TWI472548B - An epoxy resin composition, a hardened resin composition, and a cured product thereof - Google Patents

Description

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

The present invention relates to an epoxy resin composition suitable for use in electrical and electronic materials, particularly for use in optical semiconductor applications. Further, the present invention relates to a curable resin composition containing the epoxy resin composition and a cured product thereof. Further, the present invention relates to an optical semiconductor device obtained by curing and sealing with the curable resin composition.

The epoxy resin is cured by various curing agents to obtain a cured product excellent in mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, etc., and is used for an adhesive, a coating material, a laminate, a molding material, and the like. A wide range of fields such as casting materials and resists.

Among them, in the field of optoelectronics, in particular, with the recent high degree of informationization, technology for effectively utilizing optical signals that can smoothly transmit and process huge amounts of information has been developed to replace the previous signal transmission using electrical wiring. Along with this, in the field of optical components such as optical waveguides, blue LEDs, and optical semiconductors, development of resins excellent in transparency is expected.

In particular, in the field of optical parts 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.

Since the epoxy resin used for the sealing material of the optical semiconductor element such as the LED product, the glycidol represented by the bisphenol A type epoxy resin excellent in the balance of heat resistance, transparency, and mechanical properties has been widely used. Ether type epoxy resin composition.

However, the short-wavelength of the light-emitting wavelength of the light-emitting element used in the LED product (mainly blue light emission below 480 nm) results in the fact that the short-wavelength light causes the above-mentioned sealing material to be colored on the LED wafer. problem. If the above sealing material is colored, the illuminance of the LED product is eventually lowered.

Therefore, in terms of transparency, the alicyclic epoxy resin represented by 3,4-epoxycyclohexylcarboxylic acid-3',4'-epoxycyclohexylmethyl ester has a glycidyl ether type having an aromatic ring. Since the epoxy resin composition is excellent, it has been actively studied as an LED sealing material (Patent Documents 1 and 2).

On the other hand, in recent years, LED products have been further developed to be brighter in order to be suitable for illumination or backlights of TVs, so that LEDs are accompanied by more heat generation when they are turned on. Therefore, it has been reported that even if a resin composition using the alicyclic epoxy resin is colored on the LED wafer, the illuminance of the LED product is eventually lowered.

Therefore, the alicyclic epoxy resin needs to be improved in durability against light or heat (Patent Document 3).

Patent Document 1: Japanese Laid-Open Patent Publication No. Hei 9-213997

Patent Document 2: Japanese Patent No. 3618238

Patent Document 3: International Publication No. 2005/100445

Due to the problem of durability of the above-mentioned epoxy resin, a fluorinated alkane skeleton (specifically, a skeleton having Si-O bonds) which is represented by a polyfluorene oxide resin or a polyfluorene-modified epoxy resin or the like is introduced. Resin is used as a sealing material (Patent Document 3).

It is generally known that the resin having a rhodium-oxygen skeleton introduced is more stable to heat and light than an epoxy resin. Therefore, in the case of application to a sealing material for an LED product, from the viewpoint of coloring on the LED wafer, it can be said that the resin into which the azide skeleton is introduced is more excellent in durability than the epoxy resin. However, the resin having a rhodium-oxygen skeleton introduced therein is inferior in gas permeability to an epoxy resin. Therefore, in the case of using a polyoxyxylene resin or a polyoxymethylene-modified epoxy resin as the LED sealing material, although the coloring on the LED wafer is not a problem, there is still a problem that the plating is applied to the LED package. The silver component on the metal lead frame of the component (silver plating for improving the reflectance) discolors or darkens, eventually resulting in a decrease in performance as an LED article.

Thus, on the market, an epoxy resin composition having a structure which is free from the above gas permeation resistance is obtained, and an epoxy resin composition containing a alicyclic epoxy resin is obtained. LED products that are more durable than light and heat.

Accordingly, the present invention has been made in view of the above problems of the prior art, and an object thereof is to provide an epoxy resin composition which can obtain a cured product excellent in durability against light or heat.

The present inventors have diligently studied in view of the above-described actual circumstances, and as a result, have achieved the present invention.

That is, the present invention relates to:

(1)

An epoxy resin composition obtained by oxidizing a mixture of a diene compound represented by the following formula (1) and a diene compound represented by the following formula (2), which is derived from the formula (1) The ratio of the epoxy resin of the compound to the epoxy resin of the compound of the formula (2) is 10/90 to 90/10 by weight.

(wherein a plurality of R independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; and P represents a cyclohexane ring or a norbornane ring which may have a methyl group as a substituent)

(wherein a plurality of R independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms);

(2)

An epoxy resin composition obtained by oxidizing an epoxy resin obtained by oxidation of a diene compound represented by the following formula (1) with a diene compound of the following formula (2) a mixture of the epoxy resin of the compound of the formula (1) and the epoxy resin of the compound of the formula (2) in a weight ratio of 10/90 to 90/10,

(wherein a plurality of R independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; and P represents a cyclohexane ring or a norbornane ring which may have a methyl group as a substituent)

(wherein a plurality of R independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms);

(3)

The epoxy resin composition according to the above item (1) or (2), wherein the substituent R of the formula (1) and the substituent R of the formula (2) are a hydrogen atom, and the linking group P is selected. One or more of a methylcyclohexane ring, a cyclohexane ring, a methylnorbornane ring, and a norbornane ring;

(4)

The epoxy resin composition according to any one of the above items (1) to (3), wherein the oxidation is carried out by using hydrogen peroxide;

(5)

A curable resin composition comprising the epoxy resin composition according to any one of the above items (1) to (4), and a curing agent and/or a curing accelerator;

(6)

The hardenable resin composition according to the above item (5), wherein the hardener is an acid anhydride and/or a polycarboxylic acid;

(7)

A cured product obtained by hardening the curable resin composition of the above item (5) or (6);

(8)

An optical semiconductor device obtained by sealing with the curable resin composition of the above item (5) or (6).

Since the curable resin composition of the present invention is excellent in light resistance to light and heat, it is extremely useful as an optical material, particularly as an adhesive material or a sealing material for an optical semiconductor (such as an LED product).

Hereinafter, the curable resin composition of the present invention will be disclosed.

The epoxy resin composition of the present invention contains at least an epoxy resin obtained by oxidizing two kinds of diene compounds of the following formulas (1) and (2) as an essential component.

(In the formula, a plurality of R each independently represent 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.)

Further, P in the formula (1) means a structure obtained by removing two hydrogen atoms from cyclohexane or norbornane (usually a residue obtained by removing one hydrogen atom from each of different carbon atoms) The residues may also have a methyl group as a substituent.

The following formula (2)

(In the formula, a plurality of R independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

The diene compound of the above formula (1) can be produced by a known method, for example, by reacting a dicarboxylic acid (or a derivative thereof) with a cyclohexene methanol derivative.

The cyclohexene methanol derivative is not particularly limited, and examples thereof include 3-cyclohexenemethanol, 2-methyl-3-cyclohexene-1-methanol, and 3-methyl-3-cyclohexene-1. -methanol, 3-ethyl-3-cyclohexene-1-methanol, 3-methyl-3-cyclohexene-1-methanol, 3-cyclohexyl-3-cyclohexene-1-methanol, etc. Jia is 3-cyclohexene methanol. These may be used alone or in combination of two or more.

Examples of the dicarboxylic acid (or a derivative thereof) include cyclohexane-1,2-dicarboxylic acid, cyclohexane-1,2-dicarboxylic anhydride, and cyclohexane-1,2-dicarboxylic acid. Ester, diethyl cyclohexane-1,2-dicarboxylate, dipropyl cyclohexane-1,2-dicarboxylate, dicyclohexyl cyclohexane-1,2-dicarboxylate, cyclohexane-1 , cyclohexane-1,2-dicarboxylic dichloride, cyclohexane-1,2-dicarboxylic dibromide, cyclohexane-1,3-di Formic acid, dimethyl cyclohexane-1,3-dicarboxylate, diethyl cyclohexane-1,3-dicarboxylate, dipropyl cyclohexane-1,3-dicarboxylate, cyclohexane-1, Dicyclohexyl 3-dicarboxylate, cyclohexane-1,3-dimethylhydrazine chloride, cyclohexane-1,3-dimethylhydrazine bromide, cyclohexane-1,4-dicarboxylic acid, cyclohexane- Dimethyl 1,2-dicarboxylate, diethyl cyclohexane-1,4-dicarboxylate, dimethyl cyclohexane-1,4-dicarboxylate, dipropyl cyclohexane-1,4-dicarboxylate Ester, cyclohexane-1,4-dicarboxylic acid dicyclohexyl ester, cyclohexane-1,4-dimethyl hydrazine chloride, cyclohexane-1,4-dimethyl hydrazine bromine, hydrogenated nadic acid Acid), hydrogenated acid anhydride, hydrogenated dimethyl benzoate, hydrogenated urate, hydrogenation Dipropyl benzoate, hydrogenated dicyclohexyl benzoate, hydrogenated ruthenium dichloride, hydrogenated bismuth bromide, hydrogenated methyl benzoic acid, hydrogenated methyl methicillin, hydrogenated methyl Dimethyl phthalate, hydrogenated methyl dimethyl sulphate, hydrogenated methyl dimethyl benzoate, hydrogenated methyl dysenteric acid dicyclohexyl ester, hydrogenated methyl benzoic acid diterpene chloride, hydrogenated methyl Dimethyl bromide, norbornane dicarboxylic acid, norbornane-2,5-dicarboxylic acid, decane-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 dicyclohexyl ester, norbornane-2,5-dimethylhydrazine chloride, norbornane-2, 5-dimethylhydrazine bromide, norbornane-2,6-dicarboxylic acid, decane-2,6-dicarboxylic acid dimethyl ester, norbornane-2,6-dicarboxylic acid diethyl ester, norbornane- Dipropyl 2,6-dicarboxylate, dicyclohexyl-2,6-dicarboxylate, norbornane-2,6-dimethylhydrazine, norbornane-2,6-dimethyl bromide Etc., but not limited to these. These may be used alone or in combination of two or more.

As a reaction of a cyclohexene methanol derivative with a dicarboxylic acid (or a derivative thereof), a usual esterification method is suitable. Specifically, the usual esterification reaction to be used includes, for example, Fischer esterification using an acid catalyst, reaction of an anthracene halide under an alkaline condition, an alcohol reaction, condensation reaction using various condensing agents, and the like. (ADVANCED ORGANIC CHEMISTRY PartB: Reaction and Synthesis p135, 145-147, 151, etc.). Further, as a specific example, esterification of a carboxylic acid ester can also be carried out by utilizing an esterification reaction of an alcohol with a carboxylic acid (Tetrahedron vol. 36 p. 2409 (1980), Tetrahedron Letter p. 4475 (1980)). The reaction was produced by the reaction (Japanese Patent Laid-Open No. 2006-052187).

The diene compound of the above formula (1) synthesized in this manner is preferably a compound in which R is a hydrogen atom or a methyl group in the above formula (1), in terms of ease of availability. It is especially preferred that the compound is a hydrogen atom. Further, P is preferably one or more selected from the group consisting of a methylcyclohexane ring, a cyclohexane ring, a methylnorbornane ring, and a norbornane ring, and more preferably has no substitution in terms of ease of availability. The base is especially preferably a cyclohexane ring.

