JP2009107979A - Method for producing carboxylic acid-modified triglycidyl isocyanurate, epoxy resin composition, and cured product of epoxy resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a carboxylic acid-modified triglycidyl isocyanurate, and to provide an epoxy resin composition useful as a sealing material for LED (liquid crystal display) emitting short-wavelength light. <P>SOLUTION: There is provided the method for producing the carboxylic acid-modified triglycidyl isocyanurate having ≥80% light transmittance when the carboxylic acid-modified triglycidyl isocyanurate is dissolved in methyl ethyl ketone so that the concentration of the carboxylic acid-modified triglycidyl isocyanurate is 80 mass% and measurement is made with a spectrophotometer at 400 nm wavelength using a quartz cell having 1 cm optical path length. The method for producing the carboxylic acid-modified triglycidyl isocyanurate is characterized by reacting a monocarboxylic acid in an amount of 0.1-0.6 mol based on 1 mol of the triglycidyl isocyanurate in an organic solvent in the presence of a quaternary phosphonium salt. The epoxy resin composition comprises an epoxy resin component comprising >90 mass% of the carboxylic acid-modified triglycidyl isocyanurate and a curing agent. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing carboxylic acid-modified triglycidyl isocyanurate, an epoxy resin composition containing a carboxylic acid-modified isocyanurate obtained by the production method and a curing agent for epoxy resin, and a cured product of the composition. It is. The epoxy resin composition of the present invention is particularly useful as an epoxy resin composition for a light-emitting device sealing material related to an optical semiconductor such as an LED because the cured product is excellent in heat resistance and light resistance.

  Epoxy resins are excellent in heat resistance, adhesion, water resistance, mechanical strength, electrical properties, etc., so they are used in various fields such as adhesives, paints, materials for civil engineering and construction, insulating materials for electrical and electronic parts, etc. in use. As the normal temperature or heat curable epoxy resin, aromatic epoxy resins such as diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, phenol or cresol novolac type epoxy resin are generally used.

  In recent years, most of light emitting devices such as optical semiconductors (LEDs) that have been put to practical use in various display panels, image reading light sources, traffic signals, large display units, and the like are manufactured by resin sealing. The sealing resin used here generally contains the above aromatic epoxy resin and an alicyclic acid anhydride as a curing agent.

  Also, due to the dramatic progress of today's LEDs, high output and short wavelength of LED elements are rapidly becoming a reality, especially LEDs using nitride semiconductors have a short wavelength and high output light emission. Is possible. However, when an LED element using a nitride semiconductor is sealed with the above-described aromatic epoxy resin, the aromatic ring absorbs light of a short wavelength, so that the resin sealed over time deteriorates, and light emission occurs due to yellowing. There arises a problem that the luminance is significantly reduced.

Therefore, an LED sealed with an alicyclic epoxy resin obtained by oxidizing a cyclic olefin, represented by 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, has been proposed. (Patent Document 1, Patent Document 2).
However, the cured resin encapsulated with the alicyclic epoxy resin described above is very fragile, is liable to be cracked by the thermal cycle, and has extremely poor moisture resistance. Was unsuitable.

  In view of this, there has been proposed an LED mainly composed of hydrogenated bisphenol A type epoxy resin, blended with an alicyclic epoxy resin and a phosphorus antioxidant, and sealed with a methylhexahydrophthalic anhydride curing agent (patent) Reference 3). Although this epoxy cured product is excellent in colorless and transparent properties, it has a drawback that it tends to yellow due to a decrease in heat resistance, and there is a problem in applications for sealing LED elements that require heat resistance.

  Furthermore, a method using a triazine derivative epoxy resin and an acid anhydride curing agent has also been proposed (Patent Document 4). Although the heat resistance of the cured product is improved, a triazine derivative epoxy resin typified by tris- (2,3-epoxypropyl) -isocyanurate is a crystalline epoxy resin and therefore mixed with an acid anhydride curing agent. When heating, heating at 100 ° C. or higher is required. Since this mixing operation is performed at the reaction temperature of the epoxy resin and the curing agent, the epoxy resin composition is likely to be gelled, and the triazine derivative epoxy resin is crystallized when the composition is cooled. Thus, since it has the problem that workability | operativity is bad, it was very difficult to use the composition of a triazine derivative epoxy resin and an acid anhydride hardening | curing agent for a liquid LED sealing material use.

