times the valence of the polyacids, the epoxidation reaction is difficult to proceed (in some cases, the reaction proceeds faster), and a by-product is produced. The problem is that things are easy to make. When the amount is more than 10 times equivalent, not only is the post-treatment difficult, but there is a function of suppressing the reaction, which is not preferable.

Any known buffer solution can be used as the buffer solution, but an aqueous phosphate solution is preferably used in this reaction. The pH is preferably adjusted between pH 4 and 10, more preferably pH 5-9. When the pH is less than 4, the hydrolysis reaction and polymerization reaction of the epoxy group easily proceed. Moreover, when pH10 is exceeded, reaction will become extremely slow and the problem that reaction time is too long will arise.
In particular, in the present invention, it is preferable to adjust the pH to be between 5 and 9 when the polyacids which are catalysts are dissolved.
For example, in the case of a phosphoric acid-phosphate aqueous solution which is a preferable buffer, 0.1 to 10 mol% equivalent of phosphoric acid (or a phosphate such as sodium dihydrogen phosphate) is used with respect to hydrogen peroxide. And a method of adjusting the pH with a basic compound (for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, etc.).
Here, it is preferable that the pH is added so that the above-mentioned pH is obtained when hydrogen peroxide is added. It is also possible to adjust using sodium dihydrogen phosphate, disodium hydrogen phosphate, or the like. The preferred phosphate concentration is 0.1 to 60% by weight, preferably 1 to 45% by weight.

In this reaction, no buffer solution is used, and disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium phosphate, sodium tripolyphosphate, etc. (or hydrates thereof) are directly added without adjusting pH. It doesn't matter. Since the process is simplified by direct addition, it is preferable. The amount of phosphate used in this case is usually 0.1 to 5 mol% equivalent, preferably 0.2 to 4 mol% equivalent, more preferably 0.3 to 3 mol% equivalent to hydrogen peroxide. is there. In this case, if the amount exceeds 5 mol% equivalent to hydrogen peroxide, pH adjustment is required. If the amount is less than 0.1 mol% equivalent, the resulting hydrolyzate of the epoxy compound tends to proceed or the reaction is slow. The harmful effect of becoming.

This reaction is epoxidized using hydrogen peroxide. As the hydrogen peroxide used in this reaction, an aqueous solution having a hydrogen peroxide concentration of 10 to 40% by weight is preferable because of easy handling. When the concentration exceeds 40% by weight, handling becomes difficult and the decomposition reaction of the produced epoxy resin also tends to proceed.

This reaction uses an organic solvent. The amount of the organic solvent to be used is 0.3 to 10, preferably 0.3 to 5, more preferably 0.5 to 2.5 by weight with respect to the diolefin compound 1 as a reaction substrate. is there. When the weight ratio exceeds 10, the progress of the reaction is extremely slow, which is not preferable. Specific examples of organic solvents that can be used include alkanes such as hexane, cyclohexane, and heptane, aromatic hydrocarbon compounds such as toluene and xylene, and alcohols such as methanol, ethanol, isopropanol, butanol, hexanol, and cyclohexanol. It is done. In some cases, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and anone, ethers such as diethyl ether, tetrahydrofuran and dioxane, ester compounds such as ethyl acetate, butyl acetate and methyl formate, and nitriles such as acetonitrile Compounds and the like can also be used. Particularly preferred solvents are alkanes such as hexane, cyclohexane and heptane, and aromatic hydrocarbon compounds such as toluene and xylene.

As a specific reaction operation method, for example, when the reaction is performed in a batch-type reaction kettle, a diolefin compound, hydrogen peroxide (aqueous solution), polyacids (catalyst), a buffer solution, a quaternary ammonium salt, and an organic solvent are used. In addition, stir in two layers. There is no specific designation for the stirring speed. Since heat is often generated when hydrogen peroxide is added, a method of gradually adding hydrogen peroxide after each component may be added.

At this time, after adjusting the pH by adding a buffer solution (or water and phosphate) and polyacids, a quaternary ammonium salt, an organic solvent, and a diolefin compound were added, and the mixture was stirred in two layers. A technique of dropping hydrogen is used.
Alternatively, while stirring water, an organic solvent, and a diolefin compound, polyacids and phosphoric acid (or phosphate) are added, pH is adjusted, quaternary ammonium salt is added, and the mixture is stirred in two layers. However, a method of dropping hydrogen peroxide may be used.

The reaction temperature is not particularly limited, but is preferably 0 to 90 ° C, more preferably 0 to 75 ° C, particularly preferably 15 ° C to 60 ° C. When the reaction temperature is too high, the hydrolysis reaction tends to proceed, and when the reaction temperature is low, the reaction rate becomes extremely slow.

Although the reaction time depends on the reaction temperature, the amount of catalyst, etc., from the viewpoint of industrial production, a long reaction time is not preferable because it consumes a great deal of energy. A preferred range is 1 to 48 hours, preferably 3 to 36 hours, and more preferably 4 to 24 hours.

After the reaction is complete, quench the excess hydrogen peroxide. The quenching treatment is preferably performed using a basic compound. It is also preferable to use a reducing agent and a basic compound in combination. As a preferred treatment method, there is a method of quenching the remaining hydrogen peroxide using a reducing agent after neutralization adjustment to pH 6 to 10 with a basic compound. When the pH is less than 6, the heat generated when reducing excess hydrogen peroxide is large, which may cause decomposition products.

Examples of the reducing agent include sodium sulfite, sodium thiosulfate, hydrazine, oxalic acid, vitamin C and the like. The reducing agent is used usually in an amount of 0.01 to 20 times mol, more preferably 0.05 to 10 times mol, and still more preferably 0.05 to 3 times mol with respect to the number of moles of excess hydrogen peroxide. is there.
These are preferably added as an aqueous solution, and the concentration thereof is 0.5 to 30% by weight.

Basic compounds include metal hydroxides such as sodium hydroxide, potassium hydroxide, magnesium hydroxide and calcium hydroxide, metal carbonates such as sodium carbonate and potassium carbonate, phosphorus such as sodium phosphate and sodium hydrogen phosphate. Examples thereof include basic solids such as acid salts, ion exchange resins, and alumina.
The amount used is water or organic solvents (for example, aromatic hydrocarbons such as toluene and xylene, ketones such as methyl isobutyl ketone and methyl ethyl ketone, hydrocarbons such as cyclohexane, heptane and octane, methanol, ethanol, isopropyl alcohol, etc. The amount used is usually 0.01 to 20 times mol, more preferably 0.05 to 10 times the number of moles of excess hydrogen peroxide. Mole, more preferably 0.05 to 3 times mole. These may be added as water or a solution of the above-mentioned organic solvent, or may be added alone.
When a solid base that does not dissolve in water or an organic solvent is used, it is preferable to use an amount of 1 to 1000 times by weight with respect to the amount of hydrogen peroxide remaining in the system. More preferably, it is 10 to 500 times, and further preferably 10 to 300 times. In the case of using a solid base that does not dissolve in water or an organic solvent, the treatment may be carried out after separation of an aqueous layer and an organic layer described later.