The diene compound of the above formula (2) can be produced by a known method, and for example, dimerization by a cyclohexenal derivative (Tishchenko reaction, patent document: JP-A-2003-170059) No. 2004-262871, or a cyclohexene carboxylic acid derivative obtained by reacting a cyclohexene carboxylic acid derivative with a cyclohexene methanol derivative (Reference: Tetrahednon Vol. 36 p. 2409 ( 1980), a compound of the method described in Tetrahedron Letter p. 4475 (1980), and the method described in JP-A-2006-052187.

Examples of the cyclohexenal derivative include 3-cyclohexenecarbaldehyde, 2-methyl-3-cyclohexenecarbaldehyde, and 4-methyl-3-cyclohexenecarbaldehyde, but are not limited thereto. These may be used alone or in combination of two or more.

Specific examples of the cyclohexene carboxylic acid derivative include cyclohexenecarboxylic acid, methyl cyclohexenecarboxylate, ethyl cyclohexenecarboxylate, propyl cyclohexenecarboxylate, and cyclohexenecarboxylic acid. Butyl ester, hexyl cyclohexene carboxylate, cyclohexenecarboxylic acid (cyclohexenylmethyl) ester, octyl cyclohexenecarboxylate, cyclohexene methyl chloro, cyclohexene methyl bromo, methyl cyclohexene Formic acid, methyl methylcyclohexenecarboxylate, methyl cyclohexenecarboxylate, methyl cyclohexenecarboxylate, methylcyclohexenecarboxylic acid (methylcyclohexenylmethyl) ester, methyl ring Hexene guanidine chloride or the like, but is not limited thereto. These may be used alone or in combination of two or more.

Further, examples of the cyclohexene methanol derivative include the above compounds.

The epoxy resin composition of the present invention is obtained by oxidizing and epoxidizing a mixture of the compounds of the above formulas (1) and (2), or oxidizing the compounds of the formulae (1) and (2), respectively. Obtained by mixing epoxy resins. Examples of the method for oxidizing include a method of oxidizing by a peracid such as peracetic acid, a method of oxidizing by using hydrogen peroxide water, a method of oxidizing by air (oxygen), and the like, but are not limited thereto.

Specific examples of the method of epoxidation using peracid include the methods described in JP-A-2007-510772, JP-A-2006-52187, and the like.

In the method of epoxidation of hydrogen peroxide water, various methods can be applied, and, for example, JP-A-59-108793, JP-A-62-234550, and JP-A No. 5-213919, Japanese Laid-Open Patent Publication No. H11-349579, Japanese Patent Application Laid-Open No. Hei No. Hei.

In the present invention, hydrogen peroxide is more preferably used in terms of low viscosity of the product.

Hereinafter, an example of a method of epoxidation using hydrogen peroxide will be disclosed.

First, in the state of an emulsion of an organic solvent or hydrogen peroxide water, the diene compound of the above formula (1) and the diene compound of the formula (2) are used singly or in a mixture thereof (hereinafter, these are combined and only The reaction is carried out for a diene compound, a polyacid, and a quaternary ammonium salt. Further, a buffer solution can also be used in the reaction.

The polyacid used in the present invention is not particularly limited as long as it has a polyacid structure, and is preferably a polyacid containing tungsten or molybdenum, more preferably a polyacid containing tungsten, and particularly preferably a tungstate.

Specific examples of the polyacid include a tungsten acid selected from the group consisting of tungstic acid, 12-tungstophosphoric acid, 12-tungstoboronic acid, 18-tungstophosphoric acid, and 12-tungstic acid, or the like, and a salt selected from the group consisting of molybdic acid. Or a molybdenum acid or the like in phosphomolybdic acid or the like.

Examples of the counter cation of the salt include an ammonium ion, an alkaline earth metal ion, and an alkali metal ion.

Specific examples thereof include alkaline earth metal ions such as calcium ions and magnesium ions, and alkali metal ions such as sodium ions, potassium ions, and cesium ions, but are not limited thereto. The best counter cations are sodium ions, potassium ions, calcium ions, and ammonium ions.

The amount of the polyacid used is 0.5 to 0 in terms of a metal element in terms of a metal element (in the case of tungstic acid, the molar number of tungsten atoms, and if it is molybdic acid, the molar number of molybdenum atoms) is 0.5 to 0.5. 20 millimolar, preferably 1.0 to 20 millimolar, more preferably 2.5 to 15 millimolar.

As the quaternary ammonium salt, it is preferred to use a quaternary ammonium salt having a total carbon number of 10 or more, preferably 25 to 100, more preferably 25 to 55, and particularly preferably an alkyl chain of all of which is an aliphatic chain. .

Specific examples thereof include trimethylmethylammonium salt, dilauryl dimethylammonium salt, trioctylmethylammonium salt, and trialkylmethyl group (alkyl group is an octyl compound and an alkyl group is a fluorenyl group) Mixed type of compound) ammonium salt, tri-hexadecylmethyl ammonium salt, trimethyl stearyl ammonium salt, tetraamyl ammonium salt, cetyl trimethyl ammonium salt, benzyl tributyl The ammonium salt, the hexadecyldimethylammonium salt, the trihexadecylmethylammonium salt, the dihardened tallow alkyl dimethylammonium salt, and the like are not limited thereto.

Further, the anion species of the salt is not particularly limited, and specific examples thereof include a halide ion, a nitrate ion, a sulfate ion, a hydrogen sulfate ion, an acetate ion, and a carbonate ion, but are not limited thereto. Especially preferred is acetate ion.

When the carbon number exceeds 100, the hydrophobicity becomes too strong, and the solubility of the quaternary ammonium salt in the organic layer deteriorates. When the carbon number is less than 10, the hydrophilicity becomes strong, and similarly, the compatibility of the quaternary ammonium salt in the organic layer is deteriorated, which is not preferable.

The quaternary ammonium salt is used in an amount of 0.01 to 10 equivalents, more preferably 0.05 to 6 equivalents, still more preferably 0.05 to 4.5 equivalents, per several times the valence of the polyacid to be used.

For example, in the case of tungstic acid, it is divalent in terms of H ₂ WO ₄ , so the quaternary ammonium carboxylate is preferably in the range of 0.02 to 1.6 mol or 2.2 to 20 mol relative to 1 mol of tungstic acid. . Further, in the case of tungstophosphoric acid, it is trivalent, and therefore it is preferably 0.03 to 2.4 mol or 3.3 to 30 mol, and if it is tungstic acid, it is tetravalent, so it is preferably 0.04 to 3.2 mol. Or 4.4 to 40 moles.

When the amount of the quaternary ammonium carboxylate is less than 0.01 times the valence of the polyacid, the epoxidation reaction is difficult to carry out (depending on the case, the reaction is accelerated), and is easily formed. The problem of by-products. In the case of more than 10 times the equivalent amount, not only the subsequent treatment is troublesome, but also the effect of suppressing the reaction is unsatisfactory.

As the buffer, any of known buffers can be used, but in the present reaction, an aqueous phosphate solution is preferably used. The pH is preferably adjusted to be between pH 4 and 10, more preferably pH 5 to 9. When the pH is less than 4, the hydrolysis reaction and the polymerization reaction of the epoxy group are easily performed. Further, when the pH exceeds 10, the reaction becomes extremely slow and the reaction time is too long.

In particular, in the case of dissolving a polyacid as a catalyst in the present invention, it is preferred to adjust the pH to between 5 and 9.

When the method of using the buffer is, for example, a phosphoric acid-phosphate aqueous solution as a preferred buffer, a method of using 0.1 to 10 mol% of phosphoric acid (or sodium dihydrogen phosphate, etc.) with respect to hydrogen peroxide is used. Phosphate) A method of pH adjustment using a basic compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate or the like.

Here, in terms of pH, when hydrogen peroxide is added, it is preferably added so as to have the above pH. Further, it can also be adjusted using sodium dihydrogen phosphate, disodium hydrogen phosphate or the like. The preferred concentration of phosphate is from 0.1 to 60% by weight, preferably from 1 to 45% by weight.

Further, in the present reaction, a phosphate (or a hydrate thereof) such as disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium phosphate or sodium tripolyphosphate may be directly added without using a buffer solution and without pH adjustment. It is preferred because the steps are simplified by direct addition. The amount of the phosphate used at this time is usually 0.1 to 5 mol%, preferably 0.2 to 4 mol%, more preferably 0.3 to 3 mol%, based on the hydrogen peroxide. In this case, if it exceeds 5 mol% equivalent with respect to hydrogen peroxide, pH adjustment is necessary, and when it is less than 0.1 mol%, the hydrolysis of the produced epoxy compound is easily performed, or the reaction is changed. Slow and other bad conditions.

This reaction is epoxidized using hydrogen peroxide. As the hydrogen peroxide used in the present reaction, an aqueous solution having a hydrogen peroxide concentration of 10 to 40% by weight is preferred in terms of ease of handling. When the concentration exceeds 40% by weight, the decomposition reaction of the produced epoxy resin is easily performed in addition to the difficulty in handling, which is not preferable.

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 based on the diene compound 1 as a reaction substrate. When the ratio exceeds 10 by weight, the progress of the reaction becomes extremely slow and thus is not preferable. Specific examples of the organic solvent that can be used include an alkane such as hexane, cyclohexane or heptane, an aromatic hydrocarbon compound such as toluene or xylene, methanol, ethanol, isopropanol, butanol or hexanol. An alcohol such as cyclohexanol. In addition, as the case may be: methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone (anone) and other ketones, diethyl ether, tetrahydrofuran, two An ether such as an alkyl group; an esterified product such as ethyl acetate, butyl acetate or methyl formate; or a nitrile compound such as acetonitrile. Particularly preferred solvents are alkane such as hexane, cyclohexane or heptane, and aromatic hydrocarbon compounds such as toluene and xylene.

As a specific reaction operation method, for example, when a reaction is carried out using a batch reactor, a diene compound, hydrogen peroxide (aqueous solution), a polyacid (catalyst), a buffer, a quaternary ammonium salt, and an organic solvent are added. Stir the double layer. The stirring speed is not specified. Since there is a case where heat is generated when hydrogen peroxide is added, a method of gradually adding hydrogen peroxide after adding each component may be employed.

In this case, the following method is used: after adjusting the pH of the buffer (or water and phosphate) and the polyacid, adding a quaternary ammonium salt, an organic solvent, a diene compound, stirring in a double layer, and then adding a peroxide. hydrogen.

Alternatively, a method of adding a polyacid or a phosphoric acid (or phosphate) to a pH adjustment after stirring water, an organic solvent, or a diene compound, adding a quaternary ammonium salt, stirring in a double layer, and then adding dropwise may be used. hydrogen peroxide.

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

Further, the reaction time depends on the reaction temperature, the amount of the catalyst, etc., but from the viewpoint of industrial production, the long-term reaction consumes a large amount of energy, which is not preferable. A preferred range is from 1 to 48 hours, preferably from 3 to 36 hours, more preferably from 4 to 24 hours.