JP-A-9-213997 JP 2000-196151 A JP 2003-12896 A JP 2003-224305 A

  The present invention uses a carboxylic acid-modified triglycidyl isocyanurate, can improve the above-mentioned poor workability, can give a cured product excellent in heat resistance and light resistance, and in particular, an LED encapsulant that emits light of a short wavelength It is intended to provide an epoxy resin composition and a cured epoxy resin that are useful as:

The present invention for solving the above problems includes the following inventions.

(1) Light transmittance when measured with a spectrophotometer having a wavelength of 400 nm using a quartz cell having a 1 cm optical path length dissolved in methyl ethyl ketone so that the concentration of carboxylic acid-modified triglycidyl isocyanurate is 80% by mass. Is a method for producing a carboxylic acid-modified triglycidyl isocyanurate having a quaternary phosphonium salt of 0.1 to 0.6 mol of a monocarboxylic acid per mol of triglycidyl isocyanurate in an organic solvent. A process for producing a carboxylic acid-modified triglycidyl isocyanurate, characterized by reacting in the presence of

(2) The method for producing a carboxylic acid-modified triglycidyl isocyanurate according to item (1), wherein the monocarboxylic acid is an aliphatic monocarboxylic acid or alicyclic monocarboxylic acid having 11 or less carbon atoms.

(3) The monocarboxylic acid is at least one selected from acetic acid, propionic acid, butyric acid, and lactic acid, and the reaction is performed at a ratio of 0.2 to 0.5 mol of monocarboxylic acid with respect to 1 mol of triglycidyl isocyanurate. A method for producing a carboxylic acid-modified triglycidyl isocyanurate according to (1) or (2), which is characterized in that

(4) The quaternary phosphonium salt is a quaternary phosphonium salt that does not contain a halogen atom composed of chlorine, bromine, and iodine, and is any one of the items (1) to (3) A process for producing a carboxylic acid-modified triglycidyl isocyanurate as described in 1.

(5) The organic solvent is an organic solvent having a boiling point of 70 to 170 ° C. at normal pressure selected from aromatic hydrocarbons, ketones, esters and ethers, (1) to ( The method for producing a carboxylic acid-modified triglycidyl isocyanurate according to any one of items 4).

(6) (A) component; an epoxy resin containing more than 90% by mass of carboxylic acid-modified triglycidyl isocyanurate produced by the production method according to any one of items (1) to (5),
(B) component; curing agent for epoxy resin,
An epoxy resin composition comprising as an essential component.

(7) The epoxy resin composition according to item (6), wherein the epoxy resin curing agent of component (B) is an acid anhydride.

(8) An epoxy resin composition for a light emitting device sealing material, comprising the epoxy resin composition according to (6) or (7).

(9) The epoxy resin composition for a light-emitting element sealing material according to (8), wherein the light-emitting element is a light-emitting diode (LED) having a main light emission peak at 350 to 550 nm.

(10) A cured product obtained by curing the epoxy resin composition according to any one of items (6) to (9), wherein a 2 mm thick cured product is heated at 150 ° C. for 100 hours. A cured epoxy resin having a YI value (Yellowness Index) of 10 or less.

  The carboxylic acid-modified triglycidyl isocyanurate obtained by the production of the present invention has a hue close to colorless, and the cured product of the epoxy resin composition using the carboxylic acid-modified triglycidyl isocyanurate is excellent in heat resistance and light resistance. It can be particularly advantageously used as an epoxy resin composition for an LED sealing material that seals a group III nitride compound semiconductor that emits.

(Carboxylic acid modified triglycidyl isocyanurate)
The method for producing a carboxylic acid-modified triglycidyl isocyanurate according to the present invention comprises reacting 1 mol of triglycidyl isocyanurate and 0.1 to 0.6 mol of a monocarboxylic acid in an organic solvent in the presence of a quaternary phosphonium salt. This is a method for obtaining carboxylic acid-modified triglycidyl isocyanurate.