After the hydrogen peroxide quench (or before quenching), the organic layer and the aqueous layer do not separate, or if the organic solvent is not used, perform the operation by adding the above-mentioned organic solvent and react from the aqueous layer. Extract the product. The organic solvent used at this time is 0.5 to 10 times, preferably 0.5 to 5 times in weight ratio to the raw material diolefin compound. This operation is repeated several times as necessary, and the separated organic layer is purified by washing with water as necessary.
The obtained organic layer may be an ion exchange resin, a metal oxide (especially, silica gel, alumina, etc. are preferred), activated carbon (especially, preferably a chemical activated carbon), a composite metal salt (especially a basic composite metal salt). Are preferably removed), viscosity minerals (especially, lamellar clay minerals such as montmorillonite are preferred), impurities are removed, water washing, filtration and the like are performed, and then the solvent is distilled off to obtain the desired epoxy resin composition. .

The epoxy resin composition of the present invention thus obtained has the following formula (3)

(In the formula, R and P represent the same meaning as in formula (1).)
And the following formula (4)

(In the formula, R represents the same meaning as in formula (2).)
In the total weight, impurities such as an unreacted product, a partially epoxidized product, a hydrolyzate, and a decomposition product of the compound represented by formula (1) or (2) are 15% by weight. % Or less may be present.

These mixtures often become liquid when homogenized. The ratio of the compound of formula (3) (and the impurity derived from the compound of formula (1)) to the compound of formula (4) (and the impurity derived from the compound of formula (2)) is 10 / 90-90 / 10. More preferably, it is 25/75 to 80/20, particularly preferably 25/75 to 60/40, and most preferably 25/75 to 50/50. The epoxy resin composition of the present invention may be constituted by mixing and epoxidizing the compound of the formula (1) and the compound of the formula (2), or the formula (3) obtained by epoxidizing the formula (1). ) And a compound of formula (4) obtained by epoxidizing formula (2) may be mixed. In the former case, in order to obtain such a weight ratio, the compound of the formula (1) and the compound of the formula (2) are usually 10/90 to 90/10, preferably 25/75 to 80/20, particularly preferably 25 / 75 to 60/40, most preferably mixed in the range of 25/75 to 50/50 and oxidized.
By mixing the epoxy compound contained in the epoxy resin composition within the above range, the obtained cured product exhibits an excellent effect in durability against light and heat. In particular, by mixing the compound of the formula (3) and the compound of the formula (4) in the range of 25/75 to 50/50, it is possible to remarkably suppress a decrease in transmittance due to coloring, and an optical semiconductor sealing agent When it is used for the above, a high illuminance retention rate can be achieved.
In the present invention, in view of easy availability, the substituent R is preferably a hydrogen atom or a methyl group, particularly preferably a hydrogen atom, in both the compound of the formula (3) and the compound of (4). . Further, P is preferably at least one selected from a methylcyclohexane ring, a cyclohexane ring, a methylnorbornane ring and a norbornane ring, and more preferably has no substituent from the viewpoint of availability. A ring is particularly preferred.

The curable resin composition of the present invention contains the epoxy resin composition of the present invention, a curing agent and / or a curing accelerator. In the curable resin composition of the present invention, the epoxy resin composition of the present invention can be used alone or in combination with other epoxy resins. When used in combination, the proportion of the epoxy resin composition in all the epoxy resin components is preferably 70% by weight or more, particularly preferably 80% by weight or more.

Other epoxy resins that can be used in the curable resin composition of the present invention include novolac type epoxy resins, bisphenol A type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, phenol aralkyl type epoxy resins, and the like. . Specifically, bisphenol A, bisphenol S, thiodiphenol, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [ 1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetofu Non, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1, Glycidyl ethers derived from polycondensates with 4-bis (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene and the like, modified products thereof, halogenated bisphenols such as tetrabromobisphenol A, and alcohols , Cycloaliphatic epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, silsesquioxane epoxy resin (chain structure, cyclic structure, ladder structure, or a mixed structure of at least two of these) Has a glycidyl group and / or an epoxycyclohexane structure Solid or liquid epoxy resin having an epoxy resin) and the like although not limited thereto.

When using especially the curable resin composition of this invention for an optical use, combined use with an alicyclic epoxy resin or an epoxy resin of a silsesquioxane structure is preferable. Particularly in the case of an alicyclic epoxy resin, a compound having an epoxycyclohexane structure is preferable, and an epoxy resin obtained by an oxidation reaction of a compound having a cyclohexene structure is particularly preferable.
These epoxy resins include esterification reaction of cyclohexene carboxylic acid and alcohols or esterification reaction of cyclohexene methanol and carboxylic acids (Tetrahedron vol.36 p.2409 (1980), Tetrahedron Letter p.4475 (1980), etc.) And a compound obtained by oxidizing a compound that can be produced by a transesterification reaction of a cyclohexene carboxylic acid ester (a method described in Japanese Patent Application Laid-Open No. 2006-052187).
The alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, but ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentane. Diol, 1,6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1.3-propanediol, neopentyl glycol, tricyclodecane dimethanol, norbornenediol, etc. Diols, glycerol, trimethylolethane, trimethylolpropane, trimethylolbutane, triols such as 2-hydroxymethyl-1,4-butanediol, tetraols such as pentaerythritol, ditrimethylolpropane, etc. And the like. Examples of carboxylic acids include, but are not limited to, oxalic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, adipic acid, and cyclohexanedicarboxylic acid.

Furthermore, another example of the compound having an epoxycyclohexane structure in the skeleton is an acetal compound obtained by an acetal reaction between a cyclohexene aldehyde derivative and an alcohol. As a reaction method, it can be produced by applying a general acetalization reaction. For example, a method of carrying out a reaction while azeotropically dehydrating using a solvent such as toluene or xylene as a reaction medium (US Pat. No. 2,945,008), concentrated hydrochloric acid A method in which polyhydric alcohol is dissolved in the mixture and then the reaction is carried out while gradually adding aldehydes (Japanese Patent Laid-Open No. 48-96590), a method using water as a reaction medium (US Pat. No. 3,092,640), reaction A method using an organic solvent as a medium (Japanese Patent Laid-open No. 7-215979), a method using a solid acid catalyst (Japanese Patent Laid-Open No. 2007-230992), and the like are disclosed. A cyclic acetal structure is preferable from the viewpoint of structural stability.

Specific examples of these epoxy resins include ERL-4299 (all trade names, all manufactured by Dow Chemical), Eporide GT401, EHPE3150, EHPE3150CE (all trade names, all manufactured by Daicel Chemical Industries), and dicyclopentadiene diepoxide. However, the present invention is not limited to these (reference document: review epoxy resin basic edition I p76-85).
These may be used alone or in combination of two or more.