After the reaction is completed, quenching treatment of excess hydrogen peroxide is performed. The quenching treatment is preferably carried out using a basic compound. Further, it is also preferred to use a reducing agent together with a basic compound. As a preferable treatment method, after the pH neutralization is adjusted to 6 to 10 by a basic compound, the residual hydrogen peroxide is quenched using a reducing agent. When the pH is less than 6, the heat generated when the excess hydrogen peroxide is reduced is large, and there is a possibility that a decomposition product is generated.

Examples of the reducing agent include sodium sulfite, sodium thiosulfate, hydrazine, oxalic acid, and vitamin C. The amount of the reducing agent to be used is usually 0.01 to 20 moles, more preferably 0.05 to 10 moles, still more preferably 0.05 to 3 moles, per mole of the hydrogen peroxide.

These are preferably added as an aqueous solution at a concentration of 0.5 to 30% by weight.

Examples of the basic compound include metal hydroxides such as sodium hydroxide, potassium hydroxide, magnesium hydroxide, and calcium hydroxide; metal carbonates such as sodium carbonate and potassium carbonate; and phosphates such as sodium phosphate and sodium hydrogen phosphate, and ion exchange. Alkaline solid such as resin or alumina.

In terms of the amount of use, if it is dissolved in water or an organic solvent (for example, an aromatic hydrocarbon compound such as toluene or xylene, a ketone such as methyl isobutyl ketone or methyl ethyl ketone, cyclohexane or glycol In the case of a hydrocarbon such as an alkane or an octane or a solvent such as an alcohol such as methanol or ethanol or isopropanol, the amount of the hydrogen peroxide is usually 0.01 to 20 moles per mole of the excess amount of hydrogen peroxide. More preferably, it is 0.05 to 10 times moles, more preferably 0.05 to 3 times moles. These may be added in the form of a solution of water or the above organic solvent, or may be added in a monomeric manner.

In the case of using a solid base which is insoluble in water or an organic solvent, it is preferably used in an amount of from 1 to 1000 times by weight based on the amount of hydrogen peroxide remaining in the system. More preferably, it is 10 to 500 times, more preferably 10 to 300 times. In the case of using a solid base which is insoluble in water or an organic solvent, it may be treated after separation of the aqueous layer and the organic layer described below.

After the quenching of hydrogen peroxide (or before quenching), when the organic layer and the aqueous layer are not separated, or when an organic solvent is not used, the organic solvent is added to operate, and the reaction product is extracted from the aqueous layer. . The organic solvent used at this time is 0.5 to 10 times, preferably 0.5 to 5 times by weight, based on the weight of the raw material olefin compound. The organic layer separated after several times of the above operation is repeated as needed, and washed with water as needed.

The obtained organic layer is optionally ion-exchanged resin or metal oxide (especially tannin, alumina, etc.), activated carbon (particularly chemically activated carbon), and composite metal salt (particularly alkaline) The composite metal salt), the clay mineral (particularly a layered clay mineral such as montmorillonite), and the like are removed, and then washed with water, filtered, etc., and then the solvent is distilled off to obtain a target epoxy compound.

The epoxy resin composition of the present invention obtained in this manner is a molecule represented by the following formula (3) and the following formula (4), but may be present in a ratio of 15% by weight or less based on the total amount ( 1) or an unreacted substance of the compound of the formula (2), a partial epoxide, a hydrolyzate, and the like, and the like:

(wherein R and P represent the same meanings as in formula (1))

(wherein R represents the same meaning as in the formula (2)).

When the mixtures are homogeneous, they are mostly liquid. Further, the ratio of the compound of the above formula (3) (and the above-mentioned impurities derived from the compound of the formula (1)) to the compound of the above formula (4) (and the above-mentioned impurities derived from the compound of the formula (2)) is 10/90~90/10. More preferably 25/75 to 80/20, especially preferably 25/75 to 60/40, and most preferably 25/75 to 50/50. The epoxy resin composition of the present invention may be obtained by mixing and epoxidizing a compound of the formula (1) with a compound of the formula (2), or a formula (3) obtained by epoxidizing the formula (1). The compound is compounded with a compound of the formula (4) obtained by epoxidation of the formula (2). In the case of the former, 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, in order to set the above weight ratio. It is preferably 25/75 to 60/40, and is preferably mixed and oxidized in the range of 25/75 to 50/50.

The cured product obtained by mixing the epoxy compound contained in the epoxy resin composition in the above range exhibits an excellent effect on durability against light and heat. In particular, by mixing the compound of the formula (3) with the compound of the formula (4) in the range of 25/75 to 50/50, the decrease in transmittance due to coloring can be remarkably suppressed, and it is used for an optical semiconductor. In the case of a sealant, a high illuminance retention rate can be achieved.

Further, in the present invention, in terms of easiness of obtaining, it is particularly preferable that the substituent R in the compound of the formula (3) or the compound (4) is a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom. Further, P is preferably one or more selected from the group consisting of a methylcyclohexane ring, a cyclohexane ring, a methylnorbornane ring, and a norbornane ring, and more preferably has no substitution in terms of ease of availability. The base is especially preferably a cyclohexane ring.

The curable resin composition of the present invention contains the epoxy resin composition, the curing agent and/or the hardening accelerator of the present invention. In the curable resin composition of the present invention, the epoxy resin composition of the present invention may be used alone or in combination with other epoxy resins. In the case of use in combination, the ratio of the epoxy resin composition to the total epoxy resin component is preferably 70% by weight or more, and particularly preferably 80% by weight or more.

Examples of other epoxy resins which 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, and triphenylmethane type epoxy resins. Resin, phenol aralkyl type epoxy resin, and the like. Specific examples thereof include bisphenol A, bisphenol S, thiodiphenol, bismuth bisphenol, stilbene, 4,4'-biphenol, 2,2'-biphenol, 3,3', 5,5 '-Tetramethyl-[1,1'-biphenyl]-4,4'-diol, hydroquinone, resorcinol, naphthalenediol, tris-(4-hydroxyphenyl)methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc. ) with formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis(chloromethyl) )-1,1'-biphenyl, 4,4'-bis(methoxymethyl)-1,1'-biphenyl, 1,4-bis(chloromethyl)benzene, 1,4-double ( a polycondensate such as methoxymethyl)benzene or the like, a halogenated bisphenol such as tetrabromobisphenol A, a glycidyl ether compound derived from an alcohol, an alicyclic epoxy resin, or a glycidylamine system. Epoxy resin, glycidyl ester epoxy resin, sesquiterpene oxide epoxy resin (shrinkage in a helium oxide structure having a mixed structure of at least two or more of a chain shape, a ring shape, a ladder shape, or the like) Glyceryl / Epoxy or epoxy structures cyclohexane) solid or liquid epoxy resin and the like, but is not limited to such.

In particular, when the curable resin composition of the present invention is used for optical applications, it is preferred to use an epoxy resin having an alicyclic epoxy resin and a sesquiterpene oxide structure in combination. Particularly in the case of the 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.

Examples of the epoxy resin include those obtained by oxidizing a compound which can be produced by the following method: esterification reaction of a cyclohexenecarboxylic acid with an alcohol or esterification of a cyclohexene methanol with a carboxylic acid ( Tetrahedron vol. 36 p. 2409 (1980), Tetrahedron Letter p. 4475 (1980), etc., and transesterification of cyclohexene carboxylate (Japanese Patent Laid-Open Publication No. 2006-052187, etc.) method).

The alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, and examples thereof include ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, and 1,4-butanediol. , 5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopenta Glycols such as diol, tricyclodecane dimethanol, norene diol, glycerol, trimethylolethane, trimethylolpropane, trimethylolbutane, 2-hydroxymethyl- Triols such as 1,4-butanediol, tetraols such as neopentyl alcohol and di-trimethylolpropane. Further, examples of the carboxylic acid include oxalic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, adipic acid, and cyclohexanedicarboxylic acid, but are not limited thereto. .

Further, as another example of the compound having an epoxycyclohexane structure in the skeleton, an acetal compound obtained by reacting a cyclohexenal derivative with an acetal of an alcohol can be mentioned. The reaction method can be produced by applying a usual acetalization reaction. For example, a method in which a reaction solvent is used for azeotropic dehydration while using a solvent such as toluene or xylene is disclosed (U.S. Patent No. 2945008); In the case of dissolving a polyhydric alcohol in concentrated hydrochloric acid, a reaction is carried out while slowly adding an aldehyde (JP-A-48-96590); a method of using water as a reaction medium (U.S. Patent No. 3,092, 640); A method of using a solid acid catalyst (JP-A-2007-230992) or the like. In terms of stability of the structure, a cyclic acetal structure is preferred.

Specific examples of such epoxy resins include ERL-4299 (all trade names, all manufactured by Dow Chemical), EPOLEAD GT401, EHPE 3150, and EHPE 3150CE (all are trade names, both of which are It is not limited to these, but it is not limited to such a product (manufactured by Daicel Chemical Industry Co., Ltd.) and dicyclopentadiene diepoxide (Reference: General Epoxy Resin Basics I p76-85).

These may be used alone or in combination of two or more.

Further, the sesquiterpene oxide-based epoxy resin (having a glycidyl group and/or an epoxy ring in a rhodium structure having a mixed structure of at least two of a chain, a ring, a ladder, or the like) A solid or liquid epoxy resin such as a hexane structure epoxy resin is preferably used within a range that does not affect the corrosion resistance.

The curable resin composition of the present invention contains a curing agent reactive with the above epoxy resin component.

Examples of the curing agent include an amine compound, an acid anhydride compound, a guanamine compound, a phenol compound, and a carboxylic acid compound. Specific examples of the hardener which can be used include diaminodiphenylmethane, di-extended ethyltriamine, tri-ethylidenetetramine, diaminodiphenylphosphonium, isophoronediamine, and Nitro-diamine, a nitrogen-containing compound (amine, guanamine compound) such as a polyamide resin synthesized from a dilinoleic acid dimer and ethylene diamine; phthalic anhydride, trimellitic anhydride (trimellitic) Anhydride), pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylic acid anhydride, nadic anhydride, Hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butane tetracarboxylic anhydride, bicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride, methylbicyclo[2,2 , 1] heptane-2,3-dicarboxylic anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, etc.; modified by polyalcohol with various alcohols, methanol (carbinol) A carboxylic acid resin obtained by the addition reaction of the above acid anhydride; bisphenol A, bisphenol F, bisphenol S, bisphenol, stilbene, 4,4'-biphenol, 2,2'-biphenol, 3 ,3',5,5'-tetramethyl-[1,1'-biphenyl]-4,4'-diol, p-benzene Phenol, resorcinol, naphthalenediol, tris-(4-hydroxyphenyl)methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, phenols (phenol, alkyl substituted Phenol, naphthol, alkyl substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) with formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyl Acetophenone, dicyclopentadiene, furfural, 4,4'-bis(chloromethyl)-1,1'-biphenyl, 4,4'-bis(methoxymethyl)-1,1' a polycondensate of biphenyl, 1,4'-bis(chloromethyl)benzene, 1,4'-bis(methoxymethyl)benzene, and the like, and a halogenated double such as tetrabromobisphenol A A polyphenol such as a phenol, a condensate of a terpene and a phenol, a compound of imidazole, a trifluoroborane-amine complex, or an anthracene derivative, but is not limited thereto. These may be used alone or in combination of two or more.