  When the amount of monocarboxylic acid is less than 0.1 mol with respect to 1 mol of triglycidyl isocyanurate, triglycidyl isocyanurate in the resulting carboxylic acid-modified triglycidyl isocyanurate tends to precipitate as crystals, which is not preferable. On the other hand, when the amount exceeds 0.6 mol, the hue of the carboxylic acid-modified triglycidyl isocyanurate is deteriorated, and the heat resistance of the cured product is also deteriorated.

  The obtained carboxylic acid-modified triglycidyl isocyanurate was dissolved in a methyl ethyl ketone solvent so that the concentration was 80% by mass, and a light beam when measured with a spectrophotometer having a wavelength of 400 nm using a quartz cell having an optical path length of 1 cm. It is an epoxy resin having a transmittance of 80% or more.

  Triglycidyl isocyanurate is tris (2,3-epoxypropyl) isocyanurate and is preferably a purified epoxy resin having a total chlorine content of 0.3% by mass or less. If the total chlorine content exceeds 0.3% by mass, the moisture resistance reliability is remarkably deteriorated.

  Monocarboxylic acids that can be used in the reaction of the present invention are propionic acid, lactic acid, butyric acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, palmitic acid, stearic acid, isobutyric acid, pivalic acid, 2-methyllactic acid. Aliphatic monocarboxylic acids such as 2-ethylhexanoic acid and ethoxyacetic acid, cycloaliphatic monocarboxylic acids such as cyclopentanecarboxylic acid, cyclohexanecarboxylic acid and 4-methylcyclohexanecarboxylic acid.

  Among these monocarboxylic acids, monocarboxylic acids having 11 or less carbon atoms are preferable in that they do not deteriorate the characteristics of triglycidyl isocyanurate, and monocarboxylic acids selected from acetic acid, propionic acid, butyric acid, and lactic acid. Carboxylic acid-modified triglycidyl isocyanurate obtained by reacting 0.2 to 0.5 mol with 1 mol of triglycidyl isocyanurate has a nearly colorless hue, and when it is cured with a curing agent, the heat resistance is reduced. More preferable in terms of reduction.

  Carboxylic acid-modified triglycidyl isocyanurate having a nearly colorless hue can be obtained by performing the reaction of triglycidyl isocyanurate and carboxylic acid in the presence of a quaternary phosphonium salt. When a quaternary phosphonium salt is used as a catalyst, the reaction between the carboxylic acid and the epoxy group proceeds faster than the non-catalyst, and the light transmission when measured with a spectrophotometer with a wavelength of 400 nm using a quartz cell with an optical path length of 1 cm. A carboxylic acid-modified triglycidyl isocyanurate having a rate of 80% or more is more preferable because it can be produced efficiently.

  The quaternary phosphonium salts that can be used are, for example, tetrabutylphosphonium benzotriazolate, tetra-n-butylphosphonium hexafluorophosphate, tetra-n-butylphosphonium o, o-diethylphosphorodithioate, methyltributylphosphonium. -Halogen atoms selected from chlorine, bromine and iodine in one molecule such as dimethyl phosphate, tetra-n-butylphosphonium, tetrafluoroborate, tetra-n-butylphosphonium, tetraphenylborate, tetraphenylphosphonium, tetraphenylborate Non-comprising compounds are preferred.

  Organic solvents that can be used in the reaction of the present invention include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, ketones such as methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, and cyclohexanone, ethyl acetate, propyl acetate, and butyl acetate. Such as esters, tetrahydrofuran, dioxane, and the like, preferably an organic solvent having a boiling point of 70 to 170 ° C. under a normal pressure, and within a range of 20 to 200 parts by mass with respect to 100 parts by mass of triglycidyl isocyanurate. Used in

  An organic solvent having a boiling point of less than 70 ° C. at normal pressure is not preferable because the reaction temperature is low when the reaction is performed while refluxing at normal pressure, so that the reaction proceeds slowly. On the other hand, if the boiling point exceeds 170 ° C., it takes a long time at a high temperature to distill off the organic solvent, and the organic solvent tends to remain in the carboxylic acid-modified triglycidyl isocyanurate.