Also, silsesquioxane-based epoxy resins (chain, cyclic, ladder, or a mixture of at least two types of siloxane structures having a glycidyl group and / or an epoxycyclohexane structure) such as solid or The liquid epoxy resin is preferably used as long as it does not affect the corrosion gas resistance.

The curable resin composition of the present invention contains a curing agent having reactivity with the epoxy resin component.
Examples of the curing agent include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, and carboxylic acid compounds. Specific examples of the curing agent that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, and nitrogen-containing compounds such as polyamide resins synthesized from ethylenediamine and amine compounds (amines, Amide compound); phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methyl hexahydro Phthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, Cyclohe Acid anhydrides such as sun-1,2,4-tricarboxylic acid-1,2-anhydride, etc .; carboxylic acid resins obtained by addition reaction of various alcohols, carbinol-modified silicones and the aforementioned acid anhydrides; bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5,5'-tetramethyl- [1,1'-biphenyl] -4,4'-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenols (phenol, alkyl-substituted phenol) , Naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphth ) And formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis (chloromethyl) -1,1 Polycondensation with '-biphenyl, 4,4'-bis (methoxymethyl) -1,1'-biphenyl, 1,4'-bis (chloromethyl) benzene, 1,4'-bis (methoxymethyl) benzene, etc. And their modified products, polyphenols such as halogenated bisphenols such as tetrabromobisphenol A, condensates of terpenes and phenols; imidazoles, trifluoroborane-amine complexes, guanidine derivative compounds, etc. Also limited to Not. These may be used alone or in combination of two or more.
In the present invention, compounds having an acid anhydride structure and / or compounds having a carboxylic acid structure represented by the above-mentioned acid anhydrides and carboxylic acid resins are particularly preferable. An acid anhydride can form a cured product having a high hardness, and a compound having a carboxylic acid structure is preferable because it has low volatility. Among them, a compound having an acid anhydride structure and / or a compound having at least one divalent or higher carboxylic acid structure is more preferable, and a mixture of both is particularly preferable.

Examples of the compound having an acid anhydride structure include methyltetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2 , 1] Heptane-2,3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride And particularly preferred are methylhexahydrophthalic anhydride and cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride.

The compound having a carboxylic acid structure (hereinafter referred to as polycarboxylic acid) is particularly preferably a bi- to tetra-functional polycarboxylic acid, and more preferably an addition reaction of a bi- to tetra-functional polyhydric alcohol with an acid anhydride. The polycarboxylic acid obtained by this is preferable.
The bi- to tetrafunctional polyhydric alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, 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, tricyclodecanedi Diols such as methanol, dicyclopentanediene dimethanol, norbornenediol, triols such as glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, 2-hydroxymethyl-1,4-butanediol, pentaerythritol Such as tetraols such as ditrimethylolpropane and the like.
Particularly preferred alcohols include cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecane dimethanol, dicyclopentanediene dimethanol, Branched and cyclic alcohols such as norbornenediol.

Examples of acid anhydrides for producing polycarboxylic acids include methyltetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [ 2,2,1] heptane-2,3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,2,4-tricarboxylic acid-1, 2-Anhydrides are preferred.

The conditions for the addition reaction are not particularly specified. For example, there can be mentioned a method in which an acid anhydride and a polyhydric alcohol are heated and reacted at 40 to 150 ° C. in the absence of a catalyst and in a solvent, and the reaction is taken out after completion of the reaction. .

The acid anhydride and polycarboxylic acid can be used alone or in combination. When used in combination, the weight ratio of the acid anhydride to the polycarboxylic acid is 90/10 to 20/80, particularly preferably 80/20 to 30/70. By setting it as the above range, both heat resistance and workability can be balanced. If the amount of acid anhydride exceeds 90% by weight, volatility increases, which is not preferable.

In the curable resin composition of the present invention, the amount of the curing agent used is preferably 0.5 to 1.5 equivalents in terms of functional group equivalent to 1 equivalent of epoxy group of the epoxy resin component. Preferably, it is 0.7 to 1.1 equivalent, particularly preferably 0.8 to 1.0 equivalent. When used in optical applications, the amount is preferably 1.0 equivalent or less, particularly preferably 0.7 to 0.95 equivalent, more preferably 0.7 to 0.85 equivalent. When less than 0.5 equivalent or more than 1.5 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete and good cured properties may not be obtained.

In the curable resin composition of the present invention, a curing accelerator can be used in combination with a curing agent, or a curing accelerator can be used alone without using a curing agent. Specific examples of the curing accelerator that can be used include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, and 1-benzyl-2-phenylimidazole. 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6 (2′-methyl Imidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-undecylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-ethyl, 4-methylimidazole (1 ')) ethyl-s-triazine, 2,4-diamino 6 (2′-methylimidazole (1 ′)) ethyl-s-triazine isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3 , 5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole imidazoles, and imidazoles and phthalic acid , Salts with polycarboxylic acids such as isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, maleic acid and succinic acid, amides such as dicyandiamide, 1,8-diaza-bicyclo (5.4. 0) Diaza compounds such as undecene-7 and the like Salts such as tetraphenylborate and phenol novolak, salts with the above polycarboxylic acids or phosphinic acids, tetrabutylammonium bromide, cetyltrimethylammonium bromide, trioctylmethylammonium bromide and other ammonium salts, triphenylphosphine, tri ( Toluyl) Phosphines such as phosphine, tetraphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, phosphonium compounds, phenols such as 2,4,6-trisaminomethylphenol, metal compounds such as amine adducts, tin octylate, etc. And a microcapsule type curing accelerator obtained by making these curing accelerators 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. The curing accelerator is usually used in the range of 0.001 to 15 parts by weight with respect to 100 parts by weight of the epoxy resin component.

The curable resin composition of the present invention may contain a phosphorus-containing compound as a flame retardant component. The phosphorus-containing compound may be a reactive type or an additive type. Specific examples of phosphorus-containing compounds include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylylenyl phosphate, 1,3-phenylenebis ( Phosphoric esters such as dixylylenyl phosphate), 1,4-phenylenebis (dixylylenyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate); 9,10-dihydro-9-oxa Phosphanes such as -10-phosphaphenanthrene-10-oxide, 10 (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide; epoxy resin and active hydrogen of the phosphanes Contains phosphorus obtained by reacting with Poxy compounds, red phosphorus and the like can be mentioned. Phosphate esters, phosphanes or phosphorus-containing epoxy compounds are preferable, and 1,3-phenylenebis (dixylylenyl phosphate), 1,4-phenylenebis (dixylylene). Nyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate) or phosphorus-containing epoxy compounds are particularly preferred. The content of the phosphorus-containing compound is preferably phosphorus-containing compound / epoxy resin component = 0.1 to 0.6 (weight ratio). If it is less than 0.1, the flame retardancy is insufficient, and if it exceeds 0.6, there is a concern that it may adversely affect the hygroscopicity and dielectric properties of the cured product.