In the present invention, a compound having an acid anhydride structure and/or a compound having a carboxylic acid structure represented by the above acid anhydride or carboxylic acid resin is particularly preferred. The acid anhydride forms a hardened product of high hardness, and a compound having a carboxylic acid structure is preferred because of its low volatility. More preferably, it is a compound having an acid anhydride structure and/or a compound having at least one divalent or higher carboxylic acid structure, and particularly preferably a mixture of the two.

As the compound having an acid anhydride structure, methyl tetrahydrophthalic anhydride, methylic acid anhydride, dying anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and butyl are preferable. Alkane tetracarboxylic anhydride, bicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride, methylbicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride, cyclohexane-1 2,4-tricarboxylic acid-1,2-anhydride, etc., more preferably methylhexahydrophthalic anhydride or cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride.

The compound having a carboxylic acid structure (hereinafter referred to as a polycarboxylic acid) is preferably a 2- to 4-functional polycarboxylic acid, more preferably obtained by subjecting a 2- to 4-functional polyol to an acid anhydride. Polycarboxylic acid.

The 2 to 4 functional polyol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, and examples thereof include ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, and 1,4- Butylene glycol, 1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1,3 - glycols such as propylene glycol, neopentyl glycol, tricyclodecane dimethanol, dicyclopentadiene dimethanol, norbornenediol, glycerol, trimethylolethane, trimethylolpropane, Triols such as trimethylolbutane and 2-hydroxymethyl-1,4-butanediol, tetraols such as neopentyl alcohol and di-trimethylolpropane.

The preferred alcohols are cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecane dimethanol a branched or cyclic aliphatic alcohol such as dicyclopentadiene dimethanol or norbornene diol.

The acid anhydride in the case of producing a polycarboxylic acid is preferably methyltetrahydrophthalic anhydride, methylic acid anhydride, ceric anhydride, hexahydrophthalic anhydride or methylhexahydrophthalic anhydride. Butane tetracarboxylic anhydride, bicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride, methylbicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride, cyclohexane- 1,2,4-tricarboxylic acid-1,2-anhydride, and the like.

The conditions for the addition reaction are not particularly specified, and examples thereof include a method in which an acid anhydride or a polyhydric alcohol is heated at 40 to 150 ° C under a condition of no catalyst or solvent, and the reaction is completed immediately after completion of the reaction.

The acid anhydride and the polycarboxylic acid may be used singly or in combination. In the case of use in combination, the ratio of the acid anhydride to the polycarboxylic acid is from 90/10 to 20/80 by weight, particularly preferably from 80/20 to 30/70. By setting it as the said range, it can balance the heat resistance and handling property favorable. If the amount of the acid anhydride exceeds 90% by weight, the volatility increases, which is not preferable.

In the curable resin composition of the present invention, the amount of the curing agent to be used is preferably from 1 to 1.5 equivalents per equivalent of the epoxy group based on the epoxy group of the epoxy resin. More preferably, it is 0.7 to 1.1 equivalents, and particularly preferably 0.8 to 1.0 equivalents. Further, in the case of use for optical use, it is preferably 1.0 equivalent or less, more preferably 0.7 to 0.95 equivalent, still more preferably 0.7 to 0.85 equivalent. When the amount of the hardener used is less than 0.5 equivalents per equivalent of the epoxy group, or when it exceeds 1.5 equivalents, the hardening becomes incomplete and the cured physical properties are not obtained.

In the curable resin composition of the present invention, a curing accelerator may be used in combination with the curing agent, or a curing accelerator may be used alone without using a curing agent. Specific examples of the curing accelerator which can be used include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, and 2-phenyl-4-methyl. Imidazole, 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'-methylimidazolium (1')) ethyl-symmetric three 2,4-diamino-6(2'-undecylimidazolium (1')) ethyl-symmetric three 2,4-Diamino-6(2'-ethyl-4-methylimidazolium (1'))ethyl-symmetric three 2,4-Diamino-6(2'-methylimidazolium(1'))ethyl-symmetric three - an isomeric cyanuric acid adduct, a 2:3 adduct of 2-methylimidazoisocyanuric acid, a 2-phenylimidazolium isocyanurate adduct, 2-phenyl-3,5 - Dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, etc. Various imidazoles, and polycarboxylic acids such as the imidazoles and phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, maleic acid, oxalic acid Salts, guanamines such as dicyanodiamine, diaza compounds such as 1,8-diazabicyclo (5.4.0) undecene-7, and tetraphenylborate, phenol novolac a salt of varnish or the like, a salt of the above polycarboxylic acid or phosphinic acid, tetrabutylammonium bromide, cetyltrimethylammonium bromide, trioctylmethylammonium bromide Isoammonium salt, phosphine or anthracene compound such as triphenylphosphine, tris(tolylmethyl)phosphine, tetraphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, 2,4,6-three a phenol such as aminomethylphenol, an amine adduct, a metal compound such as tin octylate, etc. And the hardening accelerator is made into a microcapsule type hardening accelerator of a microcapsule, etc. Which of these hardening accelerators is used is suitably selected according to characteristics required for the transparent resin composition obtained, for example, transparency, a hardening speed, and a working condition. The curing accelerator is used in an amount of usually 0.001 to 15 parts by weight based on 100 parts by weight of the epoxy resin component.

The curable resin composition of the present invention may further contain a phosphorus-containing compound as a flame retardancy imparting component. As the phosphorus-containing compound, it may be a reactive type or an additive type. Specific examples of the phosphorus-containing compound include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylylenyl phosphate, and cresyl phosphate. Diphenyl phosphate), cresyl-2,6-dixylylenyl phosphate, 1,3-phenylenebis(bis(xylene)phosphate), 1,4 -Phenyl bis(di(xylene) phosphate), 4,4'-biphenyl (dixylylenyl phosphate) (4,4'-biphenyl (dixylylenyl phosphate); 10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10(2,5-dihydroxyphenyl) a phosphane such as -10H-9-oxa-10-phosphaphenanthrene-10-oxide; a phosphorus-containing epoxy compound obtained by reacting an epoxy resin with an active hydrogen of the above phosphane , red phosphorus, etc.; preferably phosphates, phosphines or phosphorus-containing epoxy compounds, especially 1,3-phenylene bis(di(xylene) phosphate), 1,4-phenylene double (bis(xylene) phosphate), 4,4'-biphenyl (bis(xylene) phosphate) or phosphorus-containing epoxide The content of the phosphorus-containing compound is preferably a phosphorus-containing compound/epoxy resin = 0.1 to 0.6 (weight ratio). When the amount is less than 0.1, the flame retardancy is insufficient; if it exceeds 0.6, the moisture absorption property to the cured product is Dielectric effects cause adverse effects.

Further, in the curable resin composition of the present invention, a binder resin may be blended as needed. Examples of the binder resin include butyral resin, acetal resin, acrylic resin, epoxy-nylon resin, NBR (Nitrile Butadiene Rubber)-phenol resin, and epoxy-NBR. The resin, the polyamine resin, the polyamidene resin, the polyoxyn resin, etc. are not limited thereto. The blending amount of the binder resin is preferably in a range that does not impair the flame retardancy and heat resistance of the cured product, and is usually used in an amount of 0.05 to 50 parts by weight, based on 100 parts by weight of the total of the epoxy resin component and the hardener. It is preferably 0.05 to 20 parts by weight.

In the curable resin composition of the present invention, an inorganic filler may be added as needed. Examples of the inorganic filler include crystalline cerium oxide, molten cerium oxide, aluminum oxide, zircon, calcium silicate, calcium carbonate, cerium carbide, tantalum nitride, boron nitride, zirconium oxide, forsterite, and the like. A powder such as talc, spinel, titanium dioxide or talc, or particles obtained by spheroidizing the particles, etc., but is not limited thereto. These fillers may be used singly or in combination of two or more. The content of the inorganic filler is from 0 to 95% by weight based on the curable resin composition of the present invention. Further, in the curable resin composition of the present invention, a decane coupling agent, a release agent such as stearic acid, palmitic acid, zinc stearate or calcium stearate, various preparation agents such as pigments, and various types of thermosetting may be added. Resin.

When the curable resin composition of the present invention is used for an optical material, particularly a photo-semiconductor encapsulant, a filler having a particle size of a nanometer level can be used by using the inorganic filler material used above. Does not impede transparency and enhance mechanical strength and the like. From the viewpoint of transparency, the standard of the nano-level is preferably a filler having an average particle diameter of 500 nm or less, and particularly preferably a filler having an average particle diameter of 200 nm or less.

When the curable resin composition of the present invention is used for an optical material, particularly a photo-semiconductor encapsulant, a phosphor may be added as needed. Fluorescent systems have the effect of emitting wavelength-converted yellow light to form white light, for example by absorbing a portion of the blue light emitted by the blue LED element. After the phosphor is previously dispersed in the curable resin composition, the photo-semiconductor is sealed. The phosphor is not particularly limited, and a conventionally known phosphor can be used. Examples thereof include an aluminate of a rare earth element, a thiogallic acid salt, or a protoporate. More specifically, it can be exemplified by YAG (Yttrium Aluminium Garnet) phosphor, TAG (Terbium Aluminum Garnet) phosphor, orthosilicate phosphor, thiogallate Phosphors such as phosphors and sulfide phosphors are exemplified by 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 or the like. The particle diameter of the phosphor is a particle diameter known in the art, and the average particle diameter is preferably from 1 to 250 μm, particularly preferably from 2 to 50 μm. In the case of using these phosphors, the amount thereof is preferably from 1 to 80 parts by weight, more preferably from 5 to 60 parts by weight, per 100 parts by weight of the above resin component.

When the curable resin composition of the present invention is used for an optical material, particularly a photo-semiconductor encapsulant, in order to prevent sedimentation of various phosphors upon hardening, a fine powder of cerium oxide (also referred to as Aerosil or Aerosol) is a representative thixotropy imparting agent. As the above-mentioned cerium oxide micropowder, for example, Aerosil 50, Aerosil 90, Aerosil 130, Aerosil 200, Aerosil 300, Aerosil 380, Aerosil OX50, Aerosil TT600, Aerosil R972, Aerosil R974, Aerosil R202, Aerosil R812, Aerosil R812S , Aerosil R805, RY200, RX200 (manufactured by Japan Aerosil Co., Ltd.).

When the curable resin composition of the present invention is used for an optical material, particularly a photo-semiconductor encapsulant, it may contain an amine compound as a light stabilizer or a phosphorus-based compound and an phenol as an antioxidant material in order to prevent coloration. a compound.