  After reacting triglycidyl isocyanurate and monocarboxylic acid under the above-mentioned charging conditions in a temperature range of 70 to 170 ° C. for a time of 0.5 to 10 hours, the organic solvent is usually used at a temperature of 100 to 180 ° C. Carboxylic acid-modified triglycidyl isocyanurate can be obtained by distilling off under reduced pressure and reduced pressure.

  The light transmittance is measured by dissolving in a methyl ethyl ketone solvent so that the concentration of the carboxylic acid-modified triglycidyl isocyanurate is 80% by mass (any concentration range of 79.5-80.5% by mass). The above epoxy resin solution is put into a quartz cell having an optical path length of 1 cm, and light transmittance is measured at a wavelength of 400 nm using a spectrophotometer device.

  Carboxylic acid-modified triglycidyl isocyanurate having a light transmittance of less than 80% when measured with a spectrophotometer with a wavelength of 400 nm, when cured with a curing agent, the resulting epoxy resin cured product is colored brown and the hue is extreme Therefore, it is necessary to use a carboxylic acid-modified triglycidyl isocyanurate having a light transmittance of 80% or more.

(Epoxy resin composition)
The epoxy resin composition of the present invention contains more than 90% by mass of the carboxylic acid-modified triglycidyl isocyanurate produced by the production method of the present invention and contains other epoxy resin at less than 10% by mass. 100 mass parts and the hardening | curing agent for epoxy resins can mix | blend 0.1-200 mass parts.

  When another epoxy resin is blended with carboxylic acid-modified triglycidyl isocyanurate at a ratio of 10% by mass or more, the heat resistance of the resulting cured product tends to decrease.

(Other epoxy resins)
Examples of the epoxy resin other than the carboxylic acid-modified triglycidyl isocyanurate that can be used in the present invention include the following.
Bisphenol type epoxy obtained from bisphenol A, bisphenol F, bisphenol AD, biphenol, tetramethylbiphenol, terpene diphenol, hydroquinone, methylhydroquinone, dibutylhydroquinone, resorcin, methylresorcin, bisphenol S, thiodiphenol, dihydroxydiphenyl ether and dihydroxynaphthalene Polyvalents derived from various polyhydric phenols such as resins, phenol novolac resins, cresol novolac resins, bisphenol A novolak resins, dicyclopentadiene phenol resins, terpene phenol resins, phenol aralkyl resins, biphenyl aralkyl resins and naphthol novolac resins. Epoxy resin, diaminodiphenylmethane, aminopheno And amine-type epoxy resins obtained from a variety of amine compounds such as xylene diamine, methylhexahydrophthalic hydroxy phthalic acid, various glycidyl ester type epoxy resin obtained from carboxylic acids such as dimer acid. In addition, epoxy resin of polyhydric aliphatic alcohol, epoxy resin directly hydrogenated aromatic epoxy resin such as hydrogenated bisphenol A type epoxy resin, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxy An alicyclic epoxy resin obtained by oxidizing a double bond such as a rate. Among these epoxy resins, it is more preferable to use a hydrogenated epoxy resin and an alicyclic epoxy resin because light resistance is improved.

(Curing agent for epoxy resin)
Examples of the epoxy resin curing agent that can be used in the present invention include the following.
(1) Amines; bis (4-aminocyclohexyl) methane, bis (aminomethyl) cyclohexane, m-xylylenediamine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraspiro [ 5,5] Aliphatic and alicyclic amines such as undecane, aromatic amines such as metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) pheno And tertiary amines such as 1,8-diazabicyclo- (5,4,0) -undecene-7, 1,5-azabicyclo- (4,3,0) -nonene-7 and salts thereof.