Furthermore, a binder resin can be blended with the curable resin composition of the present invention as required. 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 within 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 100 parts by weight in total of the epoxy resin component and the curing agent. Is used in an amount of 0.05 to 20 parts by weight as required.

An inorganic filler can be added to the curable resin composition of the present invention as necessary. 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 used in an amount of 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.

When the curable resin composition of the present invention is used for an optical material, particularly an optical semiconductor encapsulant, the particle size of the inorganic filler used is transparent by using a nano-order level filler. It is possible to supplement the mechanical strength and the like without hindering. 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.

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

When the curable resin composition of the present invention is used for an optical material, particularly an optical semiconductor encapsulant, for the purpose of preventing sedimentation of various phosphors upon curing, silica fine powder (also called Aerosil or Aerosol) is used. A thixotropic agent can be added. Examples of such silica fine powder include Aerosil 50, Aerosil 90, Aerosil 130, Aerosil 200, Aerosil 300, Aerosil 380, Aerosil OX50, Aerosil TT600, Aerosil R972, Aerosil R974, AerosilR202, AerosilR202, AerosilR202 Aerosil R805, RY200, RX200 (made by Nippon Aerosil Co., Ltd.), etc. are mentioned.

The curable resin composition of the present invention is an optical material, particularly an optical semiconductor encapsulant, containing an amine compound as a light stabilizer or a phosphorus compound or a phenol compound as an antioxidant for the purpose of preventing coloring. be able to.
Examples of the amine compound include tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) = 1,2,3,4-butanetetracarboxylate, tetrakis (2,2,6,6- Totramethyl-4-piperidyl) = 1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid 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, bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidinyl) ester decanedioate, 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-2 , 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 polymer, 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] heneicosan-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 amine compounds such as benzophenone compounds such as octabenzone, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3) -Tetramethylbutyl) phenol, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimide-methyl) -5-methylphenyl Benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-pentylphenyl) benzotriazole, 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 tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- [ (Hexyl) oxy] triazine compounds such as phenol and the like can be mentioned, 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. For example, TINUVIN765, TINUVIN770DF, TINUVIN144, TINUVIN123, TINUVIN622LD, TINUVIN152, CHIMASSORB944, and 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) Hos 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′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3 ′ -Biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphospho Knight, bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6- Di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) ) -3-phenyl-phenylphosphonite, tetrakis (2,4-di-tert-butyl-5-methylphenyl) -4,4'-biphenylenediphosphonite, tributyl phosphate, trimethyl phosphate, tricresyl phosphate, tri Phenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, etc. And the like.

Commercially available products can also be used as the phosphorus compound. The commercially available phosphorus compounds are not particularly limited. For example, as 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 Adeka tab 522A, Adekas tab 1178, Adekas tab 1500, Adekas tab C, Adekas tab 135A, Adekas tab 3010, and Adekas tab TPP.

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, pentae Srityl-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-butyl) Phenol), 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-pentylphenol, 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.

Commercially available products can also be used as the phenolic compound. The commercially available phenolic compounds are not particularly limited. 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, SUMITOMO CHEMICAL CO., LTD. MDP-S, Sumili zer BBM-S, Sumilizer GM, Sumilizer GS (F), Sumilizer GP, and the like.

In addition, commercially available additives can be used as resin coloring inhibitors. For example, TINUVIN 328, TINUVIN 234, TINUVIN 326, TINUVIN 120, TINUVIN 477, TINUVIN 479, CHIMASSORB 2020FDL, CHIMASSORB 119FL, and the like are 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 0.005 to 5 with respect to the curable resin composition. The range is 0.0% by weight.

When using the curable resin composition of this invention for an optical material, especially an optical semiconductor sealing agent, it is preferable to add a zinc salt and / or a zinc complex for the purpose of stability improvement. The zinc salt is a salt and / or complex having zinc ion as a central element, and preferably has a structure having a phosphate ester or phosphoric acid as a counter ion and / or a ligand.
In particular, zinc salts and / or zinc complexes of phosphoric acid and phosphoric acid esters having 1 to 30 carbon atoms (monoester, diester, triester, or mixtures thereof) are preferred. Specific examples of alkyl of the phosphate ester having 1 to 30 carbon atoms include methyl, isopropyl, butyl, 2-ethylhexyl, octyl, isodecyl, isostearyl, decanyl, cetyl and the like.
In the present invention, a phosphoric acid ester having 3 to 15 carbon atoms is particularly preferred, and the ester may be a mixture or a single product, but the main component is preferably a phosphoric acid monoester. In particular, the molar ratio of monoester, diester and triester in the phosphoric acid ester contained (substitute with the purity of gas chromatography. However, since it is necessary to carry out trimethylsilylation, there is a difference in sensitivity.) In the above, it is preferable that the abundance of the monoester is 50 area% or more at the stage of trimethylation treatment.
Such a phosphoric ester compound can be obtained by esterifying alcohol with phosphorus pentoxide, phosphorus oxychloride, phosphorus trichloride, or the like as a phosphorylating agent. These phosphoric acids can be obtained, for example, by reacting with zinc carbonate, zinc hydroxide, etc. (European Patent Application Publication No. 699708).
As the details of the zinc salt or zinc complex of such a phosphoric ester, the ratio of phosphorus atom to zinc atom (P / Zn) is preferably 1.2 to 2.3, more preferably 1.3 to 2.0. Particularly preferred is 1.4 to 1.9. That is, in a particularly preferable form, phosphoric acid ester (or phosphoric acid) is 1.9 mol or less with respect to 1 mol of zinc ion, and not a simple ionic structure but a structure in which several molecules are involved by ionic bonds or coordinate bonds. The thing which has is preferable.

As such compounds, commercially available products such as zinc carboxylate are Zn-St, Zn-St 602, Zn-St NZ, ZS-3, ZS-6, ZS-8, ZS-8, ZS-7, ZS. -10, ZS-5, ZS-14, ZS-16 (manufactured by Nitto Kasei Kogyo), XK-614 (manufactured by King Industry), 18% octope Zn, 12% octope Zn, 8% octope Zn (manufactured by Hope Pharmaceutical) Examples of the phosphate ester and / or zinc phosphate include LBT-2000B (manufactured by SC Organic Chemical) and XC-9206 (manufactured by King Industry).

Here, the ratio of the epoxy resin component to the zinc salt and / or zinc complex is 0.01 to 8% by weight, more preferably 0.05 to 5% by weight of the zinc salt and / or zinc complex with respect to the epoxy resin component. % By weight, 0.1-4% by weight. When the amount exceeds 8% by weight, the pot life of the curable resin composition becomes a problem. When the amount is less than 0.01% by weight, the effect is not remarkable.