Examples of the above amine compound include tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 1,2,3. , 4-butane tetracarboxylic acid tetrakis(2,2,6,6-tetramethyl-4-piperidyl) ester, 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] eleven Mixed ester of alkane; bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate sebacate, bis(1-undecyloxy-2,2,6 ,6-tetramethylpiperidin-4-yl)ester, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, azelaic acid bis(2,2,6,6- Tetramethyl-4-piperidinyl), bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, 4-benzylideneoxy-2,2 ,6,6-tetramethylpiperidine, 1-[2-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propanoxy]ethyl]-4-[3 -(3,5-di-t-butyl-4-hydroxyphenyl)propanoxy]-2,2,6,6-tetramethylpiperidine, methacrylic acid 1,2,2,6, 6-pentamethyl-4-piperidyl ester, {[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl}butylmalonate bis (1, 2,2,6,6-pentamethyl-4-piperidinyl), bis(2,2,6,6-tetramethyl-1-(octyloxy) sebacate 4-piperidinyl)ester, the reaction product of 1,1-dimethylethylhydroperoxide and octane, N,N',N",N"'-tetra-(4,6-bis( Butyl-(N-methyl-2,2,6,6-tetramethylpiperidin-4-yl)amino)-three -2-yl)-4,7-diazepine-1,10-diamine, dibutylamine-1,3,5-three -N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl-1,6-tetramethylenediamine and N-(2,2,6,6-tetramethyl) Polycondensate of 4-piperidinyl)butylamine, poly{[6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-tri -2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imido]hexamethylene[(2,2,6,6-tetramethyl- a polymer of 4-piperidinyl)imido]], dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, 2, 2, 4, 4-tetramethyl-20-(β-lauryloxycarbonyl)ethyl-7-oxa-3,20-diazaspiro[5.1.11.2]icosane-21-one, β- Alanine, N-(2,2,6,6-tetramethyl-4-piperidinyl)-dodecyl ester/tetradecyl ester, N-acetylindol-3-dodecyl- 1-(2,2,6,6-tetramethyl-4-piperidinyl)pyrrolidine-2,5-dione, 2,2,4,4-tetramethyl-7-oxa-3, 20-diazabispiro[5,1,11,2]icosane-21-one, 2,2,4,4-tetramethyl-21-oxa-3,20-diazabicyclo -[5,1,11,2]-docosane-20-propionic acid lauryl ester/tetradecyl ester, malonic acid, [(4-methoxyphenyl)-methylene ]-bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester, higher fatty acid ester of 2,2,6,6-tetramethyl-4-piperidinol, 1 , 1,3-benzenedicarboxamide, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl) and other hindered amines, benzophenone, etc. Benzophenone-based compound, 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-tetrahydrophthalic imide)- Methyl)-5-methylphenyl]benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, 2-(2 -hydroxy-3,5-di-third-pentylphenyl)benzotriazole, 3-(3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxybenzene a reaction product of methyl propionate and polyethylene glycol, a benzotriazole compound such as 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol, a benzoate such as 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, 2-(4,6-diphenyl-1 , 3,5-three -2-yl)-5-[(hexyl)oxy]phenol, etc. A compound or the like is particularly preferably a hindered amine compound.

As the amine compound of the above-mentioned photostabilizing material, a commercially available product as shown below can be used.

The commercially available amine-based compound is not particularly limited, and examples thereof include Tinuvin 765, Tinuvin 770df, Tinuvin 144, Tinuvin 123, Tinuvin 6221d, Tinuvin 152, and Chimassorb 944 manufactured by Ciba Specialty Chemicals. LA-52, LA-57, LA-62, LA-63P, LA-77Y, LA-81, LA-82, LA-87, etc. manufactured by Adeca.

The phosphorus compound is not particularly limited, and examples thereof include 1,1,3-tris(2-methyl-4-di(tridecyl)phosphite-5-t-butylphenyl). Butane (1,1,3-tris(2-methyl-4-ditridecylphosphito-5-t-butylphenyl)butane), distearyl pentaerythritol diphosphite, bis(2,4-di- Tributylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)neopentanediol diphosphite, phenylbisphenol A new Pentaerythritol diphosphite, dicyclohexyl neopentyl alcohol diphosphite, tris(diethylphenyl) phosphite, tris(di-isopropylphenyl) phosphite, triphosphite Di-n-butylphenyl) ester, tris(2,4-di-t-butylphenyl) phosphite, tris(2,6-di-t-butylphenyl) phosphite, phosphorous acid Tris(2,6-di-t-butylphenyl) ester, 2,2'-methylenebis(4,6-di-t-butylphenyl) (2,4-di-third) Phenyl)phosphite, 2,2'-methylenebis(4,6-di-t-butylphenyl)(2-t-butyl-4-methylphenyl)phosphite, 2,2'-methylenebis(4-methyl-6-t-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, 2, 2'-Ethylene bis(4-methyl-6-t-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, tetrakis(2,4-di- Tributylphenyl)-4,4'-biphenylenephosphonite (tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylenephosphonite), tetra (2,4-di) -T-butylphenyl)-4,3'-extended biphenyl diphosphinate, tetrakis(2,4-di-t-butylphenyl)-3,3'-extended biphenyl Phosphonate, tetrakis(2,6-di-t-butylphenyl)-4,4'-extended biphenyl diphosphinate, tetrakis(2,6-di-t-butylphenyl) )-4,3'-Exbiphenyl diphosphinate, tetrakis(2,6-di-t-butylphenyl)-3,3'-extended biphenyl diphosphinate, double 2,4-di-t-butylphenyl)-4-phenyl-phenylphosphinate, bis(2,4-di-t-butylphenyl)-3-phenyl-phenyl Phosphonate, bis(2,6-di-n-butylphenyl)-3-phenyl-phenylphosphinate, bis(2,6-di-t-butylphenyl)-4-benzene Base-phenylphosphinate, bis(2,6-di-t-butylphenyl)-3-phenyl-phenylphosphinate, tetrakis(2,4-di-t-butyl- 5-methylphenyl)-4,4'-extended biphenyl diphosphinate, tributyl phosphate, trimethyl phosphate, tricresyl phosphate (tricr Esyl phosphate), triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxyl phosphate, tributyl phosphate Oxyethyl ester, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, and the like.

Commercially available products can also be used as the phosphorus compound. The commercially available phosphorus-based compound is not particularly limited, and examples thereof include Adekastab PEP-4C, Adekastab PEP-8, Adekastab PEP-24G, Adekastab PEP-36, Adekastab HP-10, Adekastab 2112, and Adekastab 260 manufactured by Adeca. Adekastab 522A, Adekastab 1178, Adekastab 1500, Adekastab C, Adekastab 135A, Adekastab 3010, Adekastab TPP.

The phenol compound is not particularly limited, and examples thereof include 2,6-di-tert-butyl-4-methylphenol and 3-(3,5-di-t-butyl-4-hydroxyphenyl). N-octadecyl propionate, tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, 2,4-di-third -6-methylphenol, 1,6-hexanediol-bis-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], tris (3,5- Di-t-butyl-4-hydroxybenzyl)-isocyanate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl- 4-hydroxybenzyl)benzene, pentaerythritol-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 3,9-bis-{2-[ 3-(3-Tertibutyl-4-hydroxy-5-methylphenyl)-propenyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxa Spiro[5,5]undecane, triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 2,2'-butylene Bis(4,6-di-tert-butylphenol), 4,4'-butylene bis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4- Methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2-tert-butyl-6-(3-third Butyl-2-hydroxy-5-methylbenzyl -4-methylphenol acrylate, 2-[1-(2-hydroxy-3,5-di-p-pentylphenyl)ethyl]-4,6-di-third amyl phenyl acrylate Ester, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'-butylene bis(3-methyl-6-tert-butylphenol), 2- Third butyl-4-methylphenol, 2,4-di-tert-butylphenol, 2,4-di-p-pentylphenol, 4,4'-thiobis(3-methyl-6 -T-butylphenol), 4,4'-butylene bis(3-methyl-6-tert-butylphenol), bis[3,3-bis(4'-hydroxy-3'-third butyl) Phenyl)-butyric acid]-glycol ester, 2,4-di-tert-butylphenol, 2,4-di-p-pentylphenol, 2-[1-(2-hydroxy-3,5 -di-p-pentylphenyl)ethyl]-4,6-di-third-pentyl phenyl acrylate, bis[3,3-bis(4'-hydroxy-3'-t-butylbenzene) Base)-butyric acid]-diol ester and the like.

Commercially available products can also be used as the phenolic compound. The commercially available phenolic compound is not particularly limited, and examples thereof include Irganox 1010, Irganox 1035, Irganox 1076, Irganox 1135, Irganox 245, Irganox 259, Irganox 295, Irganox 3114, and Irganox 1098 manufactured by Ciba Specialty Chemicals. Irganox 1520L, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-60, Adekastab AO-70, Adekastab AO-80, Adekastab AO-90, Adekastab AO- manufactured by Adeca 330, Sumilizer GA-80, Sumilizer MDP-S, Sumilizer BBM-S, Sumilizer GM, Sumilizer GS (F), Sumilizer GP, etc. manufactured by Sumitomo Chemical Industries.

In addition to this, a commercially available additive may be used as a coloring inhibitor for the resin. For example, Tinuvin 328, Tinuvin 234, Tinuvin 326, Tinuvin 120, Tinuvin 477, Tinuvin 479, Chimassorb 2020 FDL, Chimassorb 119FL, and the like manufactured by Ciba Specialty Chemicals Co., Ltd. may be mentioned.

At least one of the above-mentioned phosphorus compound, the amine compound, and the phenol compound is preferably contained, and the amount thereof is not particularly limited, and is 0.005 to 5.0% by weight based on the curable resin composition.

When the curable resin composition of the present invention is used for an optical material, particularly in the case of a photo-semiconductor encapsulant, it is preferred to add a zinc salt and/or a zinc complex to improve stability. The zinc salt is preferably a salt having a zinc ion as a central element and/or a complex compound, and preferably has a structure of a phosphate ester or a phosphoric acid as a counter ion and/or a ligand.

More preferably, it is a zinc salt and/or a zinc complex of phosphoric acid, a phosphate having 1 to 30 carbon atoms (monoester, diester, triester or a mixture thereof). Examples of the specific alkyl group of the phosphoric acid having 1 to 30 carbon atoms include a methyl group, an isopropyl group, a butyl group, a 2-ethylhexyl group, an octyl group, an isodecyl group, an isostearyl group, and a decyl group ( Decanyl), hexadecyl and the like.

In the present invention, a phosphate having a carbon number of 3 to 15 is particularly preferable, and the ester body may be mixed or a single product, and the main component thereof is preferably a phosphoric acid monoester. Especially in the phosphate ester contained, the molar ratio of the monoester, the diester and the triester (replaced by the purity of gas chromatography, wherein the sensitivity is caused by the necessity of trimethylsulfonation) In the difference), the amount of the monoester body is preferably 50% by area or more at the stage of the trimethylation treatment.

Such a phosphate compound can be obtained by esterifying an alcohol with phosphorus pentoxide, phosphonium chloride, phosphorus trichloride or the like as a phosphorylating agent. Further, the phosphoric acid is obtained, for example, by reaction with zinc carbonate, zinc hydroxide or the like (European Patent Application Publication No. 699708).