(2) Acid anhydrides; aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexa anhydride Cyclic aliphatic acid anhydrides such as hydrophthalic acid, methylendomethylenetetrahydrophthalic anhydride, dodecenyl succinic anhydride, and trialkyltetrahydrophthalic anhydride.

(3) Multivalent phenols: catechol, resorcin, hydroquinone, bisphenol F, bisphenol A, bisphenol S, biphenol, phenol novolacs, cresol novolacs, bisphenol Divalent phenol novolacs such as A, trishydroxyphenylmethanes, aralkylpolyphenols, dicyclopentadiene polyphenols and the like.

(4) Other: BF ₃ complex compounds of amines, Bronsted acid salts such as aliphatic sulfonium salts, aromatic sulfonium salts, iodonium salts and phosphonium salts, organic acid hydrazides such as dicyandiamides, adipic acid dihydrazide and phthalic acid dihydrazide And resoles, adipic acid, sebacic acid, terephthalic acid, trimellitic acid, and polycarboxylic acids such as carboxyl group-containing polyester.

  These epoxy resin curing agents may be used singly or in combination of two or more.

  When the epoxy resin composition of the present invention is used for a light emitting device sealing material, the epoxy resin curing agent is preferably an acid anhydride, and examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, anhydrous Aromatic anhydrides such as pyromellitic acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylendoethylenetetrahydrophthalic anhydride, methylendoethylenehexahydro anhydride And cyclic aliphatic acid anhydrides such as phthalic acid and trialkyltetrahydrophthalic anhydride. Of these, hydrogenated cycloaliphatic anhydrides such as hexahydrophthalic anhydride and methylhexahydrophthalic anhydride are used, particularly in terms of improving the light resistance of the epoxy resin composition of the present invention. preferable.

  Moreover, a hardening accelerator can be mix | blended in order to accelerate | stimulate hardening of an acid anhydride. Examples of the curing accelerator include tertiary soaps, imidazoles, organic phosphine compounds or salts thereof, and metal soaps such as zinc octylate and tin octylate.

  The usage rate of the acid anhydrides is in the range of 20 to 200 parts by mass with respect to 100 parts by mass of the epoxy resin containing the carboxylic acid-modified triglycidyl isocyanurate of the component (A), and the usage rate of the curing accelerator is (A) It exists in the range of 0.01-10 mass parts with respect to 100 mass parts of carboxylic acid modification | denaturation triglycidyl isocyanurate of a component.

(Antioxidant)
When using the epoxy resin composition of this invention for light emitting element sealing materials, it is preferable to mix | blend antioxidant and to prevent the oxidative degradation at the time of a heating and to make hardened | cured material with little coloring. The antioxidant which can be used can use a phenol type, sulfur type, and phosphorus type antioxidant, and 0.01-10 mass parts of antioxidant is mix | blended in 100 mass parts of epoxy resin compositions. Specific examples of the antioxidant that can be used include the following antioxidants.

Monophenols; 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl-β- (3,5-di-t -Butyl-4-hydroxyphenyl) propionate and the like.
Bisphenols; 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-) 6-t-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 3,9-bis [1,1-dimethyl-2- {β- (3-t-butyl-4) -Hydroxy-5-methylphenyl) propionyloxy} ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane and the like.

  Polymeric phenols; 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5 -Di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, bis [3,3' -Bis- (4'-hydroxy-3'-t-butylphenyl) butyric acid] glycol ester, 1,3,5-tris (3 ', 5'-di-t-butyl-4'-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, tocophenol and the like.

Sulfur-based antioxidants:
Dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, and the like.

Phosphorous antioxidants:
Phosphites; triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, tris (2,4-di-t-butylphenyl) phosphite, Cyclic neopentanetetraylbis (octadecyl) phosphite, cyclic neopentanetetraylbi (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbi (2,4-di-t-butyl) -4-methylphenyl) phosphite, bis [2-tert-butyl-6-methyl-4- {2- (octadecyloxycarbonyl) ethyl} phenyl] hydrogen phosphite, and the like.

Oxaphosphaphenanthrene oxides; 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10- Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and the like.
Each of the above-mentioned various antioxidants can be used alone, but it is particularly preferable to use a combination of phenol / sulfur or phenol / phosphorus.