The curable resin composition of the present invention can be obtained by uniformly mixing each component. The curable resin composition of the present invention can be easily made into a cured product by a method similar to a conventionally known method. For example, the curable resin composition of the present invention includes an epoxy resin component, a curing agent and / or a curing accelerator, and a phosphorus-containing compound, a binder resin, an inorganic filler, and a compounding agent that are added as necessary. It can be obtained by mixing well using a kneader, roll or planetary mixer until uniform. Moreover, as a curing means, when the curable resin composition is in a liquid state, potting or casting, impregnating the base material, pouring the curable resin composition into a mold, casting, and curing by heating, or solid In addition, there is a technique in which the material is molded by using a casting after melting or a transfer molding machine and further cured by heating. The curing temperature and time are 80 to 200 ° C. and 2 to 10 hours. As a curing method, it can be hardened at a high temperature at a stretch, but it is preferable to raise the temperature stepwise to advance the curing reaction. Specifically, initial curing is performed at 80 to 150 ° C., and post-curing is performed at 100 to 200 ° C. As the curing stage, the temperature is preferably increased in 2 to 8 stages, more preferably 2 to 4 stages.

In addition, the curable resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. to obtain a curable resin composition varnish, glass fiber, A prepreg obtained by impregnating a base material such as carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. and heat-dried is subjected to hot press molding to obtain a cured product of the curable resin composition of the present invention. can do. In this case, the solvent is used in an amount usually accounting for 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the curable resin composition of the present invention and the solvent. Moreover, the epoxy resin hardened | cured material containing a carbon fiber can also be obtained with a RTM (Resin * Transfer * Molding) system with a liquid composition.

Also, the curable resin composition of the present invention can be used as a film-type sealing composition. Such a film-type resin composition, first, the curable resin composition of the present invention as a curable resin composition varnish as described above, applied to a release film, after removing the solvent under heating, The method of performing B-stage is mentioned, By this, a film type resin composition is obtained as a sheet-like adhesive agent. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like, and a batch film sealing of an optical semiconductor.

The epoxy resin composition of the present invention can also be suitably used as an optical semiconductor sealing material or die bond material.
When the curable resin composition of the present invention is used as a sealing material for an optical semiconductor such as a high-intensity white LED, or a die bond material, the epoxy resin composition of the present invention is used as a curing agent (curing agent composition). A curable resin composition is prepared by thoroughly mixing additives such as an acid anhydride and / or polycarboxylic acid, a curing accelerator, a coupling material, an antioxidant, and a light stabilizer. As a mixing method, a kneader, a three-roll, a universal mixer, a planetary mixer, a homomixer, a homodisper, a bead mill, or the like may be used at room temperature or with heating. The obtained curable resin composition can be used for a sealing material, or both a die-bonding material and a sealing material.

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 periphery of such a semiconductor chip is sealed with a sealing material such as an epoxy resin. The sealing material is used to protect the semiconductor chip from heat and moisture and to play a role of a lens function. The curable resin composition of the present invention can be used as this sealing material or die bond material. From the viewpoint of the process, it is advantageous to use the curable resin composition of the present invention for both the die bond material and the sealing material.

As a method for adhering a semiconductor chip to a substrate using the curable resin composition of the present invention, the curable resin composition of the present invention is applied on the substrate by dispenser, potting or screen printing, and then the curable resin is used. There is a method in which a semiconductor chip is placed on the composition and heat-cured. By this method, the semiconductor chip can be bonded to the substrate. For the heating, methods such as hot air circulation, infrared rays and high frequency can be used.

The heating condition is preferably 80 to 230 ° C. for about 1 minute to 24 hours. 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.

As a molding method of the sealing material, as described above, an injection method in which the sealing material is injected into the mold frame in which the substrate on which the semiconductor chip is fixed is inserted and then heat-cured and then molded, and the sealing material on the mold A compression molding method is used in which a semiconductor chip fixed on a substrate is immersed therein and heat-cured and then released from the mold.
Examples of the injection method include dispenser, transfer molding, injection molding and the like.
For the heating, methods such as hot air circulation, infrared rays and high frequency can be used.
For example, the heating conditions are preferably 80 to 230 ° C. for about 1 minute to 24 hours. 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.

Furthermore, the application of the curable resin composition of the present invention is not limited to the above, and can be applied to general applications in which a curable resin such as an epoxy resin is used. Specifically, adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), insulating materials (including printed circuit boards, wire coatings, etc.), sealing materials, and cyanates for substrates Examples of resin compositions and resist curing agents include additives to other resins such as acrylic ester resins.

Examples of adhesives include civil engineering, architectural, automotive, general office and medical adhesives, as well as 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 and transfer mold sealing used for capacitors, transistors, diodes, light emitting diodes, ICs, LSIs, potting sealings used for COB, COF, TAB, etc. of ICs and LSIs, flip Examples include underfill used for chips and the like, and sealing (including reinforcing underfill) when mounting IC packages such as QFP, BGA, and CSP.

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 that allow light such as visible light, infrared light, ultraviolet light, X-rays, and lasers to pass 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 field of optical recording, VD (video disc), CD / CD-ROM, CD-R / RW, DVD-R / DVD-RAM, MO / MD, PD (phase change disc), disc substrate materials 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 parts. 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 material, ferrule, sealing material, adhesive, 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, and automotive defenses Rusted steel plate, interior panel, interior material, wire harness for protection / bundling, fuel hose, automobile lamp, glass substitute. 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 wire harnesses, 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. The next generation of 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.

EXAMPLES Next, the present invention will be described more specifically with reference to examples. In the following, “parts” is “parts by weight” unless otherwise specified. The present invention is not limited to these examples. In the examples, physical property values were measured by the following methods.
Epoxy equivalent: Measured according to JIS K-7236 Viscosity: Measured using an E-type viscometer at 25 ° C. Gas chromatography (hereinafter GC):
Analysis conditions Separation column: HP5-MS (0.25 mm ID × 15 m, film thickness 0.25 μm)
Column oven temperature: set to an initial temperature of 100 ° C., heated at a rate of 15 ° C. per minute and held at 300 ° C. for 25 minutes.
Carrier gas; helium gel permeation chromatography (hereinafter GPC):
Column: Shodex SYSTEM-21 column (KF-803L, KF-802.5 (× 2), KF-802)
Linked eluent: tetrahydrofuran, flow rate 1 ml / min.
Column temperature: 40 ° C
Detection; UV (254 nm)
Calibration curve: Standard polystyrene from Shodex