As a detail of the zinc salt or the zinc complex of the above phosphate, the ratio of the phosphorus atom to the zinc atom (P/Zn) is preferably from 1.2 to 2.3, more preferably from 1.3 to 2.0. Especially good is 1.4 to 1.9. That is, in the form of Yu Jia, it is preferred that the phosphate (or phosphoric acid) is 1.9 m or less with respect to zinc ions, not a simple ion structure, but has several molecules by ion bonding or coordination. The structure of the key and the associated structure.

As the above compound, commercially available zinc carboxylates include Zn-St, Zn-St 602, Zn-St NZ, ZS-3, ZS-6, ZS-8, ZS-8, ZS-7, and ZS-. 10. ZS-5, ZS-14, ZS-16 (made by Nitto Chemical Industrial Co., Ltd.), XK-614 (manufactured by King Industry), 18% Octope Zn, 12% Octope Zn, 8% Octope Zn (manufactured by Hope Pharmaceuticals); Examples of the phosphate ester and/or zinc phosphate include LBT-2000B (manufactured by SC Organic Chemicals) and XC-9206 (manufactured by King Industry).

Here, the ratio of the epoxy resin component to the zinc salt and/or the zinc complex compound is preferably 0.01 to 8% by weight, more preferably, based on the weight ratio of the zinc salt and/or the zinc complex compound to the epoxy resin component. It is 0.05 to 5% by weight and 0.1 to 4% by weight. When it is more than 8% by weight, the pot life of the curable resin composition becomes a problem, and when it is less than 0.01% by weight, the effect is not remarkable.

The curable resin composition of the present invention is obtained by uniformly mixing the components. The curable resin composition of the present invention can be easily formed into a cured product by the same method as previously known. For example, the curable resin composition of the present invention uses an extruder, a kneader, a roll, a planetary mixer, or the like, and an epoxy resin component, a curing agent, and/or a hardening accelerator, and optionally, a phosphorus-containing compound. The binder resin, the inorganic filler, and the formulation are thoroughly mixed until they become uniform. Further, as a curing method, when the curable resin composition is in a liquid state, the curable resin composition is potted or cast and impregnated into the substrate, and The curable resin composition is introduced into a mold and cast into a shape, and is hardened by heating. In the case of a solid state, it is molded by a casting or a transfer molding machine after melting, and is then hardened by heating. The hardening temperature is 80 to 200 ° C, and the hardening time is 2 to 10 hours. As the curing method, it is possible to coagulate at a high temperature at a time, but it is preferred to carry out a hardening reaction by gradually increasing the temperature. Specifically, initial hardening is performed between 80 and 150 ° C, and post-hardening is performed between 100 ° C and 200 ° C. As the stage of hardening, it is preferred to carry out the temperature increase in 2 to 8 stages, more preferably 2 to 4 stages.

Further, the curable resin composition of the present invention is dissolved in toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethyl acetamide, N-methyl In a solvent such as a pyrrolidone, a curable resin composition varnish is formed and impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper, and dried by heating to obtain a pre-prepared product. The ingot is subjected to hot press forming, whereby a cured product of the curable resin composition of the present invention can be formed. The solvent at this time is usually used in an amount of 10 to 70% by weight, preferably 15 to 70% by weight, based on the mixture of the curable resin composition of the present invention and the solvent. Further, in the state of the liquid composition, a cured product of a curable resin containing carbon fibers may be obtained by RTM (Resin Transfer Molding).

Further, the curable resin composition of the present invention can also be used as a film-type sealing composition. The film-type resin composition is a method in which the curable resin composition of the present invention is first formed into a curable resin composition varnish as described above, and applied to a release film to remove the solvent under heating. Thereafter, B-staged; thereby, a film-type resin composition was obtained as a sheet-like adhesive. The sheet-like adhesive can be used as an interlayer insulating layer of a multilayer substrate or the like, and an integral film seal of an optical semiconductor.

The epoxy resin composition of the present invention can also be suitably used as a sealing material or a die bonding material for a photo-semiconductor.

When the curable resin composition of the present invention is used as a sealing material for a photo-semiconductor such as a high-brightness white LED or a solid crystal material, the epoxy resin composition of the present invention is used as a hardener (hardener composition). An additive such as an acid anhydride and/or a polycarboxylic acid, a curing accelerator, a coupling material, an antioxidant, or a light stabilizer is sufficiently mixed to prepare a curable resin composition. The mixing method may be carried out by using a kneader, a three-roll mill, a universal mixer, a planetary mixer, a homomixer, a homodisperser, a bead mill, or the like at room temperature or under heating. The resulting curable resin composition can be used for a sealing material or for both a die bonding material and a sealing material.

An optical semiconductor element such as a high-brightness white LED is usually made of an adhesive (solid crystal material) so as to be laminated on a substrate such as bluestone, spinel, SiC, Si, or ZnO, such as GaAs, GaP, GaAlAs, GaAsP, AlGa, or InP. A semiconductor wafer such as GaN, InN, AlN, or InGaN is formed on a lead frame, a heat release plate, or a package. There is also a type in which a wire such as a metal wire is connected to the current flowing. The semiconductor wafer is sealed with a sealing material such as an epoxy resin. The sealing material is used to protect the semiconductor wafer from heat or moisture and to function as a lens function. The curable resin composition of the present invention can be used as the above-mentioned sealing material or solid crystal material. In terms of steps, it is preferred to use the curable resin composition of the present invention for both the die bonding material and the sealing material.

As a method of adhering a semiconductor wafer to a substrate using the curable resin composition of the present invention, after the curable resin composition of the present invention is applied onto a substrate by a dispenser, immersion or screen printing, A method in which a semiconductor wafer is placed on the curable resin composition and heat-hardened. By this method, the semiconductor wafer can be attached to the substrate. A hot air circulation type, an infrared ray, a high frequency wave, etc. can be used for heating.

The heating conditions are, for example, preferably from 80 to 230 ° C for about 1 minute to 24 hours. In order to reduce the internal stress generated during heat curing, for example, it may be pre-cured at 80 to 120 ° C for 30 minutes to 5 hours, and then post-cured at 120 to 180 ° C for 30 minutes to 10 hours.

The molding method of the sealing material is an injection method in which a sealing material is injected into a mold to which a substrate having a semiconductor wafer fixed as described above is inserted, and then heat-hardened and molded; and a sealing material is previously injected into the mold. A semiconductor wafer to be immersed and fixed on a substrate, and subjected to heat curing, and then subjected to a compression molding method such as demolding from a mold.

Examples of the injection method include a dispenser, transfer molding, and injection molding.

For heating, a hot air circulation type, an infrared ray, a high frequency wave, or the like can be used. The heating conditions are, for example, preferably from 80 to 230 ° C for about 1 minute to 24 hours. In order to reduce the internal stress generated during heat curing, for example, it may be pre-cured at 80 to 120 ° C for 30 minutes to 5 hours, and then post-cured at 120 to 180 ° C for 30 minutes to 10 hours.

Further, the use of the curable resin composition of the present invention is not limited to the above, and can be applied to general use using a curable resin such as an epoxy resin. Specifically, in addition to adhesives, coatings, coating agents, molding materials (including sheets, films, FRP (Fiber Reinforced Plastics), etc.), insulating materials (including printed substrates, wire coating, etc.), sealing materials In addition, examples of the cyanate resin composition for a substrate or an adhesive for a resist to be used in other resins such as an acrylate resin may be mentioned.

Examples of the adhesive include an adhesive for electronic materials other than for civil engineering, construction, automotive, general affairs, and medical adhesives. Examples of the adhesive for electronic materials include an interlayer adhesive for a multilayer substrate such as a build-up substrate, a semiconductor adhesive such as a die bond or a primer, and a BGA (Ball Grid Array). Array) A primer for encapsulation such as a primer, an anisotropic conductive film (ACF, an anisotropic conductive paste), or an anisotropic conductive paste (ACP).

Examples of the sealant include a capacitor, a transistor, a diode, a light-emitting diode, an IC, an LSI (Large Scale Integration), etc., and a immersion, immersion, and transfer molding seal, IC or LSI. COB (Chip on Board), COF (Chip On Film), TAB (Tape Automated Bonding), etc., infusion sealing, flip chip, etc. The primer used, the sealing of the IC package such as QFP (Plastic Quad Flat Package), BGA and CSP (Chip Scale Package), etc. (including the primer for reinforcement).

The cured product obtained in the present invention can be used for various purposes represented by optical component materials. The material for optics generally means a material for use in light, such as visible light, infrared rays, ultraviolet rays, X-rays, and laser light, through the material. More specifically, in addition to the LED sealing material such as a lamp type or an SMD (Surface Mount Device) type, the following may be mentioned. A material for a liquid crystal display device such as a substrate material such as a substrate material, a light guide plate, a ruthenium sheet, a polarizing plate, a phase difference plate, a viewing angle correction film, an adhesive, or a polarizing element protective film in the field of a liquid crystal display. In addition, it is desired as a sealing material for a color PDP (plasma display) of a next-generation flat panel display, an antireflection film, an optical correction film, a casing material, a protective film for a front glass, a front glass substitute material, an adhesive, and an LED. The molding material of the LED used in the display device, the sealing material of the LED, the protective film of the front glass, the front glass substitute material, the adhesive, and the substrate in the plasma address liquid crystal (PALC) display Material, light guide plate, cymbal sheet, polarizing plate, phase difference plate, viewing angle correction film, adhesive, polarizing element protective film, in addition, protective film for front plate glass and front plate glass in organic EL (electroluminescence) display Materials, adhesives, and various film substrates in a Field Emission Display (FED), a protective film for front glass, a front glass substitute material, and an adhesive. In the field of optical recording, VD (Video Disc), CD/CD-ROM, CD-R/RW, DVD-R/DVD-RAM, MO/MD, PD (phase change disc), optical disc substrate material for optical cards, optical disc The machine reads the lens, protective film, sealing material, adhesive, and the like.

In the field of optical equipment, it is a lens material for a static camera, a viewfinder 稜鏡, a target 稜鏡, a finder cover, and a light receiving sensor unit. In addition, the camera's photographic lens and viewfinder. In addition, a projection lens, a protective film, a sealing material, an adhesive, and the like of a projection television. A material for a lens of a light sensing machine, a sealing material, an adhesive, a film, or the like. In the field of optical parts, it is a fiber material around a light switch in an optical communication system, a lens, a waveguide, a sealing material for an element, an adhesive, and the like. Optical fiber material around the optical connector, ferrule, sealing material, adhesive, and the like. In the passive components and optical circuit components, the lens, the waveguide, the sealing material for the LED, the sealing material of the CCD (Charge Coupled Device), and the adhesive are used. A substrate material, a fiber material, a sealing material for an element, an adhesive, and the like surrounding the OEIC (Optoelectronic Integrated Circuit). In the field of optical fibers, it is used for decorative display illumination, light guide tubes, etc., sensors for industrial use, display/identification, etc., as well as optical fibers for communication infrastructure construction and digital connection in homes. Among the materials surrounding the semiconductor integrated circuit, there are resist materials for microetching technology for LSI and super LSI materials. In the field of automobile/transporter, it is a lamp reflector for automobile, bearing retainer, gear part, corrosion resistant coating, switch part, headlight, engine parts, electrical parts, various internal and external parts, drive engine, brake oil tank , automotive rust-proof steel plate, interior panel (interior panel), interior materials, wire bundles for protection/bundling, fuel hoses, automotive lamps, glass substitutes. In addition, double-glazing is used for rail vehicles. In addition, the toughness imparting agent of the structural material of the aircraft, the engine peripheral member, the wire bundle for protection/bundling, and the corrosion resistant coating. In the field of construction, it is a material for interior/processing, a lampshade, a sheet, a glass interlayer film, a glass substitute, and a solar cell peripheral material. For agricultural use, it is used for covering greenhouses. As a next-generation optical/electronic functional organic material, it is an organic EL element peripheral material, an organic light refracting element, an optical amplifying element as an optical-to-optical conversion device, an optical arithmetic element, a substrate material around an organic solar cell, a fiber material, and an element. Sealing material, adhesive, etc.