(UV absorber)
When using the epoxy resin composition of the present invention for a light-emitting device sealing material, 0.01 to 10 parts by mass of an ultraviolet absorber may be blended in 100 parts by mass of the epoxy resin composition to further improve the light resistance. it can. As the ultraviolet absorber, general ultraviolet absorbers for plastics can be used, and specific examples include the following.

  Salicylic acids such as phenyl salicylate, pt-butylphenyl salicylate, p-octylphenyl salicylate; 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy Benzophenones such as -4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5 ′; -Di-tert-Buchi Phenyl) benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-) Butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-amylphenyl) benzotriazole, 2-{(2′-hydroxy-3 ′, 3 ″, 4 '' 5 '', 6 ''-tetrahydrophthalimidomethyl) -5'-methylphenyl} benzotriazole and other benzotriazoles; bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [ Hindered amines such as {3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl} methyl] butyl malonate;

(Light emitting element)
Since the epoxy resin composition of the present invention is excellent in light resistance, the light-emitting element to be sealed is preferably an element that emits light having a relatively short wavelength with a peak wavelength of 350 to 550 nm.
Examples of such a light emitting device include a group III nitride compound semiconductor formed by metal organic chemical vapor deposition (MOCVD), molecular beam crystal growth (MBE), or halide vapor deposition (HVPE). Represented by the general formula Al _x Ga _y In _1-xy N (0 ≦ x ≦ 1, 0 ≦ y ≦ 1, 0 ≦ x + y ≦ 1), a so-called binary system of Al _x GaN and InN, It includes so-called ternary systems of Al _x Ga _1-x N, Al _x In _1-x N, and Ga _x In _1-x N (where 0 ≦ x ≦ 1). Examples of the semiconductor structure include a homostructure having a MIS junction, a PIN junction, a pn junction, or the like, a heterostructure, or a double heterostructure. Various emission wavelengths can be selected depending on the material of the semiconductor layer and the degree of mixed crystal. In addition, a single quantum well structure or a multiple quantum well structure in which the semiconductor active layer is formed in a thin film in which a quantum effect is generated can be used.

(Optional component)
In the epoxy resin composition of the present invention, the following components can be added and blended as necessary.
(1) Powdery reinforcing agents and fillers such as metal oxides such as aluminum oxide and magnesium oxide, silicon compounds such as fine powder silica, fused silica and crystalline silica, transparent fillers such as glass beads, and aluminum hydroxide Metal hydroxide, others, kaolin, mica, quartz powder, graphite, molybdenum disulfide, etc.
These compounding is mix | blended in the range which does not impair the transparency of the epoxy composition of this invention, and 10-100 mass parts is suitable with respect to 100 mass parts of epoxy resin compositions of this invention.

(2) Colorants or pigments such as titanium dioxide, molybdenum red, bitumen, ultramarine blue, cadmium yellow, cadmium red and organic dyes.
(3) Flame retardants such as antimony trioxide, bromine compounds and phosphorus compounds.
(4) Ion adsorbent.
(5) Coupling agent.
These are blended in an amount of 0.01 to 30 parts by mass with respect to 100 parts by mass of the epoxy resin composition of the present invention.

(6) Furthermore, various curable monomers, oligomers and synthetic resins can be blended for the purpose of improving the properties of the epoxy cured product. For example, a diluent for epoxy resins such as monoepoxy, diols or triols, vinyl ethers, oxetane compounds, fluororesins, acrylic resins, silicone resins and the like can be used. The compounding ratio of these compounds and resins is preferably 50 parts by mass or less with respect to 100 parts by mass of the epoxy resin composition of the present invention.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, the part in an example means a mass part.