Synthesis example 1
A flask equipped with a stirrer, a reflux condenser, a stirrer, and a Dean-Stark tube was purged with nitrogen, and 140 parts of dimethyl 1,4-cyclohexanedicarboxylate (DMCD-pt manufactured by Iwatani Gas Co., Ltd.), 3-cyclohexene-1- 314 parts of methanol and 0.07 part of tetrabutoxytitanium were added, and the reaction was carried out while removing methanol produced by the reaction at 120 ° C. for 1 hour, 150 ° C. for 1 hour, 170 ° C. for 1 hour, and 190 ° C. for 12 hours. After reacting with GC, it was cooled to 50 ° C.
After cooling, 347 parts of toluene was added and homogenized, and then the reaction solution was washed 3 times with 80 parts of a 10 wt% aqueous sodium hydroxide solution, and further washed with water until the wastewater became neutral at 100 parts / time of water. Then, 240 parts of liquid diolefin compound represented by the following formula (5) was obtained by distilling off toluene and unreacted 3-cyclohexene-1-methanol under reduced pressure by heating with a rotary evaporator.
Formula (5)

Synthesis example 2
A flask equipped with a stirrer, reflux condenser, and stirrer is purged with nitrogen, 15 parts of water, 0.95 parts of 12-tungstophosphoric acid, 0.78 parts of disodium hydrogen phosphate, di-cured tallow alkyldimethylammonium acetate 2.7 parts (manufactured by Lion Akzo, 50 wt% hexane solution, Acard 2HT acetate), 180 parts of toluene, 118 parts of the diolefin compound obtained in Synthesis Example 1 were added, and the mixture was stirred again to obtain a liquid in an emulsion state. . The temperature of this solution was raised to 50 ° C., and 70 parts of 35 wt% hydrogen peroxide water was added over 1 hour while stirring vigorously, and the mixture was stirred at 50 ° C. for 13 hours. When the progress of the reaction was confirmed by gas chromatography, the raw material peak disappeared.
Next, after neutralizing with a 1% by weight aqueous sodium hydroxide solution, 25 parts of a 20% by weight aqueous sodium thiosulfate solution was added, stirred for 30 minutes, and allowed to stand. The organic layer separated into two layers was taken out, 20 parts of activated carbon (CP1 manufactured by Ajinomoto Fine Techno) and 20 parts of bentonite (Bengel SH manufactured by Hojun) were added thereto, and the mixture was stirred for 1 hour at room temperature and then filtered. The obtained filtrate was washed with 100 parts of water three times, and toluene was distilled off from the obtained organic layer to obtain 119 parts of a liquid epoxy resin (EP-1) at room temperature. The epoxy equivalent of the obtained epoxy resin was 217 g / eq. Met.

Synthesis example 3
A flask equipped with a stirrer, reflux condenser, and stirrer is purged with nitrogen, 15 parts of water, 1.9 parts of 12-tungstophosphoric acid, 1.6 parts of disodium hydrogen phosphate, di-cured tallow alkyldimethylammonium acetate Add 5.4 parts (50% by weight lion solution manufactured by Lion Akzo, Acquard 2HT acetate), 160 parts of toluene, 110 parts of 3-cyclohexene carboxylic acid 3-cyclohexene methyl ester, did. The temperature of the solution was raised to 50 ° C., and 70 parts of 35 wt% hydrogen peroxide water was added over 1 hour while stirring vigorously, and the mixture was stirred at 50 ° C. for 20 hours. When the progress of the reaction was confirmed by gas chromatography, the raw material peak disappeared.
Next, after neutralizing with a 1% by weight aqueous sodium hydroxide solution, 25 parts of a 20% by weight aqueous sodium thiosulfate solution was added, stirred for 30 minutes, and allowed to stand. The organic layer separated into two layers was taken out, and 40 parts of activated carbon (CP1 manufactured by Ajinomoto Fine-Techno) and 40 parts of bentonite (Bengel SH manufactured by Hojun) were added thereto, stirred at room temperature for 1 hour, and then filtered. The obtained filtrate was washed with 100 parts of water three times, and toluene was distilled off from the obtained organic layer to obtain 110 parts of a liquid epoxy resin (EP-2) at room temperature. The epoxy equivalent of the obtained epoxy resin is 130 g / eq. Met.

Synthesis example 4
A flask equipped with a stirrer, reflux condenser, and stirrer is purged with nitrogen, 10 parts of dicyclopentadiene dimethanol, a mixture of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride (Shin Nippon Rika ( 50 parts of Licacid MH-700 (hereinafter referred to as “anhydride H-1”) was added, and the mixture was stirred at 40 ° C. for 1 hour and 60 ° C. for 1 hour (disappearance of dicyclopentadienedimethanol by GPC) 60 parts of a curing agent composition, which was a mixture of polycarboxylic acid and acid anhydride, was obtained.
The obtained colorless liquid resin had a GPC purity of 51 area% for the structure of polycarboxylic acid and a total amount of methyl hexahydrophthalic anhydride and hexahydrophthalic anhydride of 49 area%. The functional group equivalent was 201 g / eq. Met.
Further, 12 parts of 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride (H-TMAn, hereinafter referred to as H-2, manufactured by Mitsubishi Gas Chemical) was added to the obtained curing agent composition, A uniform curing agent composition (B-1) was obtained. The weight ratio (theoretical value) of the obtained curing agent composition (B-1) was 40.3% for polycarboxylic acid, 48.9% for acid anhydride H-1, and 10 for acid anhydride H-2. 0.7%.

Synthesis example 5
A flask equipped with a stirrer, reflux condenser, and stirrer is purged with nitrogen, 10 parts of dicyclopentadiene dimethanol, a mixture of hexahydrophthalic anhydride and methylhexahydrophthalic anhydride (Shin Nippon Rika ( 50 parts of Licacid MH-700 (hereinafter referred to as “anhydride H-1”) was added, and the mixture was stirred at 40 ° C. for 1 hour and 60 ° C. for 1 hour (disappearance of dicyclopentadienedimethanol by GPC) 60 parts of a curing agent composition, which was a mixture of polycarboxylic acid and acid anhydride, was obtained.
The obtained colorless liquid resin had a GPC purity of 51 area% for the structure of polycarboxylic acid and a total amount of methyl hexahydrophthalic anhydride and hexahydrophthalic anhydride of 49 area%. The functional group equivalent was 201 g / eq. Met.
Furthermore, 6 parts of acid anhydride (H-2) was added to the obtained curing agent composition to obtain a uniform curing agent composition (B-2). The weight ratio (theoretical value) of the obtained curing agent composition (B-2) was 42.6% for polycarboxylic acid, 51.7% for acid anhydride H-1, and 5 for acid anhydride H-2. It was 6%.

Example 1
16 parts of the epoxy resin (EP-1) obtained in Synthesis Example 2 and 24 parts of (EP-2) obtained in Synthesis Example 3 were mixed uniformly to obtain the epoxy resin composition (F-1) of the present invention. Obtained.