Example

Next, the present invention will be more specifically described by way of examples, and the "parts" are "parts by weight" unless otherwise specified. Furthermore, the invention is not limited to the embodiments. Further, in the examples, the physical property values were measured by the following methods.

‧Epoxy equivalent: measured according to JIS K-7236

‧ Viscosity: measured at 25 ° C using an E-type viscometer

‧Gas Chromatography (hereinafter referred to as GC):

Analysis condition

Separation column: HP5-MS (0.25 mm I.D. × 15 m, film thickness 0.25 μm)

Column heater temperature: The initial temperature was set to 100 ° C, the temperature was raised at a rate of 15 ° C per minute, and maintained at 300 ° C for 25 minutes.

Carrier gas: helium

‧ Gel Permeation Chromatography (hereinafter referred to as GPC):

Column: Shodex SYSTEM-21 column (KF-803L, KF-802.5 (×2), KF-802)

Linked solution: tetrahydrofuran at a flow rate of 1 ml/min

Column temperature: 40 ° C

Detection: UV (ultraviolet) (254 nm)

Calibration curve: Standard polystyrene manufactured by Shodex

Synthesis Example 1

Adding dimethyl 1,4-cyclohexanedicarboxylate (DMCD-pt, DMCD-pt) to a flask equipped with a stirrer, a reflux cooling tube, a stirring device, and a Ding Stark tube while performing nitrogen purge. 314 parts of 3-cyclohexene-1-methanol and 0.07 parts of tetrabutoxytitanium are used at 120 ° C for 1 hour, at 150 ° C for 1 hour, at 170 ° C for 1 hour, and at 190 ° C for 12 hours. The reaction is carried out while removing the methanol formed by the reaction. After the reaction was carried out by GC, it was cooled to 50 °C.

After the completion of the cooling, after adding 347 parts of toluene and making it uniform, the reaction solution was washed three times with 80 parts of a 10% by weight aqueous sodium hydroxide solution, and further washed with water in 100 parts/time until the wastewater became neutral, using rotary evaporation. Toluene and unreacted 3-cyclohexene-1-methanol were distilled off under reduced pressure under heating, whereby 240 parts of a diene compound which was liquid at normal temperature represented by the following formula (5) was obtained.

Formula (5)

Synthesis Example 2

In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, 15 parts of water, 0.95 parts of 12-tungstophosphoric acid, 0.78 parts of disodium hydrogen phosphate, and 2.7 parts of dihardified tallow alkyl dimethyl ammonium acetate were added while performing nitrogen purge. (manufactured by Lion Akzo, 50% by weight of hexane solution, Arquad 2HT-Acetate), 180 parts of toluene, and 118 parts of the diene compound obtained in Synthesis Example 1, and further stirred again to prepare a solution in an emulsion state. The solution was heated to 50 ° C, and 70 parts by weight of 35 wt% hydrogen peroxide water was added thereto over 1 hour while stirring vigorously. In this state, the mixture was stirred at 50 ° C for 13 hours. The progress of the reaction was confirmed by gas chromatography, and as a result, the peak of the material disappeared.

Then, after neutralizing with a 1% by weight aqueous sodium hydroxide solution, 25 parts of a 20% by weight 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 20 parts of activated carbon (manufactured by Ajinomoto Fine-Techno, CP1) and 20 parts of bentonite (Bengel SH, manufactured by Hojun) were added thereto, and the mixture was stirred at room temperature for 1 hour, and then filtered. The obtained filtrate was washed with water three times with 100 parts of water, and toluene was distilled off from the obtained organic layer to obtain 119 parts of an epoxy resin (EP-1) which was liquid at normal temperature. The epoxy equivalent of the obtained epoxy resin was 217 g/eq.

Synthesis Example 3

In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, 15 parts of water, 1.9 parts of 12-tungstophosphoric acid, 1.6 parts of disodium hydrogen phosphate, and 5.4 parts of dihardified tallow alkyl dimethyl ammonium acetate were added while performing nitrogen purge. (manufactured by Lion Akzo, 50% by weight of hexane solution, Arquad 2HT-Acetate), 160 parts of toluene, and 110 parts of 3-cyclohexene methyl ester of 3-cyclohexenecarboxylic acid, and stirred again to prepare an emulsion State solution. The solution was heated to 50 ° C, and 70 parts by weight of 35 wt% hydrogen peroxide water was added thereto over 1 hour while stirring vigorously. In this state, the mixture was stirred at 50 ° C for 20 hours. The progress of the reaction was confirmed by gas chromatography, and as a result, the peak of the material disappeared.

Then, after neutralizing with a 1% by weight aqueous sodium hydroxide solution, 25 parts of a 20% by weight 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 40 parts of activated carbon (manufactured by Ajinomoto Fine-Techno, CP1) and 40 parts of bentonite (manufactured by Hojun, Bengal SH) were added thereto, and the mixture was stirred at room temperature for 1 hour, and then filtered. The obtained filtrate was washed with water three times with 100 parts of water, and toluene was distilled off from the obtained organic layer to obtain 110 parts of an epoxy resin (EP-2) which was liquid at normal temperature. The epoxy equivalent of the obtained epoxy resin was 130 g/eq.

Synthesis Example 4

Adding a mixture of 10 parts of dicyclopentadiene dimethanol, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride to a flask equipped with a stirrer, a reflux cooling tube, and a stirring device while performing nitrogen purge ( New Japan Physicochemical Co., Ltd., Rikacid MH-700, hereinafter referred to as anhydride H-1) 50 parts, heated and stirred at 40 ° C for 1 hour and 60 ° C for 1 hour (by GPC confirmed dicyclopentane The disappearance of enedimethanol), thereby obtaining 60 parts of a hardener composition as a mixture of a polycarboxylic acid and an acid anhydride.

The obtained hardener composition is a colorless liquid resin, and the purity obtained by GPC is: the structure of the polycarboxylic acid is 51% by area, and the total amount of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride It is 49 area%. Further, the functional group equivalent was 201 g/eq.

Further, 12 parts of 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride (manufactured by Mitsubishi Gas Chemical Co., Ltd., H-TMAn, hereinafter referred to as H-2) was added to the obtained hardener composition. A uniform hardener composition (B-1). The weight ratio (theoretical value) of the obtained hardener composition (B-1) was 40.3% for the polycarboxylic acid, 48.9% for the acid anhydride H-1, and 10.7% for the acid anhydride H-2.

Synthesis Example 5

Adding a mixture of 10 parts of dicyclopentadiene dimethanol, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride to a flask equipped with a stirrer, a reflux cooling tube, and a stirring device while performing nitrogen purge ( New Japan Physicochemical Co., Ltd., Rikacid MH-700, hereinafter referred to as anhydride H-1) 50 parts, heated and stirred at 40 ° C for 1 hour and 60 ° C for 1 hour (by GPC confirmed dicyclopentane The disappearance of enedimethanol), thereby obtaining 60 parts of a hardener composition as a mixture of a polycarboxylic acid and an acid anhydride.

The obtained hardener composition is a colorless liquid resin, and the purity obtained by GPC is: the structure of the polycarboxylic acid is 51% by area, and the total amount of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride It is 49 area%. Further, the functional group equivalent was 201 g/eq.

Further, 6 parts of an acid anhydride (H-2) was added to the obtained hardener composition to prepare a uniform hardener composition (B-2). The weight ratio (theoretical value) of the obtained hardener composition (B-2) was 42.6% for the polycarboxylic acid, 51.7% for the acid anhydride H-1, and 5.6% for the acid anhydride H-2.

Example 1

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

Examples 2 and 3, Comparative Examples 1 to 4

The hardener composition (B-1) obtained in Synthesis Example 4 was used as the hardening accelerator for the obtained epoxy resin composition (F-1) and epoxy resin (EP-1) and (EP-2). The quaternary phosphonium salt (manufactured by Nippon Chemical Industry, Hishicolin PX4MP, hereinafter referred to as catalyst C-1) was blended at a mixing ratio (parts by weight) shown in Table 1 below, and defoaming was carried out for 20 minutes. The curable resin composition obtained was subjected to vacuum defoaming for 20 minutes, and then slowly cast on a glass substrate which was formed into a dam by a heat-resistant tape so as to have a size of 30 mm × 20 mm × a height of 1 mm. The cast material was pre-cured at 120 ° C for 3 hours, and then hardened at 150 ° C for 1 hour to obtain a test piece for a transmittance of 1 mm in thickness. The obtained test piece was heat-treated at 150 ° C for 96 hours, and the degree of coloration was evaluated by a thermal history (the retention of the transmittance at 400 nm was measured and compared).

According to the above results, the curable resin composition using the epoxy resin composition (F-1) of the present invention exhibits epoxy resin (EP) regardless of whether or not the epoxy resin (EP-1) or (EP-2) is mixed. -2) The retention rate of penetration at an equivalent level or above.

Example 4, Comparative Examples 5, 6

For the epoxy resin composition (F-1) and epoxy resin (EP-2), a commercially available alicyclic epoxy resin (manufactured by Daicel Chemical Industry, Celloxide 2021P, hereinafter referred to as EP-3), a synthesis example is used. (4) The obtained hardener composition (B-1) and the quaternary phosphonium salt (C-1) as a curing catalyst were prepared by blending ratio (parts by weight) shown in Table 2 below, and defoaming was carried out for 20 minutes. (The composition is described in Table 2). These were filled in a syringe and cast into a surface mount type LED package having an outer diameter of 5 mm square (having an inner diameter of 4.4 mm and an outer wall height of 1.25 mm) using a precision discharge device to a wafer having a central light-emitting wave of 465 nm. The cast product was placed in a heating furnace, hardened at 120 ° C for 1 hour, and further cured at 150 ° C for 3 hours to obtain an LED package. After the LED was packaged, the LED was turned on under the following conditions, and the illuminance was measured. The results are shown in Table 2.

Detailed conditions for lighting

Light emission wavelength: 465 nm

Drive mode: constant current mode, 60 mA (light-emitting component specified current is 30 mA)

Drive environment: 85 ° C, 85% RH

Driving time: 200 hours

Evaluation: Illumination retention rate after lighting for 200 hours

According to the above results, it is understood that the curable resin composition using the epoxy resin composition (F-1) of the present invention can be more excellent as an LED than the epoxy resin (EP-2) or (EP-3). Hardened material.