Example 1 (Production Example 1)
In a 1 L flask, 297 g (1 mol) of tris (2,3-epoxypropyl) isocyanurate, 18 g (0.3 mol) of acetic acid, and Hishicolin PX-4MP (trade name of Nippon Chemical Industry Co., Ltd.) as a quaternary phosphonium salt; 0.15 g of methyltributylphosphonium dimethyl phosphate) and 200 g of toluene were charged, and the reaction was carried out for 5 hours while stirring at the reflux temperature (114 ° C.) of toluene. After completion of the reaction, toluene was distilled off under reduced pressure at a temperature of 110 to 140 ° C. to obtain 310 g of carboxylic acid-modified triglycidyl isocyanurate as a slightly yellow and highly viscous liquid (epoxy equivalent; 120). A solution in which 20 g of this carboxylic acid-modified triglycidyl isocyanurate was dissolved in 5 g of methyl ethyl ketone was placed in a 1 cm quartz cell, and the light transmittance determined from a spectrophotometer having a wavelength of 400 nm was 93%.

Example 2 (Production Example 2)
Carboxylic acid modification of a slightly yellow and highly viscous liquid was carried out in the same manner as in Example 1 except that the monocarboxylic acid was changed from acetic acid to 9 g (0.15 mol) of acetic acid and 13.5 g (0.15 mol) of lactic acid. 315 g of triglycidyl isocyanurate was obtained (epoxy equivalent; 122). The light transmittance at 400 nm of a solution prepared by dissolving 20 g of this carboxylic acid-modified triglycidyl isocyanurate in 5 g of methyl ethyl ketone was 93%.
After 20 g of the resin was dissolved in 5 g of methyl ethyl ketone, this solution was put into a 1 cm quartz cell, and the light transmittance determined from a spectrophotometer having a wavelength of 400 nm was 92%.

Comparative Example 1 (Comparative Production Example 1)
The same operation as in Example 1 was carried out except that the monocarboxylic acid was changed to 42 g (0.7 mol) of acetic acid to obtain 334 g of a carboxylic acid-modified triglycidyl isocyanurate having a tan and high viscosity liquid (epoxy equivalent: 150). ). After 20 g of this carboxylic acid-modified triglycidyl isocyanurate was dissolved in 5 g of methyl ethyl ketone, this solution was put into a 1 cm quartz cell, and the light transmittance determined from a spectrophotometer having a wavelength of 400 nm was 77%.

Comparative Example 2 (Comparative Production Example 2)
The same procedure as in Example 1 was carried out except that the reaction catalyst was changed from Hishicolin PX-4MP to 0.15 g of tetramethylammonium chloride to obtain 311 g of a brown and highly viscous liquid carboxylic acid-modified triglycidyl isocyanurate (epoxy equivalent). 121). After 20 g of this carboxylic acid-modified triglycidyl isocyanurate was dissolved in 5 g of methyl ethyl ketone, this solution was put into a 1 cm quartz cell, and the light transmittance determined from a spectrophotometer having a wavelength of 400 nm was 72%.

Example 3
100 parts of carboxylic acid-modified triglycidyl isocyanurate obtained in Example 1 (Production Example 1) and 140 parts of Ricacid MH-700 (trade name of Shin Nippon Rika Co., Ltd .; methylhexahydrophthalic anhydride) as a curing agent were heated at 80 ° C. After mixing until uniform, 0.5 part of Hishicolin PX-4MP (Nippon Chemical Industry Co., Ltd .; trade name: methyltributylphosphonium dimethyl phosphate) is added as a curing accelerator, stirred and dissolved to obtain an epoxy resin composition. It was.
After defoaming this composition under reduced pressure, it was poured into a mold and cured in an oven at 100 ° C. for 3 hours and then at 150 ° C. for 3 hours to obtain a cured product. The physical property values of this epoxy cured product are shown in Table 1.

Examples 4-5 and Comparative Examples 1-2
Except changing the epoxy resin as shown in Table 1, the same operation as in Example 3 was performed to obtain an epoxy resin composition, and then cured for a predetermined time to obtain a cured product. In addition, Example 4 prepared the epoxy resin composition like Example 3 except having added antioxidant. The results are shown in Table 1.