Examples 2 and 3 and Comparative Examples 1 to 4
With respect to the obtained epoxy resin composition (F-1) and the epoxy resins (EP-1) and (EP-2), the curing agent composition (B-1) obtained in Synthesis Example 4 and curing acceleration A quaternary phosphonium salt (Hishicolin PX4MP manufactured by Nippon Kagaku Kogyo Co., Ltd., hereinafter referred to as catalyst C-1) was used as an agent, and blended at a blending ratio (parts by weight) shown in Table 1 below, followed by defoaming for 20 minutes. The obtained curable resin composition was vacuum-defoamed for 20 minutes, and then gently cast on a glass substrate on which a dam was created with a heat-resistant tape so as to be 30 mm × 20 mm × height 1 mm. The cast was cured at 120 ° C. for 1 hour after pre-curing at 120 ° C. for 3 hours to obtain a test piece for transmittance having a thickness of 1 mm. About the obtained test piece, it heat-processed at 150 degreeC for 96 hours, and evaluated the degree of coloring by the heat history (The transmittance | permeability retention rate in 400 nm was measured and compared).

From the above results, the curable resin composition using the epoxy resin composition (F-1) of the present invention was mixed with the epoxy resins (EP-1) and (EP-2). The transmittance retention of the level equivalent to or higher than (EP-2) is shown.

Example 4 and Comparative Examples 5 and 6
Obtained in Synthesis Example 4 for the epoxy resin composition (F-1), the epoxy resin (EP-2), and a commercially available alicyclic epoxy resin (Celoxide 2021P, hereinafter referred to as EP-3 manufactured by Daicel Chemical Industries). The curing agent composition (B-1), a quaternary phosphonium salt (C-1) as a curing catalyst, blended at a blending ratio (parts by weight) shown in Table 2 below, and defoamed for 20 minutes ( Table 2 describes the composition). These were filled into a syringe and cast into a 5 mm outer diameter surface mount LED package (inner diameter 4.4 mm, outer wall height 1.25 mm) mounted with a chip having a central emission wave of 465 nm using a precision discharge device. The cast product was put into a heating furnace and cured at 120 ° C. for 1 hour, further at 150 ° C. for 3 hours, and an LED package was prepared. After mounting the LED, the LED was turned on under the following conditions to measure the illuminance, and the results are shown in Table 2.
Detailed lighting conditions Light emission wavelength: 465nm
Drive system: constant current system, 60 mA (light emitting element regulation current is 30 mA)
Driving environment: 85 ° C, 85% RH
Driving time: 200 hours Evaluation: Illuminance retention after lighting for 200 hours

From the above results, the curable resin composition using the epoxy resin composition (F-1) of the present invention can provide a cured product excellent as an LED compared to the epoxy resins (EP-2) and (EP-3). You can see that you can.

Synthesis Example 6
A flask equipped with a stirrer, a reflux condenser, a stirrer, and a Dean-Stark tube was purged with nitrogen, and 140 parts of dimethyl 1,4-cyclohexanedicarboxylate (DMCD-pt manufactured by Iwatani Gas Co., Ltd.), 3-cyclohexene-1- 314 parts of methanol and 0.07 part of tetrabutoxytitanium were added, and the reaction was carried out while removing methanol produced by the reaction at 120 ° C. for 1 hour, 150 ° C. for 1 hour and 170 ° C. for 20 hours. After reacting with GC, it was cooled to 50 ° C.
After cooling, 347 parts of toluene was added and homogenized, and then the reaction solution was washed 3 times with 80 parts of a 10 wt% aqueous sodium hydroxide solution, and further washed with water until the wastewater became neutral at 100 parts / time of water. After that, 5 g of chemical activated carbon (Ajinomoto Fine-Techno ZN1) was added, stirred at room temperature for 1 hour, and then the activated carbon was removed by filtration. The obtained filtrate was heated with a rotary evaporator under reduced pressure, and toluene and unreacted 3-cyclohexene-1-methanol were distilled off to obtain 235 parts of a diolefin compound represented by the above formula (5).

Synthesis example 7
A flask equipped with a stirrer, a reflux condenser and a stirrer was charged with 15 parts of water, 0.95 part of 12-tungstophosphoric acid, 0.78 part of disodium hydrogen phosphate, and trioctylmethylammonium acetate with nitrogen purging. 7 parts (50% by weight xylene solution manufactured by Lion Akzo, TOMAC-50), 170 parts of toluene, 118 parts of the diolefin compound obtained in Synthesis Example 6 were added, and the mixture was stirred again to obtain a liquid in an emulsion state. The temperature of this solution was raised to 50 ° C., and 70 parts of 35 wt% hydrogen peroxide water was added over 1 hour while stirring vigorously, and the mixture was stirred at 50 ° C. for 14 hours.
Then, the pH was adjusted to 10 with a 30 wt% aqueous sodium hydroxide solution, 25 parts of a 20 wt% aqueous sodium thiosulfate solution was added, and the mixture was stirred for 30 minutes and allowed to stand. The organic layer separated into two layers was taken out, 8 parts of activated carbon (CP1 manufactured by Ajinomoto Fine-Techno) and 10 parts of montmorillonite (Kunimine Industries Kunipia F) were added thereto, and the mixture was stirred at room temperature for 3 hours and filtered. The wet cake was washed with 50 parts of toluene and mixed with the previous filtrate. Toluene was distilled off from the obtained filtrate to obtain 120 parts of an epoxy resin (EP-4) that was liquid at room temperature. The epoxy equivalent of the obtained epoxy resin is 212 g / eq. Met.

Synthesis example 8
A flask equipped with a stirrer, a reflux condenser and a stirrer was charged with 15 parts of water, 0.9 parts of 12-tungstophosphoric acid, 1.5 parts of sodium phosphotungstate, 1.6 parts of disodium hydrogen phosphate while purging with nitrogen. Parts, 2.7 parts of trioctylmethylammonium acetate (50% by weight xylene solution from Lion Akzo, TOMAC-50), 160 parts of toluene, 110 parts of 3-cyclohexene methyl ester of 3-cyclohexenecarboxylic acid, and stirring again Thus, a liquid in an emulsion state was obtained. The temperature of this solution was raised to 46 ° C., and 70 parts of 35 wt% aqueous hydrogen peroxide was added over 30 minutes while stirring vigorously, and the mixture was stirred at 46 ° C. for 16 hours. When the progress of the reaction was confirmed by gas chromatography, the raw material peak disappeared.
Subsequently, the pH was adjusted to 10 with a 30 wt% aqueous sodium hydroxide solution, 50 parts of a 10 wt% aqueous sodium thiosulfate solution was added, and the mixture was stirred for 30 minutes and allowed to stand. The organic layer separated into two layers was taken out, and 5 parts of activated carbon (CP1 manufactured by Ajinomoto Fine-Techno) and 10 parts of montmorillonite (Kunimine Industries Kunipia F) were added thereto, followed by stirring at room temperature for 1 hour and filtration. The obtained filtrate was washed with 100 parts of water three times, and toluene was distilled off from the obtained organic layer to obtain 109 parts of a liquid epoxy resin (EP-5) at room temperature. The epoxy equivalent of the obtained epoxy resin is 129 g / eq. Met.