Synthesis Example 6

Adding dimethyl 1,4-cyclohexanedicarboxylate (DMCD-pt, DMCD-pt) to a flask equipped with a stirrer, a reflux cooling tube, a stirring device, and a Ding Stark tube while performing nitrogen purge. 314 parts of 3-cyclohexene-1-methanol and 0.07 parts of tetrabutyl titanate were subjected to removal of methanol formed by the reaction at 120 ° C for 1 hour, at 150 ° C for 1 hour, and at 170 ° C for 20 hours. reaction. After the reaction was carried out by GC, it was cooled to 50 °C.

After the completion of the cooling, after adding 347 parts of toluene and making it uniform, the reaction solution was washed three times with 80 parts of a 10% by weight aqueous sodium hydroxide solution, and further washed with water in 100 parts/time until the wastewater became neutral, and then added with chemistry. 5 g of activated carbon (manufactured by Ajinomoto Fine-Techno, ZN1) was activated, and after stirring at room temperature for 1 hour, activated carbon was removed by filtration. Toluene and unreacted 3-cyclohexene-1-methanol were distilled off under reduced pressure by heating using a rotary evaporator, whereby 235 parts of the diene compound represented by the above formula (5) was obtained.

Synthesis Example 7

In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, 15 parts of water, 0.95 parts of 12-tungstophosphoric acid, 0.78 parts of disodium hydrogen phosphate, and 2.7 parts of trioctylmethyl ammonium acetate (Lion Akzo) were added while performing nitrogen purge. A solution of 50% by weight of hexane solution, TOMAC-50), 170 parts of toluene, and 118 parts of the diene compound obtained in Synthesis Example 6 were further stirred, thereby preparing a solution in an emulsion state. The solution was heated to 50 ° C, and 70 parts by weight of 35 wt% hydrogen peroxide water was added thereto for 1 hour while stirring vigorously. In this state, the mixture was stirred at 50 ° C for 14 hours.

Then, after making it to pH 10 with a 30 weight% sodium hydroxide aqueous solution, 25 parts of 20 weight% sodium thiosulfate aqueous solution was added, and it stirred for 30 minutes, and it stood still. The organic layer separated into two layers was taken out, and 8 parts of activated carbon (manufactured by Ajinomoto Fine-Techno, CP1) and 10 parts of montmorillonite (Kunipia F, manufactured by Kunimine Industries) were added thereto, and the mixture was stirred at room temperature for 3 hours, and then filtered. . In addition, the wet cake was rinsed 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) which was liquid at normal temperature. The epoxy equivalent of the obtained epoxy resin was 212 g/eq.

Synthesis Example 8

In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, 15 parts of water, 0.9 parts of 12-tungstophosphoric acid, 1.5 parts of sodium phosphotungstate, 1.6 parts of disodium hydrogen phosphate, and 1.6 parts of trioctylmethyl group were added while performing nitrogen purge. 2.7 parts of ammonium acetate (manufactured by Lion Akzo, 50% by weight of hexane solution, TOMAC-50), 160 parts of toluene, and 110 parts of 3-cyclohexene methyl ester of 3-cyclohexenecarboxylic acid, and further stirred again. A solution in the form of an emulsion. The solution was heated to 46 ° C, and 70 parts by weight of 35 wt% hydrogen peroxide water was added thereto over 30 minutes while stirring vigorously. In this state, the mixture was stirred at 46 ° C for 16 hours. The progress of the reaction was confirmed by gas chromatography, and as a result, the peak of the material disappeared.

Then, after making it to pH 10 with a 30 weight% sodium hydroxide aqueous solution, 50 parts of 10 weight% sodium thiosulfate aqueous solution was added, and it stirred for 30 minutes, and it stood still. The organic layer separated into two layers was taken out, and 5 parts of activated carbon (manufactured by Ajinomoto Fine-Techno, CP1) and 10 parts of montmorillonite (Kunipia F. manufactured by Kunimine Co., Ltd.) were added thereto, and the mixture was stirred at room temperature for 1 hour, and then filtered. The obtained filtrate was washed with water three times with 100 parts of water, and toluene was distilled off from the obtained organic layer to obtain 109 parts of an epoxy resin (EP-5) which was liquid at normal temperature. The epoxy equivalent of the obtained epoxy resin was 129 g/eq.

Synthesis Example 9

In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, 24 parts of dicyclopentadiene dimethanol and methylhexahydrophthalic anhydride (manufactured by Nippon Chemical and Chemical Co., Ltd.) were added while performing nitrogen purge. 146 parts of Rikacid MH anhydride H-3), 30 parts of an acid anhydride (H-2), and heating and stirring at 40 ° C for 1 hour and 70 ° C for 1 hour, thereby obtaining hardening as a mixture of a polycarboxylic acid and an acid anhydride. The composition (B-3) was 100 parts.

The obtained hardener composition is a colorless liquid resin, and the purity obtained by GPC is: a structure of a polycarboxylic acid of 55 area%, an acid anhydride (H-3) of 35 area%, and an acid anhydride (H-2) of 10 areas. %. Further, the functional group equivalent was 178 g/eq.

Synthesis Example 10

In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, while performing nitrogen purge, 24 parts of 2,4-diethylpentanediol (Kyowadiol PD-9, Kyowadiol PD-9) was added thereto, and methylhexahydrogen was added. 146 parts of phthalic anhydride (manufactured by Nippon Chemical and Chemical Co., Ltd., called Rikacid MH anhydride H-3) and 30 parts of acid anhydride (H-2) were carried out at 40 ° C for 1 hour and 70 ° C for 1 hour. The mixture was heated and stirred to obtain 200 parts of a hardener composition (B-4) as a mixture of a polycarboxylic acid and an acid anhydride.

The obtained hardener composition is a colorless liquid resin, and the purity obtained by GPC is: a structure of a polycarboxylic acid of 50% by area, an acid anhydride (H-3) of 40% by area, and an acid anhydride (H-2) of 10 areas. %. Further, the functional group equivalent was 178 g/eq.

Examples 5-8 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 mixing ratios to obtain an epoxy resin composition (F-2) of the present invention. (F-5). For the epoxy resin composition obtained in the above, the hardener composition (B-3) obtained in Synthesis Example 9 was used in an amount of 0.8 mol, and the alkyl phosphate zinc catalyst as a curing catalyst (manufactured by King Industry, XC-) 9206, hereinafter referred to as C-2) For the resin 2000 ppm, the blending ratio (parts by weight) shown in Table 3 below was adjusted, and defoaming was carried out for 20 minutes. The obtained curable resin composition was subjected to vacuum defoaming for 20 minutes, and then slowly cast on a glass substrate which was formed into a barrier by a heat-resistant tape so as to have a size of 30 mm × 20 mm × a height of 1 mm. The cast material was pre-cured at 120 ° C for 3 hours, and then hardened at 150 ° C for 1 hour to obtain a test piece for a transmittance of 1 mm in thickness. The transmittance of each hardened material at 400 nm was compared. The obtained test piece was heat-treated at 150 ° C for 96 hours, and the degree of coloration was evaluated by a thermal history (the retention of the transmittance at 400 nm was measured and compared).

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 mixing ratios to obtain the epoxy resin composition (F-6) of the present invention. (F-8). For the epoxy resin composition obtained, the hardener compositions (B-3) and (B-4) obtained in Synthesis Examples 9 and 10 were used as the quaternary phosphonium salt (C-1) of the curing catalyst. Alkyl phosphate zinc (C-2), octyl phosphate (Hope Pharmaceuticals, Octope Zn, hereinafter referred to as C-3), phosphorus compound as an additive (Sanguang Co., Ltd., HCA, hereinafter referred to as C-4) Phosphorus compound (Adeca 260, hereinafter referred to as C-5), hindered amine (Adeca property, LA-62, hereinafter referred to as C _- 5), and the blending ratio (parts by weight) shown in Table 4 below. The preparation was carried out for 20 minutes to defoam (the composition is shown in Table 4). These were filled in a syringe and cast into a surface mount type LED package having an outer diameter of 5 mm square (having an inner diameter of 4.4 mm and an outer wall height of 1.25 mm) using a precision discharge device to a wafer having a central light-emitting wave of 465 nm. The cast product was placed in a heating furnace, hardened at 110 ° C for 2 hours, and further cured at 150 ° C for 3 hours to obtain an LED package. After the LED was packaged, the LED was turned on under the following conditions, and the illuminance was measured. The results are shown in Table 4.

Detailed conditions for lighting

Light emission wavelength: 465 nm

Drive mode: constant current mode, 60 mA (light-emitting component specified current is 30 mA)

Drive environment: 85 ° C, 85% RH

Driving time: 400 hours

Evaluation: 200 hours, illuminance retention after lighting for 400 hours

According to the above results, the epoxy resin composition of the present invention is excellent in optical characteristics (illuminance retention), and a cured product useful as an LED can be obtained.

The present invention has been described in detail with reference to the specific embodiments thereof, and it is understood that various changes and modifications may be made without departing from the spirit and scope of the invention.

In addition, the present application is based on Japanese Patent Application No. 2009-293479, filed on Dec. In addition, all of the reference frames cited herein are incorporated as a whole.

Claims (9)

An epoxy resin composition obtained by oxidizing a mixture of a diene compound represented by the following formula (1) and a diene compound represented by the following formula (2), which is derived from the formula (1) The ratio of the epoxy resin of the compound to the epoxy resin of the compound of the formula (2) is 10/90 to 90/10 by weight. Wherein a plurality of R independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; and P represents a cyclohexane ring or a norbornane ring which may have a methyl group as a substituent; In the formula, a plurality of R each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. An epoxy resin composition obtained by oxidizing an epoxy resin obtained by oxidizing a diene compound represented by the following formula (1) and an epoxy resin obtained by oxidizing a diene compound represented by the following formula (2) The mixture of the resins, the ratio of the epoxy resin derived from the compound of the formula (1) to the epoxy resin of the compound of the formula (2) is 10/90 to 90/10 by weight: Wherein a plurality of R independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; and P represents a cyclohexane ring or a norbornane ring which may have a methyl group as a substituent; In the formula, a plurality of R each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The epoxy resin composition according to claim 1 or 2, wherein the substituent R of the formula (1) and the substituent R of the formula (2) are a hydrogen atom, and a linking group P It is at least one selected from the group consisting of a methylcyclohexane ring, a cyclohexane ring, a methylnorbornane ring, and a norbornane ring. An epoxy resin composition according to claim 1 or 2, wherein the oxidation is carried out by using hydrogen peroxide. The epoxy resin composition of claim 3, wherein the oxidation is carried out by using hydrogen peroxide. A curable resin composition comprising the epoxy resin composition according to any one of claims 1 to 5, and a curing agent and/or a curing accelerator. A sclerosing resin composition as in claim 6 of the patent application, wherein The hardener is an acid anhydride and/or a polycarboxylic acid. A cured product obtained by hardening a curable resin composition of the sixth or seventh aspect of the patent application. An optical semiconductor device obtained by sealing with a curable resin composition of claim 6 or 7.