As is apparent from Table 1, a cured product of an epoxy resin composition prepared using 100% by mass of a carboxylic acid-modified triglycidyl isocyanurate produced by the production method of the present invention as an epoxy resin component (Examples 3 to 3). 5) has a well-balanced balance between the hue, UV resistance, heat deterioration resistance, and hygroscopic properties of cured products required for LED encapsulant applications.
On the other hand, in the production process of carboxylic acid-modified triglycidyl isocyanurate, a comparative example is produced using 0.7 mol of monocarboxylic acid exceeding 0.6 mol with respect to 1 mol of triglycidyl cyanurate. Cured product of epoxy resin composition prepared using 3 carboxylic acid modified triglycidyl isocyanurate as epoxy resin, and 90 mass using carboxylic acid modified triglycidyl isocyanurate produced by the production method of the present invention as epoxy resin component The cured product of the epoxy resin composition of Comparative Example 4 (containing 80% by mass) not contained in an amount exceeding 50% balances the properties of the cured product, such as hue, ultraviolet resistance, heat deterioration resistance, and hygroscopicity. Not well equipped.

The carboxylic acid-modified triglycidyl isocyanurate produced by the production method of the present invention is excellent as an epoxy resin component used in an epoxy resin composition for a light emitting device sealing material, and the carboxylic acid-modified triglycidyl isocyanurate is The curable epoxy resin composition used as an epoxy resin component is particularly useful as a curable epoxy resin composition for encapsulating a group III nitride compound semiconductor that emits light in a short wavelength region.

Claims (10)

  Dissolved in methyl ethyl ketone so that the concentration of carboxylic acid-modified triglycidyl isocyanurate is 80% by mass, using a quartz cell with an optical path length of 1 cm, and having a light transmittance of 80% when measured with a spectrophotometer having a wavelength of 400 nm A method for producing a carboxylic acid-modified triglycidyl isocyanurate as described above, wherein 0.1 to 0.6 mol of a monocarboxylic acid is added to 1 mol of triglycidyl isocyanurate in an organic solvent in the presence of a quaternary phosphonium salt. A process for producing a carboxylic acid-modified triglycidyl isocyanurate, characterized in that   The method for producing a carboxylic acid-modified triglycidyl isocyanurate according to claim 1, wherein the monocarboxylic acid is an aliphatic monocarboxylic acid or alicyclic monocarboxylic acid having 11 or less carbon atoms.   The monocarboxylic acid is at least one selected from acetic acid, propionic acid, butyric acid, and lactic acid, and is reacted at a ratio of 0.2 to 0.5 mol of monocarboxylic acid with respect to 1 mol of triglycidyl isocyanurate. A process for producing a carboxylic acid-modified triglycidyl isocyanurate according to claim 1 or 2.   The carboxylic acid-modified triglycidyl isocyanate according to any one of claims 1 to 3, wherein the quaternary phosphonium salt is a quaternary phosphonium salt containing no halogen atom composed of chlorine, bromine and iodine. A method for producing nurate.   The organic solvent is an organic solvent having a boiling point of 70 to 170 ° C at normal pressure selected from aromatic hydrocarbons, ketones, esters and ethers. A method for producing the carboxylic acid-modified triglycidyl isocyanurate according to item 1. (A) component; the epoxy resin which contains the carboxylic acid modification | denaturation triglycidyl isocyanurate manufactured by the manufacturing method of any one of Claims 1-5 over 90 mass%,
(B) component; curing agent for epoxy resin,
An epoxy resin composition comprising as an essential component.   The epoxy resin composition according to claim 6, wherein the epoxy resin curing agent of component (B) is an acid anhydride.   The epoxy resin composition for light emitting element sealing materials which consists of the epoxy resin composition of the said Claim 6 or 7.   The said light emitting element is a light emitting diode (LED) which has a main light emission peak in 350-550 nm, The epoxy resin composition for light emitting element sealing materials of Claim 8 characterized by the above-mentioned. A cured product obtained by curing the epoxy resin composition according to any one of claims 6 to 9, wherein a YI value (Yellowness Index) of a 2 mm thick cured product after heating at 150 ° C for 100 hours is Epoxy resin cured product that is 10 or less.