Synthesis Example 9
A flask equipped with a stirrer, a reflux condenser, and a stirrer was purged with nitrogen, and 24 parts of dicyclopentadiene dimethanol, methylhexahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd., Ricacid MH acid anhydride H) -4 parts) and acid anhydride (H-2) 30 parts, and the mixture is heated and stirred at 40 ° C. for 1 hour and 70 ° C. for 1 hour to obtain a mixture of polycarboxylic acid and acid anhydride. 100 parts of a curing agent composition (B-3) was obtained.
The obtained colorless liquid resin had a GPC purity of 55% area for the structure of polycarboxylic acid, 35 area% for acid anhydride (H-3), and 10 area% for acid anhydride (H-2). It was. The functional group equivalent was 178 g / eq. Met.

Synthesis Example 10
A flask equipped with a stirrer, a reflux condenser, and a stirrer is purged with nitrogen while 24 parts of 2,4-diethylpentanediol (Kyowa Hakko Chemical Kyowadiol PD-9), methylhexahydrophthalic anhydride is added. 146 parts (made by Shin Nippon Rika Co., Ltd., called Ricacid MH Acid Anhydride H-3) and 30 parts of acid anhydride (H-2) were added, and the mixture was heated and stirred at 40 ° C. for 1 hour and 70 ° C. for 1 hour. As a result, 200 parts of a curing agent composition (B-4), which was a mixture of polycarboxylic acid and acid anhydride, was obtained.
The obtained colorless liquid resin had a GPC purity of 50% area for the structure of polycarboxylic acid, 40 area% for acid anhydride (H-3), and 10 area% for acid anhydride (H-2). It was. The functional group equivalent was 178 g / eq. Met.

Examples 5 to 8 and Comparative Example 7
The epoxy resin (EP-4) obtained in Synthesis Example 7 and (EP-5) obtained in Synthesis Example 8 were uniformly mixed at the following blending ratios, respectively, to obtain the epoxy resin composition (F-2) of the present invention. ) To (F-5) were obtained. 0.8 mole equivalent of the curing agent composition (B-3) obtained in Synthesis Example 9 with respect to the obtained epoxy resin composition, and an alkyl phosphate zinc catalyst as a curing catalyst (XC-9206 manufactured by King Industry (hereinafter referred to as XC-9206) C-2) using 2000 ppm of resin and blended at a blending ratio (parts by weight) shown in Table 3 below, and defoamed for 20 minutes.The obtained curable resin composition was subjected to vacuum defoaming for 20 minutes. After the implementation, the mold was gently cast on a glass substrate on which a dam was created with a heat-resistant tape so as to be 30 mm × 20 mm × 1 mm in height. Curing was performed for 1 hour to obtain a test piece for transmittance of 1 mm thickness, and the transmittance of each cured product at 400 nm was compared. Arrival by history And evaluate the degree of (and the retention of transmittance was measured compared in 400 nm).

Examples 9-15
The epoxy resin (EP-4) obtained in Synthesis Example 7 and (EP-5) obtained in Synthesis Example 8 were uniformly mixed at the following blending ratios, respectively, to obtain the epoxy resin composition (F-6) of the present invention. ) To (F-8) were obtained. For these epoxy resin compositions obtained, the curing agent compositions (B-3) and (B-4) obtained in Synthesis Examples 9 and 10 were used as curing catalysts for quaternary phosphonium salts (C-1) and alkyl phosphate esters. Zinc (C-2), octyl phosphate ester (Hope Pharmaceutical Octopus Zn, hereinafter referred to as C-3), phosphorus compound (Sanko Co., Ltd., HCA, hereinafter referred to as C-4) as an additive, phosphorus compound (ADEKA 260 manufactured by ADEKA) , Hereinafter referred to as C-5), hindered amine (Adeka LA-62, hereinafter referred to as C-6), blended at the blending ratio (parts by weight) shown in Table 4 below, and defoamed for 20 minutes (The composition is described in Table 4). These were filled into a syringe and cast into a 5 mm outer diameter surface mount LED package (inner diameter 4.4 mm, outer wall height 1.25 mm) mounted with a chip having a central emission wave of 465 nm using a precision discharge device. The cast product was put into a heating furnace and cured at 110 ° C. for 2 hours and further at 150 ° C. for 3 hours to prepare an LED package. After mounting the LED, the LED was turned on under the following conditions to measure the illuminance. The results are shown in Table 4.
Detailed lighting conditions Light emission wavelength: 465nm
Drive system: constant current system, 60 mA (light emitting element regulation current is 30 mA)
Driving environment: 85 ° C, 85% RH
Driving time: 400 hours Evaluation: Illuminance retention after lighting for 200 hours and 400 hours

From the above results, it can be seen that the epoxy resin composition of the present invention is excellent in optical properties (illuminance retention) and can provide a cured product useful as an LED.

Although the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application (Japanese Patent Application No. 2009-293479) filed on December 24, 2009, which is incorporated by reference in its entirety. Also, all references cited herein are incorporated as a whole.

Claims (8)

1. An epoxy resin derived from a compound of formula (1) and a formula (2) obtained by oxidizing a mixture of a diolefin compound represented by the following formula (1) and a diolefin compound represented by the following formula (2) An epoxy resin composition characterized in that the ratio of the epoxy resin derived from the compound is 10/90 to 90/10 by weight.
   

   

   (In the formula, a plurality of R's each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. P represents a cyclohexane ring or a norbornane ring which may have a methyl group as a substituent. Is shown.)
   

   

   (In the formula, plural Rs each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
2. An epoxy resin obtained by oxidizing a diolefin compound represented by the following formula (1):
   

   

   (In the formula, a plurality of R's each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. P represents a cyclohexane ring or a norbornane ring which may have a methyl group as a substituent. Is shown.)
   Epoxy resin obtained by oxidizing the diolefin compound described in the following formula (2)
   

   

   (In the formula, plural Rs each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
   An epoxy resin composition characterized in that the ratio of the epoxy resin derived from the compound of formula (1) and the epoxy resin derived from the compound of formula (2) is 10/90 to 90/10 in weight ratio object.
3. The substituent R in the formula (1) and the substituent R in the formula (2) are hydrogen atoms, and the bonding group P is at least one selected from a methylcyclohexane ring, a cyclohexane ring, a methylnorbornane ring, and a norbornane ring. The epoxy resin composition according to claim 1 or 2.
4. The epoxy resin composition according to any one of claims 1 to 3, which is oxidized with hydrogen peroxide.
5. A curable resin composition comprising the epoxy resin composition according to any one of claims 1 to 4 and a curing agent and / or a curing accelerator.
6. The curable resin composition according to claim 5, wherein the curing agent is an acid anhydride and / or a polycarboxylic acid.
7. A cured product obtained by curing the curable resin composition according to any one of claims 5 and 6.
8. An optical semiconductor device obtained by sealing with the curable resin composition according to claim 5.